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INDUSTRIAL SOLVENTS HANDBOOK Second Edition Nicholas P. Cheremisinoff Princeton Energy Resources International Rockville, Maryland, U.S.A.
MARCEL
MARCEL DEKKER, INC.
NEW YORK • BASEL
Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress. ISBN: 0-8247-4033-5 This book is printed on acid-free paper. Headquarters Marcel Dekker, Inc. 270 Madison Avenue, New York, NY 10016 tel: 212-696-9000; fax: 212-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-260-6300; fax: 41-61-260-6333 World Wide Web http://www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities. For more information, write to Special Sales/Professional Marketing at the headquarters address above.
Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit): 10 9 8 7 6 5 4 3 2 1 PRINTED IN THE UNITED STATES OF AMERICA
CHEMICAL INDUSTRIES A Series of Reference Books and Textbooks
Founding Editor HEINZ HEINEMANN
1. Fluid Catalytic Cracking with Zeolite Catalysts, Paul B. Veriuto and E. Thomas Habib, Jr. 2. Ethylene: Keystone to the Petrochemical Industry, Ludwig Kniel, Olaf Winter, and Karl Stork 3. The Chemistry and Technology of Petroleum, James G. Speight 4. The Desulfurization of Heavy Oils and Residua, James G. Speight 5. Catalysis of Organic Reactions, edited by William R. Moser 6. Acetylene-Based Chemicals from Coal and Other Natural Resources, Robert J. Tedeschi 7. Chemically Resistant Masonry, Walter Lee Sheppard, Jr. 8. Compressors and Expanders: Selection and Application for the Process Industry, Heinz P. Bloch, Joseph A. Cameron, Frank M. Danowski, Jr., Ralph James, Jr., Judson S. Swearingen, and Marilyn E. Weightman 9. Metering Pumps: Selection and Application, James P. Poynton 10. Hydrocarbons from Methanol, Clarence D. Chang 11. Form Flotation: Theory and Applications, Ann N. Clarke and David J. Wilson 12. The Chemistry and Technology of Coal, James G. Speight 13. Pneumatic and Hydraulic Conveying of Solids, O. A. Williams 14. Catalyst Manufacture: Laboratory and Commercial Preparations, Alvin B. Stiles 15. Characterization of Heterogeneous Catalysts, edited by Francis Delannay 16. BASIC Programs for Chemical Engineering Design, James H, Weber 17. Catalyst Poisoning, L. Louis Hegedus and Robert W. McCabe 18. Catalysis of Organic Reactions, edited by John R. Kosak 19. Adsorption Technology: A Step-by-Step Approach to Process Evaluation and Application, edited by Frank L. Slejko 20. Deactivation and Poisoning of Catalysts, edited by Jacques Oudar and Henry Wise 21. Catalysis and Surface Science: Developments in Chemicals from Methanol, Hydrotreating of Hydrocarbons, Catalyst Preparation, Monomers and Polymers, Photocatalysis and Photovoltaics, edited by Heinz Heinemann and Gabor A. Somorjai 22. Catalysis of Organic Reactions, edited by Robert L. Augustine
23. Modern Control Techniques for the Processing Industries, T. H. Tsai, J. W. Lane, and C. S. Lin 24. Temperature-Programmed Reduction for Solid Materials Characterization, Alan Jones and Brian McNichol 25. Catalytic Cracking: Catalysts, Chemistry, and Kinetics, Bohdan W. Wojciechowski and Avelino Corma 26. Chemical Reaction and Reactor Engineering, edited by J. J. Carberry and A. Varma 27. Filtration: Principles and Practices, Second Edition, edited by Michael J. Matteson and Clyde Orr 28. Corrosion Mechanisms, edited by Florian Mansfeld 29. Catalysis and Surface Properties of Liquid Metals and Alloys, Yoshisada Ogino 30. Catalyst Deactivation, edited by Eugene E. Petersen and Alexis T. Bell 31. Hydrogen Effects in Catalysis: Fundamentals and Practical Applications, edited by Zoltan Paal and P. G. Menon 32. Flow Management for Engineers and Scientists, Nicholas P. Cheremisinoff and Paul N. Cheremisinoff 33. Catalysis of Organic Reactions, edited by Paul N. Rylander, Harold Greenfield, and Robert L. Augustine 34. Powder and Bulk Solids Handling Processes: Instrumentation and Control, Koichi linoya, Hiroaki Masuda, and Kinnosuke Watanabe 35. Reverse Osmosis Technology: Applications for High-Puhty-Water Production, edited by Bipin S. Parekh 36. Shape Selective Catalysis in Industrial Applications, N. Y. Chen, William E. Garwood, and Frank G. Dwyer 37. Alpha Olefins Applications Handbook, edited by George R. Lappin and Joseph L. Sauer 38. Process Modeling and Control in Chemical Industries, edited by Kaddour Najim 39. Clathrate Hydrates of Natural Gases, E. Dendy Sloan, Jr. 40. Catalysis of Organic Reactions, edited by Dale W. Blackburn 41. Fuel Science and Technology Handbook, edited by James G. Speight 42. Octane-Enhancing Zeolitic FCC Catalysts, Julius Scherzer 43. Oxygen in Catalysis, Adam Bielanski and Jerzy Haber 44. The Chemistry and Technology of Petroleum: Second Edition, Revised and Expanded, James G. Speight 45. Industrial Drying Equipment: Selection and Application, C. M. van't Land 46. Novel Production Methods for Ethylene, Light Hydrocarbons, and Aromatics, edited by Lyle F. Albright, Billy L. Crynes, and Siegfried Nowak 47. Catalysis of Organic Reactions, edited by William E. Pascoe 48. Synthetic Lubricants and High-Performance Functional Fluids, edited by Ronald L. Shubkin 49. Acetic Acid and Its Derivatives, edited by Victor H. Agreda and Joseph R. Zoeller 50. Properties and Applications of Perovskite-Type Oxides, edited by L. G. Tejuca and J. L. G. Fierro
51. Computer-Aided Design of Catalysts, edited by E. Robert Becker and Carmo J. Pereira 52. Models for Thermodynamic and Phase Equilibria Calculations, edited by Stanley I. Sandier 53. Catalysis of Organic Reactions, edited by John R. Kosak and Thomas A. Johnson 54. Composition and Analysis of Heavy Petroleum Fractions, Klaus H. Altgelt and Mieczyslaw M. Boduszynski 55. NMR Techniques in Catalysis, edited by Alexis T. Bell and Alexander Pines 56. Upgrading Petroleum Residues and Heavy Oils, Murray R. Gray 57. Methanol Production and Use, edited by Wu-Hsun Cheng and Harold H. Kung 58. Catalytic Hydroprocessing of Petroleum and Distillates, edited by Michael C. Oballah and Stuart S. Shih 59. The Chemistry and Technology of Coal: Second Edition, Revised and Expanded, James G. Speight 60. Lubricant Base Oil and Wax Processing, Avilino Sequeira, Jr. 61. Catalytic Naphtha Reforming: Science and Technology, edited by George J. Antos, Abdullah M. Aitani, and Jose M. Parera 62. Catalysis of Organic Reactions, edited by Mike G. Scaros and Michael L. Prunier 63. Catalyst Manufacture, Alvin B. Stiles and Theodore A. Koch 64. Handbook of Grignard Reagents, edited by Gary S. Silverman and Philip E. Rakita 65. Shape Selective Catalysis in Industrial Applications: Second Edition, Revised and Expanded, N. Y. Chen, William E. Garwood, and Francis G. Dwyer 66. Hydrocracking Science and Technology, Julius Scherzer and A. J. Gruia 67. Hydrotreating Technology for Pollution Control: Catalysts, Catalysis, and Processes, edited by Mario L. Occelli and Russell Chianelli 68. Catalysis of Organic Reactions, edited by Russell E. Malz, Jr. 69. Synthesis of Porous Materials: Zeolites, Clays, and Nanostructures, edited by Mario L. Occelli and Henri Kessler 70. Methane and Its Derivatives, Sunggyu Lee 71. Structured Catalysts and Reactors, edited by Andrzei Cybulski and Jacob Moulijn 72. Industrial Gases in Petrochemical Processing, Harold Gunardson 73. Clathrate Hydrates of Natural Gases: Second Edition, Revised and Expanded, E. Dendy Sloan, Jr. 74. Fluid Cracking Catalysts, edited by Mario L. Occelli and Paul O'Connor 75. Catalysis of Organic Reactions, edited by Frank E. Herkes 76. The Chemistry and Technology of Petroleum, Third Edition, Revised and Expanded, James G. Speight 77. Synthetic Lubricants and High-Performance Functional Fluids, Second Edition: Revised and Expanded, Leslie R. Rudnick and Ronald L. Shubkin
78. The Desulfurization of Heavy Oils and Residua, Second Edition, Revised and Expanded, James G. Speight 79. Reaction Kinetics and Reactor Design: Second Edition, Revised and Expanded, John B. Butt 80. Regulatory Chemicals Handbook, Jennifer M. Spero, Bella Devito, and Louis Theodore 81. Applied Parameter Estimation for Chemical Engineers, Peter Englezos and Nicolas Kalogerakis 82. Catalysis of Organic Reactions, edited by Michael E. Ford 83. The Chemical Process Industries Infrastructure: Function and Economics, James R. Couper, O. Thomas Beasley, and W. Roy Penney 84. Transport Phenomena Fundamentals, Joel L. Plawsky 85. Petroleum Refining Processes, James G. Speight and Baki Oziim 86. Health, Safety, and Accident Management in the Chemical Process Industries, Ann Marie Flynn and Louis Theodore 87. Plantwide Dynamic Simulators in Chemical Processing and Control, William L. Luyben 88. Chemicial Reactor Design, Peter Harriott 89. Catalysis of Organic Reactions, edited by Dennis Morrell 90. Lubricant Additives: Chemistry and Applications, edited by Leslie R. Rudnick 91. Handbook of Fluidization and Fluid-Particle Systems, edited by WenChing Yang 92. Conservation Equations and Modeling of Chemical and Biochemical Processes, Said S. E. H. Elnashaie and Parag Garhyan 93. Batch Fermentation: Modeling, Monitoring, and Control, Ali Cinar, Satish J. Parulekar, Cenk Undey, and Giilnur Birol 94. Industrial Solvents Handbook: Second Edition, Nicholas P. Cheremisinoff
ADDITIONAL VOLUMES IN PREPARATION Chemical Process Engineering: Design and Economics, Harry Silla Process Engineering Economics, James R. Couper Petroleum and Gas Field Processing, H. K. Abdel-Aal, Mohamed Aggour, and M. A. Fahim Thermodynamic Cycles: Computer-Aided Design and Optimization, ChihWu Re-Engineering the Chemical Processing Plant: Process Intensification, Andrzej Stankiewicz and Jacob A. Moulijn
PREFACE This volume is devoted to the use and selection of industrial solvents. The use of solvents is virtually universal for almost any manufactured item one can think of. One example is the coating industry. Practically every manufactured product requires a coating, for decorative and/or protective purposes. For some products, the "coating" is most of what we pay for. Photographic emulsions, as another example, are applied to the transparent backing, or "substrate," as viscous liquids, which then dry to form the photographic film. Various types of thin plastic sheet goods are manufactured in a similar way. Paper is another sheet good that must be coated using high-speed machinery. Long-lasting or time-release pharmaceutical pills use a special coating that is resistant to the action of stomach acid. Microelectronic fabrication requires the application of thin layers of liquid gold, because of its superior electrical conductivity. Architectural coatings, i.e., house paints, involve the use of a coating or paint, which is accompanied by the use of solvents. Similarly, automotive coating is a major component of manufacturing cost, adding about $600 per vehicle. New base coat/clear coat systems produce a beautiful jewellike appearance that certainly helps to sell the car, while at the same time providing effective rust protection. Coating products are, in fact, the first line defense in the control of rust. The economic importance of rust alone is amazing: a recent report from the Brookhaven National Laboratory estimates that 2 per cent of the nation's gross domestic product, in excess of $100 billion per year, is spent on the prevention and remediation of rust damage. Along with all of these applications, solvents are intimately used. Still another very common and widely practiced application of solvents is in solvent extraction processes used throughout the chemical manufacturing industry. The principle applied here is as follows. Many organic liquids are immiscible with water and so, when such a liquid is added to water, two layers are formed. Whether the organic layer is the upper or lower layer depends upon the relative density of the organic liquid and water. Suppose we have an aqueous solution of two components, A and B, and add to this an immiscible organic liquid. When we shake the mixture vigorously and then allow settling, if one of the components is more soluble in the organic layer than in the aqueous layer, then this component will be extracted into the organic layer. Assuming the other component is more soluble in the aqueous layer, then we will have separated the two components into different layers. If we carry out this separation in a separating funnel, then we can separate the two layers by simply draining off the lower layer. An organic liquid used for solvent extraction must be a good solvent for the solute(s) to be extracted. After being agitated with an aqueous solution, the droplets of the organic liquid should iii
iv
Preface
coalesce quickly and settle out as a separate layer. To do this, the specific density should be substantially greater or substantially less than 1 gem"3 (the specific density of water). Examples of organic solvents used for solvent extraction include chloroform (a heavy solvent that is widely used for extracting organic compounds and metal complexes from aqueous solution), benzene, and ethyl ether (which are lighter than water solvents). Solvents are also extensively used throughout the polymer industry for making polymer blends and various resins, in the synthesis of intermediates, and in the polymerization of a multitude of products. In the printing industry, solvents are synonymous with inks, being critical to drying time formulations. While the application of solvents serves the multitude of consumer needs that are a part of our everyday lives, their benefits must be weighed against environmental costs. It is estimated that about one billion pounds of organic solvents, from liquid coating operations alone, are released into the environment by chemical process and manufacturing industries each year. Government legislation has made the control of these pollutants an industrial priority and has mandated drastic reductions in volatile organic solvent (VOC) content. New formulations produced to meet these requirements have far more complex rheological and film formation behavior, and generally exhibit poorer coating performance. Candidate replacement low-VOC coatings perform poorly as well and are more prone to final product defects. The development of environmentally friendly coating products and processes through green chemistry is promising, but there are major challenges to make these newer formulations and processes economically competitive. This handbook was written at the request of the publisher, who recognized the importance of the original volume prepared by Wesley Archer. Archer's Industrial Solvents Handbook provided a comprehensive reference that examines the physical and chemical properties, uses, and toxicity of solvents in the chemical and allied process industries. The present volume makes ample use of Archer's original work, but, in addition, expands upon it with more extensive and broader discussions covering safe handling practices, health effects, physical properties, and chemical synthesis routes to some of the more important solvents. The volume is organized into two parts. Part 1 provides an extensive treatment of the major classes of organic solvents. The reader will find considerable information covering physical properties data, general use descriptions, and solubility data. The use and application of the Hansen solubility theory is
Preface
v
explained in detail as it is the primary methodology recommended for proper solvent selection. In addition, there are discussions on Internet resources that can assist in the selection of environmentally friendly solvents. Part 2 provides chemical-specific profiles on major solvents and other chemicals of importance to coating and blend applications. The reader will find detailed information on the chemical formula, synonyms, physical properties, thermodynamic properties, health and toxicity, fire-fighting and explosion characteristics, and other relevant information. A glossary of terms relevant to solvent terminology is provided at the end of the volume. There is also an extensive subject index. The volume will assist chemists, chemical engineers, product development specialists, pollution prevention specialists, researchers, and technicians in the chemical and allied industries. Special thanks are extended to Marcel Dekker, Inc., for its fine production of this volume, and in particular to Ms. Lila Harris for her expertise in styling and copyediting. Nicholas P. Cheremisinoff
CONTENTS Preface, iii Part 1 Properties and Selection of Organic Solvents, 1 Introduction and an Overview of Part 1, 1 Section 1: Industrial Organic Solvents, 3 Alcohols, 3 Aldehydes, 22 Amines, 31 Esters, 34 Ethers, 38 Glycol Ethers, 46 Halogenated Hydrocarbons, 51 Hydrocarbon Solvents (Aliphatic and Aromatic), 74 Ketones, 83 Nitroparaffins, 88 Miscellaneous Solvents, 91 Section 2: Environmental, Health and Safety Regulations, 95 EPA and Environmental Legislation, 95 Occupational Safety and Health Administration, 122 Section 3: Solvent Selection Criteria, 127 A Quick Review of Safe Practices, 127 Overview of the Theory, 130 Application of the Theory, 132 Solvent Blends, 133 Internet Resources, 142 References and Recommended Resources, 145 Part 2 Hazardous and Toxic Chemical Profiles, 147 Introduction and Overview of Part 2, 147 Acetic Acid, 149 Acetic Anhydride, 149 Acetyl Bromide, 150 Acrylamide, 151 Acrylonitrile, 152 Allyl Alcohol, 154 Allyl Chloroformate, 154 Amyl Acetate, 155 Aniline, 156 Anisoyl Chloride, 157 Benzaldehyde, 158 VII
viii
Contents
Benzene, 158 Benzonitrile, 159 Benzophenone, 160 Benzoyl Chloride, 161 Benzyl Alcohol, 162 Benzylamine, 163 Benzyl Bromide, 164 Benzyl Chloride, 164 Benzyl Chloroformate, 166 Bromobenzene, 167 N-Butyl Acetate, 167 Sec-Butyl Acetate, 168 Iso-Butyl Acrylate, 169 N-Butyl Acrylate, 170 N-Butyl Alcohol, 171 Sec-Butyl Alcohol, 171 Tert-Butyl Alcohol, 172 N-Butylamine, 173 Sec-Butylamine, 174 Tert-Butylamine, 175 Butylene Oxide, 175 N-Butyl Mercaptan, 176 N-Butyl Methacrylate, 177 Iso-Butyraldehyde, 178 N-Butyraldehyde, 179 Carbolic Oil, 179 C arbon Tetrachloride ,180 Chloroform, 181 Copper Naphthenate, 182 Creosote, Coal Tar, 183 Cresols, 184 Cumene, 184 P-Cumene, 185 Cyclohexane, 186 Cyclohexanol, 187 Cyclohexanone, 188 Cyclopentane, 188 Decahydronaphthalene, 189 Decaldehyde, 190 1-Decene, 191 N-Decyl Alcohol, 191 N-Decylbenzene, 192
Contents Diacetone Alcohol, 194 Di-N-Phthalate, 194 Di-N-Butylamine, 195 Di-N-Butyl Ether, 196 Di-N-Butyl Ketone, 197 O-Dichlorobenzene, 197 P-Dichlorobenzene, 198 Dichlorobutene, 199 1,2-Dichloroethylene, 200 Dichloroethyl Ether, 201 Dichloromethane, 202 Dichloropropane, 203 Dichloropropene, 203 Dicyclopentadiene, 204 Diethanolamine, 205 Diethylamine, 206 Diethylbenzene, 207 Diethyl Carbonate, 207 Diethylene Glycol, 208 Diethylene Glycol Dimethyl Ether, 209 Diethyleneglycol Monobutyl Ether, 209 Diethyleneglycol Monobutyl Ether Acetate, 210 Diethylene Glycol Monoethyl Ether, 211 Diethylenetriamine, 212 Diheptyl Phthalate, 212 Diisobutylcarbinol, 213 Diisobutylene, 214 Diisobutyl Ketone, 214 Diisodecyl Phthalate, 215 Diisopropanolamine, 216 Diisopropylamine, 217 Dimethyl Ether, 218 Dimethyl Sulfate, 218 Dimethyl Sulfide, 219 Dimethyl Sulfoxide, 220 Dioctyl Adipate, 221 Dioctyl Phthalate, 222 Dipentene, 222 Diphenyl Ether, 223 Dipropylene Glycol, 224 Distillates, Flashed Feed Stocks, 225 Dodecanol, 225 Dodecene, 226
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Contents
2,4-D Esters, 193 1-Dodecene, 227 Dodecyltrichlorosilane, 228 Epichlorohydrin, 229 Ethyl Acetate, 229 Ethyl Acetoacetate, 230 Ethyl Aery late, 231 Ethyl Alcohol, 232 Ethylamine, 233 Ethylbenzene, 233 Ethyl Butanol, 234 Ethyl Butyrate, 235 Ethyl Chloride, 236 Ethyl Chloroacetate, 237 Ethyl Chloroformate, 237 Ethyldichlorosilane, 239 Ethylene Chlorohydrin, 239 Ethylenediamine, 240 Ethyl Ether, 241 2-Ethyl Hexanol, 242 Ethyl Formate, 243 Ethyl Hexyl Tallate, 243 Ethyl Lactate, 244 Ethyl Mercaptan, 245 Ethyl Methacrylate, 246 Ethyl Nitrate, 246 Ethylene Glycol Monobutyl Ether, 247 Ethylene Glycol Monoethyl Ether, 248 Ethylene Glycol Monomethyl Ether, 249 Ethyleneimine, 250 Formaldehyde Solution, 250 Furfuryl Alcohol, 251 Gas Oil, Cracked, 252 Gasolines, Automotive, 253 Gasoline Blending Stocks: Alkylates, 254 Glycerine, 255 Heptane, 255 Heptanol, 256 1-Heptene, 257 N-Hexaldehyde, 258 Hexamethyleneimine, 258 Hexane, 259
Contents Hexanol, 260 1-Hexene, 261 Hexylene Glycol, 261 Isoamyl Alcohol, 262 Isobutyl Acetate, 263 Isobutyl Alcohol, 264 Isobutylamine, 265 Isodecyl Alcohol, 265 Isohexane, 266 Isooctyl Alcohol, 267 Isophorone, 268 Isopropyl Acetate, 268 Isopropyl Alcohol, 269 Isopropylamine, 270 Isopropyl Ether, 271 Isopropyl Mercaptan, 272 Isopropyl Percarbonate, 273 Kerosene, 274 Linear Alcohols, 274 Mesityl Oxide, 275 Methyl Acetate, 276 Methyl Alcohol, 277 Methyl Amyl Acetate, 278 Methyl Amyl Alcohol, 278 N-Methylaniline, 279 Methyl N-Butyl Ketone, 280 Methyl Chloroformate, 281 Methyl Cyclopentane, 282 Methyldichlorosilane, 283 Methyl Ethyl Ketone, 283 Methyl Formal, 284 Methyl Formate, 285 Methyl Isobutyl Carbinol, 286 Methyl Isobutyl Ketone, 287 Methyl Isopropenyl Ketone, Inhibited, 288 Mineral Spirits, 288 Nonanol, 289 Nonene, 290 1-Nonene, 291 Nonylphenol, 291 Octane, 292 Oils, Miscellaneous: Resin, 295
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Contents
Octanol, 293 Oils: Clarified, 294 Oils, Miscellaneous: Mineral, 294 Pentane, 296 1-Pentene, 296 Polybutene, 297 Polypropylene Glycol, 298 N-Propyl Acetate, 298 N-Propyl Alcohol, 299 Propylene Oxide, 300 Quinoline, 301 Sodium Alkyl Sulfates, 302 Sorbitol, 302 Toluene, 303 Toluene 2,4-Diisocyanate, 304 O-Toluidine, 305 Trichloroethylene, 306 Trichlorofluoromethane, 307 Trichlorosilane, 307 Tridecanol, 308 1-Tridecene, 309 Triethanolamine, 310 Triethylbenzene, 310 Triethylene Glycol, 311 Tripropylene Glycol, 312 Turpentine, 312 Undecanol, 313 1-Undecene, 314 N-Undecylbenzene, 315 Vinyltoluene, 315 M-Xylene, 316 O-Xylene, 317 P-Xylene, 318 Xylenol, 319 Glossary of Relevant Solvent Terminology, 321 Index, 337
PARTI PROPERTIES AND SELECTION OF ORGANIC SOLVENTS INTRODUCTION AND AN OVERVIEW OF PART 1 The term solvent refers to a substance in which another substance is dissolved forming a solution. Solvents are used to suspend or change the physical properties of a material. Most organic liquids can act as a solvent. Solvents represent an important component in the chemical industry processes and in the application industries that employ solvents as ingredients in the manufacture of various products. Many organic solvents also serve as chemical intermediates in the synthesis of other organic chemicals. This part of the handbook focuses on organic solvents. Specific information covered includes physical and chemical properties, typical uses, pertinent legislation, and selection criteria. The important solvent classes covered in this section include aldehydes, aliphatic and aromatic hydrocarbons, ethers, halogenated hydrocarbons, ketones, nitroparaffins, monohydric and polyhydric alcohols, glycol ethers, aliphatic and heterocyclic amines, esters, and some miscellaneous organic solvents. The first section to Part 1 is devoted to general properties and descriptions of important classes of industrial organic solvents. The second section of Part 1 provides an overview of environmental and OSHA legislation. The third section describes the use of the Hansen solubility theory in the selection of solvents in industry applications or formulations. This section contains an extensive compilation of solubility parameters for solvents. ABBREVIATIONS The following abbreviations are used in both sections of the handbook. approx. ASTM atm. calc. CC CFR CHEMTREC deg.
Approximate Value American Society of Testing Materials Atmospheres Calculated Value Closed Cup Code of Federal Regulations Chemical Transportation Emergency Center Degree 1
Industrial Solvents Handbook
gal. hr i.e. IARC ISO kg Ib LD50 LEL LFL mg min. MSA NFPA NIOSH OC OSHA oz. P2 SCBA sec SS STEL TLV tox. UEL UEP
For Example Estimated Value Grams Gallons Hour Meaning, Definition International Association for Research on Cancer International Standards Organization Kilograms Pounds Lethal Dose 50 Lower Explosive Limit Lower Flammability Limit Milligrams Minutes Mine Safety Association National Fire Protection Association National Institute of Occupational Safety and Health Open Cup Occupational Safety and Health Act Ounce Pollution Prevention Self Contained Breathing Apparatus Seconds Suspended Solids Short Term Exposure Limit Threshold Limit Value Toxic Upper Flammability Limit Upper Explosive Limit
SECTION 1 INDUSTRIAL ORGANIC SOLVENTS ALCOHOLS Alcohols contain a hydroxyl functional group (-CH2OH). Monohydric alcohols are among the most common in this class of solvents. These are straight or branched chain aliphatic hydrocarbons that contain one hydroxyl group on: • • •
a primary carbon atom (RCH2OH), a secondary carbon atom (RR,CHOC), or a tertiary carbon atom (RR[R2COH).
An important cyclic alcoholic solvent is cyclohexanol. An important aromatic alcoholic solvent is benzyl alcohol. The high hydrogen bonding character of alcoholic solvents makes these substances valuable solvents for dissolving many polymeric and resin-like materials. Alcoholic functional groups are also valuable reaction sites for a large number of synthetic reactions of commercial importance. No gaseous alcohols are known. The lower members of the homologous series of aliphatic alcohols (containing Ci to Cio) are clear colorless liquids at room temperature. They have varying solubility in water, the higher alcohols being less soluble. The alcohols higher than C^ are solids and are insoluble in water. Methanol, ethanol and propanol are miscible with water. The alcohols are miscible in all proportions with most organic liquids. As we pass up the series, the specific gravity increases. The boiling points of the straight chain alcohols increase as the number of carbon atoms in the molecule increases. For a given molecular weight, there is a decrease in the boiling point when branching of carbon atoms occurs. Thus, the primary alcohols boil at a higher temperature than the secondary alcohols of the same molecular weight, and similarly, secondary alcohols have higher boiling points than the tertiary alcohols. The boiling points are much higher than is to be expected from their molecular weights. For example, the boiling point of ethanol, 78°C, can be explained by the attraction of ethanol molecules by means of hydrogen bonds to form extended groups of molecules. Hydrogen bonds can arise in ethanol because the area around the oxygen atom is relatively rich in electrons and can attract hydroxyl hydrogen from a neighboring ethanol molecule. These intermolecular bonds are considered to be intermediate in strength between weak van der Waals' forces and the strong forces between ions. The extra energy required to break the hydrogen bonds leads to an increase in boiling point. Alcohols react with sodium and potassium with the evolution of hydrogen.
Industrial Solvents Handbook 2C2H5OH + 2Na = H 2 + 2C 2 H 5 ONa Ethylene glycol, CH 2 OHCH 2 OH, is the most important dihydric alcohol and approximately 75 % of that produced is used as an anti-freeze agent. An example of a trihydric alcohol is glycerol. Glycerol, CH 2 OH«CHOH«CH 2 OH, is the most important trihydric alcohol and it is an important industrial chemical having many uses in war and peace. Glycerol is used in the production of explosives, as a moistening agent for tobacco, as a softening agent for cellophane films, in cosmetics, in food products, as a commercial solvent, and in the manufacture of plastics known as alkyd resins, which are used in paints. The chemical properties of any given aliphatic alcohol depends on the nature of the alkyl group in the molecule and on the properties of the hydroxyl group. Alcohols react with organic acids to form esters. The reaction proceeds slowly but the rate of esterification is increased by the presence of hydrogen ions, which act as a catalyst in the reaction. Sulfuric acid in addition to acting as a source of hydrogen ions also helps to increase the yield of ester by absorbing the water as it is formed in the reaction. Alcohols are very weak acids, intermediate in strength between acetylene and water. They undergo substitution with strongly electropositive metals such as sodium. Alcohols react with phosphorus pentachloride, when the hydroxyl group is replaced by a chlorine atom. Thus, when the hydroxyl group is replaced by a chlorine atom from phosphorus pentachloride fumes of hydrogen chloride are evolved and this is used in testing for the presence of the hydroxyl group in a compound. Common names for alcohols are Methanol, Ethanol, Isopropanol, n-Butanol, Isooctanol, Methyl Isobutyl Carbinol, Isoamyl Alcohol, Isobutyl Alcohol, Cyclohexanol, Methyl Cyclohexanol. The alcohols are versatile solvents that are used in many products from antiseptics and cough syrups to coatings and adhesives. Alcohols are used extensively as base materials for further processing into other chemicals such as esters, plasticizers and synthetic lubricants. Methyl alcohol is a strongly toxic material used in glass cleaners, shellac, NCR stains, dyes, inks, lacquer solvents, fuel additives and as an extractant for oils. Isopropanol (also known as Rubbing Alcohol) is used in cosmetics, perfumes, some types of coatings, cleaners, liniments, antiseptic solutions, liquid soaps and medications.
Nomenclature The common name for an alcohol involves naming the longest chain that includes the carbon atom attached to the hydroxyl group, and affixing the suffix "ol" to the hydrocarbon name. The proper nomenclature numbering assigns the lowest number to the position of the hydroxyl group and other numbers to indicate the alkyl or others groups associated with the main hydrocarbon chain. Table 1 provides a list
Properties and Selection of Organic Solvents of common chemical names along with Chemical Abstract Index names (CA Chemical Abstract Index, American Chemical Society) and CAS numbers (Chemical Abstract Service, American Chemical Society). CAS numbers in this case refer to the major alcohol component. Table 1. Nomenclature for Common Alcohols Chemical Name Methanol Ethanol /i-Propyl alcohol Isopropyl alcohol H-Butanol sec-Butanol Isobutanol tert-Bulanol rt-Amyl alcohol Isoamyl alcohol sec-Amy\ alcohol
tert-\my\ alcohol n-Hexyl alcohol
Cyclohexanol 2- Ethyl 1-butanol Methyl isobutyl carbinol 2-Ethyl 1-hexanol n-Octyl alcohol sec-Octyl alcohol Nonyl alcohol
CA Index Name 4-methyl 2pentanol 1-octanol 2-octanol 1-nonanol
CAS Number 108-93-0 97-95-0 108-11-2
75-65-0
Decyl alcohol
1-decanol
112-30-1
71-41-0 123-51-3
Benzyl alcohol Allyl alcohol
2-propen-l-ol
100-51-6 107-18-6
Diacetone
4-hydroxy 4methyl 2pentanone
123-42-2
CA Index Name 1-propanol
CAS Number 67-56-1 64-17-5 71-23-8
2-propanol 1-butanol 2-butanol 2-methyl 1propanol 2-methyl 2propanol 1-pentanol 3-methyl 1butanol 2-pentanol
67-63-0 71-36-3 78-92-2
2-methyl 2butanol 1-heaxanol
6023-29-7
Chemical Name
75-85-4
Furfuryl alcohol
111-27-3
Tetrahydrofurfuryl alcohol
104-76-7 111-87-5 123-96-6 143-08-8
98-00-0 97-99-4
-
General Properties Physical properties for many alcohols can be found among the chemical-specific profiles provided in Part 2. Some data are reported in Tables 2 and 3. Table 2 shows alcohols with minimum boiling azeotropes with water. Table 3 reports evaporation rates for common alcohols.
Table 2. Alcohol and Water Azeotropes Alochol Azeotrope Boiling Point (°C) Ethanol 78.0 n-Propanol 87.0 Isopropanol 80.3 n-Butanol 92.7 s^c-Butanol 87.0 Isobutanol 89.8
Weight Percent Water in Vapor Phase
4.0 28.3 12.6 42.5 26.8 33.0
Industrial Solvents Handbook Alochol Amyl alcohol Cyclohexanol Methyl isobutyl carbinol 2-Ethyl 1-hexanol Diacetone alcohol
Azeotrope Boiling Point (°C) 95.8 97.8 94.3 99.1 99.6
Weight Percent Water in Vapor Phase 54.4 80.0 43.3 80.0 87.0
Table 3. Alcohol Evaporation Rates (relative to /7-Butyl Acetate; i.e., /2-Butyl Acetate =1.0) Evap. Rate Alcohol BP (°C) Methanol 2.100 65 78 Ethanol 1.600 82 2-Propanol 1.400 tert-Butyl alcohol 0.950 83 tert-Amyl alcohol 102 0.930 97 0.860 «-Propyl alcohol 2-Butanol 0.810 100 108 2-Methyl 1-propanol 0.620 118 1-Butanol 0.440 132 Methyl isobutyl carbinol 0.300 137 1-Pentanol (n-amy\ alcohol) 0.200 Diacetone alcohol 0.140 166 0.110 146 2-Ethyl 1-butanol 148 Hexanol 0.096 161 Cyclohexanol 0.050 Tetrahydrofurfuryl alcohol 0.030 178 185 2-Ethyl 1-hexanol 0.020 177 2-Octanol 0.018 0.007 1-Octanol 196 0.007 205 Benzyl alcohol 0.001 231 1-Decanol (decyl alcohol) The low surface tension of alcohols is a property which favors their use in coating formulations. Alcoholic solvents afford a wide range of evaporation rates and excellent solvency for various resins and polymer compositions. The four lowest molecular weight alcohols are completely miscible with water and with most organic solvents. Tertiary butyl alcohol, diacetone alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol are also completely soluble in water. A compilation of general physical properties data is reported in Table 4. Table 5 reports solubility data.
Properties and Selection of Organic Solvents Table 4. General Physical Properties of Alcohol Solvents Viscosity Molecular Specific Solvent BP (°C) Weight (cP at 25°C) Gravity (60/60°F) Methanol Ethanol H-Propyl alcohol Isopropyl alcohol w-Butanol sec-Butanol Isobutanol tert-Butanol «-Amyl alcohol Isoamyl alcohol sec-Amyl alcohol tert-Amyl alcohol «-Hexyl alcohol Cyclohexanol 2-Ethyl-lbutanol Methyl isobutyl carbinol 2-Ethyl-lhexanol /z-Octyl alcohol Sec-Octy\ alcohol Nonyl alcohol Decyl alcohol Benzyl alcohol Allyl alcohol Diacetone alcohol Furfuryl alcohol Tetrahydrofurfuryl alcohol
32 46 60
65 78 97
0.7965 0.7937 0.809
0.56 1.1 2
Surface Tension (20°C) dynes/cm 22.6 22.3 23.8
60
82
0.79
2.4
21.4
74 74 74 74 88 88
118 99.5 108 83 133 130
0.814 0.811 0.806 0.779 0.82 0.809
2.6 2.9 1.8 3.35 3.7 3.9
24.6 23 22.8 20.7 23.8 23.8
88
119
0.811
4.1
22.9
88
102
0.81
3.5
21.8
102
157
0.821
5.4
23.6
100 102
161 146
0.953 0.832
52.7 5.9
35.1 25
102
132
0.802
130
184
0.833
7.7
28.7
130 130
196 177
0.827 0.818
8.9 6.2
27.1 26.1
144 158 108 58 116
215 231 205 97 166
0.812 0.838 1.05 0.854 0.94
14.3 13.8 0.05 1.07 3.2
28.7 -
98
170
1.135
5
38.2
102
178
1.054
6.2
37
22.8
Industrial Solvents Handbook Table 5. Solubility Data Solvent Methanol Ethanol rt-Propyl alcohol Isopropyl alcohol /z-Butanol 5ec-Butanol Isobutanol tert-Butanol /i-Amyl alcohol Isoamyl alcohol sec-Amy] alcohol tert-Amy\ alcohol //-Hexyl alcohol Cyclohexanol 2-Ethyl-l-butanol Methyl isobutyl carbinol 2-Ethyl-l-hexanol /z-Octyl alcohol Sec-Octy\ alcohol Nonyl alcohol Decyl alcohol Benzyl alcohol Allyl alcohol Diacetone alcohol Furfuryl alcohol Tetrahydrofurfuryl alcohol
Solubility (g/100 g) Water in solvent Solvent in water Complete Complete Complete Complete Complete Complete Complete Complete 20.1 7.7 15.4 65.1
8.7
15
Complete
Complete
1.7 2 13.7 3.8 2.9 1.7 0.1 0.06 0.13 0.06 0.01 0.08 Complete Complete Complete
9.2 8.2 20.9 11.8 9.2 6 2.6 3.4 0.99 2.3 8.4 Complete Complete Complete
The following are descriptions of some of the uses of and synthesis routes for several important alcoholic solvents. Methanol One of the major end uses of methanol is for the production of methyl tertiary-butyl ether (MTBE), a motor gasoline oxygenate for octane enhancement. Continued use of MTBE in the U.S. is, however, questionable. Environmental concerns related to high groundwater contamination has caused the US EPA (Environmental Protection Agency) to reverse its position on the toxic risks associated with MTBE and has more recently recommended replacement with ethanol. Despite this, the prospects for MTBE demand growth in Europe and Asia continue to be promising. New gasoline specifications were introduced by the European Union on January 1, 2000
Properties and Selection of Organic Solvents
9
and more stringent specifications will become effective in 2005. These new regulations phase out lead content and reduce the amount of sulfur and aromatics such as benzene, a known carcinogen. The octane provided by the lead and aromatics will have to be replaced. MTBE would be the easiest and most economical source of octane. This would result in additional methanol demand growth for MTBE in Europe. Industry consultants expect methanol demand for MTBE in Asia to grow at about 7% per year for the next few years. MTBE demand will be driven by strong economic growth in the region and a focus on better air quality in the major industrial centers. For example, China has started to phase out lead in gasoline and Thailand, Korea and Taiwan require the use of oxygenates in gasoline. Miscellaneous uses of methanol form the basis for many products including silicones, refrigerants, adhesives, specialty plastics and coatings, textiles, and water-treatment chemicals. Winter driving is made safer by methanol-based windshield antifreeze. Acrylic plastic light-coverings in homes and cars are based on another methanol derivative, methyl methacrylate. Other acrylic polymers are used in water-based interior and exterior coatings where superior durability is required. Paper products are usually bleached using chlorine dioxide, a process which produces significantly fewer pollutants than traditional bleaching methods. Similar to formaldehyde and acetic acid, overall growth of other derivatives is largely driven by general economic growth with some indicators including housing starts, new car production and industrial production. The largest solvent use for methanol is as a component of windshield wash antifreeze, where it can account for up to 50% of the solution depending on local climatic conditions. While not showing substantial growth, the expanded use of summer windshield cleaning solutions has changed the seasonal nature of this market. Methanol's purity and physical properties enable it to be used to extract, wash, dry and crystallize Pharmaceuticals and agricultural chemicals. It also acts well as a solvent in the production of ethyl cellulose, polyvinyl acetate, nitrocellulose, dyes, shellacs and numerous other chemicals. Formaldehyde - Methanol is also used as a raw material for producing formaldehyde, which is used extensively in the construction industry to manufacture strand board and fiberboard. Formaldehyde continues to be the largest single end use for methanol, representing 36% of 1999 demand. Changes in the market mix of wood panel products, coupled with high growth in plastics and fibers derivatives, are providing new growth potential for formaldehyde beyond the traditional demand stemming from the construction industry. Phenol formaldehyde resins (PF) for plywood and oriented strandboard (OSB), and urea formaldehyde resins (UF) for particleboard and medium density fiberboard (MDF) are the largest markets for formaldehyde. The declining availability of old-growth timber has accelerated the switch to engineered wood products such as particleboard, OSB and MDF. Engineered wood products can use lower quality woods and wood wastes as feedstocks, providing unique advantages over solid timber products. The non-
10
Industrial Solvents Handbook
structural panels industry has addressed the health concerns related to formaldehyde emissions by using re-engineered UF resins that have reduced emissions to onetenth the level typical of older resins. Non-structural panels continue to grow and have had particular strength due to the popularity of "ready to assemble" (RTA) furniture and cabinetry markets. Particleboard overlaid with wood veneer or plastic laminates has been a mainstay for these applications. MDF is the fastest growing segment of the wood panel adhesives market. MDF is beginning to replace traditional particleboard in many applications. The unique properties of MDF — its small particle size and uniform density — allow it to be machined or pressed into complex shapes. MDF applications include construction molding trim (baseboards, copings), architectural shapes (pillars, columns), and interior automotive trim parts (interior door panels and head liners). The urea formaldehyde adhesives used to bind the wood fibers in particleboard and MDF use a high proportion of formaldehyde in comparison to other resins. Industry forecasts suggest that MDF output will continue to grow. Plywood has been the traditional structural panel, but the declining availability of high-quality veneer timber is accelerating its replacement with cost advantageous products such as OSB. OSB uses lower quality and faster growing woods which are "waferized" into small chips, combined with a phenol-formaldehyde adhesive and pressed into finished panels. OSB uses approximately twice the amount of phenol-formaldehyde adhesive per board relative to plywood. OSB is forecast to continue gaining increasing share of the structural panel market. There are a wide range of other formaldehyde specialty products and applications such as: •
1,4 Butanediol is used in the production of tetrahydrofuran, a solvent used in the manufacture of "Spandex" fibers. This market has expanded rapidly with the increased sale of specialty sport and leisure clothing.
•
Acetyl thermoplastics are made using formaldehyde resins and offer high impact and durability. They continue to find increased use in automotive and plumbing applications including molded parts, gears and pump housings.
Formaldehyde is also used in the manufacture of methylene di-para-phenylene diisococyanate (MDI) which is used to produce rigid urethane foams and elastomers. High impact resistance and the ability to recover its original shape make this the ideal material for construction of bumpers and body panels. Markets and Miscellaneous Information - Methanol is methyl alcohol and at the present 99% of the production of methanol in the world is produced either from natural gas or gases out of oil. The reformed gas is compressed and passed to a methanol reactor. Carbon monoxide and carbon dioxide react with hydrogen over a catalyst to produce methanol. Also it is possible to produce methanol and ammonia
Properties and Selection of Organic Solvents
11
in one complex by using CO2, which is produced from an ammonia plant to produce methanol and urea. Methanol can be made from renewable resources such as municipal solid waste and biomass crops. Methanol production is a major market for U.S. natural gas, using over 194 trillion Btu of domestic natural gas in 1995. The United States produces almost one-quarter of the world's supply of methanol. In 1998, U.S. methanol production capacity totaled more than 2.2 billion gallons. Methanol plants meet three-quarters of U.S. methanol demand. The remaining supply comes from imports, of which Canada supplies well over one-half. In 1998, 90% of methanol supplied to the U.S. was produced in North America, 8% from Trinidad, Venezuela and Chile, with the remaining 2% produced in Europe, Asia and the Middle East. The largest market for methanol in the U.S. is for the production of MTBE. Produced in nearly 50 U.S. plants in 14 states, it is estimated that 3.3 billion gallons of MTBE was made in 1996 for blending in clean, reformulated gasoline serving 30% of the U.S. gasoline market. MTBE displaces 10 times more gasoline than all other alternative vehicle fuels combined. The single largest use of methanol is in formaldehyde and dimethyl terephthalate production. Methanol is also used in the manufacture of methyl acrylate, methyl methacrylate, methyl chloride, dimethyl ether, dimethyl sulfate, and various other intermediates and dyes. Methanol is useful in dissolving phenolic laminating resins, ethyl cellulose, cellulose nitrate, and a variety of other resins. Low-viscosity resin solutions are possible using methanol. Methanol burns with lower emissions than hydrocarbon fuels and is used as a fuel for many gasoline and diesel-type engines, stationary and aircraft turbines, industrial boilers, and in fuel cells. Methanol burns with a pale-blue, non-luminous flame to form carbon dioxide and steam. 2CH3OH + 3O2 = 2CO2 + 4H2O Manufacture - Most of world methanol is manufactured from natural gas by a steam reforming process. Methane of natural gas is first mixed with steam at a 3/1 ratio. It is then reformed to carbon oxides and hydrogen under nickel catalyst at 1000°C and 20 atm. Carbon oxides and hydrogen react exothermically at about 70 atm pressure in the gas phase to form mainly methanol and water mixture. This reaction takes place in the presence of Cu, Al and Zn based catalyst. Crude methanol is cooled and condensed and fed through a distillation process to achieve 99.9 molepercent product purity. The process is highly integrated. It uses state-of-the-art technologies to achieve low capital cost and higher conversion efficiency. As an alternative, a partial oxidation process is also used. Methanol production economics highly depend on the feedstock selection and feedstock prices. Methanol can be manufactured from any hydrocarbon source: naphtha, oil, coal, wood, biomass, LPG, etc. The naphtha, fraction of crude oil
12
Industrial Solvents Handbook
distillation, is used as a raw material in many older facilities for the manufacture of methanol. When naphtha is reacted with a high steam ratio, under pressure and at high temperature, synthesis gas of low methane content is obtained. Most of the carbon from the naphtha is converted to carbon monoxide and carbon dioxide: 1000°C CH4 + H2O = CO + 3H2
CO + H2O = CO2 + H 2 The mixture of hydrogen and carbon oxides is compressed and is passed over a catalyst under high pressure and at high temperature, methanol is formed.
400 °C CO + 2H2 = CH3OH C02 + 2H 2 = CH3OH + H2O The mixture of methanol, water, and other impurities is distilled to produce 99.95 mole-percent methanol product purity. Oxidation - Methanol is oxidized with acidified Potassium Dichromate, K 2 Cr 2 O 7 , or with acidified Sodium Dichromate, Na 2 Cr 2 O 7 , or with acidified Potassium Permanganate, KMnO 4 , to form formaldehyde. CH3OH = HCHO + H20
2H2 + 02 = H20 If the oxidizing agent is in excess, the formaldehyde is further oxidized to formic acid and then to carbon dioxide and water. HCHO = HCOOH = CO2 + H2O Catalytic Oxidation - The catalytic oxidation of methanol using platinum wire is of interest as it is used in model aircraft engines to replace the sparking plug arrangement of the conventional petrol engine. The heat of reaction is sufficient to spark the engine. Dehydrogenation - Methanol can also be oxidized to formaldehyde by passing its vapor over copper heated to 300°C. Two atoms of hydrogen are eliminated from each molecule to form hydrogen gas and hence this process is termed dehydrogenation. Cu
300 °C CH3OH = HCHO + H 2
Properties and Selection of Organic Solvents
13
Dehydration - Methanol does not undergo dehydration reactions. Instead, in reaction with sulfuric acid the ester, dimethyl sulfate is formed. Cone. H2SO4 2CH3OH = (CH3)2SO4 + H2O
Esterification - Methanol reacts with organic acids to form esters. H+ CH3OH + HCOOH - HCOOCH3 + H2O Substitution of Methanol with Sodium - Methanol reacts with sodium at room temperature to liberate hydrogen. This reaction is similar to the reaction of sodium with ethanol. 2CH3OH + 2Na = 2CH3ONa + H2 Substitution of Methanol with Phosphorus Pentachloride - Methanol reacts with phosphorus pentachloride at room temperature to form hydrogen chloride, methyl chloride (i.e. chloroethane) and phosphoryl chloride. CH3OH + PC15 = HC1 + CH3C1 + POC13 Substitution of Methanol with Hydrogen Chloride - Methanol reacts with hydrogen chloride to form methyl chloride (i.e. chloromethane) and water. A dehydrating agent (e.g. zinc chloride) is used. ZnCl2 CH3OH + HC1 - CH3C1 + H20 Ethanol Ethanol is a monohydric primary alcohol. It melts at -117.3°C and boils at 78.5°C. It is miscible (i.e., mixes without separation) with water in all proportions and is separated from water only with difficulty; ethanol that is completely free of water is called absolute ethanol. Ethanol forms a constant-boiling mixture, or azeotrope, with water that contains 95% ethanol and 5% water and that boils at 78.15°C; since the boiling point of this binary azeotrope is below that of pure ethanol, absolute ethanol cannot be obtained by simple distillation. However, if benzene is added to 95% ethanol, a ternary azeotrope of benzene, ethanol, and water, with boiling point 64.9°C, can form; since the proportion of water to ethanol in this azeotrope is greater than that in 95% ethanol, the water can be removed from 95% ethanol by adding benzene and distilling off this azeotrope. Because small amounts of benzene may remain, absolute ethanol prepared by this process is poisonous. Ethanol acts as a drug affecting the central nervous system. Its behavioral effects stem from its effects on the brain and not on the muscles or senses themselves. It is a depressant, and depending on dose can be a mild tranquilizer or a general
14
Industrial Solvents Handbook
anesthetic. It suppresses certain brain functions. At very low doses, it can appear to be a stimulant by suppressing certain inhibitory brain functions. However, as concentration increases, further suppression of brain functions produce the classic symptoms of intoxication: slurred speech, unsteady walk, disturbed sensory perceptions, and inability to react quickly. At very high concentrations, ethanol produces general anesthesia; a highly intoxicated person will be asleep and very difficult to wake, and if awakened, be unable to move voluntarily. Alcohol levels in the brain are difficult to measure, and so blood alcohol levels are used to assess degree of intoxication. Most people begin to show measurable mental impairment at around 0.05 percent blood alcohol. At around 0.10%, mental impairment will show obvious physical signs, such as an unsteady walk. Slurred speech shows up at around 0.15%. Unconsciousness results by 0.4%. Above 0.5%, the breathing center of the brain or the beating action of the heart can be anesthetized, resulting in death. Reaching this level of blood alcohol by ingestion is unlikely, however. In a 150-pound human, it would require rapid consumption of a fifth gallon of a 100proof spirit. Ethanol is used extensively as a solvent in the manufacture of varnishes and perfumes; as a preservative for biological specimens; in the preparation of essences and flavorings; in many medicines and drugs; as a disinfectant and in tinctures (e.g., tincture of iodine); and as a fuel and gasoline additive. Denatured, or industrial, alcohol is ethanol to which poisonous or nauseating substances have been added to prevent its use as a beverage; a beverage tax is not charged on such alcohol, so its cost is quite low. Medically, ethanol is a soporific, i.e., sleepproducing; although it is less toxic than the other alcohols, death usually occurs if the concentration of ethanol in the bloodstream exceeds about 5%. Behavioral changes, impairment of vision, or unconsciousness occur at lower concentrations. Ethanol is the alcohol of beer, wines, and liquors. It can be prepared by the fermentation of sugar (e.g., from molasses), which requires an enzyme catalyst that is present in yeast; or it can be prepared by the fermentation of starch (e.g., from corn, rice, rye, or potatoes), which requires, in addition to the yeast enzyme, an enzyme present in an extract of malt. The concentration of ethanol obtained by fermentation is limited to about 10% (20 proof) since at higher concentrations ethanol inhibits the catalytic effect of the yeast enzyme. (The proof concentration of an alcoholic beverage is numerically double the percentage concentration.) For nonbeverage uses ethanol is more commonly prepared by passing ethylene gas at high pressure into concentrated sulfuric or phosphoric acid to form the corresponding ester; the acid-ester mixture is diluted with water and heated, forming ethanol by hydrolysis, and the alcohol is then removed from the mixture by distillation, usually with steam. Ethanol is used in the following ways: •
Methylated Spirits - This a very common industrial solvent, used in many processes. It is also the solvent often used in paints, resins, soaps and dyes. Methylated spirits is actually ethanol, with 10-15% methanol added.
Properties and Selection of Organic Solvents
15
Both alcohols are poisonous in such quantities, so a purple dye is added to stop people drinking it. •
After-Shaves, Perfumes and Cosmetics - The active ingredients (usually smelly!) in these products are dissolved in the ethanol solvent. As the product is 'splashed all over', the ethanol evaporates, leaving behind the ingredients.
Industrially produced ethanol has many uses including use in solvent based paints, Pharmaceuticals, perfumes, cleaning products for home and car, lacquers, and inks. Ethanol and other alcohols have been added to gasoline to produce alcoholcontaining fuels. Since ethanol contains only one partially oxidized carbon atom, it is flammable and can be used as a fuel. The usual ratio of ethanol to gasoline is ninety parts gasoline to 10 parts ethanol while that for methanol is 97 parts gasoline to 3 parts methanol. Some cars have been designed to run on pure methanol. Gasohol has higher antiknock properties (higher octane) than gasoline, burns more slowly, coolly, and completely. However, it is more expensive and energy intensive to produce and may produce environmental hazards to the individual and to the atmosphere. Ethanol burns in air with a blue flame, forming carbon dioxide and water. It reacts with active metals to form the metal ethoxide and hydrogen, e.g., with sodium it forms sodium ethoxide. It reacts with certain acids to form esters, e.g., with acetic acid it forms ethyl acetate. It can be oxidized to form acetic acid and acetaldehyde. It can be dehydrated to form diethyl ether or, at higher temperatures, ethylene. Manufacture - Ethyl alcohol is derived from two main processes, hydration of ethylene and fermentation of sugars. Hydration of ethylene is the primary method for the industrial production of ethyl alcohol, while fermentation is the primary method for production of beverage alcohol. Traditionally, industrial ethanol is manufactured via the acid catalyzed hydration of ethylene. One synthetic route of alcohol by hydration of ethene involves the use of concentrated sulfuric acid (H2SO4). Unfortunately the use of sulfuric acid complicates the process due to concerns about safety, corrosion, and the environment. Current technology allows alcohol to be produced by utilization of zeolites or silica aerogels impregnated with phosphoric or tungstic acid. The distinct advantages of this process are that the reaction can be a one stage process, the catalyst is regenerated, and concerns about safety, corrosion, and the environment are diminished. This method has been chosen due to the relative low cost of the ethylene. Ethanol is particularly useful in industrial applications because of its relatively high affinity for both water and organic compounds. The composition of other alcohols limits their flexibility as compared to ethanol. For example, methanol with one carbon (CH3OH) has reduced solubility in hydrocarbons, while increasing the chain length such as in pentanol with 5 carbon units reduces its solubility in water. Thus,
16
Industrial Solvents Handbook
varying the chain length of the alcohol modifies its solubility in different compounds making it more or less useful dependent on the situation. One problem with the industrial production and utilization of ethanol is that ethanol is the alcohol found in beverages. Thus, industrial alcohol could be the source of large amounts of beverage alcohol. But it has been the practice to tax and control alcohol for beverages and industrial ethanol could be the source for a large amount of illegal alcohol. In order to reduce the need for strict control and heavy taxation on industrially produced ethanol, the alcohol is denatured. Denaturing is a process of adding other compounds to the ethanol to render it unfit for consumption. Denaturants are selected to give the ethanol a disagreeable taste or odor and in some cases a distinctive color. In some cases the substances added are toxic and produce gastric disturbances upon ingestion and/or other unpleasant symptoms. A large number of different "denaturants" are utilized dependent upon the use for which the ethanol is intended. These denaturants include methyl isobutyl ketone, pyronate, kerosene, acetone, turpentine, amyl alcohol, methyl alcohol, and various butyl alcohols. In some cases more than one denaturant is utilized. All beverage alcohol and much of that used in industry is formed through fermentation of a variety of products including grain such as corn, potato mashes, fruit juices, and beet and cane sugar molasses. (In earlier years, until about 1947, the largest proportion of the production of industrial alcohol was from fermentation, but as noted above the hydration of ethene now provides the greatest source of industrial alcohol). Fermentation can be defined as an enzymatically anaerobic controlled transformation of an organic compound. With respect to alcohol, we are referring to the conversion of sugars to ethanol by microscopic yeasts in the absence of oxygen. The equation for the fermentation of glucose is: C 6 H 12 O 6 0'» presence of yeast) = 2CH 3 CH 2 OH + 2CO, The initial fermentation mixture contains approximately 3 to 5% ethanol such as in beer and up to 12 to 15% ethanol as in wine and sherry. Higher concentrations of ethanol cannot be achieved by fermentation, because the yeast becomes inactivated. In this case distillation is required to generate higher alcohol concentrations. Distillation is a process that uses differences in boiling points to separate compounds. In the case of alcohol and particularly ethanol, knowledge that the boiling point of pure water is 100"C while that of ethanol is 78.3°C allows the separation of the ethanol from the water by adjusting the distillation temperature to a point higher than that for ethanol but lower than that for water. Thus, the concentration of ethanol can be enhanced by removing it as a distallate from the ethanol-water solution. Spirits such as gin, scotch, bourbon, and vodka, as well as liqueurs, cordials, and bitters are examples of beverages made from distillation.
Properties and Selection of Organic Solvents
17
The distillation procedure also allows for the concentration of components of the beverage which provide some distinctive flavor. Pure ethanol (200 proof) cannot be obtained via conventional distillation of a waterethanol mixture because a constant boiling mixture forms consisting of 95 % ethanol and 5% water (190 proof). Such a mixture is referred to as an azeotrope (azeotropic refers to a liquid mixture that is characterized by a constant concentration and constant minimum or maximum boiling point which is lower or higher than any of the components). Further concentration of the ethanol can be achieved by shifting the azeotropic point via vacuum distillation or addition of another substance to the mixture. Often times the compound added is highly toxic such as benzene, therefore absolute alcohol must never be consumed. The amount of ethyl alcohol in any one beverage varies. Thus, there are differences in the amount of alcohol between beer, wine, champagne and distilled spirits. The amount of alcohol is given as a percentage and also in "proof". The proof of an alcohol beverage is equal to twice the percentage of ethyl alcohol contained therein. Thus, 100 proof ethanol is 50% and 50 proof ethanol is 25%, etc. The process of making alcohol has been around since virtually as long as man has been on this earth, though it has been immensely refined and upgraded in recent years leading to much improved efficiency. As noted, there are three main uses for ethanol (industrial, beverage, and fuel) and the production processes vary slightly for each of them, but the main steps are the same. Examples of industrial uses of ethanol would include ethanol used in perfumes, aftershaves and for cleaners. Beverage ethanol is used for drinking and must meet strict production standards because it will be used for human consumption. A vast majority of ethanol produced in the U.S. is used for fuel. It is blended with gasoline to increase the fuel blend's octane or to produce a cleaner burning fuel. Most of the ethanol plants in the country utilize a dry milling process. The major steps are outlined below. •
Milling: The corn (or barley or wheat) will first pass through hammer mills, which grind it into a fine powder called meal.
•
Liquefaction: The meal will then be mixed with water and alpha-amylase, and will pass through cookers where the starch is liquefied. Heat will be applied at this stage to enable liquefaction. Cookers with a high temperature stage (120-150°C) and a lower temperature holding period (95°C) will be used. These high temperatures reduce bacteria levels in the mash.
•
Saccharification: The mash from the cookers will then be cooled and the secondary enzyme (gluco-amylase) will be added to convert the liquefied starch to fermentable sugars (dextrose), a process called saccharification.
•
Fermentation: Yeast will then be added to the mash to ferment the sugars to ethanol and carbon dioxide. Using a continuous process, the fermenting
18
Industrial Solvents Handbook mash will be allowed to flow, or cascade, through several fermenters until the mash is fully fermented and then leaves the final tank. In a batch fermentation process, the mash stays in one fermenter for about 48 hours before the distillation process is started. •
Distillation: The fermented mash, now called "beer," will contain about 10% alcohol, as well as all the non-fermentable solids from the corn and the yeast cells. The mash will then be pumped to the continuous flow, multi-column distillation system where the alcohol will be removed from the solids and the water. The alcohol will leave the top of the final column at about 96% strength, and the residue mash, called stillage, will be transferred from the base of the column to the co-product processing area.
•
Dehydration: The alcohol from the top of the column will then pass through a dehydration system where the remaining water will be removed. Most ethanol plants use a molecular sieve to capture the last bit of water in the ethanol. The alcohol product at this stage is called anhydrous (pure, without water) ethanol and is approximately 200 proof.
•
Denaturing: Ethanol that will be used for fuel is then denatured with a small amount (2-5%) of some product, like gasoline, to make it unfit for human consumption.
•
Co-Products: There are two main co-products created in the production of ethanol: carbon dioxide and distillers grain. Carbon dioxide is given off in great quantities during fermentation and many ethanol plants collect that carbon dioxide, clean it of any residual alcohol, compress it and sell it for use to carbonate beverages or in the flash freezing of meat. Distillers grains, wet and dried, are high in protein and other nutrients and are a highly valued livestock feed ingredient. Some ethanol plants also create a "syrup" containing some of the solids that can be a separate production sold in addition to the distillers grain, or combined with it. Ethanol production is a no-waste process that adds value to the corn by converting it into more valuable products.
Propyl Alcohol /2-Propanol is a chemical intermediate used in the synthesis of n-propyl amines and n-propyl acetate. w-Propyl acetate is used in conjunction with «-propyl alcohol as a solvent blend in printing inks. n-Propanol is also widely used in the manufacture of various textile chemicals, photographic chemicals, surfactants, and fatty esters such as oleate and propyl stearate. n-Propanol is widely used in the printing ink industry as a solvent for flexographic inks to control solvent evaporation and ink drying times. Isopropanol has similar applications as an intermediate and solvent.
Properties and Selection of Organic Solvents
19
Propyl alcohol, 1-propanol, is a colorless liquid with an odor similar to ethanol. It is polar, soluble in water, and has a specific gravity of 0.8, which is lighter than water. It is a dangerous fire risk with a flammable range of 2 to 13% in air. The vapor density is 2.1, which is heavier than air. The boiling point is 207°F, the flash point is 74°F, and the ignition temperature is 77°F. It is toxic by skin absorption with a TLV of 200 ppm in air. The four-digit UN identification number is 1274. The NFPA 704 designation is health 1, flammability 3, and reactivity 0. The primary uses are in brake fluid, as a solvent, and as an antiseptic.
Butyl Alcohols n-Butanol is widely used to produce plasticizer-type esters (e.g., phthalates, phosphates, sebacates, oleates, stearates). Two important ester derivatives are nbutyl acetate and rt-butyl acrylate. These are used coating applications and are made from n-butanol. Glycol ether derivatives (e.g., ethylene glycol monobutyl ether, EB) is used in the coating industry. It is the product of the n-butyl reaction with ethylene oxide in the presence of an acid catalyst. Other important n-butyl derivatives are butyl amines and butyl esters. These are used in formulations for herbicides, as butyl xanthate ore floatation acids, butylated urea, and melamineformaldehyde resins. «-Butanol («-butyl alcohol), a four carbon straight chain alcohol, is a medium-boiling liquid that is useful as a chemical intermediate and solvent. The future of n-butanol is tied to surface coatings, either through its derivatives or in direct solvent uses. Butanol and its derivatives continue to benefit from the long-term growth of water-based coatings formulations of all kinds. Analysts estimate that nearly 70% of all exterior architectural paints and as much as 85% of interior paints are now water-based. Therefore butanol, butyl acrylate and butyl acetate, become increasingly important. Another use of n-butyl alcohol is in pesticide residue analysis. Also, it is a solvent for liquid chromatography, machinery manufacture and repair, metal degreasing, rubber manufacture, and varnish. It is also an alcohol solvent in paint. It is used in the manufacture of lacquers, dyestuffs, rayon, detergents, plasticizers, and is a dehydrating substance. Aerosol paint concentrates, automobile refmish paints, general performance sealants, herbicides, inks, insecticides for crawling insects, markers, nail enamels and polishes, paints, sealants, clay, finger paint, paint removers and thinners, scatter rugs, and bathmats may contain this chemical. The total butanol produced was approximately 211,262 Ibs in 1997. Other uses of «-butanol include a latent solvent and coupling aid in nitrocellulose lacquer formulations to improve blush resistance, flow and leveling properties of the lacquers. It is also used for urea-formaldehyde and melamine-formaldehyde resins in surface coatings and in wood laminating adhesives. In the pharmaceutical industry n-butanol is used as an extraction solvent.
20
Industrial Solvents Handbook
Isobutanol serves as a chemical intermediate in the making of isobutyl esters, isobutyl amines, and in isobutylated urea or melamine-coating resins. It is used as a solvent in coating formulations with or without the cosolvent /z-butanol. Also nitrocellulose lacquers employ isobutanol as a latent solvent, while the alcohol is an active solvent in automotive and furniture finishes, lacquers, thinners, and hot spray lacquers. Secondary-butanol is used as an intermediate in the synthesis of methyl ethyl ketone (MEK) and sec-butyl acetate. Both are good solvents used for coating formulations. s^oButanol is an active solvent for ester gum, and in natural and synthetic resins such as alkyds and urea or melamine-formaldehyde resins. It is also a useful latent solvent for nitrocellulose lacquers. It is a useful coupling agent in cleaning formulations, oil field chemical blends, and in emulsion breakers. Furfuryl Alcohol Derivatives Synonyms include Furyl Carbinol, 2-Hydroxy Methyl Furan, 2-Furan Methanol, Furfuryl alcohol resin. Furan resin, FA resin, Poly(furfuryl alcohol), Prepolymers of FA. It is a raw material for organic synthesis, producing levulic acid, resin of various furane kinds in different properties, furfuryl alcohol urea formal resin and phenolic resin. It is a fine solvent for furane resin and oil varnish and pigment as well as used in rocket fuel. It is also used in the production of synthetic fibers, rubber, agricultural chemicals and foundry products. Furfuryl alcohol resins are derivatives of agricultural waste products and complex polymers that are formed in a condensation reaction that occurs when the furfuryl alcohol is acidified. The resins have low viscosity with an odor of furfuryl alcohol. The resin systems are highly reactive and can be catalyzed using a variety of active and latent acidic catalysts. When thermoset, the resins produce polymers that are heat resistant and extremely corrosion resistant to acids, bases and solvents. Furfuryl alcohol-based resins are used as binding agents in foundry sand and as corrosion inhibitors in mortar, grout, and cement. Because of their heat resistance, furan resins are used in the manufacture of fiberglass-reinforced plastic equipment. Derivatives of furfuryl alcohol (chemical formula: C5H6O2) include tetrahydro furfuryl alcohol, furane resins and organic furfural. The direct conversion into furfuryl alcohol, methylfuran and furan via metalcatalyzed hydrogenation, reduction and decarbonylation positions furfural as a strategic and ultimate industrial source for the production of a wide range of derivatives. Furfuryl amine, furoic acid, alpha-methylfurfuryl alcohol can be produced in one step from furfural. Other important fine chemicals are 2acetylfuran, 2,5-dimethoxydihydrofuran, 5-dimethylaminomethylfurfuryl alcohol, and others.
Properties and Selection of Organic Solvents
21
Polyhydric Alcohols The most common triol is glycerol (1,2,3-propanetriol or 1,2,3-trihydroxypropane). You will also encounter the name glycerine, or glycerin, which is not as acceptable but has become familiar from its derivative nitroglycerin(e) (more properly called glycerol trinitrate). The common name for 1,2,3,4-tetrahydroxybutane is erythritol. The 5-carbon tetrol tetra(hydroxymethyl)methane is called pentaerythritol; pentaerythritol tetranitrate (PETN) is a powerful explosive. Specific optical isomers (to be defined later) of the straight-chained 5-carbon and 6-carbon polyols analogous to glycerol are arabitol and mannitol. Polyhydric alcohols (polyols) can also form ethers and polyethers, in the same way as diols (glycols). Two molecules of an alcohol in reality form an ether by losing a molecule of water between them; one molecule loses a hydrogen atom H« and the other loses a hydroxy group »OH: RO-H + HO«R = ROR + HOH Since this is the case, it is possible for a molecule with two hydroxyls on different carbon atoms to form internal ethers:
HOCH2CH2OH = / H2C
O \
+ H20 CH2
The product in this case is called ethylene oxide, and is an important monomer and reactive intermediate. A catalyst RXM (not specified here) can open the ethylene oxide ring, which then adds to itself to form polyethylene glycol (PEG): O
RXM + x •
/
^ = RX(CH 2 CH 2 0) X M H 2 C— CH2
If RXM is an alcohol ROH, the product is an ethoxylated derivative of the alcohol, RO(CH2CH2O)XH. A simple example of this type of derivative, when RXM is CH3OH and x - 2, is CH3OCH2CH2OCH2CH2OH, Methyl Carbitol®. Ethylene oxide is an epoxy compound, and can also be named 1,2-epoxyethane. Diepoxy compounds are commercially important as components of epoxy adhesives. The simplest diepoxy compound is erythritol anhydride, or 1,2,3,4diepoxybutane:
22
Industrial Solvents Handbook O
O
/\ H2C
/\ CH CH
CH2
Terminological purists will name compounds with 3-membered epoxy rings as derivatives of oxirane, the internationally recognized (IUPAC) name for ethylene oxide. Some properties of polyhydric alcohols are given in Table 6. Table 6. Properties of Polyhydric Alcohols Solvent
Molecular Weight
BP°C@ 760 mm Hg
Specific Gravity (25"C)
Viscosity (cPat 25"C)
Ethylene glycol Diethylene glycol Triethylene glycol Tetraethylene glycol Propylene glycol Dipropylene glycol Tripropylene glycol Glycerol
62 106
197.4 245.5
1.11 1.111
150
287.8
194
Water Sol. (wt.%)
16.9 25.3
Surface Tension (25"C) dynes/cm 48 44
1.12
39.4
45
Comp.
325.6
1.123
43
-
Comp.
76
187.4
1.032
48.6
36
Comp.
134
232.2
1.022
75
35
Comp.
192
265.1
1.019
57.2
34
Comp.
92
1.262® 20°C 1.005® 20°C 1.015 @ 20°C 0.9921 @ 20°C 1.06® 20°C 0.923 @ 20"C
945
63.3
Comp.
104
37.8
0.5
65-70
-
Comp.
128
43.2
Comp.
-
-
Comp.
34.4
33.1
Comp.
1,3-Butanediol
90
198(40 mm Hg) 207.5
1,4-Butanediol
90
221-231
1,5-Pentanediol
104
242
Neopentyl glycol Hexylene glycol
104
210
118
198
Comp. Comp.
ALDEHYDES Aldehydes are organic compounds that have an acyl group, R-C = O with a Hydrogen bonded to the carbonyl or acyl carbon (double bonded carbon). Aldehydes and ketones have similar chemistry activity because of the fact that they
Properties and Selection of Organic Solvents
23
both have a carbonyl carbon. The bond is polar with the oxygen atom the negative end and the carbon end being positive. This results in nucleophiles being attracted to the carbonyl carbon and bonding with it. This similarity in nucleophilic attack makes the chemistry very close as we will see. Aldehydes are named by using the following rules: 1.
Identify the longest continuous chain of carbons with the acyl or carbonyl carbon as part of the chain.
2.
Number the carbon chain so that the carbonyl (acyl) carbon is always #1.
3.
Locate and identify alphabetically the branched groups by prefixing the carbon number it is attached to. If more than one of the same type of branched group is involved use the Greek prefixes di for 2, tri for three, etc.
4.
After identifying the name, number and location of each branched group, use the alkane name corresponding to the number of carbons in the continuous chain.
5.
Drop the "e" and add the characteristic IUPAC ending for all aldehydes, "al".
6.
Alkenals involving pi bonding will require that the pi bond is located but the ending will still be "al".
Figure 1 provides some examples. Consider the structure in Figure 1(A). 1.
We find the longest continuous chain of carbons with the acyl carbon involved is five.
2.
Numbering the carbons beginning with the acyl carbon on the extreme right as carbon # 1.
3.
Identifying the branched groups, there is a methyl group on carbon #3 and a bromine on carbon #2 so we would name and locate them: 2-Bromo-3methyl.
4.
Use the alkane name corresponding to the number of carbons in the chain (5) which would be pentane.
5.
Drop the "e" and add "al" so the name is: 2-Bromo-3-methylpentanal.
Consider the structure in Figure 1(B). 1.
Notice that there is a benzene ring with the characteristic functional group attached to the ring. This would be the parent aromatic aldehyde benzaldehyde.
24
Industrial Solvents Handbook 2.
Since we have three substitutions on the benzene ring we must use numbers and number the ring carbons beginning with the carbon with the aldehyde functional group attached to it as carbon #1. We then proceed to number clockwise.
3.
We notice a chlorine attached to carbon #3 and a methyl group attached to carbon #4.
4.
Locate and identify these branches: 3-Chloro-4-methyl.
5.
Add the parent name benzaldehyde and methylbenzaldehyde.
we
have:
3-chloro-4-
H
LH^-C-H^-CH-CxH-C = O
C
CH3 Br H (A)
CH3
CH3-CH = CH-CH,-CH-C = O
H (C)
Figure 1. Structural examples of common aldehydes.
Consider the last example in Figure 1(C). 1.
Identify the longest continuous chain of carbons with the acyl carbon as one of the carbons and the double bond must be between two of the carbons in the continuous chain, which would be six carbons.
Properties and Selection of Organic Solvents
25
2.
Number the carbons in the chain so that the acyl carbon is carbon #1.
3.
Locate and identify all branches, which is only a methyl attached to carbon # 2-2-methyl.
4.
Locate the pi bond in the chain. It is between the carbons #4 and 5.
5.
Use the alkene name corresponding to the number of carbons (6): hexane.
6.
Locate the pi bond by prefixing the lowest carbon # in which the pi bond is between. It is between carbon #4 and 5 so it would be: 4-hexene.
7.
Add to the name and it becomes: 2-methyl-4-hexene.
8.
Drop the "e" and add the characteristic "al" and it becomes: 2-methyl-4hexenal.
None of the hydrogen atoms connected to an aldehyde (or ketone) are bonded to an oxygen or nitrogen so they do not attract other molecules with the strong hydrogen bonding. For this reason the aldehydes do not have as high a boiling point for the same sized alcohol that has a hydrogen bonded to an oxygen. However aldehydes do have the carbonyl structure which is polar since the oxygen is much higher in electronegativity than the carbon atom. Therefore, aldehydes will exhibit dipoledipole interactions as well as the weak London dispersion intermolecular forces which make them have higher boiling points compared to the hydrocarbons and the ethers. For example, propanal and acetone have boiling points of 49°C and 56°C, respectively. The difference is due to the slightly higher molecular mass of acetone. This is to be compared with 1-propanol of 97°C and ethyl methyl ether at 8°C and butane at 0°C. The extra strong hydrogen bonding between the 1-propanol molecules would account for its higher boiling point. The carbonyl oxygen with its lone pairs allows aldehydes to hydrogen bond with hydroxylic compounds like water and alcohols. Therefore, the low molecular mass (up to four carbons) of aldehydes allows them to be very soluble in water. This solubility is similar to alcohols and ethers which also have oxygen atoms with lone pairs of electrons. Aldehydes (and ketones) of greater than five carbons generally will not be soluble in water as are the alcohols. This is because the increased size of the hydrocarbon portion will prevent water molecules from being attracted to the organic molecules. In other words the solvation process is hampered and the water molecules are not capable of surrounding each organic molecule and separating them. The polar water molecules have little attraction for hydrocarbons. We can transform an alkene into an alkane by adding an H 2 molecule across the C = C double bond.
26
Industrial Solvents Handbook
H
H
Ni
H
H
H
H
— C
C
H
H
H
The driving force behind this reaction is the difference between the strengths of the bonds that must be broken and the bonds that form in the reaction. In the course of this hydrogenation reaction, a relatively strong H H bond (435 kJ/mol) and a moderately strong carbon-carbon j.bond (270 kJ/mol) are broken, but two strong C H bonds (439 kJ/mol) are formed. The reduction of an alkene to an alkane is therefore an exothermic reaction. What about the addition of an H7 molecule across a C = 0 double bond?
H
H
O
C
C
H
H + H,
Pt
> H
H
O H
' C
' C
H
H
H
Once again, a significant amount of energy has to be invested in this reaction to break the H — H bond (435 kJ/mol) and the carbon-oxygen nbond (375 kJ/mol). The overall reaction is still exothermic, however, because of the strength of the C — H bond (439 kJ/mol) and the O — H bond (498 kJ/mol) that are formed. The addition of hydrogen across a C = O double bond raises several important points. First, and perhaps foremost, it shows the connection between the chemistry of primary alcohols and aldehydes. But it also helps us understand the origin of the term aldehyde. If a reduction reaction in which H2 is added across a double bond is an example of a hydrogenation reaction, then an oxidation reaction in which an H2 molecule is removed to form a double bond might be called dehydrogenation. Thus, using the symbol [O] to represent an oxidizing agent, we see that the product of the oxidation of a primary alcohol is literally an "al-dehyd" or aldehyde. It is an alcohol that has been dehydrogenated.
Properties and Selection of Organic Solvents
27
O
roi
CH3CH2OH -* CH3CH This reaction also illustrates the importance of differentiating between primary, secondary, and tertiary alcohols. Consider the oxidation of isopropyl alcohol, or 2propanol, for example.
OH
O [01
The product of this reaction was originally called aketone, although the name was eventually softened to azetone and finally acetone. Thus, it is not surprising that any substance that exhibited chemistry that resembled "aketone" became known as a ketone. Aldehydes can be formed by oxidizing a primary alcohol; oxidation of a secondary alcohol gives a ketone. What happens when we try to oxidize a tertiary alcohol? The answer is simple: Nothing happens. OH
CH.CCH, -/
»
CH, There aren't any hydrogen atoms that can be removed from the carbon atom carrying the — OH group in a 3° alcohol. And any oxidizing agent strong enough to insert an oxygen atom into a C - C bond would oxidize the alcohol all the way to CO2 and H2O. A variety of oxidizing agents can be used to transform a secondary alcohol to a ketone. A common reagent for this reaction is some form of chromium(VI) — chromium in the +6 oxidation state in acidic solution. This reagent can be prepared by adding a salt of the chromate (CrO42~) or dichromate (Cr2O72) ions to sulfuric acid. Or it can be made by adding chromium trioxide (CrO3) to sulfuric
28
Industrial Solvents Handbook
acid. Regardless of how it is prepared, the oxidizing agent in these reactions is chromic acid, H2Cr04.
OH
O
CH 3 CHCH 2 CH 3
H2Cr04
' > CH 3 CCH 2 CH 3
The choice of oxidizing agents to convert a primary alcohol to an aldehyde is much more limited. Most reagents that can oxidize the alcohol to an aldehyde carry the reaction one step further they oxidize the aldehyde to the corresponding carboxylic acid. O
H,Cr04
CH 3 CH 2 OH
O
CH.CH
CH3COH
A weaker oxidizing agent, which is just strong enough to prepare the aldehyde from the primary alcohol, can be obtained by dissolving the complex that forms between CrO3 and pyridine, C 6 H 5 N, in a solvent such as dichloromethane that doesn't contain any water. O
CH3CH,OH
CrO 3 /pyridine > CH.CH CH,C1,
The common names of aldehydes are derived from the names of the corresponding carboxylic acids. O
O
HCOH
HCH
Formic Acid
Formaldehyde
O
CH3COH Acetic Acid
O
CH3CH Acetaldehyde
The systematic names for aldehydes are obtained by adding -aI to the name of the parent alkane.
Properties and Selection of Organic Solvents O
29
O
HCH
CH3CH
Methanal
Ethanal Acid
The presence of substituents is indicated by numbering the parent alkane chain from the end of the molecule that carries the — CHO functional group. For example, O
BrCH2CH2CH
3-Bromopropanal
The common name for a ketone is constructed by adding ketone to the names of the two alkyl groups on the C —O double bond, listed in alphabetical order. O
CH3CCH2CH3
Ethyl methyl ketone
The systematic name is obtained by adding -one to the name of the parent alkane and using numbers to indicate the location of the C = O group (e.g., 2-Propanone). A common aldehyde is formaldehyde. Formaldehyde has a sharp, somewhat unpleasant odor. The aromatic aldehydes in the figure below, on the other hand, have a very pleasant "flavor." Benzaldehyde has the characteristic odor of almonds, vanillin is responsible for the flavor of vanilla, and cinnamaldehyde makes an important contribution to the flavor of cinnamon. O
CH
Benzaldehyde
HO
\W/ Vanillin
\V Jl Cinnamaldehyde
Y_
CH
30
Industrial Solvents Handbook
Aldehydes play an important role in the chemistry of carbohydrates. The term carbohydrate literally means a "hydrate" of carbon, and was introduced to describe a family of compounds with the empirical formula CH2O. Glucose and fructose, for example, are carbohydrates with the formula C 6 H, 2 O 6 . These sugars differ in the location of the C = O double bond on the six-carbon chain, as shown in the figure below. Glucose is an aldehyde; fructose is a ketone.
O \ OH
H
OH
OH
H
c— c— c— c— c— c
H-
H
H
OH
H
H
H
O \
H
OH
OH
H
— c— c— c— c— c
HO
OH
H
H
H
OH
Glucose
OH
Fructose
H
Aldehydes are mainly formed by the oxidation of alcohols, for example with acidified dichromate(VI) (aq) ions. Aldehydes are formed by the partial oxidation of primary alcohols, e.g.:
H
H
H
O
2
Cr207 -(aq)
H
C— C H
H
ethanol
OH
H— C— C H ethanal
Various properties of common aldehydes are reported in Table 7.
H
31
Properties and Selection of Organic Solvents Table 7. Properties of Aldehydes Solvent Mol. BP°C@ Wt. 760mm Hg Formaldehyde 37% Aqueous formaldehyde solution Acetaldehyde Propionaldehyde Butyr-aldehyde Isobutyraldehyde 2-Furaldehyde
Specific Gravity (20°C)
Viscosity cPat 25°C
30 30
-21 98.3
0.816 1.1129
-
Surface Tension (25°C) dynes/cm -
41.1 58.1
20 48
0.7778 0.802
0.2 0.4
21.2 21.8
Complete 35
72.1 72.1
75 64
0.7982 0.7938
0.45 0.45
24.6 23.2
7.6 6.7
96.1
161.7
1.1598
1.49
41.1
8.3
Solubility Solvent in water, g/100g 95
AMINES Amines are organic derivatives of ammonia, NH3. They are classified as primary, secondary, and tertiary, just like the alcohols, based on how many alkyl groups are bonded to the nitrogen. Refer to the illustrations below.
•• N
••
N H
H
R
R
ammonia
R "
R
R
primary (1°) amine secondary (2°) amine tertiary (3°) amine
The lone pair of electrons on all amines makes them nucleophiles and also bases. Simple amines are commonly named by naming the alkyl groups attached to the nitrogen followed by the word -amine. As examples:
H methyl amine
H ethyl amine
CH2CH3
CH3 ethyl methyl amine
32
Industrial Solvents Handbook
Aromatic amines are named as derivatives of aniline. As examples:
NH,
aniline
N-methyl aniline
o-ethyl aniline
Another way of naming amines is by the Chemical Abstracts system, in which the suffix -amine is used after the name of the longest alkane chain attached to the nitrogen. Primary and secondary amines are capable of forming hydrogen bonds with each other. The following example illustrates this:
H
N
N
'^
CH, H
Tertiary amines can not form hydrogen bonds with each other, but can form hydrogen bonds with other primary or secondary amines. The ability to form hydrogen bonds imparts primary and secondary amines' relatively high boiling points for their molecular weights, although the H- - N - - H hydrogen bond is not as strong as the H- - O - - H hydrogen bond. A comparison of the boiling points of trimethylamine, (CH 3 ) 3 N, (B.P. = 2.9°C) and propylamine, CH 3 CH 2 CH 2 NH 2 , (B.P. — 48.7°C), which have the same molecular weights, illustrates the effects of hydrogen bonding. All amines, including tertiary amines, are capable of forming hydrogen bonds with water molecules, so most light amines are highly soluble in water. Ammonia, or an amine, reacts with an alkyl halide to form an alkyammonium salt, from which the resultant alkylated amine can be obtained by treatment with a strong base. Primary, secondary, and tertiary amines can also be alkylated. Alkylation can also be intermolecular as in the formation of nicotine.
33
Properties and Selection of Organic Solvents
N
CH3 Amines will react with strong acids to form alkylammonium salts. R
NH, + HC1
— NH, +
Cl
Tertiary amines react with primary or secondary alkyl halides to form quaternary ammonium salts.
(CH3)3N:; + CH3CH2CH2C1 CH,
OH
CH,— N—CH 2 CH 2 OH choline
-t (CH3)3NCH2CHCH3 + Cl CH3
OH
-N~CH2CH2- O ~
O C-
CH,
acetylcholine
Demand for amines in the U.S. is expected to grow to nearly $2 billion in 2004. Advances in volume terms will be led by specialty amines which offer stronger performance characteristics. The mature fatty and commodity amines are expected to post more modest gains. Good growth opportunities will exist in the water treatment and plastics market, while demand in the larger amines markets, which include detergents, cleaning products, personal care products and agricultural chemicals, are expected to advance more moderately. For commodity amines, service and reliability are instrumental in customer satisfaction, while product performance is paramount for more specialized products. The export market,
Industrial Solvents Handbook
34
traditionally important to U.S. producers, is expected to be more critical as industry participants strive to expand despite the relative maturity of U.S. end-use markets. In general, the U.S. amines market is quite concentrated, with about a dozen firms supplying over 90% of demand. The top four participants are Union Carbide, Air Products and Chemicals, Huntsman and Dow Chemical. The proposed merger of Dow and Union Carbide is likely to reshape the market considerably, either by creating greater concentration, by redistributing market share by way of divestiture/acquisition, or by introducing one or more new market leaders. Traditional uses of amines are in the production of powder and liquid detergents, personal care products, automobile waxes and furniture polishes. Other uses include urethane foam for furniture and automobile seat cushions, cement additives, metal working fluids, herbicides and natural gas cleaning agents for cleaner burning fuel. Amines are also used to produce shampoos, shaving creams, cosmetics, fuel and lubricant additives, dyes, pharmaceutical products, sealants and corrosion inhibitors. Table 8 provides some typical properties of aliphatic amines. Table 8. Properties of Aliphatic Amines Solvent Ethyl Diethyl Triethyl Propyl Dipropyl Tripropyl Isopropyl Diisopropyl Butyl Dibutyl Tributyl Isobutyl Diisobutyl Trisobutyl Hexyl Cyclohexyl
Mol. Wt. 45.1 73.1 101.2 59.1 101.2 143.3 59.1 101.2 73.1 129.2 185.4 73.1 129.2 185.4 101.2 99.2
BP "C @ 760 mm Hg 16.6 56.3 89.3 47.8 109.2 156 32.4 84 77.8 159 213 68 139 191 130 134
Specific Gravity (20°C) 0.6829 0.7056 0.7275 0.7173 0.74 0.7558 0.6886 0.7169 0.7414 0.767 0.7771 0.736 0.745 0.7684 0.766 0.8647 (25°C)
ESTERS Esters are compounds formed, along with water, by the reaction of acids and alcohols. Because this process is analogous to the neutralization of an acid by a base in salt formation, esters were formerly called ethereal salts. This term is misleading because esters, unlike salts, are not ionized in solution. Esters can be
Properties and Selection of Organic Solvents
35
formed from both organic and inorganic acids. For example, the simple ester ethyl nitrate may be obtained from ethyl alcohol and nitric acid (an inorganic acid), and the ester ethyl acetate may be obtained from ethyl alcohol and acetic acid (an organic acid). Another method of preparing esters is to employ not the acid itself but its chloride. For example, ethyl acetate may be prepared by the action of alcohol upon acetyl chloride, the chloride of acetic acid. Another important method of preparation is by the reaction of the silver salts of acids with an alkyl halide (usually iodine). For example, ethyl acetate may be prepared from silver acetate and ethyl iodide. Esters are broken up by the action of water into their component acids and alcohols, a reaction greatly speeded by the presence of acids. For example, ethyl acetate is broken up into acetic acid and ethyl alcohol. The conversion of an acid into an ester is termed esterification. The reaction between an ester and a metallic base is known as saponification. When the decomposition of an ester occurs upon its reaction with water, the ester is said to be hydrolyzed. The esters of organic acids are usually colorless, neutral liquids, pleasant-smelling and generally insoluble in water but readily soluble in organic solvents. Many esters have a fruity odor and are prepared synthetically in large quantities for commercial use as artificial fruit essences and other flavorings and as components of perfumes (e.g., essential oils). All natural fats and oils (other than mineral oils) and most waxes are mixtures of esters. For example, esters are the principal constituents of beef fat (tallow), hog fat (lard), fish oils (including cod-liver oil), and flaxseed oil (linseed oil). Esters of cetyl alcohol are found in the head oil of the sperm whale, and esters of myricyl alcohol in beeswax. Nitroglycerin, an important explosive, is an ester. Nitroglycerin (formula C3H5(NO3)3) is derived from glycerin by treatment with a mixture of concentrated sulfuric and nitric acids. It is a heavy, oily, colorless or light-yellow liquid, of specific gravity 1.60, with a sweet, burning taste. It gives two crystalline forms, one melting at 2.8°C (37°F), the other at 13.5°C (56.3°F). It solidifies at 12°C (53.6°F). Nitroglycerin burns quietly when heated in air, but explodes when heated above 218°C (424°F) or when heated in a closed vessel. It is very sensitive to shock and therefore dangerous to transport. Nitroglycerin is a common explosive and is usually mixed with an inert, porous material such as sawdust. When detonated, it produces about 10,000 times its own volume of gas. It is 8 times as powerful as gunpowder in proportion to relative weight, and 13 times as powerful in proportion to relative volume. Nitroglycerin is used medically, in doses of 0.2 to 0.6 mg, as an agent to cause dilation of blood vessels. Esters such as amyl acetate (banana oil), ethyl acetate, and cyclohexanol acetate are the principal solvents for lacquer preparations. Other esters, such as dibutyl phthalate and tricresyl phosphate, are used as plasticizers in lacquers. Amyl acetate is employed as odor bait in grasshopper poisons, and several of the formates are
36
Industrial Solvents Handbook
good fumigants. Esters also have an important function in organic synthesis. Esters are best described as a functional group in organic chemistry and biochemistry consisting of an organic radical united with the residue of any oxygen acid, organic or inorganic. The most common esters found in nature are fats, which are esters of glycerine and fatty acids, oleic, etc., resulting from the condensation of a carboxyl acid and an alcohol. The process is called esterification: O
R— C
+
HO
R,
Esters can participate in hydrogen bonds as hydrogen bond acceptors, but cannot act as hydrogen bond donors, unlike their parent alcohols. This ability to participate in hydrogen bonds leads them to be more water soluble than their parent hydrocarbons. But the limitations on their hydrogen bonding also make them more hydrophobic than either their parent alcohols or parent acids. Their lack of hydrogen-bond donating ability means that they can't form hydrogen bonds between ester molecules, which makes them generally more volatile than an acid or ester of similar molecular weight. Many esters have distinctive odors, which leads to their widespread use as artificial flavorings and fragrances. Esters also participate in ester hydrolysis - the breakdown of an ester by water. Esters may also be decomposited by strong acids or bases. As the result they are decomposited into alcohol and salt of carboxyl acid. Thousands of different kinds of esters are commercially produced for a broad range of applications. Within the realm of synthetic lubrication, a relatively small but still substantial family of esters has been found to be very useful in severe environment applications. Esters have been used successfully in lubrication for more than 50 years and are the preferred stock in many severe applications where their benefits solve problems or bring value. For example, esters have been used exclusively in jet engine lubricants worldwide due to their unique combination of low temperature flowability with clean high temperature operation. Esters are also the preferred stock in the new synthetic refrigeration lubricants used with CFC replacement refrigerants. Here the combination of branching and polarity make the esters miscible with the HFC refrigerants and improves both low and high temperature performance characteristics. In automotive applications, the first qualified synthetic crankcase motor oils were based entirely on esters and these products were quite successful when properly formulated. Esters have given way to PAOs in this application due to PAOs, lower cost and their formulating similarities to mineral oil. Nevertheless, esters are nearly always used in combination with PAOs in full synthetic motor oils in order to balance the effect on seals, solubilize additives,
Properties and Selection of Organic Solvents
37
reduce volatility, and improve energy efficiency through higher lubricity. The percentage of ester used in motor oils can vary anywhere from 5 to 25 % depending upon the desired properties and the type of ester employed. Like PAOs, esters are synthesized from relatively pure and simple starting materials to produce predetermined molecular structures designed specifically for high performance lubrication. Both types of synthetic basestocks are primarily branched hydrocarbons which are thermally and oxidatively stable, have high viscosity indices, and lack the undesirable and unstable impurities found in conventional petroleum based oils. The primary structural difference between esters and PAOs is the presence of multiple ester linkages (COOR) in esters which impart polarity to the molecules. This polarity affects the way esters behave as lubricants in several ways. First, the polarity of the ester molecules causes them to be attracted to one another and this intermolecular attraction requires more energy (heat) for the esters to transfer from a liquid to a gaseous state. Therefore, at a given molecular weight or viscosity, the esters will exhibit a lower vapor pressure which translates into a higher flash point and a lower rate of evaporation for the lubricant. Generally speaking, the more ester linkages in a specific ester, the higher its flash point and the lower its volatility. Second, polarity also causes the ester molecules to be attracted to positively charged metal surfaces. As a result, the molecules tend to line up on the metal surface creating a film which requires additional energy (load) to penetrate. The result is a stronger film which translates into higher lubricity and lower energy consumption in lubricant applications. Third, the polar nature of esters also makes them good solvents and dispersants. This allows the esters to solubilize or disperse oil degradation by-products which might otherwise be deposited as varnish or sludge, and translates into cleaner operation and improved additive solubility in the final lubricant. Fourth, while stable against oxidative and thermal breakdown, the ester linkage provides a vulnerable site for microbes to begin their work of biodegrading the ester molecule. This translates into very high biodegradability rates for ester lubricants and allows more environmentally friendly products to be formulated. Another important difference between esters and PAOs is the versatility in the design of ester molecules due to the high number of commercially available acids and alcohols from which to choose. For example, if one is seeking a 6 cSt (at 100°C) synthetic basestock, the choices available with PAOs are a "straight cut" 6 cSt product or a "dumbbell" blend of a lighter and heavier PAO. In either case, the properties of the resulting basestock are essentially the same. With esters, literally dozens of 6 cSt products can be designed, each with a different chemical structure selected for the specific desired property. This allows the "ester engineer" to custom design the structure of the ester molecules to an optimized set of properties determined by the end customer or defined by the application. The performance properties that can be varied in ester design include viscosity, viscosity index, volatility, high temperature coking tendencies, biodegradability, lubricity, hydrolytic stability, additive solubility, and seal compatibility.
38
Industrial Solvents Handbook
A common concern when formulating with ester basestocks is compatibility with the elastomer materials used in the seals. All esters will tend to swell and soften most elastomer seals; however, the degree to which they do so can be controlled through proper selection. When seal swell is desirable, such as in balancing the seal shrinkage and hardening characteristics of PAOs, more polar esters should be used such as those with lower molecular weight and/or higher number of ester linkages. When used as the exclusive basestock, the ester should be designed for compatibility with seals or the seals should be changed to those types which are more compatible with esters. Another potential concern with esters is their ability to react with water or hydrolyze under certain conditions. Generally this hydrolysis reaction requires the presence of significant amounts of water and heat with a relatively strong acid or base to catalyze the reaction. Since esters are usually used in very high temperature applications, high amounts of water are generally not present and hydrolysis is rarely a problem in actual use. Where the application environment may lead to hydrolysis, the ester structure can be designed to greatly improve its hydrolytic stability and additives can be selected to minimize any effects.
ETHERS The chief functional group for the ether family is the O-R group called the alkoxy group. The general structure for ethers is R-O-R'. Symmetrical ethers are those where the alkyl groups, R and R', are the same. Asymmetrical ethers are those where the R and R' are different. Simple ethers can be named by naming the alkyl groups alphabetically followed by the word "ether". For example, CH3-O-CH2-CH3 would be called using this common name approach as ethyl methyl ether. However for more complex ethers that have branching, using this common name approach is considerably more difficult. The IUPAC has come up with some rules that allow the naming of complex ethers. The rules are similar to those used in naming alcohols except the O-R group is named as any other branched group. Using the rules for alkanes, alkenes, or alkynes with the alkoxy groups identified on the longest continuous chain. The rules are as follows: 1.
Determine the longest continuous chain of carbons with the other less complex alkyl group.
2.
Number the carbons so that the O-R group is attached to the lowest numbered carbon.
3.
Determine the name of the O-R group attached to the carbon number.
4.
Identify all the branched groups including the alkoxy group and hyphenate the carbon number they are attached to the front of the branch name.
Properties and Selection of Organic Solvents
39
5.
Identify and locate each group alphabetically.
6.
Add the normal alkane name corresponding to the longest continuous chain.
The boiling points of alcohols are in general much higher than comparably sized ethers. That can be explained by the extra intermolecular forces between the alcohol molecules due to the hydrogen bonding. There is no such hydrogen bonding between the ether molecules because all the hydrogen atoms are not bonded to an oxygen or a nitrogen atom. Since there is not any possibility of hydrogen bonding the forces between the ether molecules are much weaker and can be much more easily vaporized. As an example, the boiling point of ethanol, CH3-CH2-O-H, is 78°C. The boiling point of the constitutional isomer dimethyl ether, CH3-O-CH3, is only -24°C, more than 100 degrees lower. Since the size of the molecules of the two compounds are approximately the same, this dramatic difference can only be explained by the presence of hydrogen bonding with the alcohol. Branching will tend to decrease the boiling point since a more symmetrical molecule will have less London dispersion forces and with more hydrocarbon branching around the carbinol carbon (carbon bonded to the hydroxyl group) the hydrogen bonding of fewer molecules results, and therefore the compound can be vaporized at a lower temperature. A dramatic example of this is found in the four carbon alcohols, 1butanol, 3-methyl-l-propanol, 2-butanol, and 2-methyl-2-propanol. They have boiling points of 118, 108, 100, and 83°C, respectively. The water solubility of alcohols and ethers are more similar. Low molecular weight alcohols and ethers are water soluble such as methanol, ethanol, and dimethyl ether. But four carbon alcohols and higher and three carbon ethers or higher have a much lower water solubility. This can be explained by considering the way that water molecules can disperse solute molecules into a solution. The polar water molecules are attracted to the hydroxyl group by hydrogen bonding that occurs between the hydrogens of the water molecules and the oxygen of the alcohol or ether. With smaller molecules water can more easily surround the ether or alcohol molecules effectively separating them from one another. This is called salvation and each ether or alcohol molecule is encapsulated in a water "cage". As the hydrocarbon portions of the alcohol or ether become more extensive as they would be in a higher molecular weight ether, it takes far more water molecules to achieve the same goal (solvation) if it is possible at all. The larger the solute molecules, the less likely that will occur. Increased branching will increase water solubility. This can be explained by the fact that increased branching around the caribinol carbon will mean that water molecules will have a smaller molecular surface area to surround in trying to encapsulate the organic molecule. As noted, ether molecules are not capable of forming hydrogen bonds with other ether molecules, although they can form hydrogen bonds to water. See the following example.
40
Industrial Solvents Handbook O. H
H
O
CH,CH,
'' CH7CH,
This accounts for the fact that the boiling points of ethers are similar to the B.P.'s of alkanes of approximately the same molecular weight. It also accounts for the high solubility of the smaller ethers in water. Ethers are excellent solvents for a variety of substances due to their generally nonpolar nature combined with the ability to form hydrogen bonds with certain types of molecules. They are also relatively unreactive, so they make good solvents for chemical reactions to occur in. Unfortunately, they are also highly flammable and susceptible to slow oxidation by air to form peroxides which are highly explosive. As noted symmetrical ethers with the alkyl hydrocarbon groups linked through the ether oxygen atom can be named dialkyl ethers or, more commonly, just the alkyl ether. Unsymmetrical ether structures with two different alkyl groups are named to reflect both the different alkyl groups. The name of the alkylene oxide corresponds to the hydrocarbon chain with the cyclic ether linkage being signified by the designation of oxide. The larger cyclic structures are usually classified as a heterocyclic structure such as furan, 1,4-dioxane, or 1,3-dioxolane. A series of aliphatic diether structures bear the common name "glyme" to which is attached the prefix "mono-," "di-," "tri-," or "tetra-" that denotes the number of (-CH2CH2O) groups in the molecule. The first member in the glyme series is the dimethyl ether of ethylene glycol (CH 3 OCH 2 CH 2 OCH 3 ) or monoglyme. Addition of a (CH 2 CH 2 O) group to the monoglyme yields diglyme or the dimethyl ether of diethylene glycol (CH 3 OCH 2 CH 2 OCH 2 CH 2 OCH 3 ). Addition of one or two (-CH 2 CH 2 O) groups to diglyme yields the tri- and tetraglyme solvents. The simplest ethyl ether analog is ethylene glycol diethyl ether or ethyl glyme. The corresponding diethylene glycol diether solvent is ethyl diglyme. The Grant Chemical Division of the Ferro Corporation produces diethylene glycol dibutyl ether or butyl diglyme solvent. Table 9 lists the common chemical names for the dialkyl, alkyl-vinyl, and the cyclic ether solvents along with the CA index names (Chemical Abstract Index, American Chemical Society) and the CAS numbers (Chemical Abstract Service, American Chemical Society). The CAS numbers refer to the major ether component. Refer to the Material Safety Data Sheet (MSDS) for CAS numbers of any minor impurities in the solvent.
41
Properties and Selection of Organic Solvents
Table 9. Common Names of Aliphatic and Cyclic Ethers CAS Number CA Index Name Common Name 115-10-6 Methane, oxybisMethyl ether 60-29-7 Ethane, l,l'-oxybisEthyl ether 108-20-3 Isopropyl ether Propane, 2,2'-oxybis142-91-1 Butane, l,l'-oxybisn-Butyl ether 693-65-2 Pentane, l,l'-oxybis«-Amyl ether 112-58-3 «-Hexyl ether Hexane, l,l'-oxybis1634-04-4 Methyl terbutyl ether Propane, 2-methoxy-2methylEthyl vinyl ether 109-92-2 Ethene, ethoxyEthene, n-butoxyAZ-Butyl vinyl ether 111-34-2 Ethene, IsobutoxyIsobutyl vinyl ether 109-53-5 Ethene, 2-ethylhexoxy2-Ethylhexyl vinyl ether 103-44-6 1,2-epoxypropane Propylene oxide 75-56-9 106-88-7 1 ,2-Butylene oxide Oxirane, ethyl1,4-dioxane 123-91-1 1 ,4-Dioxane 1,3-dioxolane 1,3-Dioxolane 646-06-0 Anisole 100-66-3 Benzene, methoxyFuran Furan 110-00-9 2-Methylfuran Furan, 2-methyl534-22-5 Tetrahydrofuran Furan, tetrahydro109-99-9
Preparation and Chemical Reactivity Diethyl ether is the most important commercial ether. It can be prepared by the following reaction:
CH3CH2OH
+
HOCH2CH3
H2SO4 •—> CH3CH2OCH2CH3
+
H2O
Ethers can also be prepared by the acid catalyzed addition of an alcohol to an alkene.
H
CH3 \
CH—
O— H
-t H
H
C \ CH3
CH3 I CH 3 — O— C— CH3 I CH3
Ethers with two different R groups attached to the O atom are sometimes called
42
Industrial Solvents Handbook
unsymmetrical ethers. This type of ether is most commonly prepared by the following method: 2ROH 2ROH +
+ +
2Na
*•
R'-X
2RONa + + sodium alkoxide * ROR'
+
H2
Na + X
Cleavage of ethers can occur, initiated by the attack of a Lewis acid on one of the lone pairs of electrons on the O atom of the ether. H I R - O - R ' + H+ + R-O-R'
R-O-R'
+
C1-B-C1 I Cl
* R-O-R' I Cl - B - Cl I Cl
These intermediates can then undergo cleavage. Most ethers, particularly the dialkyl ethers, react with atmospheric oxygen in a radical-chain process to form unstable, shock-sensitive, and generally explosive peroxide (-COO-) and hydroperoxide (-OOOH) compounds. Some of the widely used ethers like ethyl and isopropyl ethers, furan, and tetrahydrofuran can rapidly accumulate dangerous amounts of the peroxide compounds. Use of a dry, inert nitrogen atmosphere over the ethers and the use of a phenolic antioxidant such as 2,6-di-tertbutyl-4-methyl phenol (BHT) will prevent the formation of dangerous amounts of the peroxides. The 1,4-dioxane, 1,3-dioxolane, and glyme diethers while susceptible to air oxidation tend not to form dangerous amounts of the shocksensitive peroxides. Light and heat will accelerate the peroxide formation. Since the peroxides will concentrate upon solvent distillation one should test for the peroxide content of the solvent prior to any distillation. The common analytical method for peroxide determination involves reduction of the peroxide functional group with an excess of a reducing agent followed by back-titration of any excess reducing agent. The solvent manufacturer can supply the exact details on the peroxide determination procedures. Coated paper test strips for approximate peroxide determinations are also available from chemical supply houses. Any concentrations above minimum levels (> 0.1% peroxide) must be chemically destroyed prior to the distillation process. No distillation process should be carried to dryness because
Properties and Selection of Organic Solvents
43
of the dangers of concentrating trace amounts of the shock- and heat-sensitive peroxides. All ethers will form peroxides due to atmospheric oxidation reactions, some dialkyl ethers (e.g., ethyl and isopropyl ether) and the cyclic ethers (e.g., furan and tetrahydrofuran) are particularly prone to peroxide formation. The use of an inert nitrogen pad over the ether solvents, the addition of an antioxidant, and the exclusion of light and excessive heat will aid in preventing excessive peroxide formation.
Uses The dialkyl ethers are often used as inert solvents in organic synthesis processes since the carbon-oxygen bond in the ethers is not readily cleaved by normal acid or basic reagents. Strong acids (e.g., sulfuric acid, perchloric acid, or hydrobromic acid) will form unstable oxonium salts with the ethers. Relatively stable complexes are formed between ethers and Lewis acids such as boron trifluoride and aluminum chloride; however, the cyclic three-member epoxy compounds (e.g., propylene oxide, 1,2-butylene oxide), and the furan derivatives are readily cleaved by acidic reagents. The epoxy ether on contact with hydrochloric acid undergoes ring opening to yield the chlorohydrin derivative (e.g., RCH2(OH)CH2C1). Reaction of propylene oxide with an alcohol or phenol yields the monoether of propylene glycol. Acid hydrolysis of furan and its homologs yields ring cleavage to give dicarbonyl compounds and polymer formation. Dimethyl ether is used as a solvent in aerosol formulations. Diethyl ether as a commercial product is available in several grades and is used as an extraction solvent, reaction solvent, and as a general anesthetic. Ethyl ether is an excellent solvent for alkaloids, dyes, fats, gums, oils, resins, and waxes. Blends of ethyl ether and ethanol are excellent solvents for cellulose nitrate used in the manufacture of guncotton, in collodion solutions and pyroxylin plastics. Ethyl ether is used in the recovery of acetic acid from aqueous solutions in the cellulose acetate and plastic industry. It is used as a starter fuel for diesel engines and as a denaturant in denatured ethanol formulations. Grignard and Wurtz-Fillig synthesis reactions use diethyl ether as an anhydrous, inert reaction medium. n-Butyl ether is used in synthesis reactions that require an anhydrous, inert solvent. This ether is a valuable extraction solvent for aqueous solutions because of its low water solubility. n-Butyl ether when mixed with ethanol or butanol is an excellent solvent for ethyl cellulose. Isopropyl ether is a solvent of minor importance since its boiling point is intermediate between the two widely used solvents diethyl ether and acetone. Hazardous peroxides are formed more readily in isopropyl ether than in other dialkyl ethers. The commercial diamyl ether consists of a blend of di-AZ-amyl and di-iso-amyl ether, a small amount of isomeric amyl ethers and diamylene. A blend of diamyl ether and 20% ethanol will dissolve ethyl cellulose. /z-Hexyl ether can replace «-butyl ether in many of its applications.
44
Industrial Solvents Handbook
Methyl tert-butyl ether (MTBE) is used as an octane enhancer in gasoline. EPA regulations allow up to 2.7 wt.% oxygen in gasoline which allows 15 vol.% MTBE in gasoline. Other alkyl ethers can also be blended into gasoline up to the 2.7 wt% oxygen requirement. The stability of MTBE to oxidation and peroxide formation gives this unsymmetrical ether an advantage over other ethers in various extraction and reaction solvent applications. Furan is a valuable chemical intermediate for pharmaceuticals, insecticides, and other organic compounds. The furan ring is cleaved by aqueous acid which can lead to polymer formation. Tetrahydrofuran (THF), the saturated derivative of furan, when used as a solvent for high molecular weight polyvinyl chloride (PVC), vinyl chloride copolymers, and polyvinylidene chloride copolymers at ambient temperatures yields solutions of high solids content. Blends of THF and methyl ethyl ketone are often used for increased solvency in certain polymer compositions. Applications for THF polymer solutions include PVC top coatings of automotive upholstery, audio tape coatings of polyurethane/metal oxides on polyester tape, polyurethane coatings for fabric finishes, water-vapor barrier film coatings of PVC, and polyvinylidene chloride copolymers onto cellophane film. Tetrahydrofuran is an excellent solvent for many inks used for printing on PVC film and on PVC plastic articles. Polyvinyl chloride pipe welding cements are made by dissolving the resin in THF solvent. Other adhesive applications include cements for leather, plastic sheeting, and for molded plastic assemblies. Other uses of THF are as a chemical intermediate and as a complexing solvent for various inorganic, organometallic, and organic compounds. These THF complexes are important as Grignard reagents, catalysts for organic reactions, and in stereo-specific polymerizations. Tetrahydrofuran is the solvent of choice in many pharmaceutical reactions and applications. The excellent solvency of THF makes this solvent ideal for solvent cleaning of polymer manufacturing and processing equipment. 1,3-Dioxolane is used to dissolve a wide spectrum of polymeric materials such as acrylates, alkyds, cellulosics, epoxies, polycarbonates, polyesters, urethanes, and vinyl resins. In many cases, 1,3-dioxolane solvent can replace the chlorinated solvents that were used previously to dissolve many of these polymers. The excellent solvency of 1,3-dioxolane for polymeric compositions makes this cyclic ether a valuable component in paint remover formulations. 1,3-Dioxolane is used to treat polyester fibers for improved dye retention, application of cross-linking agents to cellulosic fibers, and bonding of acrylonitrile polymers. 1,3-Dioxolane is used in metal working and electroplating formulations, as a complexing solvent for organometallic and inorganic salts, and in the preparation of lithium battery electrolyte solutions. 1,3-Dioxolane is a valuable reactant in the polymerization reactions to produce polyacetals. Polymerization reactions of dioxolane with itself or with aldehydes and ethers are catalyzed by a Lewis acid to yield the polyacetal polymers. The methylene group (CH 2 ) bonded to the two oxygen atoms in dioxolane is susceptible to radical abstraction of a hydrogen atom and the resultant dioxolane radical species can be added across various double bond configurations.
Properties and Selection of Organic Solvents
45
1,3-Dioxolane is also used as an inhibitor for certain chlorinated solvents. 1,4Dioxane, the six-member cyclic diether, is used as an aluminum inhibitor in chlorinated solvents like 1,1,1-trichloroethane and as a solvent for certain resins and polymers. Propylene oxide and 1,2-butylene oxide cyclic ethers find their largest use as chemical intermediates. Both oxides react readily with dilute amounts of mineral acids (e.g., hydrochloric acid) to form the chlorohydrin addition product. This reactivity with acid makes these epoxy solvents valuable acid acceptor-type stabilizers for several chlorinated solvents. Trace amounts of hydrogen chloride from chlorinated solvent degradation are immediately neutralized by reaction with the propylene or 1,2-butylene oxide stabilizer. Reaction of propylene oxide with an alcohol or phenol in the presence of an acid catalyst yields the monoether of propylene glycol. Among the aliphatic diethers, methylal or dimethoxymethane is used as an intermediate in the manufacture of ion exchange resins. The diether is also used as an active or latent solvent for a wide variety of gums, resins, and waxes. Methylal is a valuable extraction solvent for pharmaceutical products and a stable, inexpensive solvent for Grignard reactions. Methylal is stable under alkaline and mild acidic conditions. Diethoxymethane (DEM) is offered by Eastman Chemical Company as a cost-effective replacement solvent for monoglyme (1,2dimethoxyethane) and methylal. The DEM diether is stable under alkaline conditions, but can be cleaved by strong acids. Diethoxymethane can be used as a chemical intermediate in many organic synthesis reactions. Diethoxymethane is useful as a solvent in lithium batteries with nonaqueous electrolytes, as a solvent for polymeric materials, and as a fuel additive. As a chemical intermediate DEM can act as an ethoxymethylating reagent for alcohols and phenols and serve as a source for formaldehyde in organic synthesis. DEM reaction with an acid chloride yields the ethyl ester of the acid, RCOCI + C 2 H 5 OCH 2 OC 2 H 5 -~RC OOC2H5. The glyme diethers marketed by the Grant Chemical Division, Ferro Corporation, are used in a wide variety of industrial applications. Most of the glyme diethers are miscible with water and hydrocarbon-type solvents. The steric arrangement of the oxygen atoms at regular intervals gives these solvents the ability to complex many metal cations. The glyme solvents are used in industrial gas purification processes. Acidic gases like carbon dioxide and hydrogen sulfide can be removed from natural gas and other gas feed stocks. Hydrogen gas can be recovered from refinery effluent gas streams by a glyme and isopropanolamine solvent blend. Catalysts for the polymerization of olefins can be prepared in glyme ether slurries. The glyme solvents will dissolve any unreacted monomer for removal from the polymer product. Butyl diglyme is used to extract gold from hydrochloric acid solutions containing other metals. Treatment of the diglyme extract with hydrogen or oxalic acid precipitates the ionic gold as gold powder.
46
Industrial Solvents Handbook
Other industrial applications that use glyme diethers as solvents include textiles, adhesive and coating formulations, and various pharmaceutical processes. Glymes are used as solvents in the production of thin photoresist films for semiconductor circuits in the electronic industry. Glymes are used also as solvent developers for photo-sensitive polymer films after exposure and transfer of the circuit pattern to the electronic chip. Butyl diglyme is used in the production of printed circuit boards. Monoglyme is used in the electrolyte solutions for lithium batteries. Glymes are used often as the reaction media for various organic reactions, as a solvent in cleaning formulations, and as a solvent in ink formulations.
GLYCOL ETHERS Ethylene glycol ethers are a group of chemicals with a wide variety of uses. Primary uses include solvents in paints, cleaners and inks. Some ethylene glycol ethers are recommended for use only in industrial applications; others have wide use in industrial, commercial and consumer applications. Ethylene glycol monoethyl ether is used in varnish removers, lacquers, and as a solvent for printing inks, duplicating fluids, and epoxy. Ethylene glycol monobutyl ether is used in hydraulic fluids, as a coupling agent for water-based coatings, in vinyl and acrylic paints and varnishes, and as a solvent for varnishes, enamels, spray lacquers, dry cleaning compounds, textiles, and cosmetics. Propylene glycol ethers are extremely good solvents having a bifunctional nature (ether-alcohol). Due to the miscibility with both polar and non-polar substances they are often used as coupling agents in, for example, water-based paints. Glycol ether acetates are clear liquids that often have a pleasant, fruity odor. Methyl proxitol acetate is widely used in the surface coatings industry as a solvent and to regulate flow and coalescence. The Shell range of propylene glycol ethers and acetates is sold under the trade name: proxitol. So methyl proxitol and methyl diproxitol are Shell names for the monomethyl ether of propylene glycol and dipropylene glycol respectively. Methyl proxitol is sometimes called MP or PM. Propylene glycol ethers and acetates are mainly used in surface coatings, printing inks, cleaners, cosmetics and agrochemical formulations. They are also used as extractants, and as coalescing agents and flow improvers in water-based paints. Propylene glycol monomethyl ether is primarily used in the manufacture of lacquers and paints, as an anti-freeze in industrial engines, a tailing agent for inks used on very high-speed presses, a coupling agent for resins and dyes in waterbased inks, and a solvent for celluloses, acrylics, dyes, inks, and stains. It is also used in cleaning products such as glass and rug cleaners, carbon and grease removers, and paint and varnish removers; and in pesticide formulations as a solvent for applications to crops and animals. Glycol ethers are general solvents, also known as cellosolves, which are used in the semiconductor industry. They are also used in surface coatings, such as lacquers,
Properties and Selection of Organic Solvents
47
paints, and varnishes; fingernail polishes and removers; dyes; writing inks; cleaners; and degreasers. Three important glycol ethers are ethylene glycol monoethyl ether (CAS #110-80-5), ethylene glycol monobutyl ether (CAS #111-762), and propylene glycol monomethyl ether (CAS #107-98-2). Ethylene glycol can form ethers with alkyl groups in the same way as ethyl alcohol: HOCH2CH2O + »CH3 = HOCH2CH2OCH3 Ethylene glycol monomethyl ether The following is a list of representative glycols and polyglycols. HOCH2CH2OH H(OCH2CH2)nOH
Ethylene glycol Polyethylene glycol; polyethylene glycol) Ethylene glycol monomethyl ether; 2CH3OCH2CH2OH methoxyethanol; Methyl Cellosolve® Ethylene glycol monoethyl ether; 2-ethoxyethanol; Cellosolve® Ethylene glycol dimethyl ether; 1,2-dimethoxyethane; monoglyme C2H5OCH2CH2OC2H5 Ethylene glycol diethyl ether; 1,2-diethoxyethane HOCH2CH2OCH2CH2OH Diethylene glycol j „„ Diethylene glycol monomethyl ether; Methyl C2H5OCH2CH2OCH2CH2OH Diethylene glycol monoethyl ether; Carbitol® CH3(OCH2CH2)2OCH3 Diethylene glycol dimethyl ether; diglyme As solvents, the major uses of glycol ethers include formulation of water- and solvent-based coatings, as ingredients in household and industrial cleaners, and as solvents for inks, textile inks and dyes, agricultural pesticides, cosmetics, and adhesives. The choice of solvent is determined by the desired water-organic solvency balance, degree of solvent-water coupling capacity, rate of evaporation, any perceived health hazards, ability to perform product function, and cost. Concerns over the toxicity problems of certain E-series glycol ethers has encouraged formulators to switch to the relatively less toxic P-series glycol ethers. The propylene glycol ether derivatives propylene glycol /2-butyl ether (PnB) and dipropylene glycol «-butyl ether (DPnB) are alternatives for the ethylene glycol n-butyl ether (EB) and diethylene glycol «-butyl ether (DB). The PnB and DPnB and corresponding E-series EB and DB glycol ethers have similar evaporation rates, the P-series solvents have good oil solvency, better ability to lower surface tension of water, excellent oil-water coupling ability, and lower toxicity than the E-series glycol ethers. All of these factors give the P-series glycol ethers excellent formulation possibilities in both old and new applications.
48
Industrial Solvents Handbook
Solvents are an important ingredient of protective coatings along with the resins, pigments, and additives. Water-based coatings include resin emulsions and dispersions while solvent-based coatings include enamels, lacquers, and varnishes. Subdivisions in solvent-based coatings include conventional low-solids and high-solids coatings. The largest single use for glycol ethers and acetates are in protective coatings. Ideal properties of these solvents include their compatibility with water and other organic solvents like alcohols, esters, aromatics, and naphtha solvents. The glycol ethers are good resin solvents, provide excellent coalescing with latexes, and good coupling of oil and water phases, offer a wide range of evaporation rates, provide low surface tension for improved wetting, and promote adhesion to porous surfaces. Based on comparative toxicity studies the lower toxicity of the P-series glycol ethers and acetates has encouraged many of the large paint companies to reformulate coatings that contain the E-series solvents ethylene glycol methyl ether (EM), ethylene glycol ethyl ether (EE), ethylene glycol methyl ether acetate (EMA), and ethylene glycol ethyl ether acetate (EEA). Restrictions of Volatile Organic Compounds (VOC) emissions has encouraged the growth of high-solids coatings and water-borne coatings. The P-series glycol ethers and acetates are excellent candidate solvents for these coating systems. Water is used in water-borne coatings as a diluent or latent solvent in combination with an active solvent such as a glycol ether. A latex emulsion (individual resin particles) gives a continuous protective film after the resin particles coalesce during the drying process. Successful film formation requires a solvent coalescent aid that softens the resin particles allowing individual particles to form a continuous film. The coalescent solvent must remain in the film until after the water evaporates from the coating. The P-series glycol ethers and acetates and the E-series ethylene glycol /z-butyl ether (EB) and diethylene glycol n-buty\ ether (DB) are excellent coalescent solvents for latex coatings. The type of latex coatings often determine which coalescent solvents afford the best film properties. Temperature is important in achieving ideal latex film formation. Each latex resin has a specific minimum filmformation temperature (MEET); the proper coalescent solvent will provide a lower MEET (at least 40°F) for ideal film formation. The amount of coalescent solvent necessary will vary and depend on resin type and the solvent's coalescent efficiency. The proper water (hydrophilic) and organic (hydrophobic) balance found in many glycol ether derivatives makes them ideal coalescent solvents. The longer C4 alkyl carbon chain in propylene glycol n-butyl ether (PnB) affords more organic solvency as compared to the shorter methyl side chain group found in dipropylene glycol methyl ether (DPM). The PnB solvent is a better choice for a coalescent solvent than the DPM since the DPM solvent is completely water soluble. Complete water solubility limits the all important organic solubility necessary for good latex film formation. Water-reducible resins that have been chemically modified to increase their water
Properties and Selection of Organic Solvents
49
solubility can be completely solubilized in water by the addition of cosolvents such as alcohols and glycol ethers. A typical water-reducible coating contains approximately 15% solvent, 55% water, and 15% resin solids. Coupling of the organic resin and the aqueous phase is an important property of the glycol ethers. Ethylene glycol «-butyl ether (EB) is used widely as a coupling solvent because of its superior coupling efficiency and excellent solvency for resins. Practical alternative cosolvents include dipropylene glycol methyl ether (DPM), blends of DPM with propylene glycol methyl ether (PM), and propylene glycol n-butyl ether (PnB) along with blends of these solvents with secondary butyl (sec-BuOH). Solvent-based coatings can be classified as conventional low-solids and high-solids (> 60% solids) coatings. Glycol ethers and acetates act as active solvents to dissolve the film-forming resins and to suspend pigments and additives. Conventional low-solids coatings contain alkyd, epoxy, nitrocellulose, polyester, and polyurethane-type resins and find use in coil coating, metal and wood furniture, automotive coatings, and machinery finishes. These coatings can be classified as thermoplastic or thermoset. Evaporation of the solvents yields the thermoplastic film while the thermoset coating is cured by a chemical cross-linking reaction or by air oxidation in a high temperature oven. Selection of the proper glycol ether depends on how the coating is cured. Ambient cured coatings often utilize EB, PM, and DPM glycol ethers and propylene glycol methyl ether acetate (PMA). For thermally cured coatings the above mentioned glycol ethers as well as blends can be used. In high temperature coil coating processes the diethylene glycol n-butyl ether and dipropylene glycol methyl ether acetate (DPMA) are often used as tailing solvents (these solvents prevent pinholes and other film defects during the last stages of cure). Low-cost hydrocarbon solvents are often added to these coatings as diluent solvents. The excellent solvency of the glycol ethers allow high hydrocarbon dilution while still maintaining resin solubility. The use of glycol ethers also helps prevent film defects such as moisture and resin blush, pinholes, orange peel, and film cracking. In the electrodeposition coating process electrically charged resin particles are deposited onto a conductive metal surface from a water dispersion. Glycol ethers serve as a resin solvent in the coating preparation step and as a coalescent solvent during film formation. Glycol ethers used in the electrodeposition process include EB, DB, and PM. Glycol ether evaporation rates, resin solvency, and surface tension effects on the coating are all important considerations when selecting the solvent system for automotive primers, enamel base and top coats, in industrial maintenance coatings, and wood coatings. Selection of the proper solvents for resin solvency can be greatly simplified by utilizing the Hansen solubility parameter theory. Glycol ethers and surfactants couple organic soils into the water phase and keep the soil suspended in the cleaner. Cleaner formulations can be classified as glass cleaners, hard surface cleaners, and industrial or heavy duty cleaners. Water is the
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Industrial Solvents Handbook
principal solvent in the glass and hard surface cleaners while the heavy duty industrial cleaners contain lower water content. Glycol ethers and various surfactants provide the oil-water coupling necessary for cleaning soiled surfaces. The available glycol ethers provide a wide range of evaporation rates and afford effective reduction of solution surface tensions. Glass cleaners require a fast evaporating glycol ether to prevent streaking of the glass. Hard surface cleaners utilize the slower evaporating solvents and the resultant longer residence time that allows the cleaner to penetrate the soils. Alcohols, ketones, acetates, and hydrocarbons are used as the principal solvents in printing inks while the glycol ethers are used as tailing solvents to control evaporation rates. The glycol ethers PM and DPM are effective in gravure and flexographic inks while the two acetates PMA and DPMA are useful in silk screen inks. In vat dyeing of textiles glycol ethers help the dyes to penetrate and saturate the fabric as well as serve as coupling aids. Glycol ethers often used in vat dyeing include DPM, TPM, PPh, DB, and DM. The surface tension reduction from the glycol ether allows deep penetration of the dyes into the fabrics during textile printing of cellulose acetate and polyester fabrics. Glycol ethers like DPM, DM, and EPh are used in floor polish formulations. The coalescing action of the glycol ethers allows the latex emulsion to dry into a smooth continuous film. The resultant film has high gloss, resistance to detergents, good adhesion and is mar resistant. Agricultural pesticides are often formulated with blends of glycol ethers and surfactants that wet and couple the active ingredients into the water phase. Certain glycol ethers are acceptable as inert ingredients in pesticide formulations. Exact information on using glycol ethers in agricultural products should be obtained from the solvent producer. Cosmetic and personal care products use glycol ethers as solvents and coupling aids. Dipropylene glycol methyl ether is often used in combination with propylene glycol in cosmetics. Ethylene glycol phenyl ether at a 1.0% level acts as a preservative in personal care products. Properties All glycol ethers have a low vapor pressure and a high potential for dermal absorption. They are nonflammable. Ethylene glycol monoethyl ether is a colorless liquid with a sweet, mild odor and slightly bitter taste. It is miscible in all proportions of acetone, benzene, carbon tetrachloride, ethyl ether, methanol, and water. It dissolves many oils, resins, and waxes. Ethylene glycol monobutyl ether is a colorless liquid with a mild, rancid, ether-like odor. It is soluble in most organic solvents and mineral oil. It mixes with acetone, benzene, carbon tetrachloride, ethyl ether, n-heptane and water; it is miscible with many ketones, ethers, alcohols, aromatic paraffin, and halogenated hydrocarbons. A synonym for ethylene glycol monobutyl ether is ethylene glycol mono-n-butyl ether. Propylene glycol monomethyl ether is a colorless liquid with a sweet ether-like odor and bitter taste. It is soluble in water, ether, acetone, and benzene. A synonym for propylene glycol monomethyl ether is l-methyl-2-hydroxypropane.
Properties and Selection of Organic Solvents
51
Inhaling glycol ethers can result in dermatitis with erythema, edema, and weeping; hyperpigmentation; and photosensitization. Exposure to ethylene glycol monoethyl ether can cause depression of the central nervous system, resulting in headaches, drowsiness, weakness, slurred speech, tremor, and blurred vision. Ethylene glycol monobutyl ether is regarded as the most toxic glycol ether used as a solvent. Exposure can result in bone marrow damage, headaches, drowsiness, weakness, slurred speech, tremor, and blurred vision. Exposure to vapors can result in respiratory, nose, throat, and eye irritation. Exposure to propylene glycol monomethyl ether can cause eye, nose, and throat irritation. High levels become objectionable because of the chemical's odor.
HALOGENATED HYDROCARBONS Halogenated hydrocarbons are solvents formed by reacting fluorine, chlorine, bromine, or iodine with a hydrocarbon molecule. The largest share of the commercially important halogenated hydrocarbon solvents are aliphatic in nature. The chlorinated solvents make up the largest portion of the aliphatic solvents. The fluorinated solvents are the second largest segment in commercial use, while the bromine and iodine derivatives have a very minor use in industry. Chlorinated solvents are colorless, volatile liquids that exhibit high solvency for greases, oils, waxes, resins, and polymers. Although cleaning processes are the largest single use of the chlorinated solvents other uses include adhesives, the electronic industry, as extraction solvents, paint and coating solvents, Pharmaceuticals, textile processing, and as reaction media. The solvents most often used in these applications include methylene chloride, 1,1,1-trichloroethane, trichloroethylene, and perchloroethylene. The largest use of perchloroethylene ("perc") is as a dry-cleaning fluid. Solvents like 1,2-dichloroethane, 1,1dichloroethane, chloroform, and carbon tetrachloride are feed stocks for the manufacturing of other chlorinated and fluorinated solvents. Environmental pressures like the stratospheric ozone depletion issue have forced the phasing out of certain halogenated solvents. For years, 1,1,1-trichloroethane (methyl chloroform) solvent has been a widely-used cold cleaning solvent and a popular vapor degreasing solvent. The other solvent being removed from the cleaning process because of the ozone depletion issue is 1,1,2trichlorotrifluoroethane (CFC 113). Commercial uses of chlorinated solvents cause serious stresses on the stability of the solvent. These stresses include heat, hydrolysis (reaction with water), metal contact, and air induced oxidation. The addition of selected organic inhibitors (stabilizers) to the solvent helps ensure solvent stability in the most stressful applications. The organic inhibitors used in proprietary chlorinated solvents include antioxidants, acid acceptors, and metal stabilizers. The unsaturated solvents like trichloroethylene and perch loroethylene require amine or phenolic-type antioxidants to minimize the potential oxidative degradation. Acid acceptors are low
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Industrial Solvents Handbook
molecular weight epoxy compounds that neutralize or react with trace amounts of hydrogen chloride (an acid) that may be formed in a chlorinated solvent application. Metal stabilizers are organic compounds that contain certain functional groups capable of reacting with trace amounts of the metal chloride formed in the solvent-metal reaction. Most of the chlorinated solvents are reactive with metals, are susceptible to hydrolysis, and undergo oxidation degradation. Perchloroethylene is the only commercially used solvent that does not normally require a metal inhibitor. However, amine or phenolic-type inhibitors are added as antioxidants. An acid acceptor may be added to perchloroethylene for very stressful applications to remove trace amounts of hydrogen chloride and to protect against metal degradation in high temperature application uses. Trichloroethylene and 1,1,1trichloroethane both require acid acceptors and metal inhibitors. An antioxidant is always added to the trichloroethylene formulations. The solvent application and type of possible metal contact will determine which inhibited grade of these two solvents is needed. Aluminum metal contact with improperly inhibited 1,1,1trichloroethane or trichloroethylene can cause catastrophic metal-solvent reactions with the resultant release of enormous amounts of gaseous hydrogen chloride. The gaseous hydrogen chloride can cause extensive equipment corrosion and require employee evacuation from the work site. Use of properly stabilized grades of the solvents will allow the safe use of the solvent with aluminum metal. The presence of large amounts of finely divided aluminum or aluminum chips is a reason however for concern of possible metal reaction. Proper inhibition of the solvents toward aluminum will allow safe use of the solvents with other less reactive metals. The presence of excessive amounts of water in the form of a separate water phase will in many cases increase solvent-induced corrosion of metals. The presence of low molecular weight alcohols added to 1,1,1-Tri can cause increased metal corrosion. The presence of aromatic hydrocarbons (e.g., toluene or xylene) in methylene chloride formulations in contact with aluminum can cause catastrophic release of gaseous hydrogen chloride. The trace amounts of aluminum chloride produced by the normally very slow aluminum-solvent reaction acts as a catalyst for the Friedel-Crafts reaction between the aromatic hydrocarbon and methylene chloride. The resultant reaction produces hydrogen chloride which reacts with aluminum to give more aluminum chloride and resulting in a runaway autocatalytic reaction. The addition of an acid acceptor or proper metal stabilizer will greatly reduce the reactivity of aluminum with methylene chloride-containing aromatic hydrocarbon diluents. Carbon tetrachloride and 1,2-dichloroethane are very reactive with aluminum. These normally uninhibited feed stock solvents should not contact any aluminum metal. Carbon tetrachloride can be inhibited against aluminum attack with the same types of stabilizers used with 1,1,1-Tri. 1,2Dichloroethane reacts with magnesium to give a Grignard reaction-type product. Thermal stability of the chlorinated solvents is excellent at their respective boiling points. However, the solvent vapors can be thermally decomposed to produce
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53
gaseous hydrogen chloride in high temperature environments (e.g., hot metal surfaces in ovens and gas fired space heaters). The amount of hydrogen chloride is neither excessive nor dangerous, but can cause metal corrosion. A welding operation in the presence of chlorinated solvent vapors can cause thermal degradation with the formation of oxidation products and gaseous hydrogen chloride. Fluorinated hydrocarbons are also susceptible to thermal breakdown and production of corrosive gaseous hydrogen fluoride. Polychloro hydrocarbons can react with certain amines to produce an ammonium salt of the amine, a chloride ion, and an organic free radical species from the chlorinated reactant: R3N + C1-CR3 = R 3 N + + Cl + -CR3 Methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane exhibit some reactivity with amines like piperidine. The most noticeable sign of reaction is the precipitation of the amine hydrochloride salt from the solvent. Trichloroethylene and perchloroethylene are susceptible to oxidative breakdown which is accelerated by high temperatures and exposure to ultraviolet (UV) light. The addition of antioxidants eliminates the potential of oxidative degradation. Hydrolysis reactions of the chlorinated solvents with water occur at a very slow but finite rate. The biggest problem is the presence of a separate water phase in contact with a metal surface and the solvent phase. The presence of the water phase encourages removal of small amounts of metal chloride salts formed by any metalsolvent reaction. The initial reaction sites are often sealed by the extremely small amounts of insoluble metal salt deposits. Removal of these insoluble and protective salt deposits into the water phase encourages further metal-solvent corrosion. A pitting-type of corrosion is often seen at the boundary line between the water and solvent phases. 1,1,2-Trichlorotrifluoroethane (CFC 113) is generally a stable molecule not prone to the reactivity that is often shown by the chlorinated hydrocarbons. The solvent blends that contain the fluorinated hydrocarbon and an alcohol display some metal reactivity which is inhibited by adding nitromethane as a stabilizer (e.g., the Freon blends discussed in Table 14.5). The vapors of a fluorinated hydrocarbon undergo thermal degradation in a high temperature oven or flame. The bromine and iodine derivatives show increased metal reactivity. The rate of metal reactivity for the halogenated hydrocarbons in increasing order is: fluoro < < chloro < < bromo < < iodo. Many of the iodohydrocarbons show a slight brown discoloration due to the liberation of minute amounts of iodine from the compound. Each halogenated solvent has distinct physical and chemical properties as well as specific toxicology characteristics. Specific toxicology information on a halogenated solvent is available in the solvent's MSDS and from the solvent producer. The most common health and overexposure hazard of these solvents is due to vapor inhalation. Overexposure may produce an anesthetic effect and depression of the
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Industrial Solvents Handbook
central nervous system, and is characterized by dizziness, loss of coordination, and the feeling of being lightheaded. A rapid reversal of the anesthetic effects occurs when the individual moves out of the area of exposure. Entrance into an area of high vapor concentrations of any organic solvent (e.g., an unventilated storage tank) can quickly lead to unconsciousness and death through respiratory failure. Specific safe tank entry instructions are available from the solvent producers. Since the halogenated solvents are heavier than air their vapors will concentrate in low areas such as pits and basements. Detection equipment is available to measure vapor concentrations of solvent. Other routes of solvent overexposure include ingestion, skin, and eye contact. Use the proper chemical gloves as recommended in the MSDS. The discussions below provide profiles on some of the more widely used chlorinated hydrocarbons. Methylene Chloride Methylene chloride is used as a solvent, especially where high volatility is required. It is a good solvent for oils, fats, waxes, resins, bitumen, rubber and cellulose acetate and is a useful paint stripper and degreaser. It is used in paint removers, in propellant mixtures for aerosol containers, as a solvent for plastics, as a degreasing agent, as an extracting agent in the pharmaceutical industry, and as a blowing agent in polyurethane foams. Its solvent property is sometimes increased by mixing with methanol, petroleum naphtha, or tetrachloroethylene. Studies indicate that there is suggestive, but not absolute, evidence that methylene chloride is a human carcinogen. Long-term respiratory exposure in excess of 25 parts per million (ppm) is reported to be associated with an increased risk of cancer of the bile duct and brain. Short term (acute) airborne exposures to high concentrations over 125 ppm may cause mental confusion, light-headedness, nausea, vomiting, and headache. Continued exposure may also cause eye and respiratory tract irritation. Exposure to methylene chloride may make symptoms of angina (chest pain) worse. Skin exposure to liquid methylene chloride may cause irritation. Liquid methylene chloride placed on the skin may cause chemical burns. Activities where exposure to methylene chloride is possible are in using paint strippers, working in laboratories, and parts degreasing. These areas should be initially and periodically assessed for exposures. Methylene chloride is a widely used chemical solvent with a diverse number of applications. It was introduced as a replacement for more flammable solvents over 60 years ago. Methylene chloride is commonly used in paint removers and industrial adhesive formulations. It also is employed in the production of flexible urethane foams, pharmaceutical products, and plastics, as a cleaning agent for fabricated metal parts, and as an extraction solvent. Methylene chloride is a member of a family of saturated aliphatic halogenated compounds. It is a colorless, volatile liquid, completely miscible with a variety of other solvents. It is produced in the United States by The Dow Chemical Company
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and Vulcan Materials Company. Total U.S. demand for the chemical in 1996 was estimated at about 285 million pounds (129,000 metric tons) of which about 20 million pounds (9000 metric tons) was imported. About 130 million pounds (59,000 metric tons) were exported. It is a highly desirable chemical for many applications because of the following characteristics: •
Its aggressive solvency makes it an ideal paint remover that does not harm wood in the removal process.
•
It has no flash point under normal use conditions and can be used to reduce the flammability of other substances, decreasing the chance of inplant fire or explosion.
•
It is an effective vapor pressure depressant in aerosols.
•
It does not contribute significantly to atmospheric pollution through the formation of smog, to the depletion of the stratospheric ozone layer, or to global warming.
Methylene chloride is the active ingredient in many formulations of paint removers including industrial paint and commercial furniture strippers, home paint removers, and products used for aircraft maintenance. The chemical has a unique ability to penetrate, blister, and lift a wide variety of paint coatings. Formulations of the chemical are used extensively in both flow-over and immersion (dip) tanks in furniture refmishing operations. For the maintenance of military and commercial aircraft, a methylene chloride-based product is often required to inspect the surface for damage. Since the mid-1990s methylene chloride has replaced 1,1,1-trichloroethane in nonflammable adhesive formulations for industrial applications, including fabrication of upholstery foam. It provides adhesive formulations with strong, instant bonding characteristics and efficacy under extremes of temperature and humidity. In foam applications, use of methylene chloride eliminates the possibility of hard seams and allows for ready compliance with flammability requirements for upholstered furniture. Methylene chloride is used in aerosols as a strong solvent, a flammability suppressant, vapor pressure depressant, and viscosity thinner. Current aerosol uses of methylene chloride include spray paints and lubricants. Methylene chloride is a leading auxiliary blowing agent used in the production of slabstock flexible polyurethane foams for the furniture and bedding industries. Evaporation of the solvent during production of the urethane polymer expands the cells of the foam, reducing its density without making it stiff or rigid. The auxiliary blowing agent also helps to control the reaction temperature, which otherwise could get sufficiently high to burn or scorch the foam interior.
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Industrial Solvents Handbook
Methylene chloride is used as an effective reaction and recrystallization solvent in the extraction of several pharmaceutical compounds and in the production of many antibiotics and vitamins. The chemical also has been used as a carrier for pharmaceutical tablet coatings. In these applications, essentially no methylene chloride is left in the coating of the tablet. Residue tolerances have been established by the Food and Drug Administration (FDA) for this particular use. Methylene chloride is employed in the manufacture of polycarbonate resin used for the production of thermoplastics. It is used as a solvent in the production of cellulose triacetate which serves as a base for photographic film. Other applications include its use in the solvent welding of plastic parts, and as a releasing agent to prevent the manufactured part from permanently bonding to the mold. It is often necessary to remove grease, oil, or similar substances used as lubricants or temporary protective coatings during metal fabrication. Methylene chloride is used extensively for this purpose, both for cold (room temperature) cleaning and vapor degreasing of metal parts. Methylene chloride is used as an extractant in the recovery and purification of a wide variety of materials including oils, fats, and waxes. The chemical is used for the decaffeination of coffee and tea, oleoresin extraction from a variety of spices, and for the extraction of hops. As with tablet coatings, little or none of the chemical remains in the finished product. Methylene chloride, also known as dichloromethane, evaporates easily, but does not burn easily. It does not appear to occur naturally in the environment. It is made from methane gas or wood alcohol. As noted it is widely used as an industrial solvent and as a paint stripper as well as in the manufacture of photographic film. The chemical may be found in a variety of household products including spray paints, automotive cleaners and some pesticide formulations. Most of the methylene chloride released to the environment results from its use as an end product by various industries and the use of aerosol products and paint removers in the home. Because methylene chloride evaporates easily, the greatest potential for exposure occurs when people breathe air contaminated as a result of the use of consumer products, such as paint strippers, that contain methylene chloride. Exposure can also result from direct contact of the liquid material with the skin. The highest and most frequent exposures to methylene chloride usually occur in workplaces where the chemical is made or used. The following summarizes pertinent information on methylene chloride. Chemical Formula Molecular Formula CAS Number Flammable Limits (@ 25°C) OSHA PEL
CH2C12 84.9 75-09-2 14% -22% solvent in air
Properties and Selection of Organic Solvents 8-hour TWA 15-minute STEL ACGIHTLV 8-hour TWA 15-minute STEL TAt>^™
.,- .. IARC Classification CERCLA Reportable Quantity (RQ) Maximum Contaminant Level (Drinking Water) RCRA Hazardous Waste Number DOT Hazard Classification DOT ID Number
57
50 ppm 2B ("possibly carcinogenic to , „, humans ) 1000 pounds 5 micrograms/liter (5 parts per billion) U 080 6.1 (packing group III) UN1593
Trichloroethylene Trichloroethylene is used widely by industry as a metal degreaser. It is especially valuable because of its cleaning properties, low flammability, and lack of a measurable flash point. Trichloroethylene also is used as a chemical process intermediate in fluorochemical and polyvinyl chloride (PVC) production. It has been used worldwide for more than 70 years. It is a colorless, volatile liquid, and is an unsaturated aliphatic halogenated hydrocarbon. In the United States, it is produced by The Dow Chemical Company and PPG Industries, Inc. In 1998, U.S. demand was about 171 million pounds (77,700 metric tons) of which about 15 million pounds (6,800 metric tons) were imported. About 84 million pounds (38,000 metric tons) were exported. The use of trichloroethylene in 1999 can be broken down into the following categories: •
chemical intermediate (—54%)
•
metal cleaning and degreasing (-42%)
•
miscellaneous (—4%)
High-purity grades of trichloroethylene are used as a feedstock in the synthesis of the refrigerant hydrofluorocarbon 134a. In this process, the trichloroethylene molecule is destroyed to form the new fluorinated compound. It also is used in the production of such chlorinated end products as polychlorinated aliphatics and flame-retardant chemicals. In polyvinyl chloride (PVC) manufacture, trichloroethylene is used as a molecular weight control agent. Among the properties that have contributed to trichloroethylene's wide acceptance as a metal cleaner and degreaser are the following:
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Industrial Solvents Handbook •
high solvency
•
low flammability
•
non-corrosiveness
•
high stability
•
low specific heat
•
low boiling point
•
low latent heat of vaporization
Trichloroethylene's advantages for metal cleaning include the ability to degrease more thoroughly and several times faster than alkaline cleaners, and its compatibility with smaller equipment that consumes less energy. Trichloroethylene is an important solvent for degreasing aluminum and for cleaning sheet and strip steel prior to galvanizing. Trichloroethylene also is used for cleaning liquid oxygen and hydrogen tanks. Commercial trichloroethylene formulations include a stabilizer system to help prevent solvent breakdown caused by contaminants, such as acids, metal chips, and fines, and exposure to oxygen, light, and heat. Trichloroethylene is also used as a solvent in some nonflammable adhesive and aerosol formulations, and as a low temperature heat-transfer medium. Other applications of trichloroethylene include its use as a solvent in the metal processing, electronics, printing, pulp and paper, and textile industries. Acute (short-term) overexposure to trichloroethylene vapor can cause central nervous system effects (e.g., light-headedness, drowsiness, headache, giddiness) which may lead to unconsciousness or prove fatal in extreme circumstances. Also, at very high exposure levels, trichloroethylene can sensitize the heart to the effects of adrenaline and similar agents, which may lead to sudden cardiac arrest. In addition, trichloroethylene may irritate the respiratory tract at high vapor concentrations. Repeated or lengthy contact with the chemical in liquid form can cause irritation of the skin and eyes. Chronic (repeated) overexposure, well in excess of recommended occupational limits, has been associated with damage to the liver and kidneys, although this is less well documented in humans than in animals. The carcinogenic potential of trichloroethylene in laboratory animals and in humans (through epidemiology studies) has been well studied. It has been shown to cause an increased incidence of liver and lung tumors in certain laboratory mice, and small increases in kidney tumors in male rats in some studies. Because of species differences in metabolism of trichloroethylene, the relevance of these results to humans is uncertain. The Clean Air Act Amendments of 1990 significantly revised the provisions of Section 112 relating to the regulation of emissions of hazardous air pollutants.
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Under the new law, EPA is required to develop national emission standards based on maximum achievable control technology, or MACT, for sources of trichloroethylene and 188 other substances within 10 years. The revised Section 112 also requires EPA to review the need for additional control of regulated sources within 8 years of the implementation of the MACT standard. Trichloroethylene also is regulated as an air toxic in most states. A standard for halogenated solvent cleaning (degreasing) with trichloroethylene and the other chlorinated solvents was promulgated in December 1994 and became effective for existing sources in December 1997. As a result, all degreasing sources using trichloroethylene will be required to obtain an operating permit from the state regulatory agency. Permitting for small degreasing sources may be deferred until 2004. EPA has determined that trichloroethylene is an acceptable alternative in many applications for methyl chloroform and chlorofluorocarbon (CFC) 113, solvents whose production has been phased out because of their potential to deplete stratospheric ozone. Trichloroethylene is controlled as a volatile organic compound (VOC) under state regulations implementing the national ambient air quality standard for ozone (smog). The available information suggests, however, that trichloroethylene exhibits relatively low photochemical reactivity when compared to many other hydrocarbon solvents. EPA has also established national drinking water regulations setting a maximum contaminant level of 5 micrograms per liter (ug/1), equal to 5 parts per billion (ppb), for trichloroethylene. The maximum contaminant level goal (MCLG) for trichloroethylene is zero. EPA has indicated that "[t]he establishment of an MCLG at zero does not imply that actual harm necessarily occurs to humans at a level somewhat above zero, but rather that zero is an aspirational goal, which includes a margin of safety, within the context of the Safe Drinking Water Act." Various states also may have drinking water regulations that apply to trichloroethylene. For various industry categories, EPA has established effluent limitation guidelines, which may contain effluent limitations for trichloroethylene. EPA also has published ambient water quality criteria for trichloroethylene for use by states in developing water quality standards. Trichloroethylene waste is considered hazardous under the federal Resource Conservation and Recovery Act (RCRA) and many state laws. The waste must be stored, transported, and disposed of in accordance with applicable RCRA and state requirements. The reportable quantity (RQ) for releases of trichloroethylene under the Comprehensive Environmental Response, Compensation, and Liability Act (Superfund) is 100 pounds. It is one of several hundred chemicals subject to material safety data sheet (MSDS), inventory, and release reporting under the Emergency Planning and Community Right-to-Know Act (Title III of the 1986 Superfund Amendments and Reauthorization Act, or SARA). In 1989, the U.S. Occupational Safety and Health Administration (OSHA) lowered the permissible exposure limit (PEL) for trichloroethylene from 100 ppm to 50 ppm for an 8-hour time-weighted average (TWA). OSHA also established a short-term
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(15-minute) exposure limit, or STEL, of 200 ppm. These actions were overturned by a federal court in 1993, and the PELs reverted to the former limits of 100 ppm (8-hour TWA), 200 ppm (ceiling), and 300 ppm (peak). Several states that adopted the lower 1989 limits, however, have not adopted the higher limit. ACGIH currently recommends threshold limit values (TLVs) of 50 ppm for an 8-hour TWA and 100 ppm for a 15-minute STEL. Trichloroethylene is subject to the OSHA Hazard Communication Standard, which imposes labeling, material safety data sheet (MSDS), and other requirements on employers and their suppliers. The following is pertinent information on trichloroethylene. Chemical Formula C2HC13 Molecular Weight 131.4 CAS Number 7901-6 Boiling Point 189°F (87°C) Weight per Gallon (@77°F) 12.11 pounds Flash Point none Flammable Limits @77°F (% solvent in air, by volume) Lower Limit 8.0 Upper Limit 9.2 (vapor saturation point) Flammable Limits @212"F (% solvent in air, by volume) Lower Limit 8.0 44.8 Upper Limit Solubility @77°F (grams/100 grams) 0.10 Trichloroethylene in water 0.04 Water in trichloroethylene OSHA PEL (see discussion in text) 8hr TWA Ceiling Peak ACGIH TLV 50 ppm 8hr TWA 100 ppm 15min STEL Cancer Classification ACGIH A5 2A IARC "reasonably anticipated" NTP 100 pounds CERCLA Reportable Quantity (RQ) 5 ppb (5 micrograms/liter) Maximum Contaminant Level (MCL) U228 RCRA Hazardous Waste No. Department of Transportation 6.1 (packing group III) Hazard Classification UN 1710 ID Number
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Perchloroethylene Perchloroethylene is a member of a family of aliphatic halogenated hydrocarbons. It is a colorless, volatile liquid that is essentially nonflammable and has no measurable flash point. In the United States, perchloroethylene is manufactured by the Dow Chemical Company, PPG Industries, Inc., and Vulcan Materials Company. Total U.S. demand for the chemical in 1998 was estimated to be about 344 million pounds (156,000 metric tons), of which about 30 million pounds (13,600 metric tons) were imported. An additional 40 million pounds (18,100 metric tons) were exported. It is the primary solvent used in commercial and industrial dry cleaning. Since being introduced to the dry cleaning industry in the late 1930s, it has replaced most other solvents because of its relatively low toxicity and nonflammability. Its other major uses are as a metal cleaning and degreasing solvent, as a solvent in automotive aerosols, and as a chemical intermediate in the production of several fluorinated compounds. For 1998, the use of perchloroethylene can be broken down into the following categories: •
chemical intermediate (—50%)
•
dry cleaning/textile processing (—25%)
•
automotive aerosols (—10%)
•
metal cleaning/degreasing (-10%)
•
miscellaneous (-5 %)
Perchloroethylene is used as a basic raw material in the manufacture of hydrofluorocarbon (HFC) 134a, a popular alternative to chlorofluorocarbon (CFC) refrigerants. It also is used in the synthesis of hydrochlorofluorocarbon (HCFC) 123 and 124 and HFC 125. Perchloroethylene is used by more than 80 percent of commercial dry cleaners, as well as some industrial cleaning establishments. It had replaced other synthetic solvents, such as carbon tetrachloride, by the late 1940s or early 1950s. A gradual shift from petroleum derivatives to perchloroethylene began in the late 1940s. This shift in solvents increased in the 1950s and early 1960s. However, in the period before 1960, petroleum derivatives were still the dominant solvents. In addition to its nonflammability and relatively low toxicity, the popularity of perchloroethylene in the dry cleaning industry can be attributed to the following properties: •
safe to use on all common textiles, fibers, and dyes
•
effective at removing fats, oils, and greases
•
free of residual odor
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Industrial Solvents Handbook •
chemically stable under all common use conditions
•
noncorrosive to the metals and other materials used in dry cleaning machinery
•
easily removed from clothes
•
energy and cost efficient (can be easily distilled and reused)
The textile industry uses perchloroethylene as a spotting agent for the removal of spinning oils and lubricants. It also is used in wool scouring and as a solvent carrier in dyes and water repellents. Perchloroethylene has replaced 1,1,1-trichloroethane in aerosol formulations for the automotive aftermarket, particularly for brake cleaning. These formulations provide auto repair shops with highly effective, nonflammable products. Many industries, including aerospace, appliance, and automotive manufacturers, use perchloroethylene for vapor degreasing metal parts during various production stages. Its high boiling point and resultant longer cleaning cycle are advantageous in removing "difficult" soils such as waxes with high melting points. The ability of the chemical to remove water during vapor degreasing is useful to jewelry manufacturers and other metal finishers. Perchloroethylene's nonflammability and low vapor pressure make it an effective cold (room temperature) metal cleaner, when used in compliance with applicable regulatory requirements. Its low vapor pressure contributes to reduced emissions from cold cleaning operations where it is employed. Perchloroethylene is used as an insulating fluid in some electrical transformers as a substitute for polychlorinated biphenyls (PCBs). Relatively small quantities of perchloroethylene are used in printing inks, aerosol specialty products, adhesive formulations, paper coatings, and silicones. In addition, perchloroethylene is a component of chemical maskant formulations used to protect surfaces from chemical etchants used in the aerospace and other industries. Under certain conditions, overexposure to perchloroethylene may cause central nervous system (CNS) and liver effects. Prolonged exposure to concentrations of 200 parts per million (ppm) or more has been associated with dizziness, confusion, headache, nausea, and irritation of the eyes and mucous tissue. At higher exposures (>600 ppm) these symptoms are intensified. Prolonged exposure to extremely high levels (> 1,500 ppm) may lead to unconsciousness due to anesthesia and, in extreme cases, death from respiratory depression. Changes in the liver and kidney of laboratory animals have been observed following prolonged exposure to concentrations of 200 ppm or more. In humans, reversible effects in liver function have been noted in persons exposed to high levels of perchloroethylene vapor for extended periods of time. No effects on the liver or kidney were seen in human volunteers exposed to up to 150 ppm, 7.5 hours per day, 5 days per week for 11
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63
weeks. For occupational exposures, there are reports of mild alterations of liver or kidney function in a few studies, but other studies have found no detectable effect. The following summarizes pertinent information on perchloroethylene. Chemical Formula Molecular Weight CAS Number Boiling Point Weight per Gallon (@60 °F) Flash Point Flammable Limits Solubility perc in water water in perc OSHA PEL 8hr TWA Ceiling Peak ACGIH TLV 8hr TWA 15min STEL Cancer Classification ACGIH IARC NTP
CERCLA Reportable Quantity (RQ) Maximum Contaminant Level (MCL) RCRA Hazardous Waste No. DOT Hazard Classification DOT ID No.
C2C14 165.9 127184 250 °F 13.6 pounds none none 150 ppm 105 ppm 100 ppm 200 ppm 300 ppm
25 ppm 100 ppm
A3 ("animal carcinogen") 2A ("probably carcinogenic to humans") "reasonably anticipated to be a human carcinogen" 100 pounds 5 micrograms/liter (5 ppb) U210 6.1 (packing group III) UN 1897
Methyl Chloroform Methyl chloroform is a versitile, all purpose solvent, popular with industry because of its powerful cleaning properties, low flammability, and low relative toxicity. It was introduced in the mid 1950s as a cold cleaning solvent substitute for carbon tetrachloride. Today, methyl chloroform is used primarily for vapor degreasing and cold cleaning of fabricated metal parts and other materials. The chemical also is used in fluoropolymer synthesis, as a solvent in adhesive and aerosol formulations, for the production of certain coatings and inks, for a variety of textile applications, and for dry cleaning leather and suede garments. Methyl chloroform is a member of a family of saturated aliphatic halogenated hydrocarbons. The colorless, volatile liquid is produced in the United States by Dow Chemical U.S.A., PPG Industries,
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Inc., and Vulcan Materials Company. Total U.S. demand for the solvent in 1989 was 308,000 metric tons (680 million pounds) of which a small percentage was imported. Permissible levels of methyl chloroform in the workplace have been established in several countries. In the United States, OSHA limits worker exposure to the chemical to a time-weighted average concentration of 350 parts per million (ppm) in the workplace air in any 8-hour work shift of a 40-hour week. This 350-ppm standard is well above the concentration at which presence of the chemical is noticeable (odor threshold = 100 ppm), and at or below EPA's estimated noobserved-effect level for short-term exposure of humans (350 to 500 ppm). OSHA also has established a short-term exposure limit, or STEL, of 450 ppm for any 15minute period. No adverse health effects are likely to arise from the industrial use of methyl chloroform when it is handled in accordance with the manufacturer's instructions. Among the properties that have contributed to the widespread use of methyl chloroform as an industrial solvent are the following: •
low toxicity
•
high solvency
•
low flammability
•
relatively high stability
•
low boiling point
•
non-photochemical atmosphere)
•
low solubility in water
•
ability to be recycled
reactivity (does
not form ozone in the lower
In addition, all commercial formulations of methyl chloroform are stabilized to retard or prevent solvent breakdown caused by contaminants, such as acids, alkalies, metal chips, and fines, and overexposure to oxygen, light, and heat. The stabilizers also help to protect the surface being cleaned. In 1989 industrial use of methyl chloroform could be summarized as follows: •
metal degreasing (—32%)
•
cold cleaning ( — 1 9 % )
•
aerosols ( — 1 1 % )
Properties and Selection of Organic Solvents •
adhesives (~9%)
•
chemical intermediate (~9%)
•
electronics (~7 %)
•
coatings and inks (-6%)
•
textiles (-3%)
•
miscellaneous (-4%)
65
Metal vapor degreasing is an important process in industrial manufacture, used to remove oils and oil-borne soils (i.e., chips, metal fines, and fluxes) from objects that have been stamped, machined, welded, soldered, molded, or diecast. Vapor degreased parts vary from tiny transistors to aircraft and spacecraft assemblies. Methyl chloroform is an excellent solvent for the cold (room temperature) cleaning of a wide variety of manufacturing equipment and products including yarns, threads, finished cloth, reinforced fiberglass, plastics, and common and exotic metals. The solvent removes most greases, oils, lubricants, waxes, adhesives, inks, fluxes, paints, stamping and drawing compounds, tars, and other soils. As an aerosol solvent, methyl chloroform can be used in conjunction with either carbon dioxide or hydrocarbon propellants to reduce the flammability of the aerosol package. The solvent can solubilize many of the active ingredients in aerosol formulations, improving the spray characteristics and reducing valve clogging. The main reasons for the use of methyl chloroform in formulations for urethane and neoprene/phenolic contact adhesives, mastics, sealants, and natural rubber tire repair cements are its ability to substantially reduce flammability, its nonphotochemical reactivity, and the favorable characteristics of the resulting adhesive formulation. The main applications of methyl chloroform in the electronics industry are in circuit board fabrication, where it is used to develop dry film photoresist, and in the semiconductor industry where it is used for secondary cleaning. Methyl chloroform serves as a raw material for the manufacture of polyvinylidene fluoride fluoropolymer. It also can be used as a raw material for the production of certain hydrochlorofluorocarbons having relatively short atmospheric residence times. In the coatings manufacturing industry, methyl chloroform is used as a solvent in the formulation of protective and decorative coatings and as a thinner to reduce the viscosity of high-solid content coatings for spray application. The chemical also can be used in the production of rotogravure and flexographic inks. In addition to the above uses, methyl chloroform is used to dry clean leather and suede products and to clean motion picture film.
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The health effects of methyl chloroform are well characterized after many years of industrial use. The primary effects of acute overexposure to the chemical are to the central nervous system (e.g., light-headedness, drowsiness, headache). Lethal effects of excessive concentrations (at 10,000 ppm) of the chemical have been reported after accidental exposure or abuse. In these cases, death resulted from respiratory and cardiac failure caused by depression of the central nervous system. Cardiac sensitization also may have contributed. Prolonged exposure (15 minutes or more) to high concentrations (1000 to 2000 ppm) of the solvent in the air results in mild irritation of the eyes and respiratory tract. In its liquid form, methyl chloroform causes irritation to the skin and eyes upon contact. Studies of workers occupationally exposed to methyl chloroform for up to 6 years have demonstrated no adverse health effects. Animal studies of chronic exposure to the chemical at levels ranging up to 1750 ppm similarly have found no adverse health effects. Under EPA's accelerated phase-out schedule adopted pursuant to the Clean Air Act, production (and import) of methyl chloroform for other than feedstock uses will be phased out in accordance with the following schedule (allowable production expressed as a percentage of 1989 production)
1994 - 50% 1995 - 30% 1996 - essential uses only The accelerated phase-out schedule contains somewhat more stringent production limits than the amended Montreal Protocol, allowing only 30 percent of 1989 production (instead of 50 percent) in 1995. Both the accelerated phase-out schedule and the amended Protocol, however, require a 50 percent reduction in 1994, and phase out production of methyl chloroform in 1996. Replacement of methyl chloroform in various uses, including metal cleaning, adhesives and coatings, and aerosols, will be directly affected by the significant new alternatives policy (SNAP) program, which EPA is in the process of implementing. A number of acceptable and unacceptable alternatives to methyl chloroform have been identified in these use sectors. EPA has provisionally designated perchloroethylene, trichloroethylene, and methylene chloride as acceptable alternatives for most methyl chloroform applications. Effective May 15, 1993, containers of and products containing methyl chloroform introduced into commerce must bear a "clearly legible and conspicious" label stating that they contain a substance which harms public health and environment by destroying ozone in the upper atmosphere. Products made using methyl chloroform must bear a label so stating unless: (i) they were manufactured solely for export and are clearly identified as such, (ii) their manufacturer has achieved a total reduction of solvent use of methyl chloroform and/or CFC-113 of 95 percent or more, or (iii) EPA determines that no acceptable substitute product or processes exists. Methyl chloroform is generally unaffected by the bans on non-
Properties and Selection of Organic Solvents
67
essential products adopted by EPA in 1993 and 1994. The following summarizes pertinent information on methyl chloroform. Chemical Formula
:CH3CCI3
Molecular Weight
133.4
CAS Number
;71-55-6
OSHA PEL 8-hour TWA
,350 ppm
15-minute STEL
450 ppm
ACGIH TLV 8-hour TWA
350 ppm
15-minute STEL
450 ppm
CERCLA Reportable Quantity (RQ)
; 1000 pounds
Maximum Contaminant Level (Drinking Water)
!i200 ug/1
RCRA Hazardous Waste Number
,U 226
DOT Hazard Classification
6.1 (packing group III)
DOT ID Number
U N 2831
Chloroform Chloroform (CHC13) is the name given to trichloromethane, CHC13, because of its supposed relation to formic acid. A colorless liquid, half as dense as water and of about the same viscosity, chloroform has a heavy, ether-like odor and a burning sweetness of taste, being about 40 times as sweet as cane sugar. It is almost insoluble in water, but it is freely miscible with organic solvents and is an important solvent for gums, resins, fats, elements such as sulfur and iodine, and a wide variety of organic compounds. Common synonyms are trichloromethane, trichloroform, freon 20, Cobehn Spray-Cleaner solvent, formyl trichloride, methane trichloride, methenyl trichloride, and methyl trichloride. Its CAS number is 67-66-3. Chloroform is nonflammable and does not form explosive mixtures at atmospheric temperatures and pressures. It is used primarily in the production of Chlorofluorocarbon (CFC-22) and plastics like vinyl chloride. Other uses include extraction and purification of some antibiotics, alkaloids, vitamins, and flavors. It has been used as a solvent in lacquers, floor polishes, artificial silk manufacture, resins, fats, greases, gums, waxes, adhesives, oils, and rubber; used as a solvent in
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photography and dry cleaning; used in fire extinguishers; and used in the preparation of dyes and pesticides. It also was once used as a general anesthetic in surgery but has been replaced by less toxic, safer anesthetics, such as ether. It now has limited use. Chloroform evaporates quickly and in its concentrated gaseous form, it will tend to settle to the ground before dispersing. It produces poisonous gas in a fire and is unstable when exposed to air, light, and/or heat, which cause it to break down to phosgene, hydrochloric acid, and chlorine. When heated to decomposition, chloroform emits toxic fumes of hydrochloric acid and other chlorinated compounds. Fire may also cause containers of it to explode. Violent reactions will occur if chloroform makes contact with strong caustics and chemically active metals such as aluminum, magnesium powder, sodium, or potassium. Contact with it can irritate skin, causing a rash or burning feeling. The liquid can cause severe eye burns. Exposure to the vapor can irritate the nose and throat. Higher levels of exposure can cause coma and even death. Immediately or shortly after exposure to chloroform, the heart may beat irregularly or stop. Exposure can also cause dizziness, lightheadedness, nausea, confusion, and headache. 100,000 ppbv (488,000 mg/m 3 ) is the maximum airborne concentration below which it is believed that nearly all individuals could be exposed for up to one hour without experiencing or developing irreversible or other serious health effects or symptoms that could impair their abilities to take protective action. Long term health effects may include damage to the liver, kidney, and nervous system. Alcohol consumption can increase the liver damage caused by chloroform. US EPA has classified chloroform as a Group B2, probable human carcinogen. US EPA estimates that, if an individual were to breathe air containing chloroform at 0.0088 ppbv (0.043 mg/m3) over his or her entire lifetime, that person would have no more than a onein-a-million increased chance of developing cancer. Chloroform is produced by reaction of chlorine with ethanol and by the reduction of carbon tetrachloride with moist iron. It was once used as a general anesthetic in surgery but has been replaced by less toxic, safer anesthetics, such as ether. Chloroform is produced as a byproduct of water, sewage, and wood pulp chlorination. Carbon Tetrachloride Carbon tetrachloride (CAS 56-23-5) is a clear, heavy liquid with a strong, aromatic odor. Its formula is CC14. It is produced in large quantities for use in the manufacturing of refrigerants and propellants for aerosol cans. It is also used as a feedstock in the synthesis of chlorofluorocarbons and other chemicals, in petroleum refining, pharmaceutical manufacturing, and general solvent use. Until the mid1960s, it was also widely used as a cleaning fluid, both in industry, where it served as a degreasing agent, and in the home, where it was used as a spot remover and in fire extinguishers.
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Carbon tetrachloride is a highly volatile liquid with a strong etherial odor similar to chloroform. It mixes sparingly with water and is not flammable. When heated to decomposition, it emits highly toxic fumes of phosgene and hydrogen chloride. There is strong evidence that the toxicity of carbon tetrachloride is dramatically increased by its interaction with alcohols, ketones, and a range of other chemicals. Carbon tetrachloride is known to deplete the ozone layer, where it is responsible for 17% of the ozone-destroying chlorine now in the stratosphere due to human activities. Carbon tetrachloride has a half-life of between 30 and 100 years. Synonyms for carbon tetrachloride are carbona; carbon chloride; carbon tet; methane tetrachloride; methane, tetrachloro-; perchloromethane; and tetrachloromethane. Its DOT Label is Poison, its CAS number is 56-23-5, and its UN number is 1846. Carbon tetrachloride is listed in the National Toxicology Program's Fifth Annual Report on Carcinogens as a "substance which may reasonably be anticipated to be carcinogen." Short-term exposure by inhalation or ingestion can cause death. Short and longterm exposure also affect the brain, the liver, and the kidneys, in some cases causing death. There is some evidence that exposure to carbon tetrachloride causes liver cancer in humans; there is limited evidence that exposure may damage the developing fetus. Repeated contact can cause thickening and cracking of the skin. Effects on the brain are usually quite rapid. The most common effects are dizziness, lightheadedness, nausea and vomiting, which can cause permanent damage to nerve cells. In severe cases, these effects can lead rapidly to stupor, coma, unconsciousness or death. Exposure can make the heart beat irregularly or stop. The chemical may irritate the eyes on contact. When carbon tetrachloride is emitted into the air, it rises to the atmosphere and depletes the ozone layer. Depletion of the ozone layer is believed to increase human exposure to ultraviolet rays, leading to increased skin cancer, eye diseases and disorders, and possible disruption of the immune system. Persons who are moderate to heavy drinkers are at greatly increased risk of liver and/or kidney injury following ingestion or inhalation of carbon tetrachloride. Substantial exposures to alcohols and ketones which increase the toxicity of carbon tetrachloride may occur in occupational settings, or in certain instances in the use of household products containing these chemicals. Five U.S. companies manufacture carbon tetrachloride: Akzo-America, formerly Stauffer Chemical, Chicago, IL; Dow, Midland, MI; LCP Chemicals and Plastics, Edison, NJ; Occidental, Dallas, TX; and Vulcan Chemical, Birmingham, AL. In 1988, 761 million pounds of carbon tetrachloride were produced in the United States. EPA offices overseeing regulations and guidelines applicable to carbon tetrachloride are Air Quality Planning and Standards, Water Regulations and Standards (for the National Pollutant Discharge Elimination System), Drinking Water, Emergency and Remedial Response, Solid Waste, and Pesticide Programs. The Occupational Safety and Health Administration (OSHA) has established
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permissible exposure limits for carbon tetrachloride. The Federal Drug Administration has listed it as a banned hazardous substance. Under Section 313 of the Emergency Planning and Community Right-to-Know Act of 1986, releases of more than one pound of carbon tetrachloride into the air, water, and land must be reported annually and entered into the Toxic Release Inventory (TRI). Carbon tetrachloride, CC14 (i.e., tetrachloromethane) is prepared by the action of chlorine on carbon disulphide in the presence of iodine, which acts as a catalyst. CS2 + C12 = CC14 + S2C12 Carbon tetrachloride may also be prepared by the free radical substitution of the hydrogen atoms of methane by chlorine. CH4 + 4C12 = CC14 + 4HC1
The bonding in carbon tetrachloride is covalent, as in methane. Chlorobenzene Chlorobenzene, also called monochlorobenzene, is a monocyclic aromatic compound. It is a colorless liquid with an aromatic almond-like odor and is manufactured for use as a solvent, is used in the production of other chemicals (pesticides), and in making certain other chemicals, rubber, dyes and grease solvents. It is used as a feedstock to produce ortho- and para- nitrochlorobenzenes and aniline; as a solvent for paints; and as a heat transfer medium. In the past, Chlorobenzene was used as an intermediate in phenol and DDT production. Chlorobenzene enters the environment from industrial and municipal discharges. Another potential source is the formation and emission of Chlorobenzene as a product of incomplete combustion in waste incinerators. Occupational exposure occurs primarily through breathing the chemical. Personnel engaged in the production and handling of Chlorobenzene would be at greatest risk. Chlorobenzene is moderately soluble in water; up to 1,000 milligrams will mix with a liter of water. Chlorobenzene is slightly persistent in water, with a half-life of between 2 to 20 days. Chlorobenzene persists in soil (several months), in air (3.5 days), and water (less than 1 day). About 99.25% of Chlorobenzene will eventually end up in air; the rest will end up in the water. Chlorobenzene is a flammable liquid and a fire hazard. It is unreactive towards water and decomposes only at high temperatures. When heated to decomposition this compound emits toxic fumes of hydrogen chloride gas, CO and CO2. Common synonyms are Monochlorobenzene, Benzene Chloride, and Chlorobenzol. It is incompatible with strong oxidizing agents and dimethyl sulfoxide. Chlorobenzene (also best known as monochlorobenzene or MCB) is a flammable liquid. It is produced in large amounts (231 million pounds in 1992) in the United States by three companies. U.S. demand is likely to remain constant over the next
Properties and Selection of Organic Solvents
71
several years. Because of environmental concerns for chlorinated organic chemicals in general, future U.S. demand for MCB is likely to decline. The largest users of MCB are companies that make nitrochlorobenzene. Companies also use MCB to make adhesives, paints, paint removers, polishes, dyes, and drugs. In the past companies have used MCB to make phenol and related chemicals, pesticides (like DDT), and aniline. Chlorobenzene can evaporate when exposed to air. It dissolves slightly when mixed with water. Most releases of chlorobenzene to the U.S. environment are to air. MCB also can evaporate from water and soil exposed to air. Once in air, MCB breaks down to other chemicals. Because it is a liquid that does not bind well to soil, MCB that makes its way into the ground can move through the ground and enter groundwater. Plants and animals are not likely to store chlorobenzene. Effects of chlorobenzene on human health and the environment depend on how much chlorobenzene is present and the length and frequency of exposure. Effects also depend on the health of a person or the condition of the environment when exposure occurs. Dichlorobenzene The compound 1,4-dichlorobenzene (CAS 106-46-7) is most commonly referred to as para-DCB or p-DCB. It is widely used as a moth killer, in space deodorizers, and in the production of polyphenylene sulfide. It is also used in the manufacture of certain resins, in the pharmaceutical industry, and as a general insecticide in farming. Synonyms for 1,4-dichlorobenzene are 1,4-dichlor-B; benzene, 1,4dichloro; benzene, p-dichloro; dichlorobenzene, para, solid; p-chlorophenyl chloride; p-DCB; p-dichlorobenzene; p-dichlorbenzol; parazene; PDB; para-DCB; paradichlorobenzene; and paradichlorobenzol. At room temperature, 1,4dichlorobenzene is a white or colorless crystalline solid with a characteristic penetrating odor. When exposed to air, it is slowly transformed from its solid state into a vapor; the released vapor then acts as a deodorizer and insect killer. It is practically insoluble in water and is soluble in alcohol, acetone, ether, chloroform, carbon disulfide, and benzene. Its chemical formula is C6H4C12. There is limited evidence that 1,4-dichlorobenzene can damage a developing fetus. Exposure can damage the lungs, liver, kidneys, and blood cells, causing anemia; it can also cause swelling of the eyes, hands, and feet. It can damage the nervous system, causing weakness, trembling, and numbness in the arms and legs. It may cause a skin allergy, which when developed can cause itching and a skin rash. Higher levels of the chemical in air, such as the levels that are sometimes associated with industrial exposure, can cause headaches, nausea, clumsiness, slurred speech, and dizziness. Levels that would result in death would be associated with an odor so intense that it would be very unpleasant, if not intolerable, and would serve as a danger warning. In industrial situations, workers exposed to 1,4dichlorobenzene at high levels are usually directed to wear respirators. Workers
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involved in the production of the chemical may be exposed to concentrations significantly higher than those encountered by the general population. High exposure levels may result from some consumer products of moth repellents and room deodorizers. Approximately 95% of the environmental release of 1,4dichlorobenzene occurs during its use, rather than during its manufacture or processing. 1,2-Dichlorobenzene (DCB, o-Dichlorobenzene, ODB, Orthodichlorobenzene), C6H4C12, is a colorless to pale yellow liquid with a pleasant aromatic odor. It is a combustible liquid and can form explosive mixtures with air at or above 151°F. Combustion and thermal decomposition products include hydrogen chloride gas, phosgene and chloro-carbons. Its flammable (explosive) limits are as follows: Lower 2.2%, Upper 9.2%. Ethylene Bichloride Ethylene dichloride (1,2-dichloroethane), otherwise known as EDC, is produced by reacting chlorine or anhydrous hydrochloric acid with ethylene. The largest single use for EDC is the production of vinyl chloride monomer, which is used to produce poly vinyl chloride (PVC). EDC can also be used in the manufacture of other organic compounds, and as a solvent. Ethylene dichloride is a colorless, oily liquid with a chloroform-like smell. It has many uses in industry, with principal ones being the following: •
As an intermediate in the manufacture of methyl chloroform, perchloroethylene, ethylene amines, polyvinyl chloride (PVC), sulfide compounds, vinyl chloride, and trichloroethane.
•
As an additive in gasoline (used as a lead scavenger), pharmaceutical products, color film, and pesticides.
•
As a solvent for rubber, tobacco extract, paint, printing inks, and varnish.
Miscellaneous uses include as an ingredient in fingernail polish, for metal degreasing, in extracting spices, and as a dry cleaning agent. Two of the major uses for this chemical are the manufacture of PVC and as a lead scavenger in gasoline. The process for making EDC begins with crude oil or natural gas and sodium chloride. The hydrocarbon raw materials are converted to ethene (ethylene), and sodium chloride is electrolyzed to pruduce chlorine. 2 NaCl + 2 H2O = C12 + 2 NaOH + H, This electrochemical process is also the major industrial route for sodium hydroxide production, so essentially the only side product from this initial reaction is hydrogen gas, which is later converted to water. Once the ethylene is produced from the crude hydrocarbons, it is reacted with chlorine gas:
Properties and Selection of Organic Solvents
73
C2H4 + C12 - C2H4C1 (1,2-dichloroethane) Although its common name would lead one to believe otherwise, EDC does not contain a double bond. In one of its major industrial processes, the manufacture of PVC, the following reaction is carried out: C2H4C1 = C2H3C1 (vinyl chloride) + HC1 The HC1 produced in this reaction is recycled to be used in the first reaction by oxidation of the hydrogen-chlorine bond. Ethylene dichloride is produced domestically by ten manufacturers. Approximately 1.2 billion Ibs. is produced in the United States per year. In 1989 nine million pounds of 1,2-Dichloroethane were released as pollution, 43.22% into the air, 2.34% into surface water, .01% onto land, 11.01% underground, 16% into public sewage, and 27.43% off site. Its EPA hazardous waste classification is D001 (ignitable waste), and its DOT hazard class is flammable liquid, with a reportable quantity of 5000 Ibs. It should be stored in a cool, dry, well-ventilated flammable liquid storage area, away from oxidizers, strong acids, chemically active metals, strong caustics, and dimethylaminopropylamine, as violent reaction can occur. 1,2-dichloroethane is regulated in the workplace under OSHA. Its legal airborne permissable exposure limit (PEL) over an 8-hour shift is 50 ppm, with a 100-ppm ceiling not to be exceeded at any time, except for an allowable peak up to 200 ppm for 5 minutes in any 3 hours of a workshift. This 50-ppm PEL is not detectable by the human nose; its odor threshold is 88 ppm. EDC is a carcinogen and a mutagen. Assessments of 1,2-dichloroethane are in progress under the authority of the Clean Air Act, Safe Drinking Water Act (SDWA), Toxic Substances Control Act (TSCA), and the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA). EDC is also listed under CERCLA as a hazardous material, and is required to be reported as such under Title III of SARA, otherwise known as the Community Right-to-Know Act. Ethylidene Dichloride (1,1-Dichloroethane) Ethylidene dichloride is primarily used as an intermediate in chemical synthesis. Acute (short-term) inhalation exposure to high levels of ethylidene dichloride in humans results in central nervous system (CNS) depression and a cardiostimulating effect resulting in cardiac arrhythmias. Studies in animals have reported effects on the kidney. No information is available on the chronic (long-term) reproductive, developmental, or carcinogenic effects of ethylidene dichloride in humans. An oral animal study reported a significantly positive dose-related trend in hemangiosarcomas, mammary tumors, liver tumors, and endometrial stromal polyps. EPA has classified ethylidene dichloride as a Group C, possible human carcinogen.
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Primary uses are: •
Ethylidene dichloride is primarily used as an intermediate in the manufacture of other chemicals such as vinyl chloride and 1,1,1trichloroethane, and to manufacture high vacuum rubber.
•
Ethylidene dichloride has limited use as a solvent for plastics, oils, and fats.
In the past, ethylidene dichloride was used as an anesthetic, but that use has been discontinued. Ethylidene dichloride is a colorless oily liquid which is very volatile. It has an odor similar to ether; the odor threshold is 120 parts per million (ppm). The chemical formula for ethylidene dichloride is C2H4C12, and the molecular weight is 98.97 g/mol. HYDROCARBON SOLVENTS (ALIPHATIC AND AROMATIC) General Information As noted by Archer, hydrocarbon solvents are compounds containing only carbon and hydrogen atoms. A large number of both aliphatic and aromatic solvent blends are produced by various petrochemical companies from the distillation refining of petroleum stock, the alkylation of certain distillation products, and the selective catalytic hydrogenation of hydrocarbon fractions. The hydrogenation process eliminates unwanted components from the hydrocarbons and also converts undesirable fractions into useful hydrocarbons. Typical reactions include the removal of nitrogen, oxygen, and sulfur containing compounds and the conversion of acetylene and aromatic and olefin hydrocarbons into saturated normal paraffins, isoparaffins, and cycloparaffins. These petroleum solvents find wide use in the chemical industry and many other industrial application uses that require solvents. The solvents are used both as active solvents to dissolve an ingredient and as inexpensive diluents for coatings and paints. Several grades of dearomatized aliphatic hydrocarbon solvents find use in industrial and institutional cleaning products. Synthetically produced isoparaffin (branched chain) and normal paraffin (straight chain) blends also find use in cleaning formulations. These paraffinic solvents are often blended with oxygenated and other solvents for effective cleaning performance. The hydrocarbon solvents offer effective cleaning power, excellent wetting ability, low corrosion, low toxicity, and low odor. A wide range of evaporation rates offers formulation flexibility. Industrial soils removed by cleaners containing the hydrocarbon solvents include petroleum- and aqueous-based metal working fluids, buffing and polishing compounds, mold-release agents, acrylic adhesives, lubricating greases, and waxes. Many of the cleaning operations may also require the use of agitation,
Properties and Selection of Organic Solvents
75
immersion spraying, ultrasonic energy, or heat (with the proper safety features in place). The synthetic isoparaffms are suitable solvents for alkyd and acrylic paint formulations. These virtually odorless solvents and their low surface tensions offer improved flow and wetting properties to the paints. The excellent wetting characteristics of these solvents are desirable in formulations such as furniture polishes, car polishes, and waterless hand cleaners. The low surface tension of these solvents reduces the amount of surfactants needed in emulsified products and affords improved wetting of pigments in ink and coating formulations. The isoparaffms are used as an inert process solvent in the manufacture of polyolefins and certain rubbers. In the slurry polymerization process the isoparaffms afford solvency for the Ziegler-type catalyst and the ethylene monomer, but no solvency for the polyolefm polymer product. The hydrocarbon blends with high cycloparaffin content have higher solvency than the straight chain paraffin hydrocarbon blends. The cycloparaffin blends find use in architectural coatings, original manufactured equipment (OME) and automotive refmish coatings, industrial metal and wood coatings, and maintenance and marine coatings. The hydrocarbon blends with high aromatic content afford slow evaporation rates and good flow and leveling performance in coil coatings. These solvents offer good solvency for acrylic, alkyd, epoxy, maleic, methacrylic, natural phenolic, polyester, polyurethane, styrene, urea and vinyl resins in industrial metal coatings, and maintenance and marine coatings. The Aromatic 100 blend is an effective chain transfer process solvent for acrylic polymerization. Other miscellaneous uses for the isoparaffin solvents, dearomatized paraffinic solvents, normal paraffinic fluids, and aromatic blends include pesticide formulation applications, wood preservatives, fat and oil extractions, cosmetic and notion formulations, paper coatings, and textile coatings and printing. Inks, paints varnishes, and lacquers are among the largest uses of the hydrocarbon solvents. Suppliers Exxon Chemical and Shell Chemical are the two largest suppliers of aliphatic and aromatic hydrocarbons, however there are a number of other players on the world market. Some of these are noted in the discussions throughout this subsection. Exxon offers catalytically synthesized isoparaffmic solvents under the tradename of Isopar, a family of dearomatized aliphatic hydrocarbon solvents under the trademark of Exxsol, while the tradename Norpar signifies three grades of high content normal paraffinic solvents with relatively narrow boiling-point ranges. Shell Chemical offers a wide range of hydrotreated hydrocarbons under the trademark of Tolu-Sol where the letter designation "HT" denotes solvents which contain very few aromatic hydrocarbons. Other nontrademark names for Shell hydrocarbon solvents include the designation "Sol," VM&P Naphtha, and Mineral Spirits.
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Industrial Solvents Handbook
Properties and Characteristics The Exxon Isopar series of solvents cover a distillation range of 98 to 311°C, have flash points from 18°F to a high of 239°F, have low surface tensions in the range of 20 to 30 dynes/cm, and recommended allowable vapor exposure threshold limit values (TLV) of 300 to 400 ppm. The isoparaffinic solvents have inherently low solvency for most resins and plastic materials (no Hansen polarity or hydrogen bonding values). The flammable limits (vol.% in air) at 25°C of the isoparaffinic solvents range from a low 1.1 vol.% to an upper limit of 11.6 vol.% solvent in air. The dearomatized aliphatic hydrocarbons sold by Exxon under the trademark Exxsol are solvents that boil in the range of 159 to 316°C, have moderately high flash points, low surface tensions, low evaporation rates, and high (300 ppm) occupational exposure limits (OEL). The presence of high cycloparaffin (naphthene) content in the Exxsols improves their solvency for certain resins. Archer's orginal volume contains chemical-specific information on these solvents (see Industrial Solvents Handbook, W. L. Archer, Marcel Dekker Inc., New York, 1996). The Tolu-Sol solvents produced by Shell Chemical are fast- to mediumevaporating hydrocarbon solvents. They are blends of aliphatic paraffins and cycloparaffins. The Tolu-Sol W HT and 6W solvents with their higher cycloparaffin content show higher solvency than the straight and branched chain paraffin solvent blends. Many of these solvent blends have large percentages of cycloparaffins and have evaporation rates much slower than the Tolu-Sol blend series. Refer to Archer's volume for chemical-specific data. Totalfina offers a comprehensive portfolio of light SBP fractions within its Hydrosol aliphatic hydrocarbon solvents range. These products have an extremely low aromatic content, typically 10 ppm, giving the user greater flexibility when formulating products. Typical applications include: •
HYDROSOL PENTANE: Expandable polystyrene, aerosols
•
HYDROSOL ISOHEXANE: process fluids
•
HYDROSOL HEXANE: Oil seed extraction, extraction of essential oils for perfumes, process fluids and adhesives
•
HYDROSOL ESS. A: Stain remover
•
HYDROSOL HEPTANE: Glues, adhesives, tires, cleaning
•
HYDROSOL ESS. 60/95: Glues, spot remover
•
HYDROSOL ESS. C: Household cleaning products, rubber manufacture, fuel for catalytic burners
Adhesives, extraction agents,
Table 10 provides some properties of these solvents.
aerosols,
Properties and Selection of Organic Solvents
77
Table 10. Properties of Light Commercial Solvents (Hydrosol Series) ir>
HYDROSOL PENTANE
HYDROSOL ISOHEXANE
HYDROSOL HEXANE
HYDROSOL HEPTANE
HYDROSOL ESSENCE A
HYDROSOL ESSENCE 60/
HYDROSOL ESSENCE C
ON
Density at 15°C kg/m3
ASTMD 4052
630
660
670
695
660
680
700
Saybolt Color
ASTMD 156
30
30
30
30
30
30
30
ASTM D 86
34
50
45
62
73
36
62
95
95
95
PROPERTIES UNITS METHOD
Boiling Range: Initial Point
°C °C
Dry Point
°c
ASTMD 1078
Flash Point Abel
°c
NFEN ISO 13736
Evaporation Rate
ether = DIN 53 170 1
Ultra Total Aromatic % Content weight Violet Total IL 013 Benzene Content
ppm
n-Hexane Content Aniline Point
ASTM D4367
Gaschromato. O /""
hydrin Formaldehyde cyanohydrin Allyl alcohol Chloromethyl methyl1 ether Sarin Tepp Vinyl acetate monomer icr late Isopropyl chloroformate Cyclohexylamine Phenol Thiophenol Propyl chloroformatee Malononitrile Furan trans-1,4-Dichlorobutene itene Piperidine
TPQ
RQ
pounds
pounds
10/10,000 100 500 500
10 10 ;500
500
500 10,000 10/10,000 500/10,000
5,000 1,000 10 500
500 500/10,000
100 500
100/10,000 1,000 10 500 500 500 500 10,000 10,000 1,000 1,000 100 10 100 1,000 1,000 10,000 500/10,000 500 500 500/10,000 500 500 1,000
100 100 10 1 500 500
10 100 5,000 1,000 100 10 10 10 5,000 1,000 10,000 1,000 100 500 1,000 100 500 1,000
107
108
Industrial Solvents Handbook
CAS
TPQ
RQ
pounds
pounds
NAME
Number
10
111444
Dichloroethyl ether
10,000
111693
Adiponitrile
1,000
1,000
115219 115264
Trichloroethylsilane
500 500
115297
Endosulfan
10/10,000
115902
Fensulfothion
500
116063
Aldicarb
100/10,000
119380
Isopropylmethylpyrazolyl dimethylcarbamate
500
500 500 1 500 1 1*
123319
Hydroquinone
500/10,000
123739
Crotonaldehyde, (E)-
1,000
124652
Sodium cacodylate
100/10,000
124878
Picrotoxin
500/10,000
126987
Methacrylonitrile
500
1,000
Dimefox
100 100 100 500
129000
Pyrene
1,000/10,000
5,000
129066
Warfarin sodium
100/10,000
140294
Benzyl cyanide
140761
Pyridine, 2-methyl-5-vinyl-
141662
Dicrotophos
143339 144490
Sodium cyanide (Na(CN)) Fluoroacetic acid
500 500 100 100
100 500 500 100 10 10
149746
Dichloromethylphenylsilane
1,000
1,000
151382
Methoxyethylmercuric acetate
500/10,000
151508
Potassium cyanide
151564
Ethyleneimine
500 10 1 100 100 100 100 10
10/10,000
152169
Diphosphoramide, octamethyl-
100 500 100
297789
Isobenzan
100/10,000
297972
Thionazin
500
298000
Parathion-methyl
100/10,000
298022
Phorate
298044
Disulfoton Amphetamine
10 500
300629 302012
1
1,000
1,000
Hydrazine
1,000
1
500/10,000
1
315184
Aldrin Mexacarbate
500/10,000
1,000
316427
Emetine, dihydrochloride
1/10,000
1
309002
Properties and Selection of Organic Solvents CAS
Number 327980 353424 359068 371620 379793 465736 470906 502396 504245 505602 506616 506683 506785 509148 514738 534076 534521 535897 538078 541253 541537 542767 542881 542905 555771 556616 556649 558258 563122 563417 584849 594423 597648 614788 624839
NAME
TPQ
RQ
pounds
pounds
Trichloronate 500 Boron trifluoride compound with 1,000 methyl ether (1:1) 10 Fluoroacetyl chloride Ethylene fluorohydrin 10 500/10,000 Ergotamine tartrate 100/10,000 Isodrin Chlorfenvinfos 500 500/10,000 Methylmercuric dicyanamide 500/10,000 Pyridine, 4-amino500 Mustard gas Potassium silver cyanide 500 Cyanogen bromide 500/10,000 Cyanogen iodide 1,000/10,000 Tetranitromethane 500 Dithiazanine iodide 500/10,000 Bis(chloromethyl) ketone 10/10,000 Dinitrocresol 10/10,000 100/10,000 Crimidine 500 Ethylbis(2-chloroethyl)amine 10 Lewisite Dithiobiuret 100/10,000 Propionitrile, 3-chloro1,000 100 Chloromethyl ether Ethylthiocyanate 10,000 Tris(2-chloroethyl)amine 100 Methyl isothiocyanate 500 Methyl thiocyanate 10,000 Methanesulfonyl fluoride 1,000 Ethion 1,000 Semicarbazide hydrochloride 1,000/10,000 Toluene-2 ,4-diisocyanate 500 Perchloromethyl mercaptan 500 Tetraethyltin 100 Thiourea, (2-methylphenyl)500/10,000 Methyl isocyanate 500
500 1,000 10 10 500 1 500 500 1,000 500 1
1,000 1,000 10 500 10 10 100 500 10 100 1,000 10 10,000 100 500 10,000 1,000 10 1,000 100 100 100 500 10
109
110
Industrial Solvents Handbook
NAME
CAS Number
TPQ
RQ
pounds
pounds
627112
Chloroethyl chloroformate
1,000
1,000
630604
Ouabain
100/10,000
639587
Triphenyltin chloride
500/10,000
640197
Fluoroacetamide
100/10,000
644644
Dimetilan
500/10,000
675149
Cyanuric fluoride
676971
Methyl phosphonic dichloride
696286
Phenyl dichloroarsine
100 100 500
100 500 100 1* 100 100
732116
Phosmet
10/10,000
760930
Methacrylic anhydride
786196
Carbophenothion
814493
Diethyl chlorophosphate
500 500 500 100
1
1303282
Arsenic pentoxide
100/10,000
1306190
Cadmium oxide
100/10,000
10 500 500 500 100 100 500 500 100 500 100 500 500 100 500 100 500 500 500 500 1* 1 100
1314621
Vanadium pentoxide
100/10,000
1,000
1314847
Zinc phosphide
500
100
1327533
Arsenous oxide
100/10,000
1
1397940
Antimycin A
1,000/10,000
1,000
1420071
Dinoterb
500/10,000
500
814686
Acrylyl chloride
824113
Trimethylolpropane phosphite
100/10,000
900958
Stannane, acetoxytriphenyl-
500/10,000
919868
Demeton-S-methyl
920467
Methacryloyl chloride
944229
Fonofos
500 100 500
947024
Phosfolan
100/10,000
950107
Mephosfolan
500
950378
Methidathion
500/10,000
991424
Norbormide
100/10,000
998301
Triethoxysilane
500
999815
Chlormequat chloride
100/10,000
1031476
Triamiphos
500/10,000
1066451
Trimethyltin chloride
500/10,000
1122607
Nitrocyclohexane
500
1124330
Pyridine, 4-nitro-, 1-oxide
500/10,000
1129415
Metolcarb
100/10,000
Properties and Selection of Organic Solvents CAS
Number 1464535 1558254 1563662 1600277 1622328
2540821 2570265 2587908
2631370 2636262 2642719 2665307 2703131
2757188 2763964 2778043 3037727
NAME
TPQ
RQ
pounds
pounds
500 Diepoxybutane Trichloro(chloromethyl)silane 100 10/10,000 Carbofuran ; 500/10,000 Mercuric acetate Ethanesulfonyl chloride, 2500 chloroAcetone thiosemicarbazide 1,000/10,000 10/10,000 Paraquat dichloride Chloroxuron 500/10,000 Valinomycin 1,000/10,000 500/10,000 Methiocarb Paraquat methosulfate 10/10,000 Phenylsilatrane 100/10,000 100/10,000 EPN Cadmium stearate 1,000/10,000 1,000/10,000 Thiocarbazide Diglycidyl ether 1,000 Prothoate 100/10,000 Oxydisulfoton 500 Dimethyl 500 phosphorochloridothioate Formothion 100 Pentadecylamine 100/10,000 Phosphorothioic acid, O,O500 dimethyl-5-(2(methylthio)ethyl)ester Promecarb 500/10,000 Cyanophos 1,000 100/10,000 Azinphos-ethyl Phosphonothioic acid, methyl-, 500 O-(4-nitrophenyl) O-phenyl ester Phosphonothioic acid, methyl-, 500 O-ethyl O-(4(methylthio)phenyl) ester Thallous malonate 100/10,000 Muscimol 500/10,000 Endothion 500/10,000 1,000 Silane, (4-
.10 100 10 :500 500
1,000 10 500 1,000 10 10 100 100 1,000 1,000 1,000 100 500 500 100 100 500
!*
1,000 100 500 500
100 1,000 500 1,000
111
112
Industrial Solvents Handbook
CAS
NAME
Number
TPQ
RQ
pounds
pounds p
52%) Phosphorus Bromine Calcium arsenate Fluorine Chlorine Selenious acid Hydrogen sulfide Hydrogen selenide Sulfur tetrafluoride Antimony pentafluoride Tellurium hexafluoride Arsenous trichloride Arsine Sodium arsenite Mevinphos Thallous chloride Selenium oxychloride Phosphine Camphechlor Demeton Chromic chloride Phosphorus oxychloride Phosphorus pentachloride Ozone Thallium sulfate Sodium selenite Sodium tellurite Nitric oxide Nitrogen dioxide Potassium arsenite Ethanol, 1,2-dichloro-, acetate Cobalt carbonyl Methamidophos
TPQ
RQ
pounds
pounds
1,000 1,000 100 500 500/10,000 500 100 1,000/10,000 500 10 100 500 100 500 100 500/10,000 500 100/10,000 500 500 500/10,000 500 1/10,000 500 500 100 100/10,000 100/10,000 500/10,000 100 100 500/10,000 1,000 10/10,000 100/10,000
1,000 1,000
1 500 1 10 10 10 100 10 100 500 100 1 100
1 10 100 500 100 1 500
i 1,000 500 100 100 100 500 10 10 1 1,000 10 100
113
114
Industrial Solvents Handbook CAS
NAME
Number 10294345 10311849 10476956 12002038 12108133 13071799 13171216 13194484 13410010 13450903 13463393 13463406 14167181 15271417
16752775 17702419 17702577 19287457 19624227 20830755 20859738 21548323 21609905 21908532 21923239 22224926 23135220 23422539 23505411 24017478 24934916 26419738
Boron trichloride Dialifor Methacrolein diacetate Paris green Manganese, tricarbonyl methylcyclopentadienyl Terbufos Phosphamidon Ethoprophos Sodium selenate Gallium trichloride Nickel carbonyl Iron, pentacarbonylSalcomine Bicyclo[2.2. l]heptane-2carbonitrile, 5-chloro-6((((methylamino)carbonyl)oxy) imino)-,(l-alpha,2-beta,4alpha,5-alpha,6E))Methomyl Decaborane(14) Formparanate Diborane Pentaborane Digoxin Aluminum phosphide Fosthietan Leptophos Mercuric oxide Chlorthiophos Fenamiphos Oxamyl Formetanate hydrochloride Pirimifos-ethyl Triazofos Chlormephos Carbamic acid, methyl-, O-
TPQ
RQ
pounds
pounds
500 100/10,000 1,000 500/10,000 100
500 100 1,000 1 100
100 100 1,000 100/10,000 500/10,000
100 100 1,000 100 500
1
10 100 500 500
100 500/10,000 500/10,000
500/10,000 500/10,000 100/10,000 100 500 10/10,000 500 500 500/10,000 500/10,000 500 10/10,000 100/10,000 500/10,000 .1,000 500 500 100/10,000
100 500 1* 100 500 10 100 500 500 500 500 10 1* 1* 1,000 500 500 1*
Properties and Selection of Organic Solvents
NAME
CAS
Number
26628228 27137855
TPQ
RQ
pounds
pounds
(((2,4-dimethyl-l ,3-dithiolan-2yl)methylene)amino)Sodium azide (Na(N3)) 500 Trichloro(dichlorophenyl) 500
115
1,000 500
silane 28347139 28772567 30674807 39196184 50782699
53558251 58270089
62207765
None
Xylylene dichloride 100/10,000 Bromadiolone 100/10,000 Methacryloyloxyethyl isocyanate 100 Thiofanox 100/10,000 Phosphonothioic acid, methyl-, 100 methylethyl)amino)ethyl) Oethyl ester Pyriminil Zinc, dichloro(4,4-dimethyl5((((methylamino)carbonyl)oxy) imino)pentanenitrile)-, (T-4)Cobalt, ((2,2'-(l,2-ethanediylbis (nitrilomethylidyne))bis(6fluorophenylato))(2-)N,N',O,O')Organorhodium Complex (PMN-82-147)
100/10,000 100/10,000
100 100
100/10,000
100
10/10,000
10
Resource Conservation and Recovery Act (RCRA) In 1965, the Solid Waste Disposal Act was enacted to improve solid waste disposal methods. It was amended in 1970 by the Resource Recovery Act. In 1976 Congress again amended the Solid Waste Disposal Act to create a new program for the management of hazardous waste. The Resource Conservation and Recovery Act (RCRA) establishes a framework for national programs to achieve environmentally sound management of both hazardous and nonhazardous wastes. RCRA also promotes resource recovery techniques and methods to reduce the generation of hazardous waste. RCRA is designed to protect human health and the environment, reduce and eliminate the generation of hazardous wastes, and conserve energy and natural resources. The Hazardous and Solid Waste Amendments of 1984 (HSWA) both expanded the scope of RCRA and increased the level of detail in many of its provisions.
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Industrial Solvents Handbook
RCRA, as amended, contains ten subtitles. Subtitle C, "Hazardous Waste Management;" Subtitle D, "State or Regional Solid Waste Plans;" Subtitle I, "Regulation of Underground Storage Tanks;" and Subtitle J, "Demonstration Medical Waste Tracking Program," constitute the regulatory portion of the law. The other subtitles provide the legal and administrative structure for achieving the objectives of the law. The EPA, U.S. Department of Commerce (DOC), U.S. Department of Energy (DOE), and U.S. Department of the Interior (DOI) each have specific responsibilities under RCRA. EPA issues guidelines and regulations for proper management of solid and hazardous wastes, oversees and approves the development of state waste management plans, and provides financial aid to agencies and firms performing research on solid waste. DOC encourages greater commercialization of proven resource recovery technologies. DOE oversees activities involving research and development of new techniques for producing energy from wastes. DOI oversees mineral waste problems, including recovery of metals and minerals and methods for stabilizing mining wastes. Under RCRA no material can be a hazardous waste unless it is a solid waste. RCRA defines a solid waste as: ... any garbage, refuse, sludge from a waste treatment plant, water supply treatment plant, or air pollution control facility and other discarded material, including solid, liquid, semisolid, or contained gaseous material resulting from industrial, commercial or mining and agricultural operations, and from community activities . . . [excluding] . . . solid or dissolved materials in domestic sewage, or solid or dissolved materials in irrigation return flows, or industrial discharges which are point sources subject to permits under Section 402 of the Federal Water Pollution Control Act . . . , or source, special nuclear, or byproduct material as defined by the Atomic Energy Act [AEA] of 1954 . . . [Section 1004(27)]. Several wastes important to DOE are excluded from the RCRA definition of solid wastes (40 CFR 261.2). They include source, special nuclear, or byproduct material as defined by the AEA [Section ll(e), (z), (aa)]; waste from extraction, beneficiation, and processing of ores and minerals, including overburden from mining uranium ores; utility wastes; oil and gas drilling muds and brines; and some wastes that are reused or recycled. The statutory definition of a hazardous waste is provided in RCRA as follows: a solid waste, or combination of solid wastes, which because of its quantity, concentration, or physical, chemical, or infectious characteristics may . . . cause, or significantly contribute to an increase in mortality or an increase in serious irreversible, or incapacitating reversible, illness; or ... pose a substantial present or potential hazard to human health or the environment when improperly treated, stored, transported, or disposed of, or otherwise managed [Section 1004(5)]. Furthermore, a solid waste is a hazardous waste if it is not excluded by regulation (40 CFR 261.4) and if it is listed (261.30) as a hazardous waste, is a waste mixture containing one or more listed hazardous wastes, or exhibits one or more
Properties and Selection of Organic Solvents
117
characteristics of hazardous waste (i.e., ignitability, corrosivity, reactivity, or toxicity) (40 CFR 261.21 to 261.24). Listed wastes meet the definition of hazardous waste regardless of the concentration of hazardous constituents. With few exceptions [e.g., spent solvents listed solely because they are ignitable (40 CFR 261.31)], the only way to have a listed waste relieved from hazardous waste management requirements is to petition EPA or a state to delist the waste (40 CFR 260.22). When listed wastes are mixed with nonhazardous wastes or materials, the mixture must be managed as hazardous waste. Two exceptions to this approach are hazardous debris meeting Land Disposal Restriction (LDR) standards [40 CFR 261.3(f)] and residues from processing certain wastes using high temperature metals recovery processing [40 CFR 261.3(c)(2)(ii)(C)]. In contrast to listed waste, a characteristic waste remains hazardous only as long as it exhibits a hazardous characteristic. Therefore, a mixture of a waste exhibiting a hazardous waste characteristic and a nonhazardous solid waste is not considered hazardous waste unless the mixture exhibits a hazardous waste characteristic. Proper identification and management of hazardous wastes are critical to the success of the cradle-to-grave program. Waste generators must determine (40 CFR 262.11) if their solid wastes are also hazardous wastes and, if so, notify EPA, or an authorized state if appropriate, of their hazardous waste management activities and obtain an EPA identification number (40 CFR 262.12). Generators must manage hazardous wastes in accordance with RCRA's on-site waste management requirements (40 CFR 262) or obtain a permit (40 CFR 264 or 265 and 270) for waste management activities. They must also verify that the transportation, treatment, storage, and disposal of their waste are conducted only by others with EPA identification numbers and authority to manage the waste. Before a hazardous waste may be shipped off-site, the generator must determine: •
whether the waste is a hazardous waste (40 CFR 262.11);
•
the proper packaging for the hazardous waste (40 CFR 262.30);
•
the necessary RCRA and U.S. Department of Transportation (DOT) labeling, marking, and placarding requirements (40 CFR 262.30-262.33); and
•
the information necessary to complete and sign the hazardous waste manifest (which includes both DOT and RCRA shipping paper information) for the waste shipment (40 CFR 262.20-262.23).
Title 40 CFR 262, Subpart B (The Manifest), addresses RCRA requirements for shipping documentation under hazardous waste manifest requirements. The manifest must include the following information (Appendix to Part 262): •
name and ID number of generator and facility to which the waste is being sent,
118
Industrial Solvents Handbook •
DOT description of waste being transported,
•
quantities of the waste being transported, and
•
address of the off-site treatment, storage, and disposal facility (TSDF) designated to receive the waste.
The purpose of the manifesting system is to establish accountability for and tracking of hazardous waste shipments. The manifest is an important feature of RCRA's "cradle to grave" system. A generator must keep a copy of each manifest for three years. The generator must also maintain records and report hazardous waste management activity, including the amount of hazardous waste produced, the transporters of the wastes, and the TSDFs in possession of the hazardous waste (40 CFR 262.40-262.44). Title 40 CFR 263 contains regulations governing the transportation of hazardous waste. In developing its regulations, EPA adopted by reference most of DOT's Hazardous Materials Transportation Act (HMTA) implementing regulations for the safe transportation of hazardous wastes (49 CFR 171 through 179). Because RCRA regulations adopted by reference rather than incorporating the specific language of DOT's HMTA regulations, a transporter must refer both to RCRA and to DOT regulations to ensure compliance when transporting hazardous waste. Anyone who transports a hazardous waste off-site via air, rail, highway, or water is subject to the RCRA transporter requirements. However, 40 CFR 262.20(f) exempts transport of hazardous wastes within or along the border of contiguous properties under the control of the same person, even if the contiguous properties are divided by a public or private right-of-way. Before implementation of this exemption with the military munitions rule (see 62 FR 6622, February 12, 1997), such transport of hazardous waste was subject to RCRA manifesting requirements. In addition, conditionally exempt small quantity generators are exempt in specified situations [40 CFR 262.20(e)]. RCRA requires an owner or operator of a TSDF to obtain a permit to operate. Congress, recognizing that a permitting program would take time to implement, established interim status as a mechanism by which existing hazardous waste management facilities could continue operation without first obtaining a RCRA permit. Owners and operators of such hazardous waste management facilities had to notify EPA that the facility exists and to file a preliminary (Part A) permit application. Interim status is also available to facilities that first become subject to RCRA permitting requirements because of regulatory changes, such as expansion of the list of solid wastes regulated as hazardous waste. Section 3005(c) of HSWA established deadlines for permitting interim-status facilities. Interim-status facilities were required to either file the Part B portion of the permit application by the applicable statutory deadline or file a closure plan and close by November 8, 1992. Interim status ends when a final determination is made to grant or deny the RCRA permit or when the facility closes (for facilities that
Properties and Selection of Organic Solvents
119
closed rather than seek a RCRA permit). Owners/operators of facilities denied a permit may appeal the decision under 40 CFR 124.19 or an equivalent state appeal processes. New facilities are ineligible for interim status and must receive a permit before construction can begin. (New facilities seeking a permit submit the Part A and Part B portions of the permit application at the same time.) Facilities operating under interim status or permits must comply with the general requirements applicable to all types of facilities and also to waste management unitspecific requirements. General requirements include providing security (40 CFR 264.14 or 265.14), planning for emergencies (40 CFR 264 Subpart D or 265 Subpart D), training personnel (40 CFR 264.16 or 265.16), properly characterizing waste to be managed in the facility (40 CFR 264.13 or 265.13), groundwater monitoring (as appropriate) (40 CFR 264 Subpart F or 265 Subpart F), planning for eventual closure of the facility (40 CFR 264 Subpart G or 265 Subpart G), and proper recordkeeping and reporting [40 CFR 264.11 or 265.11, 264.15(d) or 265.15(d), 264.16(e) or 265.16(e), 264.56(j) or 265.560), 264.71 through 264.77 or 265.71 through 265.77, and 265.94]. Unit-specific design and operating criteria are codified in 40 CFR 264 or 265 Subparts I through DD and include additional unit-specific recordkeeping requirements. Requirements for the design, operation, maintenance, and closure of hazardous waste management units are specific for each type of unit. For example, tanks must meet special tank design and operation requirements (40 CFR 264 Subpart J or 265 Subpart J). Containers used for storing hazardous wastes must satisfy requirements of 40 CFR 264 Subpart I or 265 Subpart I. In addition, unit-specific requirements that may potentially apply to DOE activities are specified for containment buildings (40 CFR 264 Subpart DD or 265 Subpart DD), waste piles (40 CFR 264 Subpart L or 265 Subpart L), incinerators (40 CFR 264 Subpart O or 265 Subpart O), surface impoundments (40 CFR 264 Subpart K or 265 Subpart K), land treatment units (40 CFR 264 Subpart M or 265 Subpart M), landfills (40 CFR 264 Subpart N or 265 Subpart N), and miscellaneous units (40 CFR 264 Subpart X) not otherwise specified in regulation, among other things. However, certain DOE waste management units do not require a RCRA permit because their management activities are exempt from permitting. Examples of exempted activities are on-site hazardous waste accumulation for less than 90 days, totally enclosed treatment, wastewater treatment only involving tanks that discharge through surface water discharges regulated under the Clean Water Act, and elementary neutralization [40 CFR 270.1(c)(2)]. Hazardous and Solid Waste Amendments (HSWA) HSWA addressed congressional concern about the adequacy of then existing waste management requirements in preventing uncontrolled releases of hazardous constituents or hazardous wastes from hazardous waste management units. Three of the HSWA initiatives were especially noteworthy in preventing or addressing hazardous waste/constituent releases.
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Industrial Solvents Handbook
First, Congress restricted land disposal of untreated hazardous waste unless it could be demonstrated that the disposal facility is adequate to prevent release of hazardous constituents from the facility as long as the waste remains hazardous (i.e., no migration demonstration) [Section 3004(d)(l)J. Congress authorized EPA to develop treatment standards to allow land disposal of treated hazardous wastes in permitted facilities that have not demonstrated compliance with no-migration requirements. The regulatory program implemented under the statutory land disposal prohibition largely focuses on establishing treatment standards that, when met, allow hazardous wastes to be disposed of in land-based units. Second, facilities were required to satisfy the minimum technology requirements (i.e., liners and leachate collection systems) for landfills and surface impoundments to prevent hazardous wastes and/or constituents from migrating into groundwater and to permit detection of releases when or if they occur [Section 3004(o)]. Third, EPA was granted the authority to require corrective action for releases of hazardous waste and hazardous constituents from any solid waste management unit, regardless of when the waste was placed in the unit, at a facility seeking a RCRA permit [Sections 3004(u) and 3004(v)]. Underground Storage Tanks Subtitle I (implemented at 40 CFR 280) was also added by HSWA. It established a program to regulate the three to five million underground storage tanks (USTs) in the United States and to prevent their leaking. Under this subtitle RCRA regulates the storage of a product (e.g., petroleum products and hazardous substances), rather than hazardous waste. Hazardous substances regulated under Subtitle I include all the hazardous substances (except those regulated as a hazardous waste under Subtitle C of RCRA) defined under CERCLA. Hazardous substances under CERCLA Section 101(14) encompass a wide variety of pollutants regulated under other federal statutes including the Clean Water Act, Clean Air Act, and Toxic Substances Control Act. Radionuclides, which are specifically excluded under RCRA's definition of solid waste, are regulated under CERCLA because they are defined as hazardous air pollutants under the Clean Air Act. Thus, radioactive materials/waste stored in USTs are within the scope of RCRA Subtitle I authority. Although within the scope of Subtitle I, tanks containing radioactive materials/wastes subject to Atomic Energy Act requirements are currently deferred from UST regulations [40 CFR 280.10(c)(2)]. Nevertheless, tanks containing radioactive materials/waste "mixed" with hazardous waste are regulated under Subtitle C. Federal agencies and departments, including DOE, that own or operate USTs are subject to and must comply with all applicable federal, state, interstate, and local requirements, except when the President determines that exemption of specific tanks from these requirements is in the "paramount" interest of the United States (RCRA, Section 9007). States with RCRA Authority Section 3006 of RCRA authorizes states to develop and enforce their own
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hazardous waste programs in place of the federal program administered by EPA. Before administrating any of the provisions of HSWA, authorized states must again go through a state program approval process. Federal Facility Compliance Act The Federal Facility Compliance Act (FFCAct, Pub. L. 102-386) was enacted on October 6, 1992, and, among other things, specifically waived sovereign immunity with respect to RCRA for federal facilities. Therefore, EPA may impose fines and penalties on federal agencies. Land Disposal Program Flexibility Act of 1996 RCRA was amended on March 26, 1996, with the passage of the Land Disposal Program Flexibility Act of 1996 (Pub. L. 104-119). Guidance on the Use of Section 7003 of RCRA In October 1997, EPA's Office of Enforcement and Compliance Assurance issued a guidance document entitled Guidance on the Use of Section 7003 of RCRA. This guidance was issued to update, expand, and supersede previous guidance on this subject, dated September 26, 1984. The guidance document states that Section 7003 of RCRA provides the Agency: . . . with broad and effective enforcement tools that can be used to abate conditions that may present an imminent and substantial endangerment to health or the environment. Section 7003 allows EPA to address situations where the handling, storage, treatment, transportation, or disposal of any solid or hazardous waste may present such an endangerment. In these situations, EPA can initiate judicial action or issue an administrative order to any person who has contributed or is contributing to such handling, storage, treatment, transportation, or disposal to require the person to refrain from those activities or to take any necessary action. Among its many benefits, Section 7003 provides EPA with a strong and effective means of furthering risk-based enforcement and implementing its strategy for addressing the worst RCRA sites first. For further information and details, please utilize the link provided above to access a complete electronic version of this guidance document. Toxic Substances Control Act Congress enacted the Toxic Substances Control Act (TSCA) in 1976, to become effective January 1, 1977. The act authorizes EPA to secure information on all new and existing chemical substances and to control any of these substances determined to cause an unreasonable risk to public health or the environment. Under earlier laws EPA had authority to control toxic substances only after damage occurred. The earlier laws did not require the screening of toxic substances before they entered the marketplace. TSCA closed the gap in the earlier laws by requiring that the health and environmental effects of all new chemicals be reviewed before they
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are manufactured for commercial purposes. TSCA has four titles as described below. Title I - Control of Toxic Substances - includes provisions for testing chemical substances and mixtures; manufacturing and processing notices; regulating hazardous chemicals substances and mixtures; managing imminent hazards; and reporting and retaining information. Title II - Asbestos Hazard Emergency Response - was added by the Asbestos Hazard Emergency Response Act (AHERA, Pub. L. 99-519), enacted by Congress on October 22, 1986. It authorizes EPA to amend its TSCA regulations to impose more requirements on asbestos abatement in schools. AHERA provides for the promulgation of federal regulations requiring inspection for asbestos and appropriate response actions in schools and mandates periodic reinspection. In addition, it requires the EPA Administrator to determine "the extent of the danger to human health posed by asbestos in public and commercial buildings and the means to respond to any such danger." AHERA was amended in 1990 by the Asbestos School Hazard Abatement Reauthorization Act (ASHARA, Pub. L. 101637) to require accreditation of persons who inspect for asbestos-containing material in school, public, and commercial buildings. It also mandates the accreditation of persons who design or conduct response actions with respect to friable asbestos-containing material in such buildings. It is important to note that public buildings are defined to include government-owned buildings (40 CFR 763, Appendix C to Subpart E - Asbestos Model Accreditation Plan). Title III - Indoor Radon Abatement - was added on October 28, 1988 (Pub. L. 100551). The purpose of this legislation was to assist states in responding to the threat to human health posed by exposure to radon. EPA is required to publish an updated citizen's guide to radon health risk, and to perform studies of the radon levels in schools and radon contamination in federal buildings. Title IV - Lead Exposure Reduction - was added on October 28, 1992 (Pub. L. 102550). The purpose of this legislation is to reduce environmental lead contamination and prevent adverse health effects as a result of lead exposure, particularly in children. Provisions include identifying lead-based paint hazards, defining levels of lead allowed in various products, including paint and toys, and establishing state programs for the monitoring and abatement of lead exposure levels, including training and certification for lead abatement workers. OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION The Occupational Safety and Health Administration (OSHA), a department of the U.S. Department of Labor, deals with maintaining health and safety in the workplace. Established under the OSHA act of 1970, this agency was set up to: •
reduce workplace hazards
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•
establish minimum standards for health and safety for industries
•
regularly inspect workplace sites to ensure compliance with standards
•
maintain a systematic method of reporting incidents of on-me-job or work-related illnesses or injuries, including those which entitle an individual to compensation
Documentary evidence showed that leading up to 1969 and 1970, more than 14,500 American workers were killed annually on or in connection with their jobs, and more than 2,200,000 were disabled each year as a result of work related accidents. During this time the enactment of health and safety laws had been left solely to the states. Many states, however, have enacted few laws and failed to appropriate the proper funds to enforce the laws. As the American worker continued to suffer crippling accidents and death at an accelerated rate, the need for federal legislation became evident. In 1970 the Occupational Safety and Health Act (OSHA) was signed into law. While individual states may still develop and enforce their own health and safety programs, these programs must be at least as effective as the federal program set forth in the Act. The purpose of OSHA is to assure, as far as possible, safe and healthy working conditions for the American workers. To accomplish this purpose, employers are required to comply with two guidelines: General Standards and the General Duty Clause. OSHA has adopted a large number of federal safety and health standards divided into various categories. These standards are measures of safety formulated to reduce employees' exposure to hazardous conditions. Some standards govern all worksites generally, and other standards address specific industries. The Act requires employer compliance with these standards. Although employers may be allowed input on which standards are adopted and can contest standards believed to be unfair, once the standard is adopted and published by OSHA, noncompliance by an employer is grounds for enforcement. General Duty Clause In addition to adhering to the general standards set forth by OSHA, employers are also required to comply with the general duty clause, also known as the "Catchall Standard." The clause requires that every employer furnish to each of its employees, "employment and a place of employment which are free from recognized hazards that are causing or are likely to cause death or serious physical harm." The clause is intended to cover serious hazards for which there are no specific standards in place, so that employees are always entitled to a relatively safe workplace. Noncompliance by an employer is also grounds for enforcement. Rights of Employees In order to accomplish the purpose of the OSHA, employees are afforded certain rights. The rights that follow are in place so that the employee has an opportunity to
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make sure that their workplace is free from hazards, and also to help facilitate enforcement of the standards set forth in the Act. The OSHA Poster - Employees have a right to know of their protections under OSHA. A notice outlining the protections and obligations under OSHA must be posted in the workplace by every employer. The notice must be posted in a conspicuous place where employee notices are usually posted. Records OSHA Form No. 200 - OSHA requires all private sector employers to maintain a log and summary (OSHA form no. 200) of occupational injuries and illnesses for each of their establishments. (Exempted are small employers with no more than ten employees.) This log and summary must be made available for inspection and copying by current and former employees or their representatives. Refusal to provide access to this log is a violation of §1904.7 of the Act. Medical and Exposure Records - Certain standards promulgated by OSHA require employers to monitor and measure employee exposure in certain instances, and to keep a record for the term of employment plus thirty years. Other standards require periodic medical examinations of employees, with records to be kept by the employer. When an employer is required to maintain exposure and medical records, §1910.1020 provides employees and their representatives with the right to access and copy those records. Inspections - One of the most important rights provided to the employee is the right to request and be involved in inspections. If an employee believes that an OSHA violation exists in the workplace, a request may be submitted to an OSHA compliance officer or Area Director. Once it has been determined that there are reasonable grounds to believe that a violation or imminent danger exists, an inspection will be conducted. Employees also have the right to point out violations during an inspection. A representative of the employees must be given the opportunity to accompany the OSHA compliance officer during the inspection. (The Act does not, however, require compensation for employees accompanying an inspection.) The employee also has the right to access and copy inspection results. Protection - The employee who exercises his right to request inspections or records, or to point out violations, has the right to be protected from retaliatory discrimination or termination. §1 l(c) of the Act provides that employees can not be discharged or otherwise discriminated against for filing complaints or instituting proceedings under the Act. An employee who believes that he has received retaliatory treatment as a result of exercising the rights accorded in the Act has the right to file a complaint alleging discrimination within 30 days of the violation. Refusal to Work - §1977.12 gives employees the right to refuse in good faith to
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expose himself to a hazardous workplace condition if the hazardous condition is such that a reasonable person would conclude that there was a real danger of death or serious illness, and that there is insufficient time due to the urgency of the situation to eliminate the danger through enforcement channels. When an employer is required to maintain exposure and medical records, §1910.1020 provides employees and their representatives with the right to access and copy those records. Procedures Employees or their representatives may file a complaint requesting an OSHA inspection when they believe that a violation of a safety or health standard or an imminent danger exists in the workplace. •
A formal complaint must be in writing, signed and set forth the grounds for the complaint with "reasonable particularity. "
•
The employer will receive a copy of the complaint, but the employee may request that his name be deleted from the employer's copy.
•
If it is determined that there are reasonable grounds to believe that a violation - or imminent danger - exists, an investigation will be conducted as soon as possible.
•
The OSHA agency may determine that an inspection was not warranted, and the complaintant will be notified. The complaintant may request a hearing on the decision.
•
Nonformal complaints, including oral complaints and unsigned written complaint may be made by employees during inspections to the inspecting compliance officer. (However formal hearings are not granted as a result of a nonformal complaint.)
•
If as a result of the inspection, the agency believes that there is an OSHA violation, a citation must be issued to the employer. The citation must be issued within six (6) months of the occurence of the violation.
•
If an employee believes that he has been discharged or discriminated against as a result of exercising his rights under OSHA, he may file a complaint with the OSHA agency.
•
The employee may file a complaint in writing to the OSHA agency within thirty (30) days of the alleged violation. The complaint should set out with particularity the allegations of the violation.
•
An l i e violation is established when it is shown that the employee's
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If the OSHA agency determines that an lie violation has occurred, an action will be brought in federal district court to restrain the violation and obtain other appropriate relief. (However if the agency determines that no violation has occurred, the employee may not sue the employer in a private action.)
In 1983, OSHA announced the Hazard Communication Standard (HCS) which creates a right-to-know policy for workers who manufacture and handle hazardous chemicals. Items covered under the HCS include labeling of chemical containers, the use of Material Safety Data Sheets (MSDSs), the development of worker training programs and the use of written hazard communication programs. These requirements will many times provide the workers with sufficient information to make their own safety judgments. OSHA inspectors may enter any plant for the purpose of conducting inspections in regards to worker safety and whether the plant is in compliance with OSHA regulations. Violations will result in a citation that requires the plant management to correct the problem. Civil penalties can be assessed in the event of a worker's injury or death due to a hazardous chemical substance. Limits for Air Contaminants The greatest physical hazard for most organic chemicals is overexposure by vapor inhalation or absorption of the chemical through the skin. All of the chemicals regulated by OSHA are listed in Tables Z-l, Z-2, and Z-3 in 29 CFR 1910.10001048 of the OSHA regulations. A similar list of Threshold Limit Values (TLV) for chemical substances is listed in the latest edition of the TLV issued by the American Conference of Governmental Industrial Hygienists (ACGIH) organization (Kemper Woods Center, 1330 Kemper Meadow Drive, Cincinnati, OH 45246; 513-742-2020). OSHA Table Z-l sets the limits on air contaminants by listing the Permissible Exposure Limit (PEL), which is equivalent to the 8-hr Time Weighted Average (TWA) for a chemical. The stated PEL value is established at a level below which a worker should not expect to have any health problems with the chemical. PEL values have regulatory status while TWA values or TLVs are viewed as recommendations. The TLV or TWA values are sometimes subject to change because of the availability of new toxicological information. The PEL values are periodically reviewed and updated as needed. Many of the solvents discussed in this book do not have assigned OSHA PEL values or TWA and TLV values as recommended by the ACGIH organization. The MSDS for a chemical will, however, list under Section 5, "Health Hazard Data," any of the available pertinent toxicological data on the solvent along with recommendations for exposure limits. These data may come from technical papers published in the open literature and from toxicology testing of a particular chemical.
SECTION 3 SOLVENT SELECTION CRITERIA
The Hansen solubility parameter theory can be used to classify solvents in terms of their nonpolar, polar and hydrogen bonding characteristics. Use of the theory allows one to systematically search for a solvent substitute or to determine the solubility of a resin/polymer in a certain solvent or solvent blend. For example, the theory can be applied to identifying a suitable solvent substitute whereby a more environmentally friendly or less toxic solvent may be substituted for in a particular application. The most common applications of the theory are in the formulation of new solventbased coatings or reformulating of an existing solvent-based coating with a new solvent blend, and the selection of a suitable solvent or blend in an industrial process. Other uses of the theory include pigment-solvent interactions in terms of suspension behavior, the compatibility of plasticizers and polymers, the critical strain behavior of commercial plastics in the presence of solvents, in determining the effects of solvents on other mechanical properties of the polymers and the affinities of organic solvents in biological systems. A QUICK REVIEW OF SAFE PRACTICES A solvent is a liquid that dissolves another substance to form a solution. Solvents can dissolve solids, liquids or gases. Water is a solvent. Every day, people dissolve soap in water creating a soap solution. Different classes of solvents dissolve different substances more readily. For example, some oils readily dissolve in mineral spirits, but not in water. Organic solvents have a variety of uses. Solvents are used in cleaning to dissolve stains, dirt or grease, which is then removed when the solvent is washed away. The dirt on a wool suit is removed when it dissolves in the perchloroethylene used by dry cleaners. Grease on metal parts is often removed with mineral spirits ("varsol"). Many solvents are ingredients in coatings (paints, enamels, varnishes, shellacs and lacquers), pesticides and resins. Examples of other applications include disinfectants (isopropyl alcohol to kill germs) and as anti-freeze agents (ethylene glycol). Many solvents are a potential fire hazard. A solvent is flammable and a serious fire hazard if its flash point (the lowest temperature at which a vapour given off by a liquid will catch on fire if in contact with a spark or other ignition source) is below 37.8°C (100°F). It is less of a fire hazard if it is combustible [flash point between 37.8°C and 93.3°C (200°F)]. At or above 93.3°C the fire hazard is low. Organic solvents are not corrosive (caustic or acidic). Work practices must be reviewed to see if a solvent can be used in a different manner or if the quantity can be reduced. Replacing spray systems with covered diptanks for parts cleaning can reduce inhalation exposure. Many times a less 127
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hazardous or less toxic solvent in the same class of solvents may do the job just as well. Sometimes a less hazardous product or a product with a more easily controlled hazard can be used. Some corrosives can be substituted for solvents, but in these cases workers need to be protected from the corrosive. Many solvents vaporize easily, creating an inhalation hazard. The first choice for protecting the respiratory system is a local exhaust ventilation system. If the solvent is a fire hazard, ensure that the ventilation system is spark/explosion proof. Many solvents dissolve oils, fats and greases readily. This same property allows them to remove fats and oils from the skin and to enter the body through the skin. Proper Personal Protective Equipment (PPE) is an important aspect in protecting the worker. Organic solvents can also dissolve and be absorbed through materials used to make PPE, therefore, select PPE that is resistant to the solvent being used. Gloves and other PPE need to be changed frequently to prevent exposure from absorbed solvents. Sparks, flames, cigarettes and pilot lights can ignite flammable solvents. These ignition sources should never be in the vicinity of flammable or combustible solvents. These solvents need to be stored in a proper flammable storage facility when not in use. Many solvents have common health effects. Solvents possess a wide variety of chemical and physical properties. With this diversity there are many different health effects associated with overexposure to solvents. Most solvents irritate the skin, eyes, nose and throat. Irritation of the skin may lead to skin problems (dermatitis). Many cause headaches, nausea, vomiting and dizziness. Long-term exposure may damage the liver, kidney, respiratory system and/or nervous system. Specific organic solvents may be sensitizers (cause an allergic reaction) of the skin or the respiratory system. Some organic solvents are suspect carcinogens and others are associated with adverse reproductive effects (for example, infertility or miscarriage). Solvents may affect the same body systems as alcoholic beverages. Consequently, the adverse health effects on the body may be compounded when solvent exposure and alcohol consumption occur at the same time. Alcohols are frequently used in the workplace to dissolve substances such as shellacs, vinyls, acrylics, epoxies, and silicones. Low melting points result in some alcohols being used as an anti-freeze agent. Most alcohols are a fire hazard and are either flammable or combustible. Alcohols enter the body through inhalation, skin absorption, and ingestion. Acute symptoms from overexposure range from fatigue, incoordination, and behaviorial changes to coma. Methanol (wood alcohol) can damage the optic nerve and impair vision. Ethanol is the least toxic. However, a more toxic denaturant is added so that the ethanol is undrinkable. Isopropyl alcohol is one of the least toxic and often a good substitute for the more toxic alcohols. Aliphatic hydrocarbons are often found in coatings and insecticides. They are excellent degreasers and solvents for acrylics and epoxies. Common aliphatics include mineral spirits, paint thinner, petroleum distillates, VM&P Naphtha, kerosine, gasoline, and heptane. Some of these substances are extremely flammable and present a fire and explosion hazard. Symptoms of acute exposure also include
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headache and fatigue. Chronic overexposure to certain aliphatic hydrocarbons, such as n-hexane, can cause dermatitis and damage to the nervous system resulting in temporary blindness, paralysis, weakness in the arms and legs, and mental disorders. Only some of the effects are reversible. Other aliphatic hydrocarbons are less toxic. Aromatic hydrocarbons derive their name from the "pleasant" odor attributed to many of these substances. These substances are used in printing; fibreglassreinforced products' industries; manufacture of coatings and consumer products; and in glues and veneers. Common aromatics include toluene (toluol), xylene (xylol), coal-tar naphtha, styrene, and benzene. Additional acute symptoms of overexposure include fatigue, weakness, confusion, dermatitis and chemical pneumonia. Aromatic hydrocarbons are readily absorbed through the skin and subsequently affect the lungs, skin, blood, eyes, kidneys and nervous system. Some are associated with reproductive hazards. Benzene suppresses production of blood cells and can cause leukemia. Chlorinated hydrocarbons are commonly used as degreasers, drycleaning agents, rubber solvents and paint strippers. They are found in coatings, resins and tars. Common chemicals in this class include perchloroethylene, methylene chloride, carbon tetrachloride, methyl chloroform and trichloroethylene. When exposed to heat or ultraviolet light many chlorinated hydrocarbons will form phosgene gas, which is extremely hazardous. Chlorinated hydrocarbons readily evaporate, presenting an inhalation hazard. They are also easily absorbed through the skin. Other symptoms of overexposure include sleepiness, dermatitis, and erratic heartbeat. Long-term exposure may damage the eyes, skin, kidney, liver and central nervous system. Many are suspect carcinogens. Glycols are water soluble. They are used as lubricants, as ingredients in cosmetics and coatings, and to lower the freezing point of liquids. They do not present the fire hazard associated with many other organic solvents. Some glycols such as propylene glycol and triethylene glycol have relatively low toxicity causing mild skin and eye irritation. Others, such as ethylene glycol, cause more severe irritation, headaches, and nausea and damage the liver and kidneys. Glycol Ethers and their acetates are often used as solvents in coatings, resins and dyes. Glycol ethers include butyl cellusolve (2-butoxyethanol), cellusolve (2ethoxyethanol), methyl cellusolve (2-methoxyethanol), and cellusolve acetate (2ethoxyethyl acetate). Most common glycol ethers are combustible. Many glycol ethers are readily absorbed through the skin. This exposure route can be more serious than inhalation. Acute effects from overexposure to glycol ethers include irritation and headaches. Chronic exposure affects several different organ systems in the body. Many, including cellusolve and methyl cellusolve, are known to have serious reproductive effects in humans and/or animals. However, this is not the case with butyl cellusolve. Esters have differing chemical properties and as a result their uses, health effects and physical effects vary. For example, methyl formate used in fumigants and
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insecticides is a fire and explosion hazard. The body converts it to methanol and the symptoms of overexposure are similar to methanol. Other esters include ethyl acetate, isopropyl acetate, methyl acetate, sec-amylacetate, and isoamyl acetate (banana oil). In general, effects attributed to esters include headaches, drowsiness, dermatitis and irritation of the eyes, nose and respiratory systems. Ethers are ingredients in dyes, resins, waxes, cellulose nitrate and fuels. Many ethers are extremely flammable and form peroxides during extended storage that may explode. Examples of ethers are ethyl ether, tetrahydrofuran, dioxane and isopropyl ether. Ethers are also irritants and can cause health effects similar to other organic solvents. Some ethers have an anaesthetic effect. Dioxane exposure is associated with liver and kidney damage. It is also a suspect carcinogen. Ketones are solvents for dyes, resins and waxes. They are also used in the manufacture of plastics, synthetic fibers, explosives, cosmetics and medicines. Examples of ketones are acetone, methyl ethyl ketone (MEK) cyclohexanone and isophorone. Some ketones such as acetone and MEK are extremely flammable. Several ketones are absorbed through the skin. Symptoms associated with overexposure include those common to many other organic solvents. Methyl butyl ketone may cause muscle weakness and numbness in the hands and feet. Some damage the liver and kidneys. Other solvents include Freon, turpentine, dimethylformamide (DMF), and carbon disulfide. Exposure to high concentrations of Freon may cause irregular heartbeats. It also forms phosgene gas when heated. Turpentine causes irritation, headaches, dizziness and balance problems. It can be a sensitizer. Mineral spirits are often used as a substitute. DMF can cause headaches, dizziness, nausea, liver damage, and dermatitis. It is a suspect carcinogen for testicular cancer. Carbon disulfide is absorbed through the skin. Overexposure causes headaches, dizziness, poor sleep, nervousness and psychosis. It can also damage the liver, kidney and nervous systems. It is extremely flammable. Some useful references are the following: •
A Workers' Guide to Solvent Hazards, by Cameron Wright and the Waterloo Public Interest Research Group, University of Waterloo, Ontario, N2L3G1 (1985).
•
Handbook of Industrial Toxicoloy and Hazardous Materials, by. N. P. Cheremisinoff, Marcel Dekker Publishers, NY (1999).
•
Encyclopedia of Occupational Health and Safety, 3rd edition, edited by Luigi Parmeggiani, International Labour Organization (1983).
OVERVIEW OF THE THEORY Solvent selection rules are applied by calculating the solubility parameters of the solvent or solvent blend to be replaced and then selecting new solvents that have similar solubility parameters. The concept is that the total solubility parameter value can be represented as a dispersion (nonpolar) 5d, a polar 8P, and a hydrogen-
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bonding 5h component. The total solubility parameter can be mathematically expressed as the square root of the sum of the squares of the nonpolar, polar, and hydrogen-bonding components:
5, = (Sd» + &,» + 5h'T
(1)
The total solubility parameter of a resin or polymer is the point in threedimensional space where the three partial solubility parameter vectors meet at the center point of an idealized spherical envelope. The distance in space between the two sets of parameters (solvent and polymer) is expressed by the radius of interaction, ijR: = [4('5d - J8d)2+ (J5P -
('5h -
(2)
The radiius of interaction parameter expresses the degree of mutual solubility. Reasonable compatibility between solvent and resin/polymer is determined if the value of 'JR is < 10. Solubility comparisons can be made by using computer-based spreadsheets. By using the resin solubility data and solvent solubility parameters to determine the degree of resin solubility in the solvent, one can develop a list of likely solvent blends that can be verified by laboratory scale testing. Figure 2 illustrates the idealized spherical solubility envelope for a polymer. The total solubility parameter 5t of a material is a point in the three-dimensional space where the three partial Hansen solubility parameters intersect. If the calculated radius of interaction of the solvent and resin combination is less than the radius of the resin solubility sphere, then the solvent will most likely dissolve the resin and the solvent's solubility point will lie within the solubility sphere of the resin. A poor resin solvent combination will have a solubility point outside of the resin envelope. Application of the Hansen solubility theory will shorten the time and effort needed for solvent selection and substitution.
Figure 2. Idealized spherical solubility envelope.
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In Equation (2) the / terms correspond to the parameters of the resin, and the j terms to the parameters of the solvent. The three-dimensional envelop for a polymer or resin is determined by measuring the solubility behavior of the resin in a number of solvents that have a range of varying nonpolarity, polarity, and hydrogen-bonding character. Computer models exist that can take resin solubility data and compute the three solubility parameters of the resin along with the radius of the resin solubility sphere. Resin values for many solvents can be found in the literature. This handbook provides values for a few hundred chemicals. APPLICATION OF THE THEORY The concept of solubility parameters as it relates to the internal energy of a solution and solute was first introduced by Hildebrand (1916, 1970). Internal pressure is defined as the energy needed to vaporize one cubic centimeter of a substance. In Hildebrand's theory molecules with similar internal pressures will attract and interact with each other. Internal energy is described by the cohesive energy density (CED). The theory predicts that dissolution of a solute will occur in a solvent or solvent blend having similar CED value. Solubility parameters in the originally stated theory have the units of (cal/cm 3 )' /J . In modern SI convention the units are as follows: 1 cal'Vcm3'2 = 2.05 J' /2 /cm 3/2 or MPa'/2cm3 In older literature one will find that if the dispersion (nonpolar) value for a material is in the range of 6.0 and 9.0, the units of value are 1 cal'/!/cm3/2. Hence, simply multiply these values by 2.05 to obtain units in SI. Solutes and solvents having similar total solubility values are miscible, whereas substances with significantly different values are not compatible. This method of solubility classification works well with chemicals of hydrocarbon-like structure and that do not exhibit significant polarity or hydrogen-bonding tendencies (i.e., water-like). However, the total solubility parameter value can be better represented by three components; namely dispersion or nonpolar (8d), polar (5P), and hydrogen bonding (8 h ). Molecular structure determines the polarity and hydrogen-bonding characteristics of a solvent or polymeric resin system. Little interaction or association between hydrocarbon molecules is reflected by a large nonpolar solubility parameter for the molecule. An example of this is hexane. In contrast, polar behavior in a molecule like acetone is attributed to the partial dipole structure of the carbonyl (C = O) group. The partial charge separation imparts polarity to the molecule. Acetone also has some hydrogen-bonding characteristic. Both alcohols and glycol ethers exhibit intermolecular hydrogen bonding through interaction of the hydrogen and oxygen atoms. This gives the molecule high hydrogen-bonding characteristics. Increasing the number of carbon atoms in the solvent results in a decrease in the hydrogenbonding component.
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Example 1 Hexane is a solvent with only hydrogen and carbon atoms and has a 100% nonpolar character, 5h = 14.9. Acetone is a solvent with carbon, hydrogen, and polar carbonyl group. It has a nonpolar 5d = 15.5, a polar 5P = 10.4, and 5h = 7.0. Methyl alcohol is a solvent with nonpolar §d = 15.1, a polar 5p = 12.3, and 8h = 22.3. The percentage of each delta value of the total solubility parameter of the three solvents are:
Solvent Hexane Acetone Methanol
Nonpolar 100 47 30
% of Total Solubility Parameter Polar Hydrogen-bonding 0 0 32 21 22 48
SOLVENT BLENDS The values for a solvent blend can be calculated from the volume fraction O of each solvent component: O = 0,8, + 0262 + ...
(3)
New nonpolar, polar, and hydrogen-bonding values for the solvent blend are computed in three separate expressions using the three solubility parameter values of each solvent. Blends of two or three solvents with different solubility values can yield a solvent blend with intermediate values that match a particular resin. Two non-resin solvents can be blended to give a solvent mixture that dissolves the resin. As noted earlier the measurement of the degree of solubility parameter match between solvent and resin is determined by the radius of interaction defined by Equation (2). In this equation, the / terms correspond to the parameters of the resin and they terms to the parameters of the solvent. The expression provides a measure of the distance in three-dimensional space between the total solubility paramenters of the resin and solvent. The total solubility paramter, 8t, represents a point in space where the three partial solubility paramenter vectors converge. If the calculated radius of interaction of the solvent and resin combination is less than the radius of the resin solubilty sphere, then the solvent will most likely dissolve the resin and the solvent's solubility point will fall within the solubility sphere of the resin. Refer back to Figure 2. A poor resin solvent would have a solubility point that lies outside of the resin envelope. Table 14 provides a comprehensive list of solvent solubility data reported by Barton (1990) and Archer (1996, 1992). The following example taken from Archer (3) helps to illustrate application of the theory.
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Example 2 Neither xylene nor metanol are good solvents for a D.E.N. epoxy novolac 438 resin. However, computations suggest that a 50/50 (by volume) solvent blend should be able to dissolve the epoxy resin. Using the Hansen parameters for xylene and methanol from Table 14, the solubility parameters for the blend are computed as follows: J
6d = 0.5(17.6) + 0.5(15.1) = 16.35
J
6P = 0.5(1.0) + 0.5(12.3) = 6.65
J
5h - 0.5(3.1) + 0.5(22.3) = 12.7
The center point coordinates and radius of the solubility sphere of the epoxy resin obtained from laboratory experiments are: J 5d - 20.3 J 5p = 15.4 J 5h = 5.3 radius of sphere = 1 5 . 1 Substituting the solubility parameter values for resin and solvent blend into the radius of interaction equation (Equation (2)) results in ijR — 13.9. Since the computed distance between the center point coordinates of resin and solvent blend was less than the radius of the shere (15.1), the solvent blend should dissolve the epoxy resin. The solvent blend's center point coordinate (i.e., the total solubility parameter) falls inside the resin sphere volume. Archer reported that laboratory testing of the 50/50 xylene/methanol blend confirmed that the mixture was a good solvent for the epoxy resin. Table 14. Hansen Solubility Prameters (Data of Archer (1996)) Solvent 5D Acetic acid 14.5 Acetone 15.5 Acetonitrile 153 Acetophenone 19.6 Acrylonitrile 16.4 16.2 Allyl alcohol Alpha-pinene ( + /-, racemic) 15.6 15.7 Amyl acetate Aniline 19.4 Anisole (methoxybenzene) 17.8 Benzene 18.4
5P 8 10.4 18 8.6 17.4 10.8 4.3 3.3 5.1 4.1 0.0
5H 14 7 6 3.7 6 16.8 0.0 6.8 10.2 6.7 2
Properties and Selection of Organic Solvents Solvent Benzonitrile Benzyl alcohol Butylene glycol Butylene glycol dimethyl ether Butylene glycol ethyl ether Butylene glycol methyl ether Butylene glycol n-butyl ether Butylene glycol n-propyl ether Butylene glycol propylene glycol n-butyl ether Butyronitrile Carbon tetrachloride Chlorobenzene Chloroform cis-Decalin Cumene (isopropylbenzene) Cyclohexane Cyclohexanol Cyclohexanone Cyclohexylamine Decalin (mixture of cis and trans isomers) Diacetone alcohol Dibasic ester, Dupont DBE-3 Dibasic ester, Dupont DBE-4 Dibasic ester, Dupont DBE-5 Dibasic ester, Dupont DBE-9 Dibutylene glycol Dibutylene glycol n-butyl ether Dichlorodifluoromethane Diethanolamine Diethyl carbonate Diethyl phthalate Diethyl succinate Diethylamine Diethylene glycol Diethylene glycol butyl ether Diethylene glycol butyl ether acetate Diethylene glycol ethyl ether Diethylene glycol ethyl ether acetate Diethylene glycol methyl ether Diethylene glycol n-propyl ether Diethylenetriamine Diethylketone
5D 17.4 18.4 16.5 14.4 15.5 15.4 15.8 15.6 15.6 15.3 17.8 19.0 17.8 18.9 16.2 16.8 17.4 17.8 17.2 18.0 15.8 17.0 17.0 17.0 17.0 16.4 15.7 12.3 17.2 18.0 17.6 16.2 14.9 16.6 16.0 16.0 16.1 16.8 16.2 16.0 16.7 15.8
5P 9 6.3 11.1 4.5 6.6 8.0 5.4 6.5 5.5 12.4 0.0 4.3 3.1 0.0 7.0 0.0 4.1 6.3 3.1 0.0 8.2 4.3 5.1 4.7 4.7 9.5 5.2 2 7.8 3.1 9.6 4.1 2.3 14.7 7.0 4.1 9.2 6.4 7.8 7.2 13.3 7.6
135 SH 3.3 13.7 23.4 3.7 12.4 13.5 10.0 11.2 7.8 5.1 0.6 2 5.7 0.0 0.0 0.2 13.5 5.1 6.5 0.0 10.8 9.2 10.2 9.8 9.8 20.0 6.7 0.0 21.3 6.1 4.5 9.2 6.1 20.5 10.6 8.2 12.2 15.8 12.6 11.3 14.3 4.7
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Solvent Diglyme (diethylene glycol dimethyl ether) Diisobutyl ketone Diisobutylcarbinol Diisopropyl naphthalenes 1,4- and 2,6- isomers Dimethyl carbonate Dimethyl phthalate Dimethyl sulfoxide Di-n-butyl phthalate Di-n-butyl sebacate Di-n-propyl carbonate Di-n-propylamine Dioctyl phthalate Dipropylene glycol Dipropylene glycol dimethyl ether Dipropylene glycol ethyl ether Dipropylene glycol isopropyl ether Dipropylene glycol methyl butyl ether Dipropylene glycol methyl ether Dipropylene glycol methyl ether acetate Dipropylene glycol n-butyl ether Dipropylene glycol n-hexyl ether Dipropylene glycol n-propyl ether Eastman C-ll ketone Ethanol Ethyl acetate Ethyl benzene Ethyl caprate (ethyl decanoate) Ethyl caproate (ethyl hexanoate) Ethyl caprylate (ethyl octanoate) Ethyl cinnamate Ethyl ether Ethyl formate Ethyl lactate Ethyl n-amyl ketone Ethyl n-butyl ketone Ethyl- 3-ethoxypropionate Ethylene carbonate (Texacar ec) (mp 37°C) Ethylene glycol Ethylene glycol 2-ethylhexyl ether Ethylene glycol butyl ether acetate Ethylene glycol diacetate Ethylene glycol dibutyrate
8D
15.8 16.0 14.9 16.6 15.8 18.6 18.4 17.8 13.9 15.6 15.4 16.6 15.9 14.0 15.2 14.9 14.5 15.1 15.1 15.4 15.7 15.3 16.2 15.8 15.8 17.8 15.8 15.6 15.8 18.4 14.6 15.5 16.0 14.6 14.1 16.2 19.4 17.0 19.3 17.6 16.4 16.0
5P 6.2 3.7 3.1 0.4 3.7
10.9
10.8 16.4
10.2
8.6 4.5 4.1 1.4 7.0
4.1 4.1 8.0 4.1 3.1
20.2
18.4
4.8 6.6 7.1 2.4 6.8 5.3 5.6 6.0 6.8 2.1 8.8 5.3 0.6 2.1 2.9 2.5 8.2 2.9 8.4 7.6 7.2 7.4 9.2
21.7 11.0
5,. 9.2 4.1
10.8 0.0 4.9
2.7
11.4 11.2 5.3
12.6 4.3 9.0 6.7
10.2 4.1
19.4 7.2 1.4 5.5 6.6 5.9 4.1 5.1 8.4
12.5 5.7 7.0 9.4 5.1
10.5
26.0 13.3 10.0 12.9
3.5
8.4
3.7 6.1
Properties and Selection of Organic Solvents Solvent Ethylene glycol ethyl ether Ethylene glycol ethyl ether acetate Ethylene glycol hexyl ether Ethylene glycol methyl ether Ethylene glycol methyl ether acetate Ethylene glycol n-butyl ether Ethylene glycol propyl ether (Ektasolve EP) Ethylene glycol propylene glycol n-butyl ether Ethylenediamine Exxate 600 (hexyl acetates) Exxate 700 (heptyl acetates) Exxate 800 (octyl acetates) Exxate 900 (nonyl acetates) Exxatea 1000 (decyl acetates) Exxate 1300 (tridecyl acetates) Formamide Formic acid Fur an Furfuryl alcohol Gamma-butyrolactone Glycerol Glyme (ethylene glycol dimethyl ether) Heptane Hexanol (2-methyl-l-pentanol) Hexyl acetate (2-methyl-l-pentyl acetate) Hexylene glycol (2-methyl-2,4-pentanediol) Isobutanol Isobutyl acetate Isobutyl heptyl ketone Isobutyl isobutyrate Isopentane (2-methylbutane) Isophorone Isopropyl acetate Isopropyl ether Isopropyl palmitate Mesityl oxide (4-methyl-3-penten-2-one) Mesitylene Methanol Methyl acetate Methyl amyl acetate Methyl caproate Methyl ethyl ketone
5D 16.2 15.9 16.2 16.2 15.9 16.0 16.0 15.8 16.6 15.0 15.2 14.6 14.6 14.8 14.8 17.2 14.3 17.8 17.4 19.0 17.4 15.2 15.3 14.1 15.0 15.7 16.0 15.1 14.8 15.1 13.7 16.6 15.6 13.5 14.3 16.4 18.0 15.1 15.5 16.4 15.6 16.0
5P 9.2 4.7 5.4 9.2 5.5 6.2 6.2 6.2 8.8 5.7 5.1 7.0 6.8 6.6 5.9 26.2 11.9 1.8 7.6 16.6 12.1 2.7 0.0 8.6 7.0 8.4 5.7 3.7 5.9 2.9 0.0 8.2 3.3 4.7 3.9 6.1 0.0 12.3 7.2 6.6 3.3 9.0
137 «H
14.3 10.6 9.0 16.4 11.6 11.4 13.3 9.2 17.0 3.1 1.6 5.3 4.7 4.1 3.7 19.0 16.6 5.3 15.1 7.4 29.3 7.6 0.0 12.7 6.4 17.8 15.8 6.3 3.7 5.9 0.0 7.4 8.8 1.4 3.7 6.1 0.6 22.3 7.6 5.7 7.0 5.1
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Solvent Methyl isoamyl ketone Methyl isobutyl carbinol Methyl isobutyl ketone Methyl isopropyl ketone Methyl n-butyl ketone Methyl n-butyrate Methyl n-hexyl ketone Methyl n-propyl ketone Methyl oleate Methyl t-butyl ether Methylcyclohexane Methylcyclopentane Methylene chloride Mono ethanol amine Morpholine n-Amyl acetate n-Butanol n-Butyl acetate n-Butyl alcohol n-Butyl benzyl phthalate n-Butyl lactate n-Butyl stearate n-Butylamine n-Decane n-Eiosane (mp 36-38 °C) N-Ethylmorpholine N-Formyl morpholine n-Hexadecane (mp 18°C) n-Hexane Nitrobenzene Nitroethane Nitromethane N-Methyl-2-pyrrolidinone N-Methylmorpholine n-Nonane n-Octane Nonylphenol n-Pentane n-Propyl acetate n-Propyl alcohol n-Propylamine N-(2-Aminoethyl) piperazine
OD
16.0 15.4 15.3 14.8 14.1 15.6 15.2 15.8 14.5 13.7 16.0 15.8 18.2 17.2 18.8 16.2 16.0 15.8 16.0 19.1 15.8 14.6 16.2 15.8 16.6 16.6 16.6 16.4 15.0 20.0 16.0 15.8 18.0 18.0 15.8 15.6 16.5 14.6 16.4 16.0 17.0 15.6
SP 5.7 3.3 6.1 6.2 8.0 4.3 7.2 9.0 3.9 3.5 0.0 3.5 6.4 15.6 4.9 2.1 5.7 3.7 5.7 11.3 6,6 3.7 4.5 0.0 0.0 7.6 11.7 0.0 0.0 8.6 15.5 18.8 12.3 8.2 0.0 0.0 4.1 0.0 6.6 6.8 4.9 11.7
SH
4.1 12.3 4.1 8.2 7.2 7.8 3.9 7.6 3.7 5.1 1.0 0.0 6.2 21.3 9.2 8.6 15.8 6.3 15.8 3.1 10.3 3.5 8.0 0.0 0.0 0.6 10.0 0.0 0.0 4.1 4.5 5.1 7.2 8.6 0.0 0.0 9.2 0.0 8.2 17.4 8.6 9.0
Properties and Selection of Organic Solvents Solvent N,N-Dimethyl acetamide N,N-Dimethylethanolamine N , N-Dimethy Iformamide o-Dichlorobenzene o-Xylene p-Cymene (4-isopropyl toluene) Propionitrile Propylene carbonate (Texacar pc) Propylene glycol Propylene glycol butylene glycol n-butyl ether Propylene glycol diacetate Propylene glycol dimethyl ether Propylene glycol ethyl ether Propylene glycol ethyl methyl ether Propylene glycol ethylene glycol n-butyl ether Propylene glycol isopropyl ether Propylene glycol methyl butyl ether Propylene glycol methyl ether Propylene glycol methyl ether acetate Propylene glycol n-butyl ether Propylene glycol n-hexyl ether Propylene glycol n-propyl ether Propylene glycol phenyl ether Propylene glycol t-butyl ether Propylene oxide p-Xylene Pyridine Quinoline t-Amyl alcohol (2-methyl-2-butanol) t-Butyl alcohol (mp 25 °C) Tetrachloroethylene Tetraethylene glycol Tetraglyme (tetraethylene glycol dimethyl ether) Tetrahydrofuran Tetrahydrofurfuryl alcohol Tetralin Texanol ester-alcoholb Texasolve h (hexane-heptane mixture)0 Texasolve s-66 (mineral spirits) Texasolve s-lo (low aromatics/odor mineral spirits) Texasolve v (vm&p naphtha) Texasolve b (commercial hexane)
5D 16.8 13.5 17.4 19.3 17.8 16.6 15.3 20.0 16.8 15.6 15.8 14.2 15.4 14.4 15.9 15.1 14.6 15.6 16.1 15.6 15.9 15.5 18.7 15.4 13.5 17.6 19.0 19.4 13.7 15.2 19.0 16.6 15.8 16.8 20.1 19.7 15.2 15.2 15.8 15.6 15.0 15.0
5P 11.5 8.6 13.7 6.4 1 0.6 14.3 18.0 9.4 5.5 3.5 5.0 7.0 4.2 6.4 7.5 3.6 7.2 6.1 5.8 5.8 6.3 5.7 6.8 8.2 1.0 8.8 7.0 10.0 5.7 6.5 5.7 2.1 5.7 10.3 2.1 6.2 0.0 0.0 0.0 0.0 0.0
139 5H 10.2 13.9 11.3 3.3 3.1 0.0 5.5 4.1 23.3 7.8 8.8 4.9 13.5 3.7 8.0 13.4 1.4 13.6 6.6 11.2 8.8 12.4 11.3 9.3 10.5 3.1 5.9 7.6 12.5 15.2 2.9 16.8 8.2 8.0 16.0 2.9 9.8 0.0 0.0 0.0 0.0 0.0
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Industrial Solvents Handbook
Solvent Texasolve c (commercial heptane) Texasolve s (mineral spirits) Toluene Toluene diisocyanate trans-Decalin Trichlorofluoromethane Tricresyl phosphate (mp 90°C) Triethanolamine Triethyl phosphate Triethylamine Triethylene glycol Triethylene glycol butyl ether Tiiethylene glycol ethyl ether Triethylene glycol methyl ether Triethylene glycol n-propyl ether Triglyme (triethylene glycol dimethyl ether) Trimethyl phosphate Tri-n-butyl phosphate Tripropylene glycol Tripropylene glycol ethyl ether Tripropylene glycol isopropyl ether Tripropylene glycol methyl butyl ether Tripropylene glycol methyl ether Tripropylene glycol n-butyl ether Tripropylene glycol n-propyl ether Water Xylene (mixed isomers) 1 , 1 , l-Trichloroethane 1 , 1 ,2,2-Tetrachloroethane 1 , 1 ,2-Trichloroethylene 1,1,2-Trichlorotrifluoroethane (Freon 113) 1,1-Dichloroethane 1 , 1-Dichloroethylene 1,2-Butylene carbonate 1,2-Cyclohexane carbonate 1,2-Decane carbonate 1,2-Dichloroethane 1,2-Dichlorotetrafluoroethane (Freon 114) 1,2-Dimethyl imidazole 1,2-Dodecane carbonate 1,2-Hexane carbonate 1,4-Dioxane (p-dioxane)
OD 15.4 15.8 18.0 15.4 18.0 15.3 19.0 17.3 16.7 17.8 16.0 16.2 16.0 15.8 16.1 15.8 16.7 16.4 14.6 15.0 14.7 14.2 14.9 15.2 15.1 16.5 20.1 16.8 18.8 18.0 14.7 16.5 17.0 17.0 17.6 16.4 19.1 12.6 17.4 16.4 16.6 19.0
OP 0.0 0.0 1.4 16.4 0.0 2.0 12.3 22.4 11.4 0.0 12.5 7.0 7.8 8.2 7.9 2.3 15.9 6.4 4.7 7.1 6.4 5.1 6.8 5.8 6.4 23.5 1.8 4.3 5.1 3.1 1.6 8.2 6.8 6.2 5.3 3.1 7.4 1.8 12.7 2.7 4.7 1.8
5,, 0.0 0.0 2.0 7.8 0.0 0.0 4.5 23.3 9.2 1.0 18.6 7.4 9.7 10.9 8.6 8.2 10.2 4.3 15.6 9.2 9.0 -3.0 10.4 6.8 8.0 14.8 2.5 2.0 9.4 3.2 0.0 0.4 4.5 9.8 9.2 7.0 4.1 0.0 10.7 6.6 8.6 7.4
Properties and Selection of Organic Solvents Solvent SD 17.5 1-Decanol (decyl alcohol) l-Isopropyl-2-methyl imidazole 15.6 20.6 1- Methyl naphthalene 18.0 1-Nitropropane 17.0 1-Octanol 15.9 1-Pentanol (N-amyl alcohol primary) 16.0 1-Propanol 14.4 1-Tridecanol 14.1 2,2,4-Trimethylpentane 13.7 2,2-Dimethylbutane 14.1 2,3-Dimethylbutane 15.8 2-Butanol 15.9 2-Ethyl hexanol 16.2 2-Ethylhexyl acetate 15.8 2-Ethyl-l-butanol 16.0 2-Ethyl-l-hexanol 14.4 2-Methylpentane 15.6 2-Methyl-l-butanol 16.2 2-Nitropropane 2-Octanol 16.1 17.8 2-Phenoxyethanol 15.8 2-Propanol 19.4 2-Pytrolidinone 17.0 3-Isopropyl-2-oxazolidinone Methylpentane 14.6 a Exxate is a trademark of the Exxon Chemical Company; b Texanol of the Eastman Chemical Company; c Texasolve is a trademark Refining Corporation.
141
OP OH 10.0 2.6 8.8 8.6 4.7 0.8 4.1 11.3 11.9 3.3 13.9 4.5 17.4 6.8 9.0 3.1 0.0 0.0 0.0 0.0 0.0 0.0 5.7 14.5 11.8 3.3 12.1 5.9 13.5 4.3 3.3 11.9 0.0 0.0 4.7 13.7 12.1 4.1 4.9 11.0 5.3 12.3 6.1 16.4 17.4 11.3 7.8 10.0 0.0 0.0 is a trademark of the Texaco
Other uses of the solubility parameter theory include its application in assessing pigiment-solvent interactions in terms of suspension behavior. Settling rates of pigments in solvents provide a measure of the interaction and enable characterizaton of the pigments in terms of the solubility paramters. Data on pigment solubility values can help to select suitable ingredients for coating formulations. A solvent is expected to suspend a pigment if the radius of interaction ijR for the solvent-pigment combination is less than the experimentally determined radius of the pigment envelope (analogous the procedure for the spherical radius of a polymer). The compatibility of plasticizers and polymers can also be examined using solubility parameter theory. Henry (1974) applied the Hansen theory to correlate the critical strain behavior of commercial plastics in the presence of solvents. Areas of maxium susceptibility to cracking and crazing occurred when solvents
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Industrial Solvents Handbook
had both a polar and hydrogen bonding value in the range of 3 to 15 MPa'/2 units. Barton (1991) provides a summary of polymer-solvent interactions and the effects of solvents on the mechanical properties of polymers. Hansen and Anderson (1988) examined the affinities of organic solvents in biological systems using solubility paramter methods, and introduced the term realtive energy difference (RED) as a measure of the relative affinity of a solvent for a material. The RED is defined as the ratio of UR/ 'R or the radius of interaction of the solvent-substance divided by the characteristic radius of the substance. If RED < 1.0, the solvent would be expected to be compatible with the substance, whereas for RED > 1.0, poorer solvents would be expected. An RED value of zero would indicate a perfect match between solubility values of the solvent and the substance. Beerbower (1971) developed the following expression for estimating the surface tension of a solvent using the solubility parameters: a - 0.0715(V m )" 3 [ 52d + 0.632(82p + 5 2 h )]
(4)
where V m is the solvent's molecular volume, defined as the molecular weight/specific gravity. The reader may refer to the references at the end of this section for more detailed discussions and applications.
INTERNET RESOURCES As ozone-depleting and hazardous solvents were banned, or made very expensive, it became obvious that substitutes were necessary. Finding appropriate substitutes became a very labor-intensive effort. To minimize the effort of locating replacements solvents, a multitude of solvent substitution data systems were created. Unfortunately, each of these systems provides the user with only part of the solution. No system interfaced with any other system. Each system had a unique interface with its own command language. The user was left in a situation of having to access many systems, each with different information and a unique interface. The World Wide Web has not helped the situation. Using the Web for finding information on solvent alternatives is always a challenge. A massive amount of time can be consumed with using basic web search capabilities to attempt to find the information. Despite these drawbacks, the reader can find some resources to help serve as solvent substitution databases along with tools on the World Wide Web. One such site is the U.S.EPA sponsored site at the following url: http://es.epa.gov/ssds/ssds.html#issds. On this the reader can find links to the following resources. Integrated Solvent Substitution Data System (ISSDS) was created to provide the
Properties and Selection of Organic Solvents
143
quick retrieval of information regarding solvents and process alternatives for a variety of cleaning agents and cleaning processes. It is based on data distributed across the Internet. ISSDS supports users who are experts in the field of solvent substitution, as well as those who have minimal exposure to this type of information. The novice ISSDS user can perform solvent searches using the Guided Query. As the users become more educated, they move to the Assisted Query. When a user becomes familiar with ISSDS contents, they migrate to the Direct Query. The Guided Query provides the user with a specific set of questions and allows them to choose from a list of answers. This results in a ranked list of either substitute solvents or cleaning processes. The user selects the category of information to be selected, such as general information, vendor information, case studies, references, and DOD information. The result is a ranked list of documents that contain the requested information. The Assisted Query provides minimal guidance for entering answers to a selected set of generalized questions. The user selects the category of information to be selected, as described about. The result is the ranked list of documents. The Direct Query allows a knowledgeable user to control the query content. The user enters a cutoff score, the query text, and marks the data collections to be checked for the specified query. Currently, ISSDS accesses information from the following data collections: •
Solvent Alternative Guide (SAGE) - SAGE is a logic tree system that evaluates the user's current operating scenario and then identifies possible surface cleaning alternative solvent chemistries and processes that best suits the defined operating and material requirements. It provides the toplevel search parameters for the Guided Query method.
•
Hazardous Solvent Substitution Data System (HSSDS) - HSSDS is an online, comprehensive system of information on alternatives to hazardous solvents and related subjects. The HSSDS contains product information, material safety data sheets, and other related information.
•
Solvent Handbook Database System (SHDS) - SHDS is a database providing access to environmental and safety information on solvents used in maintenance facilities and paint strippers. SHDS contains empirical data from laboratory testing.
•
Tri-Services Pollution Prevention (P2) Technical Library - The TriServices P2 Technical Library is an electronic resource maintained by the Naval Facilities Engineering Service Center (NFESC). To foster technology transfer with other organizations, the NFESC has made the P2 Library available by direct access or by search facilities.
•
Pollution Prevention Publications Bibliography - The Pollution Prevention Publications Bibliography is collection that provides general reference to a variety of solvent data.
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Industrial Solvents Handbook •
Defense Logistics Agency (DLA) Environmental Products Catalog - The DLA Environmental Products Catalog contains vendor information for both solvent and processes.
•
Pollution Prevention Case Studies - The case studies collection contains information on alternative processes, materials and management practices for pollution prevention and hazardous waste minimization.
•
Vendor Information - The vendor information database and equipment classification system was created by the University of Wisconsin-Solid and Hazardous Waste Education Center with funding from the Great Lakes Protection Fund. The Development of VENDINFO has been supported by the Solid and Hazardous Waste Education Center and the U.S. EPA. The vendor information can be searched directly using equipment or process classification terms.
•
Air Force Ozone Depleting Chemicals (ODC) Information Exchange - The Air Force Ozone Depleting Chemicals (ODC) Information Exchange provides an information exchange service to the Air Force weapons system community to aid in complying with federally mandated ODC reduction goals.
•
DoD Ozone-Depleting Substance (ODS) MILSPEC Database - The DoD Ozone Depleting Substance (ODS) MILSPEC contains a listing of military and federal specifications which may require the use of Class I ODSs. The database is maintained by the U.S. Navy CFC & Halon Information Clearinghouse.
In 1992, the EPA Air and Energy Engineering Lab (AEERL) initiated a program to assist in the selection of nonpolluting industrial surface cleaning alternatives. The objective of the program was to make the identification of cleaning options simple yet based on the latest technical and economic feasibility information available. This objective could be most easily accomplished through the use of electronic equipment and a logic tree format. The resulting system, called SAGE for Solvent Alternatives Guide, incorporates the speed and ability of the computer to evaluate a large number of operating parameters and conditions to identify the most viable surface cleaning option. The first BETA test version 1.0, of SAGE was released in May of 1993 and placed on the EPA Control Technology Center Bulletin Board for down loading and review. Version 1.0 included only metal parts cleaning and was designed to test the SAGE concept for selecting surface cleaning alternatives. Since its release there have been over 1000 downloads of SAGE from the CTC bulletin board and another 500 copies of the system disk has been mailed to requestors. Many of the responses from users of the BETA test version indicate that the system in a few minutes confirmed their prior conclusions derived from many hours of study and analysis. The report also gave many users greater insight into the technical considerations and requirements for use of the various options which were previously unknown. The results of the responses have validated the concept used
Properties and Selection of Organic Solvents
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in the SAGE system. SAGE is not a database, rather a PC based logic tree system that evaluates the user's present operating scenario and then identifies possible surface cleaning alternative solvent chemistries and processes that best suits the defined operating and material requirements. The system asks a series of questions concerning the user's existing operation such as: part size, present processing chemistry, part cost, production rate, and contaminants. Based on the answers provided, a number of recommended options are provided which represent the alternate cleaning chemistry and/or process most likely to succeed. The report generated by SAGE presents the recommended options and important technical parameters. It also provides information on environmental considerations that must be taken into account, regulations that must be addressed when using the alternative, safety requirements, economic considerations, and equipment requirements, and other information that must be considered when implementing the recommended alternative. Finally, the report will include examples of case studies with a similar operating scenario and requirements.
REFERENCES AND RECOMMENDED RESOURCES 1.
Hildebrand, J., J. Am. Chem. Soc., 38, 1452, 1916.
2.
Hildebrand, J., Prausnitz, J. M., and Scott, R. L., Regular and Related Solutions, Van Nostrand-Reinhold Inc., Princeton, NJ, 1970.
3.
Archer, W. L., Industrial Solvents Handbook, Marcel Dekker, Inc., NY, 1996.
4.
Burrell, H., Am. Chem. Soc., Division of Organic Coatings Plastic Chemistry, Reprints 28(1), 682-708, 1968.
5.
Hansen, C. M., I&EC Prod. Res. Devel, 8(1), 2-11, March 1969.
6.
Barton, A. F. M., Handbook of Solubility and Other Cohesion Parameters, 2'"' Edition, CRC Press Inc., Boca Raton, FL, 1991.
7.
Barton, A. F. M., Handbook of Polymer-Liquid Interaction Parameters and Solubility Parameters, CRC Press Inc., Boca Raton, FL, 1990.
8.
Archer, W. L., Am. Paint Coating J., 38-45, March, 1992.
9.
Hansen, C. M., and Pierce, P. E., I&EC Prod. Res. Devel., 13(4), 218225, 1974.
10.
Small, P. A., J. Appl. Chem., 3, 71, 1953.
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11.
Shareef, K. M. A., Yaseen, M., Mahmood Ali, M., and Reddy, P. J., J. Coating TechnoL, 58(733), 35-44, 1986.
12.
Hansen, C. M., J. Paint TechnoL, 39(505), 104-117, 1967.
13.
Henry, L. F., Polym. Eng. Sci., Vol. 14, 167, 1974.
14.
Hansen, C. M., and Anderson, B. H., Am. Ind. Hyg. Assoc. J., 49(6), 301-308, 1988.
15.
Beerbower, A., J. Colloid Interface Sci., 35, 126, 1971.
16.
Davies, J. T., and Rideal, E. K., Intetfacial Phenomena, 2'"' Edition, Academic Press, NY, pp. 372-374, 1963.
PART 2 HAZARDOUS AND TOXIC CHEMICAL PROFILES INTRODUCTION AND OVERVIEW OF PART 2 This part of the handbook contains a compilation of chemical and physical properties, hazard characteristics, lexicological, fire and explosion information, and safe handling practices for solvents and a selection of other chemicals of industrial importance. Chemical specific information is compiled in accordance with an alphabetical listing based on the most commonly used chemical name. The most common chemical name designation is based either on (1) that designation specified in the Code of Federal Regulations (CFR), Titles 46 and 49, or (2) a common name for those chemicals known to be hazardous during shipment. As such, for most common names, the shipping name recommended by the U.S.' Department of Transportation (DOT) is used as it appears in Title 49 of the CFR. For each chemical entry, there are six data or information fields that are provided. These information fields are as follows: •
Chemical Designation - A list of common synonyms is given. Synonym names are alternative systematic chemical names and commonly used trivial names for chemicals. An index of synonyms is provided at the end of the handbook to assist the reader in identifying a particular chemical and researching chemical hazards information in the event that the common name of the chemical is not known. The data field also contains the chemical formula. The chemical formula is limited to a commonly used one-line formula. In the case of some organic chemical compounds it has not been possible to represent the chemical structure within such limitation.
•
Observable Characteristics - This includes the physical state of the chemical under normal conditions of handling and shipping, its characteristic color and odor. The color description provided is that for pure liquid. The reader should recognize that occasionally the color of a chemical changes when it dissolves in water or becomes a gas. Similarly, the odor description is that for pure material. The term "characteristic" is used in those cases when no other reasonable description of the chemical's odor could be found.
•
Physical and Chemical Properties - Information provided for each chemical includes the material's physical state, its molecular weight, boiling point, freezing point, critical properties (temperature and pressure), specific gravity, vapor (gas) density, the ratio of specific heats of vapor, and various
147
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Industrial Solvents Handbook thermodynamic properties. The following are more detailed explanations of the information field entries. The Physical State at 15°C and 1 atm is provided, which indicates whether the chemical is a solid, liquid, or gas after it has reached equilibrium with its surroundings at "ordinary" conditions of temperature and pressure. The Molecular Weight is the weight of a molecule of the chemical relative to a value of 12 for one atom of carbon. The molecular weight is useful in converting from molecular units to weight units, and in calculating the pressure, volume and temperature relationships of gaseous substances. The Boiling Point at 1 atm, the Freezing Point, and the Critical Temperature data are each given in three sets of units as follows: °F, °C, °K. Entries for Critical Pressure are given in three sets of units: psia, atm, MN/m 2 . The entries for Specific Gravity are typically based on 4°C unless otherwise specified. Thermodynamic properties include the Ratio of Specific Heats of Vapor (Gas), The Latent Heat of Vaporization, Heat of Combustion, and Heat of Decomposition. These data are given in the following three sets of units: Btu/Ib, cal/g, J/kg.
•
Health Hazards Information - Information given includes recommended personal protective equipment for hazard materials handling specialist, typical symptoms following exposure to the chemical, general first aid treatment procedures, and various toxicological information including toxicity by ingestion, inhalation and short term exposures. Additional information includes the liquid or solid irritant characteristics and odor threshold data.
•
Fire Hazards - Information compiled includes flash point temperature, flammable limits (explosivity range) in air, a list of fire extinguishing agents to be used, along with a list of fire extinguishing units not to be used, special by-products or hazards of combustion, a description of the chemical's behavior under a fire situation, the ignition temperature, its electrical hazard rating, and its burning rate (if applicable). The burning rate is based on experimentally reported literature data for a standing pool of liquid chemical. If a data field has the entry "no data", it means that none could be found. If the entry "not pertinent" is given , it means that the property or characteristic does not apply. As an example, for a nonvolatile chemical, the flash point temperature has no significance.
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Chemical Reactivity - Information provided includes the chemical's reactivity when in contact with water, as well as its chemical reactivity with common materials such as metals, plastics and organic matter. Information of the chemical's stability during transport is also given. Where appropriate, information on recommended neutralizing agents for acids and caustics is provided. Finally, information on whether the material polymerizes, along with a recommended inhibitor of polymerization, is given where appropriate.
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ACETIC ACID Chemical Designations — Synonyms: Ethanoic Acid, Glacial Acetic Acid, Vinegar Acid; Chemical Formula: CH3COOH. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Characteristic vinegar, pungent; vinegar-like; sharp. Physical and Chemical Properties — Physical State at 15°C and 1 aim.: Liquid; Molecular Weight: 60.05; Boiling Point at 1 atm.: 244, 117.9, 391.1; Freezing Point: 62.1, 16.7, 290; Critical Temperature: 611, 321.6, 594.8; Critical Pressure: 839, 57.1, 5.78; Specific Gravity: 1.051 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.145; Latent Heat of Vaporization: 17.1, 96.7, 4.05; Heat of Combustion: -5645, -3136, -131.3; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Protective clothing should be worn when skin contact can occur. Respiratory protection is necessary when exposed to vapor. Complete eye protection is recommended; Symptoms Following Exposure: Breathing of vapors causes coughing, chest pains, and irritation of the nose and throat; may cause nausea and vomiting. Contact with skin and eyes causes burns; General Treatment for Exposure: INHALATION: Move the victim immediately to fresh air. If breathing becomes difficult, give oxygen and get medical attention immediately. INGESTION: If the victim is conscious, have him drink water or milk. Do not induce vomiting. SKIN OR EYE CONTACT: Flush immediately with lots of clean running water; wash eyes for at least 15 min. and get medical attention as quickly as possible; remove contaminated clothing; Toxicity by Inhalation (Threshold Limit Value): 10 ppm; Short-Term Exposure Limits: 40 ppm for 5 min.; Toxicity by Ingestion: LD50 0.5 to 5.0 g/kg (rat); Late Toxicity: No data; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that workers will find high concentrations very unpleasant. Effects are temporary; Liquid or Solid Irritant Characteristics: This is a fairly severe skin irritant; may cause pain and secondary burns after a few minutes of contact; Odor Threshold: 1.0 ppm. Fire Hazards — Flash Point (°F): 112 OC; 104 CC; Flammable Limits in Air (%): 5.4 - 16.0; Fire Extinguishing Agents: Water, alcohol foam, dry chemical or carbon dioxide; Fire Extinguishing Agents Not To Be Used: None; Special Hazards of Combustion Products: Irritating vapors produced when heated; Behavior in Fire: Not Pertinent; Ignition Temperature (°F): 800; Electrical Hazard: Not Pertinent; Burning Rate: 1.6 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: Corrosive, particularly when diluted. Attacks most common metals including most stainless steels. Excellent solvent for many synthetic resins or rubber; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Dilute with water, rinse with sodium bicarbonate solution; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. ACETIC ANHYDRIDE Chemical Designations — Synonyms: Ethanoic Anhydride; Chemical Formula: CH3CO-O-COCH3. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Very strong; pungent; vinegar-like
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characteristic odor. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 102.09; Boiling Point at 1 atm.: 282, 139, 412; Freezing Point: -101, -74.1, 199.1; Critical Temperature: 565, 296, 569; Critical Pressure: 679, 46.2, 4.68; Specific Gravity: 1.08 at 20"C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.093; Latent Heat of Vaporization: 119, 66.2, 2.77; Heat of Combustion: -7058, -3921, -164.2; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Protective clothing when skin contact might occur; respiratory protection is necessary for all exposures; complete eye protection is recommended; Symptoms Following Exposure: Liquid is volatile and causes little irritation on unprotected skin. However, causes severe burns when clothing is wet with the chemical, or if it enters gloves or shoes; causes skin and eye burns and irritation of the respiratory tract. Nausea and vomiting may develop after exposure; General Treatment for Exposure: INHALATION: Move the victim immediately to fresh air; if breathing becomes difficult, give oxygen, and seek medical attention immediately. INGESTION: Do not induce vomiting. SKIN OR EYE CONTACT WITH LIQUID OR VAPOR: Flush immediately with clean, running water; wash eyes for at least 15 minutes; seek medical attention immediately; Toxicity by Inhalation (Threshold Limit Value): 5 ppm; Short-Term Exposure Limits: No data found; Toxicity by Ingestion: 0.5 to 5.0 g/kg (rat); Late Toxicity: Not pertinent; Vapor (Gas) Irritant Characteristics: Vapor is moderately irritating such that personnel will not usually tolerate moderate or high concentrations; Liquid or Solid Irritant Characteristics: Fairly severe skin irritant; may cause pain and second degree burns; burns skin after a few minutes of contact; Odor Threshold: 0.14 ppm. Fire Hazards - Flash Point (°F): 136 OC; 120 CC; Flammable Limits in Air (%): 2.7 - 10.0; Fire Extinguishing Agents: Water spray, dry chemical, alcohol foam, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water and foam react, but heat liberated is not enough to create a hazard. Dry chemical forced below the surface can cause foaming and boiling; Special Hazards of Combustion Products: Irritating vapors generated upon heating; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 600; Electrical Hazard: Not pertinent; Burning Rate: 3.3 mm/min. Chemical Reactivity — Reactivity with Water: Reacts slowly with water, but considerable heat is liberated when contacted with spray water; Reactivity with Common Materials: Corrodes iron, steel and other metals; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Dilute with water and use sodium bicarbonate solution to rinse; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. ACETYL BROMIDE Chemical Designations — Synonyms: No common synonyms; Chemical Formula: CH 3 COBr. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Acrid and sharp. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 122.95; Boiling Point at 1 atm: 169, 76, 349; Freezing Point: -141.7, -96.5, 176.7; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific
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Gravity: 1.66 at 16°C (liquid); Vapor (Gas) Density: 4.24; Ratio of Specific Heats of Vapor (Gas): 1.44; Latent Heat of Vaporization: 106, 59, 2.5; Heat of Combustion: No data; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Safety goggles; gloves; adequate ventilation; provisions for flushing eyes or skin with water; Symptoms Following Exposure: Inhalation results in primary irritation of the respiratory tract; symptoms of lung damage may be delayed. Contact with liquid produces primary irritation of eyes and severe skin damage; delayed blistering of the skin often occurs; General Treatment for Exposure: INHALATION: Remove the victim from the contaminated area. If breathing has stopped, give artificial respiration. If breathing is difficult, give oxygen. Watch victim carefully for any signs of delayed lung damage. EYES: Flush with water for at least 15 min. and seek medical attention. SKIN: Flush with water and treat chemical burns as needed; Toxicity by Inhalation (Threshold Limit Value): No data; Short-Term Exposure Limits: No data; Toxicity by Ingestion: Oral rat LD50 3,310 mg/kg (acetic acid). Note that this chemical decomposes violently in water, forming bromic acid and acetic acid; Late Toxicity: No data; Vapor (Gas) Irritant Characteristics: No data; Liquid or Solid Irritant Characteristics: No data; Odor Threshold: S.OxlO" 4 ppm. Fire Hazards — Flash Point: Data not available; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: Carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water; Special Hazards of Combustion Products: Toxic and irritating hydrogen bromide fumes may form in fires; Behavior in Fire: Do not apply water to adjacent fires. Reacts with water to produce toxic and irritating gases; Ignition Temperature: Data not available; Electrical Hazard: Data not available; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: Reacts violently, forming corrosive and toxic fumes of hydrogen bromide; Reactivity with Common Materials: Attacks and corrodes wood and most metals in the presence of moisture. Flammable hydrogen gas may collect in enclosed spaces; Stability During Transport: Stable if protected from moisture; Neutralizing Agents for Acids and Caustics: Flood with water, rinse with dilute sodium bicarbonate or soda ash solution; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. ACRYLAMIDE Chemical Designations — Synonyms: Acrylic Amide 50%, Propenamide 50%; Chemical Formula: CH2 = CHCONH2—H2O. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Clear; Odor: None. Physical and Chemical Properties — Physical State at 15 °C and 1 atm.: Liquid; Molecular Weight: 71 (solute only); Boiling Point at 1 atm.: Data not available (Vapor Pressure 0.033 atm at 125°C; Freezing Point: 183, 84, 357; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.05 at 25°C; Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Not pertinent; Heat of Combustion: Not pertinent; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Safety glasses with side shields;
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clean body-covering clothing; rubber gloves, boots, apron as dictated by circumstances; in absence of proper environmental control, use approved dust respirator; Symptoms Following Exposure: Has produced central nervous system damage, which is partly reversible. Effects can be produced by oral or skin contact as well as by injection. Chronic acrylamide poisoning can cause midbrain disturbance and peripheral neuropathy. Contact with liquid can cause moderate irritation of eyes and skin and may cause moderate transient corneal injury; General Treatment for Exposure: INHALATION: if ill effects occur, immediately get patient to fresh air, keep him quiet and warm, and get medical help. INGESTION: if ingested, immediately give large amounts of water (or milk if immediately available), then induce vomiting and get medical help. EYES: immediately flush with plenty of water for at least 15 min. and get medical promptly. SKIN: immediate, continuous, and thorough washing in flowing water is imperative, preferably deluge shower with abundant soap; if burns are present, get medical help; discard all contaminated clothing and wearing accessories; Toxicity by Inhalation (Threshold Limit Value): 0.3 mg/m 3 ; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 3; oral rat LD50 = 170 mg/kg; Late Toxicity: Repeated exposure to small amounts may cause essentially reversible neurological effects; Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Not pertinent. Fire Hazards — Flash Point: Not flammable; Flammable Limits in Air (%): Not flammable; Fire Extinguishing Agents: Not pertinent; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Toxic oxides of nitrogen may form in fire; Behavior in Fire: Sealed containers may burst as a result of polymerization; Ignition Temperature: Not pertinent; Electrical Hazard: Not pertinent; Burning Rate: Not pertinent. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: Data not available; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: May occur at temperature above 50°C (120°F); Inhibitor of Polymerization: Oxygen (air) plus 50 ppm of copper as copper sulfate. ACRYLONITRILE Chemical Designations — Synonyms: Cyanoethylene, Fumigrain, Ventox, Vinyl Cyanide; Chemical Formula: CH, = CHCN. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Mild; pungent, resembling that of peach seed kernels. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 53.06; Boiling Point at 1 atm.: 171, 77.4, 350.6; Freezing Point: -118, -83.6, 189.6; Critical Temperature (°F, °C, °K): 505, 263, 536; Critical Pressure: 660, 45, 4.6; Specific Gravity: 0.8075 at 20"C (liquid); Vapor (Gas) Density: 1.8; Ratio of Specific Heats of Vapor (Gas): 1.151; Latent Heat of Vaporization: 265, 147, 6.16; Heat of Combustion: -14,300, -7930, -332; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Airsupplied mask, industrial chemical type, with approved canister for acrilonitrile in
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low (less than 2%) concentrations; rubber or plastic gloves; cover goggles or face mask; rubber boots; slicker suit; safety helmet; Symptoms Following Exposure: Similar to those of hydrogen cyanide. Vapor inhalation may cause weakness, headache, sneezing, abdominal pain, and vomiting. Similar symptoms shown if large amounts of liquid are absorbed through the skin; lesser amounts cause stinging and sometime blisters; contact with eyes causes severe irritation. Ingestion produced nausea, vomiting and abdominal pain; General Treatment for Exposure: Skilled medical treatment is necessary; call physician for all cases of exposure. INHALATION: remove victim to fresh air. (Wear an oxygen or fresh-air-supply mask when entering contaminated area). INGESTION: induce vomiting by administering strong solution of salt water, but only if victim is conscious. SKIN: remove contaminated clothing and wash affected area thoroughly with soap and water. EYES: hold eyelids apart and wash with continuous gentle stream of water for at least 15 min.. If victim is not breathing, give artificial respiration until physician arrives. If he is unconscious, crush an amyl nitrite ampule in a cloth and hold it under his nose for 15 seconds in every minute. Do not interrupt artificial respiration while doing this. Replace ampule when its strength is spent and continue treatment until condition improves or physician arrives; Toxicity by Inhalation (Threshold Limit Value): 20 ppm; Short-Term Exposure Limits: 40 ppm for 30 min.; Toxicity by Ingestion: Grade 3; LD50 = 50 to 500 mg/kg (rat, guinea pig); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapor is moderately irritating such that personnel will not usually tolerate moderate or high vapor concentrations; Liquid or Solid Irritant Characteristics: If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin. Large amounts may be absorbed through the skin and cause poisoning; Odor Threshold: 21.4 ppm (Sense of smell fatigues rapidly). Fire Hazards — Flash Point (°F): 30 CC; 31 OC; Flammable Limits in Air (%): 3.05-17.0; Fire Extinguishing Agents: Dry chemical, alcohol foam, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water or foam may cause frothing; Special Hazards of Combustion Products: When heated or burned, ACN may evolve toxic hydrogen cyanide gas and oxides of nitrogen; Behavior in Fire: Vapor is heavier than air and may travel a considerable distance to a source of ignition and flash back. May polymerize and explode; Ignition Temperature (°F): 898; Electrical Hazard: Class I, Group D; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: Attacks copper and copper alloys; these metals should not be used. Penetrates leather, so contaminated leather shoes and gloves should be destroyed. Attacks aluminum in high concentrations; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: May occur spontaneously in absence of oxygen or on exposure to visible light or excessive heat, violently in the presence of alkali. Pure ACN is subject to polymerization with rapid pressure development. The commercial product is inhibited and not subject to this reaction; Inhibitor of Polymerization: Methylhydroquinone (35-45 ppm).
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ALLYL ALCOHOL Chemical Designations — Synonyms: 2-Propen-l-ol-Vinylcarbinol; Chemical Formula: CH2 = CHCH 2 OH. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Characteristic, pungent; sharp; causes tears. Physical and Chemical Properties — Physical State at 15 °C and 1 atm.: Liquid; Molecular Weight: 58.08; Boiling Point at 1 atm.: 206, 96.9, 370.1; Freezing Point: -200, -129, 144; Critical Temperature: 521.4, 271.9, 545.1; Critical Pressure: 840, 57, 5.8; Specific Gravity: 0.852 at 20°C (liquid); Vapor (Gas) Density: 2.0; Ratio of Specific Heats of Vapor (Gas): 1.12; Latent Heat of Vaporization: 295, 164, 6.87; Heat of Combustion: -13,720, -7620, -319.0; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Organic canister or air pack; rubber gloves, goggles; other protective equipment as required to prevent all body contact; Symptoms Following Exposure: Vapors are quite irritating to eyes, nose and throat. Eye irritation may be accompanied by complaints of photophobia and pain in the eyeball; pain may not begin until 6 hours after exposure. Liquid may cause firstand second-degree burns of the skin, with blister formation; underlying part will become swollen and painful, and local muscle spasms may occur; General Treatment for Exposure: INHALATION: remove victim from contaminated area and administer oxygen; get medical attention immediately. SKIN: remove liquid with soap and water. EYES: flush with continuous stream of water for 15 min.; Toxicity by Inhalation (Threshold Limit Value): 2 ppm; Short-Term Exposure Limits: 5 ppm for 30 min; Toxicity by Ingestion: Grade 3; LD50 = 50 to 500 mg/kg (mouse, rat); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapor is moderately irritating such that personnel will not usually tolerate moderate or high vapor concentration; Liquid or Solid Irritant Characteristics: Causes smarting of the skin and first-degree burns on short exposure; may cause secondary burns on a long exposure; Odor Threshold: 0.78 ppm. Fire Hazards — Flash Point (°F): 72 CC; 90 OC; Flammable Limits in Air (%): 2.5 - 18; Fire Extinguishing Agents: Dry chemical, alcohol foam, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Toxic vapor is generated when heated; Behavior in Fire: Vapor heavier than air and may travel a considerable distance to a source of ignition and flash back; Ignition Temperature (°F): 829; Electrical Hazard: Not pertinent; Burning Rate: 2.7 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable at ordinary temperatures and pressures; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. ALLYL CHLOROFORMATE Chemical Designations — Synonyms: Allyl Chlorocarbonate; Chemical Formula: CH2 = CH CH 2 O COC1. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Extremely irritating, causes tears; pungent. Physical and Chemical Properties — Physical State at 15 °C and 1
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atm.: Liquid; Molecular Weight: 120.5; Boiling Point at 1 atm.: 113, 45, 318; Freezing Point: -112, -80, 193; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.139 at 20°C (liquid); Vapor (Gas) Density: 4.15; Ratio of Specific Heats of Vapor (Gas): 1.0804; Latent Heat of Vaporization: 100, 56, 2.3; Heat of Combustion: -7,800, -4,300, -180; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Vapor-proof protective goggles and face shield; plastic or rubber gloves, shoes and clothing; gas mask or self-contained breathing apparatus; Symptoms Following Exposure: Vapor irritates eyes and respiratory tract. Contact with liquid cause eye and skin irritation, and ingestion irritates mouth and stomach; General Treatment for Exposure: INHALATION: remove from exposure; support respiration if necessary; call physician. EYES: if irritated by either vapor or liquid, flush with water for at least 15 min. SKIN: wash with large amounts of water for at least 15 min. INGESTION: do NOT induce vomiting; give water; call physician; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 3; LD50 = 50 to 500 mg/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors are moderately irritating such that personnel will not usually tolerate moderate or high vapor concentrations; Liquid or Solid Irritant Characteristics: Fairly severe skin irritant. May cause pain and second-degree burns after a few minutes' contact; Odor Threshold: 1.4 ppm. Fire Hazards — Flash Point (°F): 92 OC; 88 CC; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: Dry chemical, foam, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: When heated to decomposition, emits highly toxic phosgene gas; Behavior in Fire: Vapor heavier than air and may travel a considerable distance to a source of ignition and flash back; Ignition Temperature: Data not available; Electrical Hazard: Data not available; Burning Rate: 4.9 mm/min. Chemical Reactivity — Reactivity with Water: Reacts slowly generating hydrogen chloride; Reactivity with Common Materials: Corrosive metals; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Flush with water, rinse with sodium bicarbonate solution; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. AMYL ACETATE Chemical Designations — Synonyms: Amyl Acetate, Mixed Isomers; Pentyl Acetates; Chemical Formula: CHjCOOCjH,,. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless to yellow; Odor: Pleasant banana-like; mild; characteristic banana- or pear-like odor; Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 130.19; Boiling Point at 1 atm.: 295, 146, 419; Freezing Point: 160 CC; Flammable Limits in Air (%): Not pertinent; Fire Extinguishing Agents: Dry chemical, carbon dioxide, or foam; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Data not available; Behavior in Fire: Heavy, irritating black smoke is formed; Ignition Temperature (°F): 637; Electrical Hazard: Not pertinent; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common
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Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. CRESOLS Chemical Designations — Synonyms: Cresylic Acids; Hydroxy toluenes; Methylphenols; Oxytoluenes; Tar Acids; Chemical Formula: CH3Cft H 4 OH. Observable Characteristics — Physical State (as normally shipped): Liquid or solid; Color: Colorless or dark to yellow; Odor: Sweet, tarry. Physical and Chemical Properties — Physical State at 15"C and 1 atm.: Liquid; Molecular Weight: 108.13; Boiling Point at 1 atm.: >350, > 177, >450; Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.03-1.07 at 20"C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.073; Latent Heat of Vaporization: (est.) 200, 110, 4.6; Heat of Combustion: -14,720 to -14,740, -8,180 to -8,190, -342.5 to -342.9; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Organic vapor canister unit; rubber gloves; chemical safety goggles; face shield; coveralls and/or rubber apron; rubber shoes or boots; Symptoms Following Exposure: Vapors cause irritation of eyes, nose, and throat. Contact with skin or eyes causes severe burns. Chemical is rapidly absorbed through skin; General Treatment for Exposure: Call a physician. INHALATION: remove to fresh air. INGESTION: have victim drink water or milk; do NOT induce vomiting. SKIN OR EYES: flush immediately with plenty of water for at least 15 min.; remove contaminated clothing immediately and wash before reuse; discard contaminated shoes; Toxicity by Inhalation (Threshold Limit Value): 5 ppm; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2; LD50 = 0.5 to 5 g/kg (rat, rabbit); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Fairly severe skin irritant; may cause pain and second-degree burns after a few minutes' contact; Odor Threshold: 5 ppm. Fire Hazards — Flash Point (°F): 175-185 OC; 178 CC; Flammable Limits in Air (%): LEL: 1.4 (ortho); 1.1 (meta or para); Fire Extinguishing Agents: Water, dry chemical, carbon dioxide, and foam; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Flammable toxic vapors given off in a fire; Behavior in Fire: Sealed closed containers can build up pressure if exposed to heat (fire); Ignition Temperature °F): 1110 (o-cresol); 1038 (m- or p-cresol); Electrical Hazard: Data not available; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. CUMENE Chemical Designations
— Synonyms: Cumol; Isopropylbenzene;
Chemical
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Formula: C6H5CH(CH3)2. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Strong, slightly irritant; fragrant; aromatic. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 120.19; Boiling Point at 1 atm.: 306.3, 152.4, 425.6; Freezing Point: -140.9, -96.1, 177.1; Critical Temperature: 676.2, 357.9, 631.1; Critical Pressure: 465.5, 31.67, 3.208; Specific Gravity: 0.866 at 15°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.059; Latent Heat of Vaporization: 134, 74.6, 3.12; Heat of Combustion: -17,710, -9,840, -412.0; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: As necessary to avoid skin exposure. If concentration in air is greater than 1000 ppm, use selfcontained breathing apparatus; Symptoms Following Exposure: narcotic action with long-lasting effects; depressant to central nervous system; General Treatment for Exposure: INHALATION: move patient immediately to fresh air; administer artificial respiration or oxygen if necessary; seek medical attention. SKIN OR EYES: wash exposed skin surfaces thoroughly; flush eyes thoroughly with water for 15 min; Toxicity by Inhalation (Threshold Limit Value): 50 ppm; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 3; LD50 = 50 to 500 mg/kg; Late Toxicity: None reported; Vapor (Gas) Irritant Characteristics: Vapors cause a slight smarting of the eyes or respiratory system if present in high concentration. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 1.2 ppm. Fire Hazards — Flash Point (°F): 111 CC; Flammable Limits in Air (%): 0.9-6.5; Fire Extinguishing Agents: Foam, carbon dioxide, or dry chemical; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 797; Electrical Hazard: Data not available; Burning Rate: 50 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. P-CUMENE Chemical Designations — Synonyms: Cymol; p-Isopropyltoluene; Isopropyltoluol l-Methyl-4-Isopropyl-benzene; Methyl Propyl Benzene; Chemical Formula: pCH3C6H4CH(CH3)2. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Mild, pleasant; aromatic, solvent-type. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 134.2; Boiling Point at 1 atm.: 351, 177, 450; Freezing Point: -90.2, -67.9, 205.3; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.857 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: 122, 67.8, 2.84; Heat of Combustion: -18,800, -10,400, -437; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended
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Personal Protective Equipment: Self-contained or air-line breathing apparatus; solvent-resistant rubber gloves; chemical splash goggles; Symptoms Following Exposure: Inhalation causes impairment of coordination, headache. Contact with liquid causes mild irritation of eyes and skin. Ingestion causes irritation of mouth and stomach; General Treatment for Exposure: INHALATION: remove victim from contaminated area; administer artificial respiration if necessary; call physician. SKIN: wipe off liquid; wash well with soap and water. INGESTION: induce vomiting; get medical attention Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2; oral rat LDjo^ 4,750 mg/kg. Oral human TD10 (lowest toxic dose) = 86 mg/kg (affects central nervous system); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors are nonirritating to eyes and throat; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 140 OC; 117 CC; Flammable Limits in Air (%): 0.7-5.6; Fire Extinguishing Agents: Foam, dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 817; Electrical Hazard: Data not available; Burning Rate: 6.1 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
CYCLOHEXANE Chemical Designations — Synonyms: Hexahydrobenzene; Hexamethylene; Hexanaphthene; Chemical Formula: (CH 2 ) 6 . Observable Characteristics— Physical State (as normally shipped): Liquid; Color: Colorless; Odor: resembling benzene; mild, sweet, resembling chloroform. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 84.16; Boiling Point at 1 atm.: 177.3, 80.7, 353.9; Freezing Point 43.8, 6.6, 279.8; Critical Temperature: 536.5, 280.3, 553.5; Critical Pressure: 591, 40.2, 4.07; Specific Gravity: 0.779 at 20°C (liquid); Vapor (Gas) Density: 2.9; Ratio of Specific Heats of Vapor (Gas): 1.087; Latent Heat of Vaporization: 150, 85, 3.6; Heat of Combustion: -18,684, -10,380, -434.59; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Hydrocarbon vapor canister, supplied-air or hose mask, hydrocarbon-insoluble rubber or plastic gloves, chemical goggles or face splash shield, hydrocarbon-insoluble rubber or plastic apron; Symptoms Following Exposure: Dizziness, with nausea and vomiting. Concentrated vapor may cause unconsciousness and collapse; General Treatment for Exposure: INHALATION: remove victim to fresh air; if breathing stops, apply artificial respiration and administer oxygen. SKIN OR EYE CONTACT: remove contaminated clothing and gently flush affected areas with water for 15 min. Call a physician; Toxicity by Inhalation (Threshold Limit Value): 300 ppm; Short-Term
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Exposure Limits: 300 ppm for 60 min; Toxicity by Ingestion: Grade 2; LD50 = 0.5 to 5 g/kg; Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Vapors cause a slight smarting of the eyes or respiratory system if present in high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point : -4 CC; Flammable Limits in Air (%): 1.33-8.35; Fire Extinguishing Agents: Foam, carbon dioxide, dry chemical; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 518; Electrical Hazard: Data not available; Burning Rate: 6.8 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
CYCLOHEXANOL Chemical Designations — Synonyms: Adronal; Anol; Cyclohexyl Alcohol; Hexalin; Hexahydrophenol; Hydro xycyclohexane; Chemical Formula: (CH2)5CHOH. Observable Characteristics — Physical State (as normally shipped): Solid or liquid; Color: Colorless to faintly yellow; Odor: Like camphor. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Solid; Molecular Weight: 100.16; Boiling Point at 1 atm.: 322, 161, 434; Freezing Point: 74.5, 23.6, 296.8; Critical Temperature: 666, 352, 625; Critical Pressure: 540, 37, 3.7; Specific Gravity: 0.947 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.071; Latent Heat of Vaporization: 196, 109, 4.56; Heat of Combustion: -16,000, -8910, -373; Heat of Decomposition: Not pertinent; Health Hazards Information — Recommended Personal Protective Equipment: Goggles or face shield; Symptoms Following Exposure: Narcosis, depression of the central nervous system tending to produce sleep or unconsciousness; General Treatment for Exposure: Eye contact is more hazardous than inhalation, skin irritation, or ingestion. Flush eyes with water and remove victim to fresh air; Toxicity by Inhalation (Threshold Limit Value): 50 ppm; ShortTerm Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2; LD50 = 0.5 to 5 g/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause a slight smarting of the eyes or respiratory system if present in high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: Causes smarting of the skin an first-degree burns on short exposure and may cause secondary burns on long exposure; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 160 OC; 154 CC; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: Water, foam, carbon dioxide, or dry chemical; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 572; Electrical Hazard: Data not
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available; Burning Rate: 3.9 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. CYCLOHEXANONE Chemical Designations — Synonyms: Anone; Hytrol O; Nadone; Pimelic Ketone; Sextone; Chemical Formula: (CH2)5CO. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless to slightly yellow; Odor: Like peppermint and acetone. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 98.15; Boiling Point at 1 aim.: 312.4, 155.8, 429.0; Freezing Point: -24.2, 31.2, 242.0; Critical Temperature: 673, 356, 629; Critical Pressure: 560, 38, 3.8; Specific Gravity: 0.945 at 20"C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.084; Latent Heat of Vaporization: 160, 91, 3.8; Heat of Combustion: -15,430, -8570, -358.8; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Chemical goggles; Symptoms Following Exposure: Inhalation of vapors from hot material can cause narcosis. The liquid may cause dermatitis; General Treatment for Exposure: Immediately flush eyes with plenty of water; call a physician; Toxicity by Inhalation (Threshold Limit Value): 50 ppm; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2; LD5() = 50 to 5 g/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapor is moderately irritating such that personnel will not usually tolerate moderate or high vapor concentrations; Liquid or Solid Irritant Characteristics: Causes smarting of the skin and first-degree burns on short exposure and may cause secondary burns on long exposure; Odor Threshold: 0.12 ppm. Fire Hazards — Flash Point (°F): 129 OC; 111 CC; Flammable Limits in Air (%): 1.1 LEL; Fire Extinguishing Agents: Water, dry chemical, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 788; Electrical Hazard: Data not available; Burning Rate: 4.2 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. CYCLOPENTANE Chemical Designations — Synonyms: Pentamethylene; Chemical Formula: C 5 H I0 . Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Like gasoline; mild, sweet. Physical and Chemical Properties — Physical State at 15"C and 1 atm.: Liquid; Molecular Weight: 70.1; Boiling Point at 1 atm.: 120.7, 49.3, 322.5; Freezing Point: -137.0, -93.9, -179.3; Critical Temperature: 461.5, 238.6, 511.8; Critical Pressure: 654, 44.4, 4.51; Specific Gravity: 0.74 at 20°C (liquid); Vapor (Gas) Density: 2.4; Ratio of Specific
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Heats of Vapor (Gas): 1.1217; Latent Heat of Vaporization: 179, 94, 3.9; Heat of Combustion: -19,990, -11,110, -465; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Hydrobarbon canister, supplied air, or hose mask; rubber or plastic gloves; chemical goggles or face shield; Symptoms Following Exposure: Inhalation causes dizziness, nausea, and vomiting; concentrated vapor may cause unconsciousness and collapse. Vapor causes slight smarting of eyes. Contact with liquid causes irritation of eyes and may irritate skin if allowed to remain. Ingestion causes irritation of stomach. Aspiration produces severe lung irritation and rapidly developing pulmonary edema; central nervous excitement followed by depression; General Treatment for Exposure: INHALATION: remove to fresh air; if breathing stops, apply artificial respiration and administer oxygen. EYES: flush with water for at least 15 min.; call a physician. SKIN: flush well with water, then wash with soap and water. INGESTION: do NOT induce vomiting; guard against aspiration into lungs. ASPIRATION: enforce bed rest; give oxygen; get medical attention; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: 300 ppm for 60 min.; Toxicity by Ingestion: Grade 2; LD50 = 0.5 to 5 g/kg; Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Vapors cause slight smarting of the eyes or respiratory system if present in high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 175 OC; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: Foam, dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Irritating hydrogen chloride vapor may form in fire; Behavior in Fire: Data not available; Ignition Temperature: Data not available; Electrical Hazard: Data not available; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: May attack some forms of
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plastics; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DIACETONE ALCOHOL Chemical Designations — Synonyms: Diacetone; 4-Hydroxy-4-Metrhyl-2Pentanone; Tyranton; Chemical Formula: CH3C(OH)(CH3)CH2COCH3. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless to yellow; Odor: Mild, pleasant. Physical and Chemical Properties — Physical State at 15"C and 1 atm.: Liquid; Molecular Weight: 116.16; Boiling Point at 1 atm.: 336.6, 169.2, 442.4; Freezing Point: -45.0, -42.8, 230.4; Critical Temperature: 633, 334, 607; Critical Pressure: 380, 36, 3.6; Specific Gravity: 0.938 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.052; Latent Heat of Vaporization: 150, 85, 3.6; Heat of Combustion: (est.) -13,000, -7,250, -303; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Air pack or organic canister, rubber gloves, goggles; Symptoms Following Exposure: Vapor is irritant to the mucous membrane of the eye and respiratory tract. Inhalation can cause dizziness, nausea, some anesthesia. Very high concentration have a narcotic effect. The liquid is not highly irritating to the skin but can cause dermatitis; General Treatment for Exposure: INHALATION: remove victim to fresh air. Give artificial respiration if breathing has stopped. EYES OR SKIN: wash affected skin areas with water; flush eyes with water and get medical care if discomfort persists; Toxicity by Inhalation (Threshold Limit Value): 50 ppm; Short-Term Exposure Limits: 150 ppm for 30 min.; Toxicity by Ingestion: Grade 2; LD50 = 0.5 to 5 g/kg (rat); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 142 OC; 125 CC; Flammable Limits in Air (%): 1.8-6.9; Fire Extinguishing Agents: Dry chemical, alcohol foam, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature ("F): 1118; Electrical Hazard: Not pertinent; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water : No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DI-N-AMYL PHTHALATE Chemical Designations — Synonyms: Diamyl Phthalate; Dipentyl Phthalate; Phthalic Acid, Diamyl Ester; Phthalic Acid, Dipentyl Ester; Chemical Formula: C 6 H4(COOC 5 H,,) 2 . Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: None. Physical and Chemical
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Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 306; Boiling Point at 1 atm.: Very high; Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.82 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: 140, 76, 3.2; Heat of Combustion: -13,900, -7,720, -323; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles or face shield; rubber gloves; Symptoms Following Exposure: Inhalation of vapors from very hot material may cause headache, drowsiness, and convulsions. Hot vapors may irritate eyes; General Treatment for Exposure: INHALATION: move to fresh air. EYES: flush with water. SKIN: wipe off; flush with water; wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Data not available; Late Toxicity: Causes birth defects in rats (skeletal and gross abnormalities); Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 245 CC; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: Foam, dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water or foam may cause frothing; Special Hazards of Combustion Products: Data not available; Behavior in Fire: Data not available; Ignition Temperature: Data not available; Electrical Hazard: Data not available; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: May attack some forms of plastics; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DI-N-BUTYLAMINE Chemical Designations — Synonyms: 1-Butanamine, n-butyl; Dibutylamine; Chemical Formula: (C4H9)2NH. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Weak ammonia. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 129.25; Boiling Point at 1 atm.: 319.3, 159.6, 432.8; Freezing Point: -80, -62, 211; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.759 at 20°C (liquid); Vapor (Gas) Density: 4.5; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: 130, 72.3, 3.03; Heat of Combustion: -18,800, -10,440, -436.8; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles or face shield; rubber gloves; Symptoms Following Exposure: Inhalation causes irritation of nose, throat, and lungs; coughing; nausea; headache. Ingestion causes irritation of mouth and stomach. Contact with eyes causes irritation. Contact with skin causes irritation and dermatitis; General Treatment for Exposure: INHALATION: move from exposure; if breathing has stopped, start artificial respiration. INGESTION: give large amounts of water. EYES: irrigate with water for 15 min. get medical attention for
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possible eye damage. SKIN: wash with large amounts of water for 15 min.; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 3; oral LD50 = 360 mg/kg (rat); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Severe skin irritant. Causes second- and third-degree burns on short contact and is very injurious to the eyes; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 125 OC; Flammable Limits in Air (%): 1.1 (LFL); Fire Extinguishing Agents: "Alcohol" foam, dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Toxic oxides of nitrogen may form in fires; Behavior in Fire: Data not available; Ignition Temperature: Data not available; Electrical Hazard: Data not available; Burning Rate: 5.84 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: May corrode some metals and attack some forms of plastics; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DI-N-BUTYL ETHER Chemical Designations — Synonyms: n-Dibutyl Ether; n-Butyl Ether; Butyl Ether; 1-Butoxybutane; Dibutyl Ether; Dibutyl Oxide; Chemical Formula: C 4 H y OC 4 H g ; Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Mild, ether-like. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 130.2; Boiling Point at 1 atm.: 288, 142, 415; Freezing Point: -139.7, -95.4, 177.8; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.767 at 20°C (liquid); Vapor (Gas) Density: 4.5; Ratio of Specific Heats of Vapor (Gas): 1.0434; Latent Heat of Vaporization: 120, 68, 2.8; Heat of Combustion: 17,670, -9,820, -411; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles or face shield; rubber gloves; Symptoms Following Exposure: Inhalation causes irritation of nose and throat. Liquid irritates eyes and may irritate skin on prolonged contact. Ingestion causes irritation of mouth and stomach; General Treatment for Exposure: INHALATION: remove to fresh air. EYES: after contact with liquid, flush with water for at least 15 min. SKIN: wipe off, wash well with soap and water; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 1; oral LD50 = 7,400 mg/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 92 OC; Flammable Limits in Air (%): 1.5-7.6; Fire Extinguishing Agents: Dry chemical, "alcohol" foam, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent;
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Behavior in Fire: Vapor is heavier than air and may travel a considerable distance to source of ignition and flash back; Ignition Temperature (°F): 382; Electrical Hazard: Data not available; Burning Rate: 5.7 mm/min. Chemical Reactivity — Reactivity with Water No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DI-N-BUTYL KETONE Chemical Designations — Synonyms: 5-Nonanone; Chemical Formula: CH3(CH2)3CO(CH2)3CH3. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: White to light yellow; Odor: Data not available. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 142; Boiling Point at 1 atm.: 370, 188, 461; Freezing Point: 21, -6, 267; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.822 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: 161, 89.6, 3.75; Heat of Combustion: -16,080, -8,930, -374; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Rubber gloves; goggles or face shield; Symptoms Following Exposure: Inhalation causes irritation of nose and throat. Ingestion causes irritation of mouth and stomach. Contact with eyes or skin causes irritation; General Treatment for Exposure: INHALATION: remove to fresh air; administer artificial respiration if needed. EYES: flush with water for at least 15 min. SKIN: flush with water; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Data not available; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Data not available. Fire Hazards — Flash Point: Data not available; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: Foam, dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Data not available; Behavior in Fire: Data not available; Ignition Temperature : Data not available; Electrical Hazard: Data not available; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: May attack some forms of plastics; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. O-DICHLOROBENZENE Chemical Designations — Synonyms: 1,2-Dichlorobenzene; Downtherm E; Orthodichlorobenzene; Chemical Formula: o-C6H4C!2. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Aromatic; characteristic aromatic. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 147.01; Boiling Point at 1 atm.:
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356.9, 180.5, 453.7; Freezing Point: 0.3, -17.6, 255.6; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.306 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.080; Latent Heat of Vaporization: 115, 63.9, 2.68; Heat of Combustion: -7,969, -4,427, -185.4; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Organic vapor-acid gas respirator; neoprene or vinyl gloves; chemical safety spectacles, face shield, rubber footwear, apron, protective clothing; Symptoms Following Exposure: Chronic inhalation of mist vapors may result in damage to lungs, liver, and kidneys. Acute vapor exposure can cause symptoms ranging from coughing to central nervous system depression and transient anesthesia. Irritating to skin, eyes, and mucous membranes. May cause dermatitis; General Treatment for Exposure: INHALATION: remove victim to fresh air, keep him quiet and warm, and call a physician promptly. INGESTION: no known antidote; treat symptomatically; induce vomiting and get medical attention promptly. EYES AND SKIN: flush with plenty of water; get medical attention for eyes; remove contaminated clothing and wash before reuse; Toxicity by Inhalation (Threshold Limit Value): 50 ppm; ShortTerm Exposure Limits: 50 ppm for 15 min.; Toxicity by Ingestion: Grade 2; LD5() = 0.5 to 5 g/kg; Late Toxicity: Causes liver and kidney damage in rats. Effects unknown in humans; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 4.0 ppm; 50 ppm. Fire Hazards - Flash Point (°F): 165 OC; 155 CC; Flammable Limits in Air (%): 2.2-9,2; Fire Extinguishing Agents: Water, foam, dry chemical or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Irritating vapors including hydrogen chloride gas, chlorocarbones, chlorine; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 1198; Electrical Hazard: Not pertinent; Burning Rate: 1.3 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. P-DICHLOROBENZENE Chemical Designations — Synonyms: Dichloricide; Paradow; Paradi; Paramoth; Paradichlorobenzene; Santochlor; Chemical Formula: p-C6H4C!2 Observable Characteristics — Physical State (as normally shipped): Solid; Color: White; Odor: Aromatic. Physical and Chemical Properties — Physical State at 15"C and 1 atm.: Solid; Molecular Weight: 147.01; Boiling Point at 1 atm.: 345.6, 174.2, 441.4; Freezing Point: 130, 53, 326; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.458 at 20°C (solid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Not pertinent; Heat of Combustion: Not pertinent; Heat of Decomposition: Not pertinent. Health Hazards Information —
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Recommended Personal Protective Equipment: Full face mask fitted with organic vapor canister for concentrations over 75 ppm; clean protective clothing; eye protection; Symptoms Following Exposure: INHALATION: irritation of upper respiratory tract; over-exposure may cause depression and injury to liver and kidney. EYES: pain and mild irritation; General Treatment for Exposure: INHALATION: if any ill effects develop, remove patient to fresh air and get medical attention. If breathing stops, give artificial respiration. EYES: flush with plenty of water and get medical attention if ill effects develop. SKIN AND INGESTION: likely no problems; Toxicity by Inhalation (Threshold Limit Value): 75 ppm; Short-Term Exposure Limits: 50 ppm for 60 min.; Toxicity by Ingestion: Grade 2; LD50 = 0.5 to 5 g/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 15-30 ppm. Fire Hazards — Flash Point (°F): 165 OC; 150 CC; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: Water, foam, carbon dioxide, or dry chemical; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Vapors are irritating. Toxic chlorine, hydrogen chloride and phosgene gases may be generated in fires; Behavior in Fire: Not pertinent; Ignition Temperature: No data; Electrical Hazard: Not pertinent; Burning Rate: 1.3 mm/min (approx.). Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
DICHLOROBUTENE Chemical Designations — Synonyms: l,4-Dichloro-2-butene; 2-Butylene Dichloride; l,4-Dichloro-2-butylene; cis-l,4-Dichloro-2-butene; trans-1,4Dichloro-2-butene; Chemical Formula: C1CH2CH = CHCH2C1. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Characteristic; sweet, pungent. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 125.0; Boiling Point at 1 atm.: 313, 156, 429; Freezing Point: cis: -54, -48, 225; trans: 37, 3, 276; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.112 at 20°C (liquid); Vapor (Gas) Density: 4; Ratio of Specific Heats of Vapor (Gas): 1.0874; Latent Heat of Vaporization: 130, 73, 3.1; Heat of Combustion: -17,500, -9,720, -407; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Rubber gloves; chemical splash goggles; rubber boots and apron; barrier cream; organic canister mask; Symptoms Following Exposure: Inhalation of vapor irritates nose and throat. Contact with eyes causes intense irritation and tears. Contact of liquid with skin causes severe blistering and dermatitis. Ingestion causes severe irritation
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of mouth and stomach; General Treatment for Exposure: INHALATION: remove from exposure; provide low-pressure oxygen if required; keep under observation until edema is ruled out. EYES: irrigate immediately for 15 min.; call physician. SKIN: wash immediately and thoroughly with soap and water; treat as a chemical burn. INGESTION: induce vomiting; call physician; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 3; oral LD50 (l,4-dichloro-2-butene) = 89 mg/kg (rat); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Data not available. Fire Hazards — Flash Point: Data not available; Flammable Limits in Air (%): 1.5-4; Fire Extinguishing Agents: Water, foam, dry chemical ,or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Decomposition vapors contain phosgene and hydrogen chloride gases; both are toxic and irritating; Behavior in Fire: Not pertinent; Ignition Temperature: Data not available; Electrical Hazard: Data not available; Burning Rate: 2.6 mm/min. Chemical Reactivity — Reactivity with Water: Reacts slowly to form hydrochloric acid; Reactivity with Common Materials: Corrodes metal when wet; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. 1,2-DICHLOROETH YLENE Chemical Designations — Synonyms: Acetylene Dichloride; symDichloroethylene; Dioform; cis- or trans-1,2-Dichloroethylene; Chemical Formula: C1CH = CHC1. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Ethereal, slightly acrid; pleasant, chloroform-like. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 97.0; Boiling Point at 1 aim.: cis: 140, 60, 333; trans: 118, 48, 321; Freezing Point: cis: -114, -81, 192; trans: -58, -50, 223; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.27 at 25°C (liquid); Vapor (Gas) Density: 3.34; Ratio of Specific Heats of Vapor (Gas): 1.1468; Latent Heat of Vaporization: 130, 72, 3.0; Heat of Combustion: -4,847.2, -2,692.9, -112.67; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Rubber gloves; safety goggles; air supply mask or self-contained breathing apparatus; Symptoms Following Exposure: Inhalation causes nausea, vomiting, weakness, tremor, epigastric cramps, central nervous depression. Contact with liquid causes irritation of eyes and (on prolonged contact) skin. Ingestion causes slight depression to deep narcosis; General Treatment for Exposure: INHALATION: remove from further exposure; if breathing is difficult, give oxygen; if victim is not breathing, give artificial respiration, preferably mouth-tomouth; give oxygen when breathing is resumed; call a physician. EYES: flush with water for at least 15 min. SKIN: wash well with soap and water. INGESTION: give gastric lavage and cathartics; Toxicity by Inhalation (Threshold Limit Value):
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200 ppm; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2; oral LD50 = 770 mg/kg (rat); Late Toxicity: Produces liver and kidney injury in experimental animals; Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 37CC; Flammable Limits in Air (%): 9.7-12.8; Fire Extinguishing Agents: Dry chemical, foam, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Phosgene and hydrogen choride fumes may form in fires; Behavior in Fire: Vapor is heavier than air and may travel a considerable distance to a source of ignition and flash back; Ignition Temperature: Data not available; Electrical Hazard: Data not available; Burning Rate: 2.6 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Will not occur under ordinary conditions of shipment. The reaction is not vigorous; Inhibitor of Polymerization: None used. DICHLOROETHYL ETHER Chemical Designations — Synonyms: Bis(2-chloroethyl) Ether; 2,2'-Dichloroethyl Ether; Dichlorodiethyl Ether; Di-(2-chloroethyl) Ether; Chlorex; DCEE; beta,beta'-Dichloroethyl Ether; Chemical Formula: (C1CH2CH2)2O. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Sweet, like chloroform. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 143.0; Boiling Point at 1 atm.: 353, 178, 451; Freezing Point: -62, -52, 221; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.22 at 20°C (liquid); Vapor (Gas) Density: 4.93; Ratio of Specific Heats of Vapor (Gas): 1.0743; Latent Heat of Vaporization: 143, 79.5, 3.33; Heat of Combustion: -7,530, -4,180, -175; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles or face shield; rubber gloves; protective clothing; Symptoms Following Exposure: Inhalation of vapor causes irritation of nose, coughing, nausea. Liquid irritates eyes and causes mild irritation of skin. (Can be absorbed in toxic amounts through the skin). Ingestion causes irritation of mouth and stomach, symptoms of systemic poisoning; General Treatment for Exposure: INHALATION: remove from exposure; support respiration; call physician if needed. EYES: irrigate with copious quantities of water for 15 min.; call physician. SKIN: wipe off, wash well with soap and water. INGESTION: induce vomiting; get medical attention; Toxicity by Inhalation (Threshold Limit Value): 5 ppm; Short-Term Exposure Limits: 35 ppm for 30 min.; Toxicity by Ingestion: Grade 3; oral LD50 = 75 mg/kg (rat); Late Toxicity: Said to be carcinogenic; Vapor (Gas) Irritant Characteristics: Vapors are moderately irritating such that personnel will not usually tolerate moderate or high vapor concentrations; Liquid or Solid Irritant Characteristics: Causes smarting of the skin and first-degree burns on short exposure; may cause second-degree burns on long exposure; Odor Threshold: Data not available. Fire Hazards — Flash
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Point (°F): 180 OC; 131 CC; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: Water, foam, dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: May form phosgene or hydrogen chloride in fires; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 696; Electrical Hazard: Data not available; Burning Rate: 2.4 mm/min. Chemical Reactivity — Reactivity with Water : No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: V; Inhibitor of Polymerization: Not pertinent. DICHLOROMETHANE Chemical Designations — Synonyms: Methylene Chloride; Methylene Dichloride; Chemical Formula: CH2C12. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Pleasant, aromatic; like chloroform; sweet, ethereal. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 84.93; Boiling Point at 1 atm.: 104, 39.8, 313; Freezing Point: -142, -96.7, 176.5; Critical Temperature: 473, 245, 518; Critical Pressure: 895, 60.9, 6.17; Specific Gravity: 1.322 at 20"C (liquid); Vapor (Gas) Density: 2.9; Ratio of Specific Heats of Vapor (Gas): 1.199; Latent Heat of Vaporization: 142, 78.7, 3.30; Heat of Combustion: Not pertinent; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Organic vapor canister mask, safety glasses, protective clothing; Symptoms Following Exposure: INHALATION: anesthetic effects, nausea and drunkenness. SKIN AND EYES: skin irritation, irritation of eyes and nose; General Treatment for Exposure: INHALATION: remove from exposure. Give oxygen if needed. INGESTION: no specific antidote. SKIN AND EYES: remove contaminated clothing; wash skin or eyes if affected; Toxicity by Inhalation (Threshold Limit Value): 500 ppm; Short-Term Exposure Limits: 100 ppm for 60 min.; Toxicity by Ingestion: Grade 2; LD50 = 0.5 to 5 g/kg; Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 205-307 ppm. Fire Hazards — Flash Point : Not flammable under conditions likely to be encountered; Flammable Limits in Air (%): 12-19; Fire Extinguishing Agents: Not pertinent; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Dissociation products generated in a fire may be irritating or toxic; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 1184; Electrical Hazard: Not pertinent; Burning Rate: Not pertinent. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
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DICHLOROPROPANE Chemical Designations — Synonyms: 1,2-Dichloropropane; Propylene Bichloride; Chemical Formula: CH3CHC1CH2C1. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Sweet. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 102.9; Boiling Point at 1 atm.: 206, 96.4, 369.6; Freezing Point: -148, -100, 173; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.158 at 20°C (liquid); Vapor (Gas) Density: 3.5; Ratio of Specific Heats of Vapor (Gas): 1.094; Latent Heat of Vaporization: 122, 67.7, 2.83; Heat of Combustion: 7,300, 4,100, 170; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Air supply in confined area, rubber gloves, chemical goggles, protective coveralls and rubber footwear; Symptoms Following Exposure: Contact with skin or eyes may cause irritation; General Treatment for Exposure: INHALATION: remove to fresh air. SKIN OR EYES: wash skin thoroughly with soap and water. Flush eyes with water for 15 min. Call a doctor; Toxicity by Inhalation (Threshold Limit Value): 75 ppm; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2; LD50 = 0.5 to 5 g/kg (guinea pig); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 70 OC; 60 CC; Flammable Limits in Air (%): 3.4-14.5; Fire Extinguishing Agents: Foam, carbon dioxide, dry chemical; Fire Extinguishing Agents Not to be Used: Not pertinent; Special Hazards of Combustion Products: Toxic and irritating gases may be generated; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 1035; Electrical Hazard: Not pertinent; Burning Rate: (est.) 3.2 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DICHLOROPROPENE Chemical Designations — Synonyms: 1,3-Dichloropropene; Telone; Chemical Formula: C1CH2CH = CHC1. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Sweet; like chloroform. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 110.98; Boiling Point at 1 atm.: 170, 77, 350; Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.2 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.116; Latent Heat of Vaporization: 113, 62.8, 2.63; Heat of Combustion: 6,900, 3,900, 160; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective
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Equipment: An approved full face mask equipped with a fresh black canister meeting specifications of the U.S. Bureau of Mines for organic vapors, a full face self-contained breathing apparatus, or full face air-supplied respirator; Symptoms Following Exposure: Smarting of skin and eyes. Prolonged contact of liquid with skin may cause second-degree burns; General Treatment for Exposure: INHALATION: remove patient to fresh air, keep warm and quiet; call physician immediately; give artificial respiration if breathing has stopped. INGESTION: call physician immediately. Induce vomiting by giving an emetic, e.g., 2 tablespoons table salt in glass of warm water. SKIN OR EYES: immediately remove contaminated clothing and shoes. Wash skin with soap and plenty of water. For eyes, flush immediately with plenty of water for at least 15 min. Call physician; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 3; LD50 = 50 to 500 mg/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Causes smarting of the skin and first degree burns on short exposure and may cause secondary burns on long exposure; Odor Threshold: Data not available. Fire Hazards — Flash Point ("F): 95 CC; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: water, dry chemical, foam, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Toxic and irritating gases may be generated; Behavior in Fire: Not pertinent; Ignition Temperature: Data not available; Electrical Hazard: Data not available; Burning Rate: (est.) 3.4 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DICYCLOPENTADIENE Chemical Designations — Synonyms: Dicy; 3a,4,7,7a-Tetrahydro-4,7-methanoindene; Chemical Formula: C, 0 H 12 . Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Camphor-like. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 132.31; Boiling Point at 1 atm.: 338, 170, 443; Freezing Point: 41, 5, 278; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.978 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Not pertinent; Heat of Combustion: -18,800, -10,400, -437; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Air-supplied mask in confined areas, rubber gloves, safety glasses; Symptoms Following Exposure: Vapor irritates mucous membranes and respiratory tract, causes nausea, vomiting, headache, and dizziness. Direct contact irritates eyes; General Treatment for Exposure: INHALATION: remove victim from contaminated area and call physician if unconscious; if breathing is irregular or
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stopped, give oxygen and start resuscitation. EYES OR SKIN: flush with plenty of water for 15 min.; Toxicity by Inhalation (Threshold Limit Value): 75-100 ppm; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2; oral rat LD50 0.82 g/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: < 0.003 ppm. Fire Hazards — Flash Point (°F): 90 OC; Flammable Limits in Air (%): 0.8-6.3; Fire Extinguishing Agents: Foam, carbon dioxide, dry chemical, or water spray; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 941; Electrical Hazard: Data not available; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: May occur in presence of acids, but not hazardous; Inhibitor of Polymerization: Not pertinent. DIETHANOLAMINE Chemical Designations — Synonyms: Bis(2-hydroxyethyl)amine; DBA; 2,2'Dihydroxydiethyl Amine; Di(2-hydroxyethyl)amine; 2,2'-Iminodiethanol; Chemical Formula: (HOCH2CH2)2NH. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Mild ammoniacal; faint, fishy; characteristic. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Solid; Molecular Weight: 105.14; Boiling Point at 1 atm.: 515.1, 268.4, 541.6; Freezing Point: 82, 28, 301; Critical Temperature: 828, 442, 715; Critical Pressure: 470, 32, 3.2; Specific Gravity: 1.095 at 28°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.053; Latent Heat of Vaporization: 266, 148, 6.20; Heat of Combustion: -10,790, -6,000, -251; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Full face mask or amine vapor mask only, if required; clean body covering clothing, chemical goggles; Symptoms Following Exposure: Irritation of eyes and skin. Breathing vapors may cause coughing, a smothering sensation, nausea, headache; General Treatment for Exposure: INHALATION: no problem likely. Get medical attention if ill effects develop. INGESTION: induce vomiting if large amounts are swallowed and call a physician. Treat symptomatically. No known antidote. EYES: flush with plenty of water for at least 15 min. and get medical attention promptly. SKIN: flush with water. Wash contaminated clothing before reuse; Toxicity by Inhalation (Threshold Limit Value): Not pertinent; Short-Term Exposure Limits: Not pertinent; Toxicity by Ingestion: Grade 2; LD50 = 0.5 to 5 g/kg (rat); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Causes smarting of the skin and first-degree burns
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on short exposure and may cause secondary burns on long exposure; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 305 OC; Flammable Limits in Air (%): 1.6 (calc.) -9.8 (est); Fire Extinguishing Agents: Water, alcohol foam, carbon dioxide, dry chemical; Fire Extinguishing Agents Not To Be Used: Addition of water may cause frothing; Special Hazards of Combustion Products: Irritating vapors are generated when heated; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 1224; Electrical Hazard: Not pertinent; Burning Rate: 0.74 mm/min. Chemical Reactivity — Reactivity with Water : No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Flush with water; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DIETHYLAMINE Chemical Designations — Synonyms: DEN; Chemical Formula: (CH 3 CH 2 ) 2 NH; Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Ammoniacal; sharp, fishy. Physical and Chemical Properties — Physical State at 15"C and 1 atm.: Liquid; Molecular Weight: 73.14; Boiling Point at 1 atm.: 132, 55.5, 328.7; Freezing Point: -57.6, -49.8, 223.4; Critical Temperature: 434.3, 223.5, 496.7; Critical Pressure: 538, 36.6, 3.71; Specific Gravity: 0.708 at 20"C (liquid); Vapor (Gas) Density: 2.5; Ratio of Specific Heats of Vapor (Gas): 1.079; Latent Heat of Vaporization: 170, 93, 3.9; Heat of Combustion: -17,990, -9,994, -418.4; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Chemical safety goggles, rubber gloves, and apron; Symptoms Following Exposure: Irritation and burning of eyes, skin and respiratory system. High concentration of vapor can cause asphyxiation; General Treatment for Exposure: In case of contact, flush skin or eyes with plenty of water for at least 15 min.; for eyes, get medical attention; Toxicity by Inhalation (Threshold Limit Value): 25 ppm; Short-Term Exposure Limits: 100 ppm for 30 min.; Toxicity by Ingestion: Grade 2; LD50 = 0.5 to 5 g/kg (rat); Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Vapor is moderately irritating such that personnel will not usually tolerate moderate or high vapor concentrations; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 0.14 ppm. Fire Hazards — Flash Point ("F): 5 OC; Flammable Limits in Air (%): 1.8-9.1; Fire Extinguishing Agents: Dry chemical, carbon dioxide, or alcohol foam; Fire Extinguishing Agents Not To Be Used: Data not available; Special Hazards of Combustion Products: Vapors are irritating; Behavior in Fire: Vapors are heavier than air and may travel considerable distance to a source of ignition and flash back; Ignition Temperature (°F): 594; Electrical Hazard: Data not available; Burning Rate: 6.7 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No hazardous reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Flush with water; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
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DIETHYLBENZENE Chemical Designations — Synonyms: No common synonyms; Chemical Formula: C6H4(C2H5)2. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Characteristic aromatic; like benzene; like toluene, Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 134.21; Boiling Point at 1 atm.: 356, 180, 453; Freezing Point: < 160, 15 g/kg; Late Toxicity: Causes damage to eye in dogs, pigs, rats, and rabbits; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards - Flash Point (°F): 203 OC; Flammable Limits in Air (%): 3-6.3; Fire Extinguishing Agents: Water, foam, dry chemical, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Sulfur dioxide, formaldehyde, and methyl mercaptan may form; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 572; Electrical Hazard: Not pertinent; Burning Rate: 2.0 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DIOCTYL ADIPATE Chemical Designations — Synonyms: Adipic Acid, Bis(2-ethylhexyl) Ester; Adipol 2EH; Di(2-ethylhexyl) Adipage; DOA; Chemical Formula: C8H17OOC(CH2)4COOC8H17. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Mild characteristic. Physical and Chemical Properties — Physical State at 15"C and 1 atm.: Liquid; Molecular Weight: 371; Boiling Point at 1 atm.: Very high; Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.928 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Not pertinent; Heat of Combustion: -15,430, -8,580, -359; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: None required; Symptoms Following Exposure: Low toxicity; no reports of injury in industrial handling; General Treatment for Exposure: SKIN AND EYES: wipe off and wash skin with soap and water. Treat like lubricating oil. Flush eyes with water. Remove to fresh air; Toxicity by Inhalation (Threshold Limit Value): Not pertinent; Short-Term Exposure Limits: Not pertinent; Toxicity by Ingestion: Grade 1; LD50 = 5 to 15 g/kg; Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Vapors are nonirritating to the eyes and throat; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Not pertinent. Fire Hazards — Flash Point (°F): 390 OC; Flammable Limits in Air
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(%): Data not available; Fire Extinguishing Agents: Data not available; Fire Extinguishing Agents Not To Be Used: Data not available; Special Hazards of Combustion Products: None; Behavior in Fire: Not pertinent; Ignition Temperature: Data not available; Electrical Hazard: Data not available; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DIOCTYL PHTHALATE Chemical Designations — Synonyms: Bis(2-ethylhexyl) Phthalate; Di(2ethylhexyl) Phthalate; OOP; Octoil; Phthalic Acid, Bis(2-ethylhexyl) Ester; Chemical Formula: o-C6H4[COOCH2CH(C2H5)(CH2)3CH3]2. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Very slight, characteristic. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 390.6; Boiling Point at 1 atm.: 727, 386, 659; Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.980 at 25"C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Not pertinent; Heat of Combustion: -15, 130, -8,410, -352; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Not required; Symptoms Following Exposure: Produces no ill effects at normal temperatures but may give off irritating vapor at high temperature; General Treatment for Exposure: Leave contaminated area; wash skin with soap and water; flush eyes with water; Toxicity by Inhalation (Threshold Limit Value): Not pertinent; Short-Term Exposure Limits: Not pertinent; Toxicity by Ingestion: Grade 0; LD50 > 15 g/kg (rat); Late Toxicity: Not established; Vapor (Gas) Irritant Characteristics: Nonirritating to the eyes and throat; Liquid or Solid Irritant Characteristics: No appreciable hazard. Practically harmless to the skin; Odor Threshold: Not pertinent. Fire Hazards — Flash Point ("F): 425 OC; Flammable Limits in Air (%): Not pertinent; Fire Extinguishing Agents: Dry powder, carbon dioxide, foam; Fire Extinguishing Agents Not To Be Used: Water or foam may cause frothing; Special Hazards of Combustion Products: None; Behavior in Fire: Not pertinent; Ignition Temperature: Data not available; Electrical Hazard: Not pertinent; Burning Rate: Not pertinent. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DIPENTENE Chemical Designations — Synonyms: Limonene; para-Mentha-l,8-diene; Phellandrene; Terpinene; delta-l,8-Terpodiene; Chemical Formula: C 10 H 16 . Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Pleasant, pine-like; lemon-like. Physical and Chemical
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Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 136.2; Boiling Point at 1 atm.: 352, 178, 451; Freezing Point: -40, -40, 233; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.842 at 21°C (liquid); Vapor (Gas) Density: 4.9; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: 140, 77, 3.2; Heat of Combustion: -19,520, -10,840, -454; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Solvent-resistant gloves; safety glasses or face shield; self-contained breathing apparatus for high vapor concentrations; Symptoms Following Exposure: Liquid irritates eyes; prolonged contact with skin causes irritation. Ingestion causes irritation of gastrointestinal tract; General Treatment for Exposure: INHALATION: remove victim from contaminated area; administer artificial respiration if necessary; call physician. EYES: flush with water for 15 min.; call physician. SKIN: wash with soap and water. INGESTION: induce vomiting; call physician; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2; oral LD50 = 4,600 mg/kg (rat); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause a slight of the eyes or respiratory system if present in high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 115 CC; Flammable Limits in Air (%): 0.7-6.1; Fire Extinguishing Agents: Foam, dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Containers may explode; Ignition Temperature (°F): 458; Electrical Hazard: Data not available; Burning Rate: 5.5 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DIPHENYL ETHER Chemical Designations — Synonyms: Phenyl Ether; Diphenyl Oxide; Phenoxybenzene; Chemical Formula: C6H5OC6H5. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Weak geranium. Physical and Chemical Properties — Physical State at 15°C and 1 atm: Solid; Molecular Weight: 170.2; Boiling Point at 1 atm.: 495, 257, 530; Freezing Point: 81, 27, 300; Critical Temperature: 921, 494, 767; Critical Pressure: 478, 32.5, 3.30; Specific Gravity: 1.07 at 27°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: 130, 72, 3.0; Heat of Combustion: -15,520, -8,620, -361; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles or face shield; rubber gloves; Symptoms Following Exposure: Inhalation may cause nausea because of disagreeable odor. Contact of liquid with eyes causes mild irritation. Prolonged exposure of skin to
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liquid causes reddening and irritation. Ingestion produces nausea; General Treatment for Exposure: EYES: flush with water for at least 15 min. SKIN: wipe off, wash with soap and water. INGESTION: induce vomiting and get medical attention; Toxicity by Inhalation (Threshold Limit Value): 1 ppm; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2; oral LD50 = 3,370 mg/kg (rat); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: 0.1 ppm. Fire Hazards — Flash Point (°F): 239 CC; Flammable Limits in Air (%): 0.8-1.5; Fire Extinguishing Agents: Dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water or foam may cause frothing; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 1.148; Electrical Hazard: Data not available; Burning Rate: 3.2 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DIPROPYLENE GLYCOL Chemical Designations - Synonyms: No common synonyms; Chemical Formula: (CH 3 CHOHCH 2 ) 2 O. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Practically none. Physical and Chemical Properties — Physical State at 15"C and 1 ami.: Liquid; Molecular Weight: 134.17; Boiling Point at 1 atm.: 420, 232, 505; Freezing Point: >-40, >-40, >233; Critical Temperature: 720, 382, 655; Critical Pressure: 529, 36, 3.6; Specific Gravity: 1.023 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.0; Latent Heat of Vaporization: 170, 96, 4.0; Heat of Combustion: -11,650, -6470, -271; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Safety glasses with side shields or goggles; shower and eye bath; Symptoms Following Exposure: Minor eye irritation; General Treatment for Exposure: EYES: irrigate briefly with water; if any ill defects, get medical attention. SKIN AND INGESTION: if any ill defects develop, get medical attention; Toxicity by Inhalation (Threshold Limit Value): Not pertinent; ShortTerm Exposure Limits: Not pertinent; Toxicity by Ingestion: Grade 1; LD50 = 5 to 15 g/kg (rat); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Nonirritating to the eyes and throat; Liquid or Solid Irritant Characteristics: No appreciable hazard. Practically harmless to the skin; Odor Threshold: Not pertinent. Fire Hazards — Flash Point (°F): 280 OC; Flammable Limits in Air (%): LFL = 2.2% (approx.); Fire Extinguishing Agents: Water fog, alcohol foam, carbon dioxide, dry chemical; Fire Extinguishing Agents Not To Be Used: Water or foam may cause frothing; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature: Data not available; Electrical Hazard: Not pertinent; Burning Rate: 2.0 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with
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Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DISTILLATES: FLASHED FEED STOCKS Chemical Designations — Synonyms: Petroleum Distillate; Chemical Formula: Not pertinent. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Gasoline. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: Not pertinent; Boiling Point at 1 atm.: 58-275, 14-135, 287-408; Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.71-0.75 at 15°C (liquid); Vapor (Gas) Density: 3.4; Ratio of Specific Heats of Vapor (Gas): 1.054; Latent Heat of Vaporization: 130-150, 71-81, 3.03.4; Heat of Combustion: -18,720, -10,400, -435.4; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Data not available; Symptoms Following Exposure: INHALATION: irritation of upper respiratory tract; dizziness, headache, coma, respiratory arrest; cardiac arrhythmias may occur. ASPIRATION: severe lung irritation, coughing, pulmonary edema, signs of bronchopneumonia; acute central nervous system excitation, followed by depression. INGESTION: irritation of mouth and stomach, other symptoms as above; General Treatment for Exposure: Seek medical attention. INHALATION: maintain respiration, administer oxygen. ASPIRATION: enforce bed rest; administer oxygen. INGESTION: do NOT induce vomiting; lavage carefully if appreciable quantity was swallowed; guard against aspiration into lungs. EYES: wash with copious amounts of water. SKIN: wipe off and wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): No single TLV applicable; Short-Term Exposure Limits: 500 ppm for 30 min.; Toxicity by Ingestion: Grade 2; LD50 = 0.5-5 g/kg; Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Vapors cause a slight smarting of the eyes or respiratory system if present in high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 0.25 ppm. Fire Hazards — Flash Point (°F): (a) 15 g/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause a slight smarting of the eyes or respiratory system if present in high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 120 CC; 134 OC; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: Water fog, foam, carbon dioxide, dry chemical; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 400 (est.); Electrical Hazard: Not pertinent; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. 1-DODECENE Chemical Designations — Synonyms: Adacene-12; alpha-Dodecylene; Chemical Formula: CH3(CH2)9CH = CH2. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Mild, pleasant. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 168.31; Boiling Point at 1 atm.: 415, 213, 486; Freezing Point: -31, -35, 238; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.758 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.032; Latent Heat of Vaporization: 110, 61.0, 2.55; Heat of Combustion: -18,911, -10,506, -439.87; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Protective gloves; goggles or face shield; Symptoms Following Exposure: No inhalation hazard expected. Aspiration hazard if ingested. Minor skin and eye irritation; General Treatment for Exposure: INHALATION: remove victim to fresh air. INGESTION: do NOT induce vomiting! Give vegetable oil and demulcents; call physician. EYE: flush wight water for 15 min. SKIN: wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Data not available; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause a slight smarting of the eyes or respiratory system if present in high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 174; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: Foam, dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 491; Electrical Hazard: Not pertinent; Burning Rate: 5.8 mm/min. Chemical Reactivity
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— Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. DODECYLTRICHLOROSILANE Chemical Designations — Synonyms: No common synonyms; Chemical Formula: CH 3 (CH 2 ) u SiCl 3 . Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Sharp, like hydrochloric acid; pungent and irritating. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 303.7; Boiling Point at 1 atm.: >300, > 149, >422; Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.03 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Not pertinent; Heat of Combustion: -11,000, -6,200, 260; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Acid-vapor type respiratory protection; rubber gloves; chemical worker's goggles; other protective equipment as necessary to protect eyes and skin; Symptoms Following Exposure: Inhalation irritates mucous membrane. Contact with liquid causes severe burns of eyes and skin. Ingestion causes severe burns of mouth and stomach; General Treatment for Exposure: INHALATION: remove from exposure; support respiration; call physician if needed. EYES: flush with water for 15 min.; obtain medical attention immediately. SKIN: flush with water; obtain medical attention if skin is burned. INGESTION: if victim is conscious, give large amounts of water, then milk or milk of magnesia; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 3; LD50 = 50 to 500 mg/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Severe skin irritant. Causes second- and third-degree burns on short contact and is very injurious to the eyes; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): > 150 OC; Flammable Limits in Air (%): Data not available; Fire Extinguishing Agents: Dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water, foam; Special Hazards of Combustion Products: Hydrochloric acid and phosgene fumes may form in fires; Behavior in Fire: Difficult to extinguish; re-ignition may occur. Contact with water applied to adjacent fires produces irritating hydrogen chloride fumes; Ignition Temperature: Data not available; Electrical Hazard: Data not available; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: Generates hydrogen chloride (hydrochloric acid); Reactivity with Common Materials: Reacts with surface moisture to generate hydrogen chloride, which is corrosive to most metals; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Flush with water, rinse with sodium bicarbonate or lime solution; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
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EPICHLOROHYDRIN Chemical Designations — Synonyms: l,Chloro-2,3-epoxypropane; Chloromethyloxirane; gamma-Chloropropylene oxide; 3-Chloro-l,2-propylene oxide; Chemical Formula: O«CH2*CH«CH2C1. Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Pungent, garlic; sweet, pungent; like chloroform. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 92.53; Boiling Point at 1 atm.: 239.4, 115.2, 388.4; Freezing Point: -72.6, -58.1, 215.1; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.18 at 20°C (liquid); Vapor (Gas) Specific Gravity: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.155; Latent Heat of Vaporization: 176, 97.9, 4.10; Heat of Combustion: 8143, -4524, -189.4; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Air pack or organic canister mask; protective gloves and goggles; Symptoms Following Exposure: Vapor is irritating to eyes, nose, and throat; may cause headache, nausea, vomiting, and central nervous system depression. Rapidly fatal if swallowed, i.e. nausea, vomiting, and collapse. Skin contact is irritating; General Treatment for Exposure: INHALATION: remove victim to fresh air, keep him warm and quiet, and get medical attention immediately; if breathing stops, start artificial respiration. INGESTION: induce vomiting (but only if victim is conscious and without convulsions) and call a physician promptly; no specific antidote known. EYES OR SKIN: immediately flush with water for at least 15 min. and get medical attention; remove contaminated clothing and wash before reuse; Toxicity by Inhalation (Threshold Limit Value): 5 ppm; Short-Term Inhalation Limits: 10 ppm for 30 min.; Toxicity by Ingestion: Grade 3, LD50 = 50 to 500 mg/kg; Late Toxicity: Causes cancer in experimental animals; Vapor (Gas) Irritant Characteristics: Vapor is moderately irritating such that personnel will not usually tolerate moderate or high vapor concentrations; Liquid or Solid Irritant Characteristics: Fairly severe skin irritant. May cause pain and second-degree burns after a few minutes contact; Odor Threshold: 10 ppm. Fire Hazards — Flash Point (°F): 92 OC; 100 CC; Flammable Limits in Air (%): 3.8-21.0; Fire Extinguishing Agents: Alcohol foam, dry chemical, carbon dioxide, water spray; Fire Extinguishing Agents Not To Be Used: Avoid use of dry chemical if fire occurs in container with confined vent; Special Hazards of Combustion Products: Toxic irritating vapors are generated when heated; Behavior in Fire: Containers may explode in fire because of polymerization; Ignition Temperature (°F): 804; Electrical Hazard: Not pertinent; Burning Rate: 2.6 mm/min. Chemical Reactivity — Reactivity with Water: Mild reaction; not likely to be hazardous; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Can polymerize in presence of strong acids and bases, particularly when hot; Inhibitor of Polymerization: None used. ETHYL ACETATE Chemical Designations — Synonyms: Acetic acid, ethyl ester, Acetic ester, Acetic
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ether, Ethyl ethanoate; Chemical Formula: CH3COOCH2CH3. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Pleasant, fruity. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 88.11; Boiling Point at 1 atm.: 171, 77, 350; Freezing Point: -117, -83, 190; Critical Temperature: 482, 250, 523; Critical Pressure: 558, 38, 3.8; Specific Gravity: 0.902 at 20°C (liquid); Vapor (Gas) Density: 3.0; Ratio of Specific Heats of Vapor (Gas): 1.080; Latent Heat of Vaporization: 158, 87.6, 3.67; Heat of Combustion: -10,110, -5,616, -235,1; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Organic vapor canister or air mask; goggles or face shield; Symptoms Following Exposure: Headache, irritation of respiratory passages and eyes, dizziness and nausea, weakness, loss of consciousness; General Treatment for Exposure: INHALATION: if victim is overcome, move him to fresh air immediately and call a physician; if breathing is irregular or stopped, start resuscitation and administer oxygen. EYES: flush with water for at least 15 min.; Toxicity by Inhalation (Threshold Limit Value): 400 ppm; Short-Term Exposure Limits: 1000 ppm for 15 min.; Toxicity by Ingestion: Grade 2; LD50 = 0.5-5 g/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapor cause a slight smarting of the eyes or respiratory system if present in high concentration. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 1 ppm. Fire Hazards — Flash Point ("F): 24 CC; 55 OC; Flammable Limits in Air (%): 2.2-9.0; Fire Extinguishing Agents: Alcohol foam, carbon dioxide, or dry chemical; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 800; Electrical Hazard: Class I, Group D; Burning Rate: 3.7 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. ETHYL ACETOACETATE Chemical Designations — Synonyms: Acetoacetic acid, ethyl ester, Acetoacetic ester; Diacetic ether; Chemical Formula: CH3COCH2COOC2H5. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Agreeable, fruity. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 130.1; Boiling Point at 1 atm.: 363, 184, 457; Freezing Point: 600; Electrical Hazard: Data not available; Burning Rate: 3.0 mm/min. Chemical Reactivity — Reactivity with Water: Reacts violently to form hydrogen chloride (hydrochloric acid); Reactivity with Common Materials: Reacts with surface moisture to evolve hydrogen chloride, which is corrosive to common metals; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Flood with water, rinse with sodium bicarbonate or lime solution; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. METHYL ETHYL KETONE Chemical Designations — Synonyms: 2-Butanone; Ethyl methyl ketone; MEK; Chemical Formula: CH3COCH2CH3 Observable Characteristics — Physical State
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(as shipped): Liquid; Color: Colorless; Odor: Like acetone; pleasant; pungent. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 72.11; Boiling Point at 1 atm.: 175.3, 79.6, 352.8; Freezing Point: -123.3, -86.3, 186.9; Critical Temperature: 504.5, 262.5, 535.7; Critical Pressure: 603, 41.0, 4.15; Specific Gravity: 0.806 at 20°C (liquid); Vapor (Gas) Specific Gravity: 2.5; Ratio of Specific Heats of Vapor (Gas): 1.075; Latent Heat of Vaporization: 191, 106, 4.44; Heat of Combustion: -13,480, -7491, -313.6; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Organic canister or air pack; plastic gloves; goggles or face shield; Symptoms Following Exposure: Liquid causes eye burn. Vapor irritates eye, nose, and throat; can cause headache, dizziness, nausea, weakness, and loss of consciousness; General Treatment for Exposure: INHALATION: remove victim from exposure; if breathing has stopped, start resuscitation and administer oxygen. EYES: wash with plenty of water for at least 15 min. and call physician; Toxicity by Inhalation (Threshold Limit Value): 200 ppm; Short-Term Inhalation Limits: 290 mg/m 3 for 60 min.; Toxicity by Ingestion: Grade 2, LD50 = 0.5-5 g/kg (rat); Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Vapors causes a slight smarting of the eyes or respiratory system if present in high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of skin; Odor Threshold: 10 ppm. Fire Hazards — Flash Point (°F): 20 CC; 22 OC; Flammable Limits in Air (%): 1.8-11.5; Fire Extinguishing Agents: Alcohol foam dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 961; Electrical Hazard: Class I, Group D; Burning Rate: 4.1 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. METHYL FORMAL Chemical Designations — Synonyms: Dimethoxymethane; Dimethylformal; Formaldehyde dimethylacetat; Methylal; Methylene dimethyl ether; Chemical Formula: CH 2 (OCH 3 ) 2 . Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Mild, ethereal; chloroform-like. Physical and Chemical Properties — Physical State at 15°C and 1 atm: Liquid; Molecular Weight: 76.1; Boiling Point at 1 atm.: 108, 42, 315; Freezing Point: -157, -105, 168; Critical Temperature: 419, 215, 488; Critical Pressure: Not pertinent; Specific Gravity: 0.861 at 20°C (liquid); Vapor (Gas) Specific Gravity: 2.6; Ratio of Specific Heats of Vapor (Gas): 1.0888; Latent Heat of Vaporization: 161.5, 89.8, 3.76; Heat of Combustion: -10,970, -6,100, -255; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Self-contained breathing apparatus or all-purpose canister mask; gloves; rubber gloves; chemical safety goggles; impervious apron and boots;
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Symptoms Following Exposure: Inhalation causes irritation of respiratory system and depression of central nervous system. Liquid causes irritation of eyes and will irritate skin if allowed to remain. Ingestion causes depression of central nervous system; General Treatment for Exposure: INHALATION: remove victim from contaminated area and administer artificial respiration and oxygen if necessary. EYES: flush with plenty of water; get medical attention. SKIN: flush with plenty of water. INGESTION: induce vomiting, then give gastric lavage and saline cathartics; subsequent treatment is symptomatic and supportive; Toxicity by Inhalation (Threshold Limit Value): 1,000 ppm; Short-Term Inhalation Limits: Data not available; Toxicity by Ingestion: Grade 1; LD50 = 5-15 g/kg; Late Toxicity: Liver and kidney injury may follow high exposures; Vapor (Gas) Irritant Characteristics: Vapors causes a slight smarting of the eyes or respiratory system if present in high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 0 OC; Flammable Limits in Air (%): 1.6-17.6; Fire Extinguishing Agents: Dry chemical, foam, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Irritating formaldehyde smoke may be present in smoke; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 459; Electrical Hazard: Data not available; Burning Rate: 5.5 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. METHYL FORMATE Chemical Designations — Synonyms: Formic acid, methyl ester; Chemical Formula: HCOOH3. Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Pleasant; agreeable. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 60.1; Boiling Point at 1 atm.: 89.2, 31.8, 305; Freezing Point: -147.6, -99.8, 173.4; Critical Temperature: 417, 214, 487; Critical Pressure: 870, 59.2, 6.00; Specific Gravity: 0.977 at 20°C (liquid); Vapor (Gas) Specific Gravity: 2.07; Ratio of Specific Heats of Vapor (Gas): 1.1446; Latent Heat of Vaporization: 202, 112, 4.696; Heat of Combustion: -6,980, -3,880, -162; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles or safety glasses; self-contained breathing apparatus; rubber gloves; Symptoms Following Exposure: Inhalation causes irritation of mucous membranes. Prolonged inhalation can produce narcosis and central nervous symptoms, including some temporary visual disturbance. Contact with liquid irritates eyes and may irritate skin if allowed to remain. Ingestion causes irritation of mouth and stomach and central nervous system depression, including visual disturbances; General Treatment for Exposure: INHALATION: remove to fresh air and rest; if pulmonary edema develops, administer oxygen; call physician. EYES:
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irrigate with water for 15 min. SKIN: wash thoroughly with soap and water. INGESTION: do NOT induce vomiting; get medical attention; Toxicity by Inhalation (Threshold Limit Value): 100 ppm; Short-Term Inhalation Limits: Data not available; Toxicity by Ingestion: Grade 1; LD50 — 5-15 g/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors are moderately irritating such that personnel will not usually tolerate moderate or high concentrations; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): -26 CC; Flammable Limits in Air (%): 5-22.7; Fire Extinguishing Agents: Dry chemical, carbon dioxide, alcohol foam; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Vapor is heavier than air and may travel a considerable distance to source of ignition and flash back; Ignition Temperature (°F): 853; Electrical Hazard: Data not available; Burning Rate: 2.5 mm/min. Chemical Reactivity — Reactivity with Water: Slow reaction to form formic acid and methyl alcohol; reaction is not hazardous; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. METHYL ISOBUTYL CARBINOL Chemical Designations — Synonyms: Isobutyl methyl carbinol; Methyl Alcohol; MAOH; 4-Methyl-2-pentanol; MIBC; MIC; Chemical Formula: (CH 3 ) 2 CHCH 2 CH(OH)CH 3 . Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Mild, sharp, non-residual. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 102.18; Boiling Point at 1 atm.: 269.2, 131.8, 405; Freezing Point: < -130, 15 g/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Not pertinent. Fire Hazards — Flash Point (°F): 210 CC, 225 OC; Flammable Limits in Air (%): 2.6-12.5; Fire Extinguishing Agents: Water fog, alcohol foam, carbon dioxide, or dry chemical; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 790; Electrical Hazard: Not pertinent; Burning Rate: 1.5 mm/mm. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. N-PROPYL ACETATE Chemical Designations — Synonyms: Acetic acid; Propyl ester; Methylacetic anhydride; Propanoic anhydride; Propionyl oxide; Chemical Formula: CH 3 COOCH 2 CH 2 CH 3 . Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Mild fruity. Physical and Chemical Properties — Physical State at 15°C and 1 atm: Liquid; Molecular Weight: 102.13; Boiling Point at 1 atm: 214.9, 101.6, 374.8; Freezing Point: -139, -95.0, 178.2;
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Critical Temperature: 529, 276, 549; Critical Pressure: 485, 33, 3.3; Specific Gravity: 0.886 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.071; Latent Heat of Vaporization: 145, 80.3, 3.36; Heat of Combustion: (at 15°C) -10,320, -5,740, -240; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Air-supplied mask or chemical canister; goggles or face shield; protective gloves; Symptoms Following Exposure: Contact with skin and eyes causes no serious injury. High vapor concentrations will be irritating and will cause nausea, vomiting, and dizziness, with final loss of consciousness; General Treatment for Exposure: INHALATION: remove victim to fresh air; give artificial respiration if breathing has stopped; give oxygen if will breathing is difficult. SKIN AND EYES: flush with water; Toxicity by Inhalation (Threshold Limit Value): 200 ppm; Short-Term Exposure Limits: 200 ppm for 60 min.; Toxicity by Ingestion: Grade 2; LD50 = 0.5 to 5 g/kg; Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Vapors causes a slight smarting of the eyes or respiratory system if present in high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 70 mg/m3. Fire Hazards — Flash Point (°F): 58 CC, 65 OC; Flammable Limits in Air (%): 2.0-8.0; Fire Extinguishing Agents: For small fires use carbon dioxide or dry chemical. For large fires, use alcohol foam; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 842; Electrical Hazard: Not pertinent; Burning Rate: No data. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. N-PROPYL ALCOHOL Chemical Designations — Synonyms: Ethylcarbinol; 1-Propanol; Propylalcohol; Chemical Formula: CH3CH2CH2OH. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Resembles that of ethyl alcohol. Physical and Chemical Properties — Physical State at 15°C and 1 atm: Liquid; Molecular Weight: 60.10; Boiling Point at 1 atm: 207.0, 97.2, 370.4; Freezing Point: -195.2, -126.2, 147.0; Critical Temperature: 506.5, 263.6, 536.8; Critical Pressure: 750, 51, 5.2; Specific Gravity: 0.803 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 2.1; Latent Heat of Vaporization: 292.7, 162.6, 6,808; Heat of Combustion: -13,130, -7,296, -305.5; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Air-supplied respirator for high concentrations; goggles or face shield; plastic gloves; Symptoms Following Exposure: Contact with eyes extremely irritating and may cause burns. Vapors irritate nose and throat. In high concentrations, may cause nausea, dizziness, headache, and stupor; General Treatment for Exposure: INHALATION: remove
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victim to fresh air; call a physician. SKIN OR EYE CONTACT: flush at once with plenty of water; get medical care for eyes; Toxicity by Inhalation (Threshold Limit Value): 200 ppm; Short-Term Exposure Limits: 400 ppm for 30 min.; Toxicity by Ingestion: Grade 2; LD50 = 0.5-5 g/kg (rat); Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Vapors causes a slight smarting of the eyes or respiratory system if present in high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: No appreciable hazard. Practically harmless to the skin; Odor Threshold: 30 ppm. Fire Hazards — Flash Point (°F): 81 OC, 77 CC; Flammable Limits in Air (%): 2.1-13.5; Fire Extinguishing Agents: Carbon dioxide for small fires, and alcohol foam for large fires; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 700; Electrical Hazard: Class I, Group D; Burning Rate: 2.9 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. PROPYLENE OXIDE Chemical Designations — Synonyms: 1,2-Epoxypropane; Methyloxirane propene oxide; Chemical Formula: CH3CHCH2O. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Ethereal; characteristic; sweet, alcoholyc; like natural gas. Physical and Chemical Properties — Physical State at 15"C and 1 atm: Liquid; Molecular Weight: 58.08; Boiling Point at 1 atm: 93.7, 34.3, 307.5; Freezing Point: -169.4, -11.9, 161.3; Critical Temperature: 408.4, 209.1 482.3; Critical Pressure: 714, 48.6, 4.92; Specific Gravity: 0.830 at 20"C; Vapor (Gas) Density: 2.0; Ratio of Specific Heats of Vapor (Gas): 1.133; Latent Heat of Vaporization: 205, 114, 4.77; Heat of Combustion: -13,.000, -7,221, -302.3; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Air-supplied mask; rubber or plastic gloves; vapor-proof goggles; Symptoms Following Exposure: Inhalation may introduce headache, nausea, vomiting, and unconsciousness; mild depression of central nervous system; lung irritation. Slightly irritating to skin, but covered contact may cause burn. Very irritating to eyes; General Treatment for Exposure: INHALATION: remove person to fresh air immediately, keep quit and warm; call a physician; if breathing stop, start artificial respiration. SKIN OR EYE CONTACT: immediately flush with plenty of water for at 15 min.; immediately remove contaminated clothing, watch bands, rings, etc. to prevent confiding product to skin; for eyes get medical attention; Toxicity by Inhalation (Threshold Limit Value): 100 ppm; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2; LD50 = 0.5-5 g/kg (rat); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors is moderatory irritating such that personnel will not short exposure; may cause secondary burn on long exposure; Liquid or Solid Irritant Characteristics: Causes smarting on the skin and first-degree burns on short exposure; may causes
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secondary burns on long exposure; Odor Threshold: 200 ppm. Fire Hazards — Flash Point (°F): -35 CC, -20 OC; Flammable Limits in Air (%): 2.1-38.5; Fire Extinguishing Agents: Carbon dioxide or dry chemical for small fires. Alcohol or polymer foam for large fires.; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Containers may explode. Vapors are heavier than air and can travel to a source of ignition and flash back; Ignition Temperature (°F): 869; Electrical Hazard: Class I, Group B; Burning Rate: 3.3 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Polymerization can occur when this product is exposed to high temperatures or is contaminated with alkalies, aqueous acids, amines, and acidic alcohols; Inhibitor of Polymerization: Not pertinent. QUINOLINE Chemical Designations — Synonyms: 1-Azanapthalene; 1-Benzazine; Benzo(b)pyridine; Chinoline; Leucol; Chemical Formula: C9H7N. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless to brown; Odor: Strong, unpleasant. Physical and Chemical Properties — Physical State at 15°C and 1 aim.: Liquid; Molecular Weight: 129; Boiling Point at 1 atm.: 459, 237, 510; Freezing Point: 5, -15, 258; Critical Temperature: 948, 509, 782; Critical Pressure: Data not available; Specific Gravity: 1.095 at 20°C (liquid); Vapor (Gas) Density: 4.5; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: (est.) 155, 86, 3.6; Heat of Combustion: -15,700, -8,710, -365; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: U. S. Bu. Mines approved respirator: rubber gloves; safety glasses with side shields or chemical goggles: coveralls or rubber apron; Symptoms Following Exposure: Inhalation of vapors or dust causes irritation of respiratory tract, ingestion causes burns of mucous membranes, severe diarrhea, pallor, sweating, weakness, headache, dizziness, tinnitus, shock, and severe convulsions: may also cause siderosis of the spleen and tubular injury to the kidney. Contact with eyes causes irritation. Can be absorbed from wounds or through unbroken skin, producing severe dermatitis, methemoglobinemia, cyanosis, convulsions, tachycardia, dyspnea, and death; General Treatment for Exposure: INHALATION: remove victim to fresh air; if he is not breathing, give artificial respiration, preferably mouth-to-mouth; if breathing is difficult, give oxygen, call a physician. INGESTION: give activated charcoal; administer gastric lav age with water; consult physician. EYES: flush with water for IS min. SKIN: flush with water; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 3, oral LD50 = 460 mg/kg (rat); Late Toxicity. Data not available; Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: 71 ppm. Fire Hazards — Flash Point (°F): 225 CC; Flammable Limits in Air (%): No data; Fire
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Extinguishing Agents: Water, dry chemical, foam, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Toxic oxides of nitrogen form in fires; Behavior in Fire: Exposure to heat can result in pressure build-up in closed containers, resulting in bulging or even explosion; Ignition Temperature (°F): 896; Electrical Hazard: No data; Burning Rate: 4.1 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: Attacks some forms of plastics; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. SODIUM ALKYL SULFATES Chemical Designations — Synonyms: Sodium hydrogen alkyl sulfate; Chemical Formula: C n H 2n+1 OSO 2 ONa. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless to pale yellow; Odor: Weak Detergent. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid or solid; Molecular Weight: Not pertinent; Boiling Point at 1 atm: Decomposes; Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: Data not available; Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Not pertinent; Heat of Combustion: Not pertinent; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles or face shield; rubber gloves; Symptoms Following Exposure: In general, these chemical have a moderate order of toxicity. Repeated skin contact with concentrated solutions may cause dermatitis. Ingestion may cause gastrointestinal discomfort, vomiting, and diarrhea; General Treatment for Exposure: INGESTION: induce vomiting and follow with gastric lavage. SKIN: wash off with water; Toxicity by Inhalation (Threshold Limit Value): Not pertinent; Short-Term Exposure Limits: Not pertinent; Toxicity by Ingestion: Grade 2, LD50 = 0.5-5 g/kg; Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Non-volatile; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing .and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Not pertinent. Fire Hazards — Flash Point: Not flammable; Flammable Limits in Air (%): Not flammable; Fire Extinguishing Agents: Not pertinent; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Irritating vapors are generated in fires; Behavior in Fire: Not pertinent; Ignition Temperature: Not pertinent; Electrical Hazard: Not pertinent; Burning Rate: Not pertinent. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. SORBITOL Chemical Designations
—
Synonyms:
D-Glucitol;
Hexahydric
alcohol;
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1,2,3,4,5,6-Hexanehexol; Sorbit; Sorbo; Sorbol; Chemical Formula: CH2OH(CHOH)4CH2OH. Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Odorless. Physical and Chemical Properties — Physical State at 15°C and 1 aim.: Solid; Molecular Weight: 182.17; Boiling Point at 1 arm.: Very high; Freezing Point: 230, 110, 383; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.49 at 15°C (liquid); Vapor (Gas) Specific Gravity: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Not pertinent; Heat of Combustion: (est.) -6,750, -3,750, -157; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles or face shield; protective clothing for hot liquid; Symptoms Following Exposure: Hot liquid will burn skin; General Treatment for Exposure: Only for burns caused by hot liquid; Toxicity by Inhalation (Threshold Limit Value): Not pertinent; Short-Term Inhalation Limits: Not pertinent; Toxicity by Ingestion: None; Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Nonvolatile; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Not pertinent. Fire Hazards — Flash Point (°F): 542; Flammable Limits in Air (%): Not flammable; Fire Extinguishing Agents: Water; Fire Extinguishing Agents Not To Be Used: Not data; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature: No data; Electrical Hazard: Not pertinent; Burning Rate: No data. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. TOLUENE Chemical Designations — Synonyms: Methylbenzen, Methylbenzol, Toluol; Chemical Formula: C6H6CH3. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Pungent; aromatic, benzenelike; distinct, pleasant. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 92.14; Boiling Point at 1 atm.: 231.1, 110.6, 383.8; Freezing Point: -139, -95.0, 178.2; Critical Temperature: 605.4, 318.6, 591.8; Critical Pressure: 596.1, 40.55, 4.108; Specific Gravity: 0.867 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.089; Latent Heat of Vaporization: 155, 86.1, 3.61; Heat of Combustion: 17,430, -9686, -405.5; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Air-supplied mask; goggles and face shield; plastic gloves; Symptoms Following Exposure: Vapors irritate eyes and upper respiratory tract; cause dizziness, headache, anesthesia, respiratory arrest. Liquid irritates eyes and causes coughing, gagging distress, and rapidly developing pulmonary edema. If ingested causes vomiting, griping, diarrhea, depressed respiration; General Treatment for Exposure: INHALATION: remove victim to fresh air, give artificial respiration and oxygen if needed; call a doctor. INGESTION: do NOT induce vomiting; call a doctor. EYES: flush with
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water for at least 15 min. SKIN: wipe off, wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): 100 ppm; Short-Term Exposure Limits: 600 ppm for 30 min.; Toxicity by Ingestion: Grade 2, LD50 = 0.5-5 g/kg; Late Toxicity: Kidney and liver damage may follow ingestion; Vapor (Gas) Irritant Characteristics: Vapors cause a slight smarting of the eyes or respiratory system if present in high concentration. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 0.17 ppm. Fire Hazards — Flash Point (°F): 40 CC, 55 OC; Flammable Limits in Air (%): 1.277.0; Fire Extinguishing Agents: Carbon dioxide or dry chemical for small fire; ordinary foam for large fires; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Vapors are heavier than air and may travel considerable distances to a source of ignition and flash back; Ignition Temperature (°F): 997; Electrical Hazard: Class I, Group D; Burning Rate: 5.7 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. TOLUENE 2,4-DIISOCYANATE Chemical Designations — Synonyms: Hylene T; Mondur TDS; Nacconate 100; 2,4-Tolylene diisocyanate; TDE; Chemical Formula: l-CH 3 C 6 H 3 (NCO) 2 -2,4. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless to light yellow; Odor: Sweet, fruity, pungent. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Solid; Molecular Weight: 174.16; Boiling Point at 1 atm.: 482, 250, 523; Freezing Point: 68-72, 2022, 293-295; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.22 at 25°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Not pertinent; Heat of Combustion: (est.) -10,300, -5720, -239; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Organic vapor canister; goggles and face shield; rubber gloves; boots and apron; Symptoms Following Exposure: Irritates eyes and skin. Potent sensitizer and lung irritant if inhaled. May produce bronchospasm (asthma), pneumonitis, bronchitis, and pulmonary edema. Nocturnal cough and shortness of breath are common. Repeated low-level exposure may produce chronic lung disease. Oral toxicity is low; General Treatment for Exposure: INHALATION: remove victim to fresh air; administer artificial respiration and oxygen if needed; call a doctor. EYES: flush with water; wipe off with rubbing alcohol; wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): 0.02 ppm; Short-Term Exposure Limits: 0.02 ppm for 5 min.; Toxicity by Ingestion: Grade 2, LD50 = 0.5 to 5 g/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapor is moderately irritating such that personnel will not usually tolerate moderate or high vapor concentration; Liquid or Solid
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Irritant Characteristics: Fairly severe skin irritant; may cause pain and seconddegree burns after a few minutes' contact; Odor Threshold: 0.4-2.14 ppm. Fire Hazards — Flash Point (°F): 270 OC; Flammable Limits in Air (%): 0.9-9.5; Fire Extinguishing Agents: Water, foam, dry chemical, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water or foam may cause frothing; Special Hazards of Combustion Products: Irritating vapors are generated upon heating; Behavior in Fire: Not pertinent; Ignition Temperature (°F): >300; Electrical Hazard: Not pertinent; Burning Rate: No data. Chemical Reactivity — Reactivity with Water: A non violent reaction occurs forming carbon dioxide gas and an organic base; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Slow polymerization occurs at temperatures above 113°F. The reaction is not hazardous; Inhibitor of Polymerization: Not pertinent. O-TOLUIDINE Chemical Designations — Synonyms: 2-Amino-l-methyl-benzene; 2Aminotoluene; 2-Methylaniline; o-Methylaniline; Chemical Formula: 1,2CH3C6H4NH. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Clear to light yellow; turns yellow, brown or deep red on exposure to air and light; Odor: Aromatic, aniline-like. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 107.2; Boiling Point at 1 atm.: 392, 200, 473; Freezing Point: -11, -24, 249; Critical Temperature: 790, 421, 694; Critical Pressure: 544, 37.0, 3.75; Specific Gravity: 0.998 at 20"C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: 179.1, 99.5, 4.16; Heat of Combustion: -16,180, -8,990, -376; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Chemical safety goggles; face shield; Bu. Mines approved respirator; leather or rubber safety shoes; butyl rubber gloves; Symptoms Following Exposure: Absorption of toxic quantities by any route causes cyanosis (blue discoloration of lips, nails, skin); nausea, vomiting, and coma may follow. Repeated inhalation of low concentration may cause pallor, low-grade secondary anemia, and loss of appetite. Contact with eyes causes irritation; General Treatment for Exposure: Get medical attention following all exposured to this compound. INHALATION: move to fresh air. INGESTION: if victim is conscious, promptly induce vomiting by giving lukewarm soapy water or mustard and water. EYES: flush with copious amounts of water for at least 15 min., holding lids apart. SKIN: remove all contaminated clothing; wash affected areas immediately and thoroughly with plenty of warm water and soap; Toxicity by Inhalation (Threshold Limit Value): 5 ppm; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2, oral LD50 = 900 mg/kg (rat); Late Toxicity: Causes tumors in urinary bladder of rats; Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 167 OC, 85 CC; Flammable Limits in Air (%): No data; Fire Extinguishing Agents: Foam, dry chemical, or carbon dioxide; Fire
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Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Toxic oxides of nitrogen and flammable vapors may form; Behavior in Fire: No data; Ignition Temperature (°F): 900; Electrical Hazard: No data; Burning Rate: 3.6 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. TRICHLOROETHYLENE Chemical Designations - Synonyms: Algylen; Clorilen; Gemalgene; Threthylene; Trethylene; Tri; Trihloran; Trihloroethelene; TriClene; Trielene; Triline; Trimar; Chemical Formula: CHC1 = CC12. Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Chloroform-like; ethereal. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 131.39; Boiling Point at 1 atm.: 189, 87, 360; Freezing Point: -123.5, -86.4, 186.8; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: Not pertinent; Vapor (Gas) Specific Gravity: 4.5; Ratio of Specific Heats of Vapor (Gas): 1.116; Latent Heat of Vaporization: 103, 57.2, 2.40; Heat of Combustion: Not pertinent; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Organic vapor-acid gas canister; self-contained breathing apparatus for emergencies; neoprene or vinyl gloves; chemical safety goggles; face-shield; neoprene safety shoes; neoprene suit or apron for splash protection; Symptoms Following Exposure: INHALATION: symptoms range from irritation of the nose and throat to nausea, an attitude of irresponsibility, blurred vision, and finally disturbance of central nervous system resulting in cardiac failure. Chronic exposure may cause organic injury. INGESTION: symptoms similar to inhalation. SKIN: defatting action can cause dermatitis. EYES: slightly irritating sensation and lachrymation; General Treatment for Exposure: Do NOT administer adrenaline or epinephrine; get medical attention for all cases of overexposure. INHALATION: remove victim to fresh air; if necessary, apply artificial respiration and/or administer oxygen. INGESTION: have victim drink water and induce vomiting; repeat three times; then give 1 tablespoon Epsom salts in water. EYES: flush thoroughly with water. SKIN: wash thoroughly with soap and warm water; Toxicity by Inhalation (Threshold Limit Value): 100 ppm; Short-Term Inhalation Limits: 200 ppm for 30 min.; Toxicity by Ingestion: Grade 3, LD50 = 50 to 500 mg/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapor cause slight smarting of the eyes or respiratory system if present in high concentration. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 50 ppm. Fire Hazards — Flash Point (°F): 90 CC; practically nonflammable; Flammable Limits in Air (%): 8.0-10.5; Fire Extinguishing Agents: Water fog; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Toxic and irritating vapors
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are produced in fire situations; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 770; Electrical Hazard: Not pertinent; Burning Rate: Not pertinent. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. TRICHLOROFLUOROMETHANE Chemical Designations — Synonyms: Arcton 9; Freon 11; Isceon 11; Eskimon 11; Frigen 11; Isotron 11;F-11; Genetron 11; Ucon 11; Chemical Formula: CFC13. Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Odorless; weak chlorinated solvent. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 137.4; Boiling Point at 1 atm.: 4.8, 23.8, 297.0; Freezing Point: -168, -111, 162; Critical Temperature: 388, 198, 471; Critical Pressure: 639.4, 43.5, 4.41; Specific Gravity: 1.49 at 20°C (liquid); Vapor (Gas) Specific Gravity: 4.7; Ratio of Specific Heats of Vapor (Gas):(est.) 1.128; Latent Heat of Vaporization: 78.3, 43.5, 1.82; Heat of Combustion: Not pertinent; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Air line respirator; rubber gloves; monogoggles; Symptoms Following Exposure: Breathing concentration approaching 10% in air will cause dizziness and drowsiness. Contact with tissues may cause frostbite; General Treatment for Exposure: INHALATION: remove victim to not-contaminated area and apply artificial respiration if breathing has stopped; call a physician immediately; oxygen inhalation may be utilized. SKIN: if frostbite has occurred, flush areas with warm water; Toxicity by Inhalation (Threshold Limit Value): 1000 ppm; Short-Term Inhalation Limits: Data not available; Toxicity by Ingestion: Data not available; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Non-irritating; Liquid or Solid Irritant Characteristics: May cause frostbite; Odor Threshold: Data not available. Fire Hazards — Flash Point: Not flammable; Flammable Limits in Air (%): Not flammable; Fire Extinguishing Agents: Not pertinent; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Produces toxic and irritating vapors when heated to its decomposition temperature; Behavior in Fire: Not pertinent; Ignition Temperature: Not flammable; Electrical Hazard: Not pertinent; Burning Rate: Not pertinent. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. TRICHLOROSILANE Chemical Designations — Synonyms: Silicochloroform, Trichloromonosilane; Chemical Formula: SiHCl3. Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Sharp, choking, like hydrochloric acid. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: liquid;
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Molecular Weight: 135.5; Boiling Point at 1 atm.: 90, 32, 305; Freezing Point: -197, -127, 146; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.344 at 20°C (liquid); Vapor (Gas) Specific Gravity: 4.9; Ratio of Specific Heats of Vapor (Gas): Data not available; Latent Heat of Vaporization: 85, 47, 2.0; Heat of Combustion: -6,500, -3,600, -150; Heat of Decomposition: Data not available. Health Hazards Information — Recommended Personal Protective Equipment: Acid-vapor-type respiratory protection; rubber gloves; chemical worker's goggles; other protective equipment as necessary to protect skin and eyes; Symptoms Following Exposure: Inhalation causes severe irritation of respiratory system. Liquid causes severe burns of eyes and skin. Ingestion causes severe burns of mouth and stomach; General Treatment for Exposure: INHALATION: remove victim from exposure; if breathing is difficult or stopped, give artificial respiration; call physician. EYES or SKIN: flush with plenty of water immediately for at least 15 min., and get medical attention. INGESTION: do NOT induce vomiting; give large amount of water; get medical attention; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Inhalation Limits: Data not available; Toxicity by Ingestion: Grade 2, oral LD50 = 1,000 mg/kg (rat); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause severe irritation of eyes and throat and can cause eye and lung injure. They cannot be tolerated even at low concentrations; Liquid or Solid Irritant Characteristics: Severe skin irritation. Causes second- and third-degree burns on short contact and is very injurious to the eyes; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): -18 OC, > -58 CC; Flammable Limits in Air (%): 1.2-90.5; Fire Extinguishing Agents: Dry chemical, carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water, foam; Special Hazards of Combustion Products: Toxic hydrogen chloride and phosgene gases may form; Behavior in Fire: Difficult to extinguish; reignition may occur. Also, vapor is heavier than air and can travel to a source of ignition and flash back; Ignition Temperature (°F): 220; Electrical Hazard: No data; Burning Rate: No data. Chemical Reactivity — Reactivity with Water: Reacts violently to form hydrogen chloride fumes (hydrochloric acid); Reactivity with Common Materials: Reacts with surface moisture to form hydrochloric acid which corrodes metals and generates flammable hydrogen gas; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Flush with water and rinse with sodium bicarbonate or lime solution; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. TRIDECANOL Chemical Designations — Synonyms: Isotridecanol; Isotridecyl alcohol; 1tridecanol; Chemical Formula: C,2H25CH2OH. Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Mild alcoholic. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: liquid; Molecular Weight: 200.37; Boiling Point at 1 atm.: 525, 274, 547; Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.846 at 20°C (liquid); Vapor (Gas) Specific Gravity: Not
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pertinent; Ratio of Specific Heats of Vapor (Gas): 1.027; Latent Heat of Vaporization: 120, 64, 2.7; Heat of Combustion:: -12,200, -6,790, -284; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Synthetic rubber gloves; chemical goggles. Symptoms Following Exposure: Inhalator hazard slight. Skin contact results in moderate irritation. Liquid contact with eyes causes severe irritation and possible eye damage. General Treatment for Exposure: EYES: promptly flush with clean water for at least 15 min. and see a physician. SKIN: wash exposed area with soap and water; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Inhalation Limits: Data not available; Toxicity by Ingestion: Data not available; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors are nonirritating to the eye and throat; Liquid or Solid Irritant Characteristics: No appreciable hazard. Practically harmless to the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 250 OC; Flammable Limits in Air (%): No data; Fire Extinguishing Agents: Alcohol, dry chemical, water fog; Fire Extinguishing Agents Not To Be Used: Water or foam may cause frothing; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature: No data; Electrical Hazard: Not pertinent; Burning Rate: No data. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. 1-TRIDECENE Chemical Designations — Synonyms: Undecylethylene; Chemical Formula: CH3(CH2)10CH = CH2. Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Mild, pleasant. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: liquid; Molecular Weight: 182.35; Boiling Point at 1 atm.: 451, 233, 506; Freezing Point: -11, -24, 249; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.765 at 20 °C (liquid); Vapor (Gas) Specific Gravity: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.029; Latent Heat of Vaporization: 110, 59, 2.5; Heat of Combustion:: -19,048, -10,582, -443.05; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles of face shield. Symptoms Following Exposure: Liquid may irritate eyes. General Treatment for Exposure: EYES: flush with water for 15 min.; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Inhalation Limits: Not pertinent; Toxicity by Ingestion: Data not available; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Non-volatile; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Not pertinent. Fire Hazards — Flash Point (°F): 175 (est.); Flammable Limits in Air (%): No data; Fire Extinguishing Agents: Dry chemical, foam, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent;
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Ignition Temperature: No data; Electrical Hazard: Not pertinent; Burning Rate: No data. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. TRIETHANOLAMINE Chemical Designations — Synonyms: 2,2'2"-Nitrilotriethanol; Triethilolamine; Trihydroxytriethylamine; Tris(hydroxyethy)amine; Chemical Formula: (HOCH2CH2)3N. Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Mild ammoniacal. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: liquid; Molecular Weight: 149.19; Boiling Point at 1 atm.: decomposes; Freezing Point: 70.9, 21.6, 294.8; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.13 at 20°C (liquid); Vapor (Gas) Specific Gravity: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: 176, 97.8, 4.10; Heat of Combustion:: -11,050, -6140, -257; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles of face shield; rubber gloves and boots; Symptoms Following Exposure: Liquid may irritate eyes and skin; General Treatment for Exposure: EYES: flush with water for 15 min.; call a doctor. SKIN: wipe off, wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): Not pertinent; Short-Term Inhalation Limits: Not pertinent; Toxicity by Ingestion: Data not available; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Non-volatile; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Not pertinent. Fire Hazards — Flash Point (°F): 355 CC, 375 OC; Flammable Limits in Air (%): No data; Fire Extinguishing Agents: Alcohol foam, dry chemical, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water or foam may cause frothing; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature: No data; Electrical Hazard: Not pertinent; Burning Rate: No data. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Dilute with water; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. TRIETHYLBENZENE Chemical Designations — Synonyms: 1,3,5-Triethylbenzene; symTriethylbenzene; Chemical Formula: C6H3(C2H5)3-1,3,5. Observable Characteristics — Physical State (as shipped): Liquid; Color: Colorless; Odor: Weak aromatic. Physical and Chemical Properties — Physical State at 15 °C and 1 atm.: liquid; Molecular Weight: 162.27; Boiling Point at 1 atm.: 421, 216, 489; Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.861 at 20°C (liquid); Vapor (Gas) Specific Gravity: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.039; Latent Heat of Vaporization: 120, 65, 2.7; Heat of Combustion: Data not available;
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Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles or face shield; rubber gloves; Symptoms Following Exposure: Eye irritation by vapors or liquid. Central nervous system depression. Prolonged skin contact with liquid can cause dermatitis; General Treatment for Exposure: EYES: flush with water for at least 15 min.; call a doctor. SKIN: wipe off, wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Inhalation Limits: Data not available; Toxicity by Ingestion: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause a slight smarting of the eyes or respiratory system if present in high concentration. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 181 OC; Flammable Limits in Air (%): No data; Fire Extinguishing Agents: Dry chemical, foam, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature: No data; Electrical Hazard: Not pertinent; Burning Rate: Not pertinent. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. TRIETHYLENE GLYCOL Chemical Designations — Synonyms: Di-beta-hydroxyethoxy-ethan; 2,2'Ethylenedioxydiethanol; Ethylene glycol dihydroxydiethyl ether; TEG; Triglycol; Chemical Formula: HO(CH2CH2O)3CH. Observable Characteristics — Physical State (as shipped):Liquid; Color: Colorless; Odor: Very mild, sweet. Physical and Chemical Properties — Physical State at 15°C and 1 aim.: liquid; Molecular Weight: 150.17; Boiling Point at 1 atm.: 550, 288, 561; Freezing Point: 24.3, -4.3, 268.9; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.125 at 20°C (liquid); Vapor (Gas) Specific Gravity: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.039; Latent Heat of Vaporization: 180, 99, 4.1; Heat of Combustion:: -10,190, -5,660, -237.0; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: goggles; plastic gloves; Symptoms Following Exposure: Vapors and liquid are unlikely to cause harm; General Treatment for Exposure: flush eyes and skin with water; Toxicity by Inhalation (Threshold Limit Value): Not pertinent; Short-Term Inhalation Limits: Not pertinent; Toxicity by Ingestion: Grade 1, LD50 = 5 to 15 g/kg (guinea pig); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors are non-irritating to the eyes and skin; Liquid or Solid Irritant Characteristics: No appreciable hazard. Practically harmless to the skin; Odor Threshold: Not pertinent. Fire Hazards — Flash Point (°F): 350 CC, 330 OC; Flammable Limits in Air (%): 0.9-9.2; Fire Extinguishing Agents: Alcohol foam, dry chemical, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water or foam may cause frothing; Special
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Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature ("F): 700; Electrical Hazard: Not pertinent; Burning Rate: 1.7 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. TRIPROPYLENE GLYCOL Chemical Designations — Synonyms: No common synonyms; Chemical Formula: HO(C3H6)2C3HAOH. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Characteristic. Physical and Chemical Properties — Physical State at 15"C and 1 atm.: Liquid; Molecular Weight: 192.26; Boiling Point at 1 atm.: Not pertinent (decomposes) 523, 273, 546; Freezing Point: (sets to glass) -49, -45, 228; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.022 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Data not available; Heat of Combustion: (est.) -13,700, -7,661, -318; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Plastic gloves; safety glasses of face shield; Symptoms Following Exposure: Nonirritation; no symptoms observed by any exposure route; General Treatment for Exposure: INGESTION: if large amounts are swallowed, induce vomiting; treat symptomatically. EYES: or SKIN: flush with water, get medical attention if ill effects develop; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2, oral LD50 = 3,000 mg/kg (rat); Late Toxicity: Vapors are nonirritating to eyes and throat; Vapor (Gas) Irritant Characteristics: No appreciable hazard. Practically harmless to the skin; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Odorless. Fire Hazards — Flash Point ("F): 285 OC; Flammable Limits in Air (%): 0.8-5.0; Fire Extinguishing Agents: Alcohol foam, dry chemical, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Acrid fumes of acids and aldehydes may form in fires; Behavior in Fire: No data; Ignition Temperature: No data; Electrical Hazard: No data; Burning Rate: No data. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: May attack some forms of plastics and elastomers; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. TURPENTINE Chemical Designations — Synonyms: D.D. turpentine, Gum turpentine, Spirits of turpentine, Sulfate turpentine, Turps, Wood turpentine; Chemical Formula: C 10 H, 6 . Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Aromatic, rather unpleasant, penetrating. Physical and Chemical Properties — Physical State at 15°C and 1 atm: Liquid; Molecular
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Weight: Not pertinent; Boiling Point at 1 atm.: 302-320, 150-160, 423-433; Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.86 at 15°C; Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Not pertinent; Heat of Combustion: Data not available; Heat of Decomposition: Data not available. Health Hazards Information — Recommended Personal Protective Equipment: Organic canister or air-supplied mask; goggles or face shield; rubber gloves; Symptoms Following Exposure: Vapors cause headache, confusion, respiratory distress. Liquid irritates skin. If ingested, can irritate the entire digestive system and may injure kidneys. If liquid is taken into lungs, causes several pneumonitis; General Treatment for Exposure: INHALATION: remove victim to fresh air; call a doctor; administer artificial respiration and oxygen if required. INGESTION: give water and induce vomiting; call a doctor. EYES: flush with water for at least 15 min. SKIN: wipe off, wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): 100 ppm; Short-Term Exposure Limits: 200 ppm for 30 min.; Toxicity by Ingestion: Grade 2, LD50 = 0.5-5 g/kg; Late Toxicity: None; Vapor (Gas) Irritant Characteristics: Vapor causes a slight smarting of the eyes or respiratory system if present in high concentration. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may be cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 95 CC; Flammable Limits in Air (%): 0.8 (LEL); Fire Extinguishing Agents: Foam, dry chemical, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Forms heavy black smoke and soot; Ignition Temperature (°F): 488; Electrical Hazard: Not pertinent; Burning Rate: 2.4 mm/min. Chemical Reactivity — Reactivity with Water No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. UNDECANOL Chemical Designations — Synonyms: Hendecanoic alcohol; 1-Hendecanol; nHendecylenic alcohol; 1-Undecanol; Undecyl alcohol; Undecylic alcohol; Chemical Formula: CH3(CH2)9CH2OH. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Faint alcohol. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 172.30; Boiling Point at 1 atm.: 473, 245, 518; Freezing Point: 60.6, 15.9, 289.1; Critical Temperature: 739, 393, 666; Critical Pressure: 308, 21, 2.1; Specific Gravity: 0.835 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.032; Latent Heat of Vaporization: Not pertinent; Heat of Combustion: (est.) -18,000, -10,000, -419; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles and face shield; Symptoms Following Exposure: Liquid can irritate eyes; General Treatment for Exposure: Wash eyes
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with water for at least 15 min.; Toxicity by Inhalation (Threshold Limit Value): Not pertinent; Short-Term Exposure Limits: Not pertinent; Toxicity by Ingestion: Grade 2, LD50 = 0.5-5 g/kg; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: None; Liquid or Solid Irritant Characteristics: No appreciable hazard. Practically harmless to the skin; Odor Threshold: Not pertinent. Fire Hazards — Flash Point (°F): 200 OC; Flammable Limits in Air (%): No data; Fire Extinguishing Agents: Foam, carbon dioxide, or dry chemical; Fire Extinguishing Agents Not To Be Used: Water or foam may cause frothing; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent; Ignition Temperature: No data; Electrical Hazard: Not pertinent; Burning Rate: No data. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. 1-UNDECENE Chemical Designations — Synonyms: n-Nonylethylene; Chemical Formula: CH3(CH2)gCH = CH2. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Mild, pleasant. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 154.2; Boiling Point at 1 atm.: 378.9, 192.7, 465.9; Freezing Point: -56, 49, 224; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.750 at 20°C (solid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): 1.035; Latent Heat of Vaporization: 154, 85.8, 3.59; Heat of Combustion: -19,084, -10,602, -443.89; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles or face shield; rubber gloves; Symptoms Following Exposure: Aspiration hazard if ingested. Slight skin and eye irritation. No inhalation hazard expected; General Treatment for Exposure: INHALATION: remove victim to fresh air. INGESTION: do NOT lavage or induce vomiting; give vegetable oil and demulcents; call a doctor. EYES: flush with water for 15 min. SKIN: wipe off, wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Data not available; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Slight smarting of eyes and respiratory system at high concentrations. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 160 OC; Flammable Limits in Air (%): No data; Fire Extinguishing Agents: Foam, dry chemical, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Not pertinent Ignition Temperature: No data; Electrical Hazard: Not pertinent; Burning Rate: 4.8 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents
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for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. N-UNDECYLBENZENE Chemical Designations — Synonyms: 1-Phenylundecane; Chemical Formula: C6H5(CH2)10CH3. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Mild. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 232.4; Boiling Point at 1 atm.: 601, 316, 589; Freezing Point: 23, -5, 268; Critical Temperature: 918.1, 492.3, 765.5; Critical Pressure: 234, 15.9, 1.61; Specific Gravity: 0.855 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: 101.27, 56.26, 2.354; Heat of Combustion: -19,490, -10,830, -453.1; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Goggles or face shield; rubber gloves; Symptoms Following Exposure: Ingestion may cause intestinal disturbances. Contact with eyes causes mild irritation; General Treatment for Exposure: INGESTION: induce vomiting if large amount has been swallowed. EYES: flush with water. SKIN: remove spills on skin or clothing by washing with soap and water; Toxicity by Inhalation (Threshold Limit Value): Data not available; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Data not available; Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant Characteristics: Data not available; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 285 CC; Flammable Limits in Air (%): No data; Fire Extinguishing Agents: Foam, dry chemical, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: No data; Behavior in Fire: No data; Ignition Temperature: No data; Electrical Hazard: No data; Burning Rate: No data. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: May attack some forms of plastics; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Stable; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. VINYLTOLUENE Chemical Designations — Synonyms: Methylystyrene; Chemical Formula: CH3C6H4CH = CH2. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Disagreeable. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 118.18; Boiling Point at 1 atm.: 333.9, 167.7, 440.9; Freezing Point: -106.6, -77.0, 196; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 0.897 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): (est.) 1.060; Latent Heat of Vaporization: 150, 83.5, 3.50; Heat of Combustion: -17.710, -9840, -412.0; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Air-supplied mask, goggles or lace shield, plastic gloves; Symptoms
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Following Exposure: Vapors irritate eyes and nose, high levels cause dizziness drunkenness, and anesthesia. Liquid irritation eyes and may irritate skin; General Treatment for Exposure: INHALATION: remove person to fresh air, give artificial respiration and oxygen if needed; call a doctor. INGESTION: do NOT induce vomiting; no known antidote. Call a doctor. EYES: flush with water for at least 15 min. SKIN: wipe off, wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): 100 ppm; Short-Term Exposure Limits: 400 ppm for 5 min.; Toxicity by Ingestion: Grade 2, LD50 = 0.5 to 5 g/kg (rat); Late Toxicity: Data not available; Vapor (Gas) Irritant Characteristics: Vapors cause moderate irritation such that personnel will find high concentrations unpleasant. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 50 ppm. Fire Hazards — Flash Point (°F): 137 OC, 125 CC; Flammable Limits in Air (%): 0.8-11; Fire Extinguishing Agents: Water fog, foam, carbon dioxide, or dry chemical; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Containers may explode or rupture in fires due to polymerization; Ignition Temperature (°F): 914; Electrical Hazard: Not pertinent; Burning Rate: 6.0 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Slow at ordinary temperatures but when hot may rupture container. Also polymerized by metal salts such as those of iron or aluminum; Inhibitor of Polymerization: Tertiary Butylcatechol (typically 10 to 50 ppm). M-XYLENE Chemical Designations — Synonyms: 1,3-Dimethilbenzene, Xylol; Chemical Formula: m-C6H4(CH3)2. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Like benzene; characteristic aromatic. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 106,16; Boiling Point at 1 atm.: 269.4, 131.9, 405.1; Freezing Point: -54.2, -47.9, 225.3; Critical Temperature: 680.5, 343.8, 617.0; Critical Pressure: 34.95, 513.8, 3.540; Specific Gravity: 0.864 at 20°C; Vapor (Gas) Density: 36.4 dynes/cm = 0.0364 N/m at 30"C; Ratio of Specific Heats of Vapor (Gas): 1.071; Latent Heat of Vaporization: 147, 81.9, 3.43; Heat of Combustion: -17,554, -9752, -408.31; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Approved canister or Air-supplied mask; goggles and face shield; plastic gloves and boots; Symptoms Following Exposure: Vapors cause headache and dizziness. Liquid irritates eyes and skin. If taken into lungs, causes severe coughing, distress, and coma; can be fatal. Kidney and liver damage can occur; General Treatment for Exposure: INHALATION: remove victim to fresh air; administer artificial respiration and oxygen if required; call a doctor. INGESTION: do NOT induce vomiting; call a doctor. EYES: flush with water for at least 15 min. SKIN: wipe off, wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): 100
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ppm; Short-Term Exposure Limits: 300 ppm for 30 min.; Toxicity by Ingestion: Grade 3, LD50 = 50 to 500 g/kg; Late Toxicity: Kidney and liver damage; Vapor (Gas) Irritant Characteristics: Vapor causes a slight smarting of the eyes or respiratory system if present in high concentration; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening of the skin; Odor Threshold: 0.05 ppm. Fire Hazards — Flash Point (°F): 84 CC; Flammable Limits in Air (%): 1.1-6.4; Fire Extinguishing Agents: Foam, dry chemical, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Vapor is heavier than air and may travel a considerable distance to a source of ignition and flash back; Ignition Temperature (°F): 986; Electrical Hazard: Class I, Group D; Burning Rate: 5.8 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. O-XYLENE Chemical Designations — Synonyms: 1,2-Dimethilbenzene; Chemical Formula: oC6H4(CH3)2. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Benzene-like; characteristic aromatic. Physical and Chemical Properties — Physical State at 15 "C and 1 atm.: Liquid; Molecular Weight: 106,16; Boiling Point at 1 atm.: 291.9, 144.4, 417.6; Freezing Point: -13.3, -25.2, 248.0; Critical Temperature: 674.8, 357.1, 630.3; Critical Pressure: 36.84, 541.5, 3.732; Specific Gravity: 0.880 at 20°C; Vapor (Gas) Density: 30.53 dynes/cm = 0.03053 N/m at 15.5 °C; Ratio of Specific Heats of Vapor (Gas): 1.068; Latent Heat of Vaporization: 149, 82.9, 3.47; Heat of Combustion: -17,558, -9754, -408.41; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Approved canister or air-supplied mask; goggles and face shield; plastic gloves and boots; Symptoms Following Exposure: Vapors cause headache and dizziness. Liquid irritates eyes and skin. If taken into lungs, causes severe coughing, distress, and coma; can be fatal. Kidney and liver damage can occur; General Treatment for Exposure: INHALATION: remove victim to fresh air; administer artificial respiration and oxygen if required; call a doctor. INGESTION: do NOT induce vomiting; call a doctor. EYES: flush with water for at least 15 min. SKIN: wipe off, wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): 100 ppm; ShortTerm Exposure Limits: 300 ppm for 30 min.; Toxicity by Ingestion: Grade 3, LD50 = 50 to 500 mg/kg; Late Toxicity: Kidney and liver damage; Vapor (Gas) Irritant Characteristics: Vapor causes a slight smarting of the eyes or respiratory system if present in high concentration. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may be cause smarting and reddening of the skin; Odor Threshold: 0.05 ppm. Fire Hazards — Flash Point (°F): 63 CC; 75 OC; Flammable Limits in Air (%): 1.17.0; Fire Extinguishing Agents: Foam, dry chemical, or carbon dioxide; Fire
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Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Vapor is heavier than air and may travel considerable distance to a source of ignition and flash back; Ignition Temperature (°F): 869; Electrical Hazard: Class I, Group D; Burning Rate: 5.8 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent. P-XYLENE Chemical Designations — Synonyms: 1,4-Dimethilbenzene; Chemical Formula: pC6H4(CH3)2. Observable Characteristics — Physical State (as normally shipped): Liquid; Color: Colorless; Odor: Like benzene; characteristic aromatic. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Liquid; Molecular Weight: 106,16; Boiling Point at 1 atm.: 280.9, 138.3, 411.5; Freezing Point: 55.9, 13.3, 286.5; Critical Temperature: 649.4, 343.0, 616.2; Critical Pressure: 34.65, 509.4, 3.510; Specific Gravity: 0.861 at 20°C; Vapor (Gas) Density: 28.3 dynes/cm = 0.0283 N/m at 20°C; Ratio of Specific Heats of Vapor (Gas): 1.071; Latent Heat of Vaporization: 150, 81, 3.4; Heat of Combustion: -17,559, -9754.7, -408.41; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Approved canister or air-supplied mask; goggles and face shield; plastic gloves and boots; Symptoms Following Exposure: Vapors cause headache and dizziness. Liquid irritates eyes and skin. If taken into lungs, causes severe coughing, distress, and coma; can be fatal. Kidney and liver damage can occur; General Treatment for Exposure: INHALATION: remove victim to fresh air; administer artificial respiration and oxygen if required; call a doctor. INGESTION: do NOT induce vomiting; call a doctor. EYES: flush with water for at least 15 min. SKIN: wipe off, wash with soap and water; Toxicity by Inhalation (Threshold Limit Value): 100 ppm; Short-Term Exposure Limits: 300 ppm for 30 min.; Toxicity by Ingestion: Grade 3, LD50 = 50-500 mg/kg; Late Toxicity: Kidney and liver damage; Vapor (Gas) Irritant Characteristics: Vapor causes a slight smarting of the eyes or respiratory system if present in high concentration. The effect is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may be cause smarting and reddening of the skin; Odor Threshold: 0.05 ppm. Fire Hazards — Flash Point (°F): 81 CC; Flammable Limits in Air (%): 1.1-6.6; Fire Extinguishing Agents: Foam, dry chemical, or carbon dioxide; Fire Extinguishing Agents Not To Be Used: Water may be ineffective; Special Hazards of Combustion Products: Not pertinent; Behavior in Fire: Vapor is heavier than air and may travel considerable distance to a source of ignition and flash back; Ignition Temperature (°F): 870; Electrical Hazard: Class I, Group D; Burning Rate: 5.8 mm/min. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
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XYLENOL Chemical Designations — Synonyms: Cresylic acid; 2,6-Dimetuylphenol; 2Hydroxy-m-xylene; 2,6-Xylenol; vic-m-Xylenol; Chemical Formula: 2,6(CH3)2C6H3OH. Observable Characteristics — Physical State (as normally shipped): Solid or liquid; Color: Light yellow-brown; Odor: Sweet tarry. Physical and Chemical Properties — Physical State at 15°C and 1 atm.: Solid or liquid; Molecular Weight: 122.2; Boiling Point at 1 atm.: 413, 212, 485; Freezing Point: -40 to +106, -40 to +45, 233 to 318; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.01 at 20°C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: 212.74, 118.19, 4.9451 at 25°C; Heat of Combustion: -15,310, -8,500, -356 at 25°C; Heat of Decomposition: Not pertinent. Health Hazards Information — Recommended Personal Protective Equipment: Organic canister mask; goggles and face shield; rubber gloves; other protective clothing to prevent contact with skin; Symptoms Following Exposure: Vapor irritates eyes, nose, and throat and readily absorbed through mucous membranes and lungs; producing general toxic symptoms (weakness, dizziness, headache, difficult breathing, twitching). Contact with skin causes temporary prickling and intense burning, then local anesthesia. Affected areas initially show white discoloration, wrinkling, and softening, then become red, then brown or black (signs of gangrene). Extensive burns may permit absorption of chemical to produce toxic symptoms described above. Ingestion causes irritation of mouth and stomach, nausea, abdominal pain, weakness, dizziness, headache, difficult breathing, and twitching; General Treatment for Exposure: Get medical attention at once following exposure to this compound. INHALATION: remove patient immediately to fresh air; irritation of nose or throat may be somewhat relieved by spraying or gargling with water-until all odor is gone; 100% oxygen inhalation is indicated for cyanosis or respiratory distress; keep patient warm, but not hot. EYES: flood with running water for 15 min.; if physician is not immediately available, continue irritation for another 15 min.; do not use oils or oily ointments unless ordered by physician. SKIN: wash affected areas with large quantities of water or soapy water until all odor is gone; then wash with alcohol or 20% glycerin solution and more water; keep patient warm, but not hot; cover chemical burns continuously with compresses wet with saturated solution of sodium thiosulphate; apply no salves or ointments for 24 hrs after injury. INGESTION: give large quantities of liquid (salt water, weak sodium bicarbonate solution, milk, or gruel) followed by demulcent such as raw egg white or corn starch paste; if profuse vomiting does not follow immediately, give a mild emetic (such as 1 tbsp. mustard in glass of water), or tickle back of throat. Repeat procedure until vomitus is free of the odor. Some demulcent should be left in stomach after vomiting. Keep patient comfortably warm; Toxicity by Inhalation (Threshold Limit Value): 45 ppm; Short-Term Exposure Limits: Data not available; Toxicity by Ingestion: Grade 2, oral LD50= 1,070 mg/kg (mouse); Late Toxicity: Damage to heart muscle, and changes in liver, kidney in rats; Vapor (Gas) Irritant Characteristics: Data not available; Liquid or Solid Irritant
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Characteristics: Data not available; Odor Threshold: Data not available. Fire Hazards — Flash Point (°F): 186; Flammable Limits in Air (%): 1.4 (LEL); Fire Extinguishing Agents: Water, dry chemical, carbon dioxide, foam; Fire Extinguishing Agents Not To Be Used: Not pertinent; Special Hazards of Combustion Products: Toxic vapor of unburned material may form in fire; Behavior in Fire: Not pertinent; Ignition Temperature (°F): 1,110; Electrical Hazard: Data not available; Burning Rate: Data not available. Chemical Reactivity — Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
GLOSSARY OF RELEVANT SOLVENT TERMINOLOGY Acid: A classification of substances that liberate hydrogen ions in water, and are normally sour and corrosive, with a pH lower than 7. A compound or atom that donates protons. Acrylic: A synthetic resin used in high-performance water-based coatings. A coating in which the binder contains acrylic resins. Adhesion: The ability of dry paint to attach to and remain fixed on the surface without blistering, flaking, cracking or being removed by tape. Aerosol: A product that uses compressed gas to spray the coating from its container. Air-drying: The process of drying fully during exposure to air at normal temperatures. Alternate Term(s): Drying Alcohol: A large classification of organic compounds containing one or more hydroxyl groups attached to carbon atoms. Aliphatic: Any non-aromatic organic compound. Alkali: A classification of substances that liberate hydroxide ions in water to form caustic and corrosive solutions, which turn litmus paper blue, with a pH higher than 7, for example sodium hydroxide. A compound that reacts with or neutralizes hydrogen ions. Alkyd: Synthetic resin modified with oil. Coating that contains alkyd resins in the binder. Amide: A functional group which can act as an epoxy resin curing agent. Anti-fouling Paint: Paints formulated especially for boat decks and hulls, docks and other below-water-line surfaces and structures to prevent the growth of barnacles and other organisms. Aromatic: Any organic compound containing de-localized electrons in a ring structure, e.g. benzene, benzoic acid. Base: A classification of substances which when combined with an acid will form a salt plus water, usually producing hydroxide ions when dissolved. Basecoat (BC)/Clear: A paint system in which the color effect is given by a highly pigmented basecoat. Gloss and durability are given by a subsequent clearcoat. 321
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Binder: Solid ingredients in a coating that hold the pigment particles in suspension and attach them to the substrate. Consists of resins (e.g., oils, alkyd, latex). The nature and amount of binder determine many of the paint's performance properties, e.g. washability, toughness, adhesion, color retention, etc. Blistering: Formation of dome-shaped projections in paints or varnish films resulting from local loss of adhesion and lifting of the film from the underlying surface. Body: The thickness or viscosity of a fluid. Boiled Oil: Linseed (sometimes soya) oil that was formerly heated for faster drying. Today, chemical agents are added to speed up the drying process. Bond: The form of linkage between the individual atoms in a a molecule. Breakdown Products: Compounds resulting from transformation of an organic substance through chemical, photochemical, and/or biochemical reactions. Burning: The rapid oxidization of a substance in a manner that releases thermal energy. Butadiene: A gas which is chemically combined with styrene to create a resin used in latex binders, styrene-butadiene. Calorific Value: The amount of heat or energy generated by a specified quantity of a fuel source. Specific energy is the correct way of referring to the heat available from a fuel, but many people still refer to calorific value. There are empirical equations which estimate the specific energy. One expression given below is for net specific energy. The gross specific energy is applicable to a boiler. Historically the gross specific energy was referred to as the higher calorific value and the net specific energy as the lower calorific value. Q N = (46.704 - 8.802p 2 xl0 6 + 3.67pxlQ- 3 ) x {1 - 0.01(x + y + s)} + 0.01(9.420s - 2) where: p = density at 15°C, in kg/m 3 x = water content ,expressed as a percentage by mass y = ash content, expressed as a percentage by mass s = sulphur content, expressed as a percentage by mass Carbon: A common non-metallic element, occurring naturally as diamond, charcoal and graphite. One of the most important elements for the development of life and the storage of energy.
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323
Carbon Chain: The atomic structure of hydrocarbons in which a series of carbon atoms, saturated by hydrogen atoms, form a chain. Volatile oils have shorter chains. Fats have longer chain lengths, and waxes have extremely long chains. Carbon Cycle: The continuous process of combining and releasing carbon and oxygen thereby storing and emitting heat and energy. Catabolism + anabolism = metabolism. The diagram below illustrates the cyclical process. \ Solar Energy Photosynthesis 6CO2 + 6H2O
'*••... ^—* C6H12O6 + 6O? Chorophyll Hexose Sugar
Catabolic Reactions 6H2O + 6CO2 ^ -^r— 6O2 + C6H12O6 Respiration
^'
Energy needed for anabolic reactions
Carboxyl Carboxylic: The uni-valent acid radical (-COOH) present in most organic acids, thus making them biodegradable. Catalyst: A substance which without itself undergoing any permanent chemical change facilitates or enables a reaction between other substances. Chalking: Formation of a powder on the surface of a paint film caused by disintegration of the binder during weathering. Can be affected by the choice of pigment or binder. CHP: Combined Heat and Power. A phrase used to suggest greater efficiency obtained when the waste heat from generating electricity can be used locally to provide low temperature heat for processing or domestic heating. Chroma: A measurement of color. The degree of saturation of a hue. A color at its full intensity has maximum chroma. Clear Coating: A transparent protective and/or decorative film; generally the final coat of sealer applied to automotive finishes. Coalescent Aid: The small amount of solvent contained in latex coatings. Not a true solvent since it does not actually dissolve the latex resins, the coalescent aid helps the latex resins flow together, aiding in film formation.
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Coat: A single layer of paint on a surface. Coating: A paint, varnish, lacquer or other finish used to create a protective and/or decorative layer. Generally used to refer to paints and coatings applied in an industrial setting as part of the original equipment manufacturer's (OEM) process. Cohesion: A bonding together of a single substance to itself. Internal adhesion. Colorant: Concentrated color (dyes or pigments) that can be added to paints to make specific colors. Colorfast: Non-fading in prolonged exposure to light. Color Retention: The ability of paint to keep its original color. Major threats to color retention are exposure to ultraviolet radiation and abrasion by weather or repeated cleaning. Combustion: A reaction in which a substance produces heat or light by combination with oxygen, producing an oxide. Corrosion Inhibitive: A type of metal paint or primer that prevents rust by preventing moisture from reaching the metal. Zinc phosphate, barium inelaborate and strontium chromate (all pigments) are common ingredients in corrosioninhibitive coatings. These pigments absorb any moisture that enters the paint film. Creosote: A liquid coating made from coal tar once used as a wood preservative. It has been banned for consumer use because of potential health risks. Cure, Curing: The process whereby a liquid coating becomes a hard film. Degreasing: The removal from the substrate of contaminants which would otherwise give rise to surface defects and performance failures, e.g. poor adhesion. Diesel: Non-volatile mineral fuel with a high flash point used in compression ignition engines, as invented by Dr Rudolf Diesel in 1895, originally running on peanut oil. The name of the inventor was then transferred by the petrochemical industry to the fossil fuel that became the substitute for the organic oils for which this form of engine was originally developed. Diluent: A liquid used in coatings to reduce the consistency and make a coating flow more easily. The water in latex coatings is a diluent. A diluent may also be called a "Reducer," "Thinner," "Reducing Agent" or "Reducing Solvent." Driers: Various compounds added to coatings to speed the drying. Dry Colors: Powder-type colors to be mixed with water, alcohol or mineral spirits and resin to form a paint or stain.
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Drying Oil: An oil that when exposed to air will dry to a solid through chemical reaction with air: linseed oil, tung oil, perilla, fish oil, soybean oil. Drying: The process of change of a coating from the liquid to the solid state by evaporation of solvent, chemical reaction of the binding medium, or a combination of these processes. When drying takes place during exposure to air at normal temperatures, it is called 'air-drying'; if it can be accelerated by the application of a moderate degree of heat it is called 'Force-drying' (or Low-bake), as distinct from High-bake. Alternate Term(s): Binder, Air-drying, Force-drying, Stoving, Lowbake, High-bake Enamel: A topcoat paint which forms a film by chemical crosslinking of its component molecules during the cure. Earth Pigments: Those pigments that are obtained from the earth, including barytes, ocher, chalk and graphite. Eggshell: Gloss lying between semigloss and flat. Emulsion: A mixture of solids suspended in a liquid. Emulsion Paint: Coating in which resins are suspended in water, then flow together with the aid of an emulsifier. Example: latex paint. Enamel: Broad classification of paints that dry to a hard, usually glossy finish. Most equipment-coating enamels require baking. Enamels for walls do not. Energy of Activation: The amount of energy required as heat or pressure to disbalance an otherwise stable but energy storing compound so that it will release its potential energy. The energy that must be overcome to allow an otherwise exothermic reaction to proceed. Entropy: A measure of the unavailability of the thermal energy within a system for conversion into mechanical work All energy transformations (i.e. chemical to chemical, chemical to thermal) increase entropy. Environmental Management: Process to manage the environmental aspects of a company, plant, building, site, etc. Environmental management systems (EMS) can obtain ISO 14001 certification or, in Europe, Eco-Management and Audit Scheme (EMAS) registration. Enzyme: An organic proteinaceous compound that catalyses a specific biochemical reaction. Epoxy: Extremely tough and durable synthetic resin used in some coatings. Epoxy coatings are extremely tough, durable and highly resistant to chemicals, abrasion, moisture and alcohol.
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Ester: A classification of organic compounds occurring naturally as oils and fats, produced by replacing the hydrogen of an acid by an alkyl, aryl, radical. A compound of an organic acid bonded via an ester bond to an alcohol. Esterification: Production of ester by reacting alcohol and carboxylic acid Me-0 H +
°-N ^ c /VV\A/ —> H0/
°\ M e — 0 —XX C /VVN/V + H 9 0
Ethanol: C2H6O. An organic alcohol, also called ethyl alcohol, formed when fermenting sugars or glycerin. Extender: Ingredients added to paint to increase coverage, reduce cost, achieve durability, alter appearance, control rheology and influence other desirable properties. Less expensive than prime hiding pigments such as titanium dioxide. Examples: barium sulphate, calcium carbonate, clay, gypsum, silica, talc. May also improve coating performance. FAME: Fatty Acid Methyl Ester. Fat: A classification of natural esters of glycerol, and fatty acids existing as solids at room temperature. Film Build: Amount of thickness produced in an application. Millimeters (mils) of dry film per mils of applied wet film. Film Thickness: Depth or thickness of the dry coating in millimeters. Fire Resistance: The ability of a coating to withstand fire or to protect the substrate to which it is applied from fire damage. Fire Retardant: A coating which will (1) reduce flame spread, (2) resist ignition when exposed to high temperature or (3) insulate the substrate and delay damage to the substrate. Flat: A surface that scatters or absorbs the light falling on it so as to be substantially free from gloss or sheen (0-15 gloss on a 60-degree gloss meter). Force Dry: Baking the paint between room temperature and 150"F to speed the drying process. Fossil: Remains of organic materials, subsequently buried within the earth's crust, often carbonized as a result of intense heat and/or pressure. Free: Liberated. In the case of triglycerides, meaning the fatty acid hydrocarbon chains are detached from glycerol, and thereby become free fatty acids.
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Gloss: The luster or shininess of paints and coatings. Different types of gloss are frequently arbitrarily differentiated, such as sheen, distinctness-of-image gloss, etc. Trade practice recognizes the following gloss levels, in increasing order of gloss: flat (or matte) — practically free from sheen, even when viewed from oblique angles (usually less than 15 on 60-degree meter); eggshell — usually 20-35 on 60degree meter; semi-gloss - usually 35-70 on 60-degree meter; full-gloss - smooth and almost mirror-like surface when viewed from all angles, usually above 70 on 60-degree meter. Gloss Meter: A device for measuring the light reflectance of coatings. Different brands with the same description (such as semi-gloss or flat) may have quite different ratings on the gloss meter. Glycerin Glycerol: C3H8O3. A sweet greasy organic substance, produced as a result of hydrolyzing triglycerides. Grease: Oily or fatty matter, normally of organic origin, consisting of hydrocarbon chains. Hardener: Curing agent for epoxies or fiberglass. Hazardous Waste: Any unusable by-product derived from the repair and/or painting process that cannot be disposed of through normal waste disposal streams. These products can be potentially harmful to the environment and require special handling as well as professional disposal. Federal, State and Local laws apply and may differ in their scope. Hydrocarbon: A compound of hydrogen and carbon, often occurring as long atomic chains in which each carbon atom is attached to two hydrogen atoms forming a long chain. They store a great deal of energy. Hydrogen: The lightest gaseous element, and simplest of all atoms, occurring rarely in nature as a single atom, but common in the form of water, and in all organic compounds Indicator: A substance which changes color at a given stage in or as a result of a chemical reaction. Inert: A material that will not react chemically with other ingredients. Intumescence: A mechanism whereby fire-retardant paints protect the substrates to which they are applied. An intumescent paint puffs up when exposed to high temperatures, forming an insulating, protective layer over the substrate. Kerosene: Dodecane (Kerosene) C12H26 commonly used mineral fuel oil used as aviation fuel and central heating consisting of many hydrocarbons containing molecules with about 10 to 16 carbon atoms.
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Lacquer: A fast-drying usually clear coating that is highly flammable and dries by solvent evaporation only. Can be reconstituted after drying by adding solvent. Latex-based Paint: General term used for water-based emulsion paints made with synthetic binders such as 100% acrylic, vinyl acrylic, terpolymer or styrene acrylic. A stable emulsion of polymers and pigment in water. Life-cycle Analysis: A total valuation of a process, in which all the inputs and outcomes of a reaction are fully considered. Linseed Oil: Drying oil made from the flax seed. Used as a solvent in many oilbased paints. "Boiled" linseed oil can be used to protect wood from water damage. Sometimes used as a furniture polish. Lipid: A classification of organic compounds, including fatty acids, oils, waxes and steroids, that are insoluble in water but soluble in organic solvents. Liquid Driers: Solution of soluble driers in organic solvents. Lithopone: A white pigment of barium sulfate and zinc sulfide. Marine Paint: Coating specially designed for immersion in water and exposure to marine atmosphere. Material Safety Data Sheet (MSDS): Information sheet that lists any hazardous substance that comprises one percent or more of the product's total volume. Also lists procedures to follow in the event of fire, explosion, leak or exposure to hazardous substance by inhalation, ingestion or contact with skin or eyes. Coatings manufacturers are required to provide retailers with an MSDS for every product they sell to the retailer. Methanol: CH 3 OH. A volatile colorless alcohol, derived originally as wood alcohol, used as a racing fuel and as a solvent. Also called methyl alcohol. Maximum Contaminant Level (MCL): Maximum permissible level of a contaminant in water that is delivered to any user of a public water system. MCLs are enforceable standards established by the U.S. Environmental Protection Agency. Methylation - The addition of a methyl group (-CH3) to a molecule or atom through a chemical reaction. Micrograms per Liter (/*g/L): A unit expressing the concentration of constituents in solution as weight (micrograms) of solute per unit volume (liter) of water; equivalent to one part per billion in most stream water and ground water. Mineral Spirits: Paint thinner. Solvent distilled from petroleum.
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Methoxide: NaO-CH3: The salt of methanol, sodium methoxide. Monomer: Substance composed of low molecular weight molecules capable of reacting with like or unlike molecules to form a polymer. MWVF: Modified Waste Vegetable Fat. The generic form of fuel made from nontransesterified fats that are made suitable for use in normal engines by blending with solvents. Naphtha: A petroleum distillate used mostly by professionals (as opposed to do-ityourself painters) for cleanup and to thin solvent-based coatings. A volatile organic compound (see VOC). Natural Resins: Resins from trees, plants, fish and insects. Examples: damars, copals. Nonvolatile: The portion of a coating left after the solvent evaporates; sometimes called the solids content. Octane: C g H, g . Inflammable hydrocarbon of the alkane series, containing 8 carbons. Oil: A broad range of inflammable and often volatile organic compounds insoluble in water but soluble in organic solvents. In biological systems, a fat that is liquid at room temperature (20°C). Oil Paint: A paint that contains drying oil, oil varnish or oil-modified resin as the film-forming ingredient. The term is commonly and incorrectly used to refer to any paint soluble by organic solvents. Oleoresin: A natural plant product that contains oil and resins. Turpentine is an example. Organic: Compounds that contain carbon, which are often created as a result of a life process. Oxidation: Burning in oxygen, normally highly exothermic (heat releasing), but also any increase in oxidization state (i.e. loss of electrons). Results in the formation of an oxide, rusting or corroding. Oxygen: A common gaseous element, occurring naturally in the air, water, and most minerals and organic substances, essential to the reciprocal processes of plant and animal life. Highly reactive combining with other atoms, molecules and compounds through a process known as burning. Exists in the air as free molecules Oz (Oa = ozone), and also dissolves in water. Vast quantities are present in all biological systems, and in combined form in minerals and rocks.
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Paint: A coating including resin, a solvent, additives, pigments and, in some products, a diluent. Paints are generally opaque, and commonly represent the portion of the industry known as "architectural coatings." Paint Remover: A chemical that softens old paint or varnish and permits it to be easily scraped off. Also called "stripper." Penetrating Finish: A finish that sinks into the substrate, as opposed to settling on the surface. Petrochemical: Substances derived from the winning of fossil hydrocarbons, in the form of crude oil or natural gas, and tars. Photosynthesis: The process used within living organisms by which energy from the sun is stored in carbohydrates made from carbon dioxide and water, using chlorofyll from plants. It is the major natural energy collecting reaction, occurring mainly in plants. Plants use chlorophyll (a green photo-active pigment) to capture solar energy within the chemical bonds of synthesized sugar molecules. The process effectively reduces carbon dioxide and water to produce sugar and oxygen.
6CO2 + 6H2O
solar
* C6H12O6 + 6O2 chlorophyll , hexose sugar
Plants then synthesize other sugars, proteins, DNA, starch, cellulose and fats from these simple hexoze sugars. Pigment: Insoluble, finely ground materials that give paint its properties of color and hide. Titanium dioxide is the most important pigment used to provide hiding in paint. Other pigments include anatase titanium, barium metaborate, barium sulphate, burnt sienna, burnt umber, carbon black, China clay, chromium oxide, iron oxide, lead carbonate, strontium chromate, Tuscan red, zinc oxide, zinc phosphate and zinc sulfide. Polychlorinated Biphenyls (PCBs): A mixture of chlorinated derivatives of biphenyl, marketed under the trade name Aroclor, with a number designating the chlorine content (such as Aroclor 1260). PCBs were used in transformers and capacitors for insulating purposes and in gas pipeline systems as a lubricant. Further sale for new use was banned by law in 1979. Polycyclic Aromatic Hydrocarbon (PAH): A class of organic compounds with a fused-ring aromatic structure. PAHs result from incomplete combustion of organic carbon (including wood), municipal solid waste, and fossil fuels, as well as from
Glossary
331
natural or anthropogenic introduction of uncombusted coal and oil. PAHs include benzo(a)pyrene, fluoranthene, and pyrene. Polymer: A substance whose molecules consist of one or more structural units repeated any number of times; vinyl resins are examples of true polymers. Polymerization: The interlocking of molecules by chemical reaction to produce very large molecules. The process of making plastics and plastic-based resins. Poly vinyl Chloride: A synthetic resin used in the binders of coatings. Tends to discolor under exposure to ultraviolet radiation. Commonly called "vinyl." Primer: First complete coat of paint of a painting system applied to a surface. Such paints are designed to provide adequate adhesion to new surfaces or are formulated to meet the special requirements of the surfaces. Protein: A type of organic compound normally consisting of one or more amino acid chains, essential to all living organisms Reduction: Classically, the removal of oxygen. Modern chemistry expands this concept to all compounds as defined as loss of electrons. Resin: Synthetic or natural material used as the binder in coatings. Can be translucent or transparent, solid or semi-solid. Examples: acrylic, alkyd, copal ester, epoxy, polyurethane, polyvinyl chloride, silicone. RME: Rapeseed Methyl Ester. The form of fuel created by transesterifying fat as a Fatty Acid Methyl Ester, or FAME Rosin: Natural resin obtained from living pine trees or from dead tree stumps and knots. Saturated: Refers to containing the maximum number of hydrogen molecules, i.e. when every carbon atom in a hydrocarbon chain is attached to two hydrogen atoms. Semi-gloss Finish: Finish that has a low luster sheen. Semi-gloss paints are formulated to give this result (usually 35-70 degrees on a 60-degree meter). Shellac: A coating made from purified lac dissolved in alcohol, often bleached white. Silicone: A resin used in the binders of coatings. Also used as an additive to provide specific properties, e.g., defoamer. Paints containing silicone are very slick and resist dirt, graffiti and bacterial growth, and are stable in high heat. Solids: The part of the coating that remains on a surface after the vehicle has evaporated. The dried paint film. Also called Nonvolatile.
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Solid color: A coating which contains colored pigments only, i.e., does not contain pigments such as aluminums and micas. Solvent: A liquid, usually volatile, which is used to reduce viscosity. This is essential in both manufacturing and application processes. Solvents evaporate during application and drying of paint and therefore do not become a part of the dried film. In conventional coatings the solvents are organic compounds (Alcohols, Esters and Ketones) whilst in waterborne systems there is a mix of organic solvents with water. Solvent Waste Disposal Practices: Waste disposal can take a number of forms: septic systems, municipal and industrial landfills, surface impoundments, wasteinjection wells, and direct application of stabilized wastes to the land. In addition to these regulated forms of disposal, a considerable amount of unregulated disposal, such as illegal dumping and accidental spills, contributes to groundwater contamination. Perhaps the best-known sources of groundwater contamination are associated with the storage or disposal of liquid and solid wastes. The organic substances most frequently reported in groundwater as resulting from waste disposal in decreasing order of occurrence are: trichloroethylene (TCE) chloroform tetrachloroethylene(PCE) 1,1,1 -trichloroethane
benzene creosote toluene
pentachlorophenol phenolic compounds xylene
(1) Septic systems are the largest source by volume of waste discharged to the land. These systems are sources of bacteria, viruses, nitrate, phosphorus, chloride and organic substances, including organic solvents such as trichloroethylene that are sold commercially to "clean" the systems. In 1980, about 22 million domestic disposal systems were in operation, and about one-half million new systems are installed each year. It is estimated that from one-third to one-half of existing systems could be operating improperly because of poor location, design, construction or maintenance practices. Even when operating properly, systems can be spaced so densely that their discharge exceeds the capacity of the local soil to assimilate the pollutant loads. Because the 10- to 15-year design life of many septic systems built during the 1960s and 1970s is now exceeded, groundwater contamination caused by septic system failure probably will increase in the future. (2) Landfills: About 150 million tons of municipal solid waste and 240 million tons of industrial solid waste are deposited in 16,400 landfills across the U.S. each year. Some hazardous waste material may be deposited in municipal landfills and underlying groundwater may become contaminated. Wastes deposited at industrial landfills include a large assortment of trace metals, acids, volatile organic compounds and pesticides, which may cause significant local contamination. (3) Surface Impoundments: Surface impoundments are used to store, treat or dispose of oil and gas brines, acidic mine wastes, industrial wastes (mainly liquids, animal wastes, municipal treatment plant sludges and cooling water). For the most part, these impoundments contain non-hazardous wastes: however, hazardous wastes are
Glossary
333
known to be treated, stored and disposed of by 400 facilities involving about 3,200 impoundments. Some of these impoundments have significant potential for contaminating groundwater. (4) Injection Wells: In some parts of the U.S., injection wells dispose of liquid wastes underground. Of particular concern is the widespread use of drainage wells to dispose of urban stormwater runoff and irrigation drainage. Contaminants associated with drainage wells include suspended sediments; dissolved solids; bacteria; sodium; chloride; nitrate; phosphate; lead; and organic compounds, including pesticides. (5) Land Application of Wastes: In many places, solid and liquid wastes are placed or sprayed on the land, commonly after treatment and stabilization. The U.S. Environmental Protection Agency (EPA) has estimated that more than 7 million dry tons of sludge from at least 2,463 publicly owned waste treatment plants are applied to about 11,900 parcels of land each year. Contamination can occur from improper land-disposal techniques. Source Reduction: Steps taken to reduce waste generation and toxicity at the source through more effective utilization of raw materials and reformulation. Specular Gloss: Mirror-like finish (usually 60 degrees on a 60-degree meter). State: In organic chemistry, will produce CO2 + H2O + (possibly other compounds). Stearine: A glyceryl ester of stearic acid, derived from animal fats and used as tallow in the manufacture of candles and soap. Substrate: Any surface to which a coating is applied. Tallow: One of the harder organic fats derived from animal carcasses, made by rendering the internal body fat found within the abdominal cavity under the backbone and surrounding the kidneys (suet). This material was greatly used in manufacture of soap and candle wax. Thinner: A blend of volatile organic solvents added to the paint to reduce it to the correct viscosity for application. Titanium Dioxide: White pigment in virtually all white paints. Prime hiding pigment in most paints. Transesterification: The process of making bio-diesel by the separation of the three hydrocarbon chains from a lipid triglyceride to form glycerol, and bio-diesel. Triglyceride: A triple ester formed from glycerine (propan l,2,3,triol) and three fatty acids. Turpentine: Distilled pine oil, used as a cleaner, solvent or thinner for oil-based and alkyd coatings.
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Urethane: An important resin in the coatings industry. A true urethane coating is a two-component product that cures when an isocyanate (the catalyst) prompts a chemical reaction that unites the components. Ultraviolet Light: That portion of the spectrum which is largely responsible for the degradation of paint films. Invisible to the eye, causes sunburn. Unsaturated: Any carbon structure containing double or occasionally triple bonds. Many vegetable oils U.V. Absorbers: Chemicals added to paint to absorb Ultraviolet radiation present in sunlight. Vapor: The gaseous state of any substance which is usually liquid at normal temperature and pressure. Vapor Density: The relative density or weight of a material in its vapor state (with no air present) compared with an equal volume of air at ambient temperature. Vapor Permeable: Property of allowing material.(Porosity is air permeability.)
a
vapor
to
pass
through
a
Vapor Pressure: The outward pressure of a mass of a given vapor at a specified temperature, used as an indicator of volatility. Expressed in mm of Hg at 20 degrees C. Variable: A quantity or condition that is subject to change during a process. Varnish: A solution or suspension of resins in a liquid vehicle capable of forming a decorative and/or protective coating as the vehicle dries by oxidation. Varnishing: A process whereby a sheet, usually printed or unprinted paper, paperboard or similar substrate is coated with a film forming liquid. Varnishing Machine: A machine used for varnishing paper cardboard or similar stock. Varnish-on Decal: a decal designed to be applied to a surface by means of a coating of varnish applied at the time just preceding placement of the decal. Vat Dyes: Synthetic organic dyes in paste or powder form. Vee Lock: A display lock used in shaping light weight stock. Vegetable Parchment: (Parchment) A grease and water resistant paper made by passing unsized paper through sulfuric acid to gelatinize the surface.
Glossary
335
Vehicle: the fluid portion of screen printing ink which acts as a carrier for the pigment. Veiling: Gold and organic colors applied to glass in a threadlike texture. Vermilion: A red mineral pigment containing sulfide of mercury. Vibration Flocking: The erection of applied flock fibers by passing the flocked substrate over a beater or vibrator bar, as opposed to the erection of the flock by electrostatic means. Victoria Blue: A clean, red shade organic blue dye or pigment. Vinyl: Synthetic plastic product which can be made in film, sheet and other forms. Sheets can be manufactured in either rigid or flexible constructions. Generally more flexible and formable than polyesters, they are resilient and abrasive resistant. A tough, virtually unbreakable plastic formed by polymerization of compounds, suitable for indoor or outdoor displays, signs, screen printed inflatable toys, and other 3-D fabrications, etc. Viscometer: An instrument for measuring the viscosity of liquids at specified temperature and atmospheric conditions, by measuring the force required to move one layer over another without turbulence. Viscosity: The ability of a fluid to respond to movement. A high viscosity will resist movement, and a low viscosity will flow quickly. This is not necessarily the same as density. Viscosity is normally measured comparatively by the time a given volume of liquid will pass through a pipe of fixed diameter. Viscosity Coefficient: The constant of proportionality of the viscous force to the velocity gradient between two parallel Newtonian fluid layers. Viscous: Description of a material that is thick, resistant to flow and having a high viscosity. Vitreous Enamel: An enamel that requires fusion at high temperature to form its characteristic hard glossy surface. Sometimes called porcelain enamel. VM & P: A naphtha of high flash point solvent employed in the manufacture of some inks. The initials by which it is called are for Varnish Maker's and Painter's naphtha. V.O.C.: Abbreviation for Volatile Organic Compound, which refers generally to organic solvents. Voids: (1) Holes appearing in fired decorative films; (2) the failure of ink to completely define a graphic feature.
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Industrial Solvents Handbook
Volatile: Subject to evaporation at a relatively low temperature. Volatile Organic Compound: Organic chemicals and petrochemicals that emit vapors while evaporating. In paints, VOC generally refers to the solvent portion of the paint which, when it evaporates, results in the formation of paint film on the substrate to which it was applied. Volatility: The defining quality of a liquid that evaporates quickly when exposed to air. Volume Solids: Solid ingredients as a percentage of total ingredients. The volume of pigment plus binder divided by the total volume, expressed as a percent. Highvolume solids mean a thicker dry film with improved durability. Volumetric Dilatancy: Term used to describe a flow characteristic of material which behaves like a solid rather than a fluid, typically having a high solids concentration. Water-based: Coatings in which the majority of the liquid content is water. White Lead: Lead carbonate.
alpha-dodecylene, 227 alpha-furyIcarbinol, 251 alpha-hexene261 alpha-hydroxy toluene, 162 alpha-oxodiphenylmethane, 160 alpha-oxoditane, 160 amines. 31-34 aminobenzene, 156 aminoethane, 233 amyl acetate, 155 amylcarbinol, 260 anesthesia ether, 241 aniline oil, 156 aniline, 156 anilinomethane, 279 anisoyl chloride , 157 Anol, 187 Anone, 188 Arcton 9, 307 aromatic alcoholic solvents, 3 aromatic hydrocarbons, 1, 74-83 azacycloheptane, 258 azanapthalene, 301 azeotrope, 5, 13 azirane, 250 aziridine, 250
INDEX acetic acid, 149, 167-168, 229, 263, 268, 299 acetic anhydride, 149 acetic ester, 229 acetoacetic acid, 230 acetoacetic ester, 230 acetyl bromide, 150 acetyl thermoplastics, 10 acetylene dichloride, 199 acrylamide, 151 acrylic acid, 169, 170, 231 acrylic amide, 151 acrylic plastic, 9 acrylic polymers, 9 acrylonitrile, 152 Adacene-12, 227 adipic acid, bis(2-ethylhexyl) ester, 221 Adipol 2EH, 221 Adronal, 187 agricultural chemicals, 9 alcohol evaporation rates, 6 alcohol, 3, 5, 6, 232 Aldehyde C-10, 190 aldehydes, 1, 22-24,26-30 alfa-n-amylene, 296 Algylen, 306 aliphatic alcohols, 3, 4 aliphatic amines, 1 aliphatic hydrocarbons, 1, 74-83, 128 alkenals, 23 alkyd resins, 4 alkylates, 254 allyl alcohol, 6, 154 allyl chlorocarbonate, 154 allyl chloroformate, 154 alpha-aminotoluene, 163 alpha-bromotoluene, 164 alpha-butylene oxide, 175 alpha-chlorotoluene, 164 alpha-decene, 191
benzaldehyde, 158 benzazine, 301 benzene, 13, 158 benzenecarbinol, 162 benzenecarbonyl chloride, 161 benzinoform, 180 benzo(b)pyridine, 301 benzoic acid nitrile, 159 benzoic aldehyde, 158 benzol, 158 benzole, 158 benzonitrile, 159 benzophenone, 160 benzoyl chloride, 161 benzoylbenzene, 160 benzyl alcohol, 3,6, 162 benzyl bromide, 164 benzyl chloride, 164
337
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Industrial Solvents Handbook
benzyl chlorocarbonate, 166 benzyl chloroformate, 166 benzyl ester, 166 benzylamine, 163 benzylcarbonyl chloride, 166 bis(2-aminoethyl)amine, 212 bis(2-chloroethyl) ether, 201 bis(2-ethylhexyl) ester, 222 bis(2-ethylhexyl) phthalate, 222 bis(8-methylonyl)ester, 215 blue oil, 156 bromobenzene, 167 bromobenzol, 167 bromotoluene, alpha, 164 butanal, 179 butanol, 19, 171 butanone, 283 butene resins, 297 butoxydiethylene glycol, 209 butoxydiglycol, 209 butoxyethyl 2,4dichlorophenoxyacetate, 193 butoxyethyl ester, 193 butyl "Carbitol" acetate, 209-210 butyl 2-methacrylate, 177 butyl 2-methyl-2-propenoate, 177 butyl 2-propenoate, 170 butyl acetate, 167 butyl acrylate, 170 butyl alcohol, 19, 171, 264 butyl aldehyde, 179 butyl Cellosolve, 247 butyl ester, 167, 170, 177 butyl ethanoate, 167 butyl ether, 196 butyl methacrylate, 177 butylamine, 173 butylene hydrate, 171 butylene oxide, 175 butyraldehyde, 179 butyric acid, 235 butyric aldehyde, 179 butyric ether, 235 C-10 alcohol, 191
capraldehyde, 190 capric alcohol, 191 capric aldehyde, 190 caproaldehyde, 258 caproic aldehyde, 258 capronaldehyde, 258 Carbitol, 211 carbobenzoxy chloride, 166 carbolic oil, 179 carbon tetrachloride, 68-70, 180 carbonic acid diethyl ester, 207 catalytic oxidation of methanol, 12 catalytic oxidation, 12 cellophane films, 4 Cellosolve, 248 chemical industry processes, 1 Chinoline, 301 chloracetic acid, 237 Chloretane, 236 Chlorex, 201 chlorobenzene, 70-71 chlorocarbonic acid, methyl ester, 281 chloroform, 67-68, 181 chloroformic acid, 166, 237, 281 chloromethyloxirane, 229 chlorotoluene, alpha, 164 Clean Air Act, 95-103 Clorilen, 306 coal tar, 183 coating formulations, 6 cod oil, 295 cologne sprit, 232 Colonial spirit, 277 Columbian spirit, 277 Community Right-To-Know Act, 95, 104 copper naphthenate , 182 creosote, 183 cresols, 184 cresote oil, 183 cresylic acids, 184 Croplas EH, 243 Cumene, 184 Cumol, 184
Index cyanobenzene, 159 cyclic alcoholic solvents, 3 cyclohexane, 186 cyclohexanol, 3, 4, 6, 187 cyclohexanone, 188 cyclohexyl alcohol, 187 cyclopentane, 188, 282 Cymol, 185 DCEE, 201 dead oil, 183 decahydro naphthalene, 189 decaldehyde, 190 Decalin, 189 Decanal, 190 decane, 189 decarbonylation, 20 decene, 191 decyl alcohol, 6 decylbenzene, 192 dehydration, 18 dehydrogenation, 12 DEN, 206 denatured alcohol, 232 denaturing, 18 dextrose, 17 D-glucitol, 302 di-(2-chloroethyl) ether, 201 di(2-ethylhexyl) Adipage, 221 di(2-ethylhexyl) phthalate, 222 diacetic ether, 230 diacetone alcohol, 6, 194 diamyl ester, 194 diamyl phthalate, 194 di-beta-hydroxyethoxy-ethane, 312 DIBK, 214 dibutyl ether, 196 dibutyl oxide, 196 dibutylamine, 195 dichloricide, 198 dichlorobenzene, 71-72 dichlorobutene, 199 dichlorodiethyl ether, 201 dichloroethylene, 199 dichloromethane, 202
339
dichloropropane, 203 dichloropropene, 204 dicyclopentadiene, 205 diethanolamine, 205 diethyl carbonate, 207 diethyl ether, 15 diethylamine, 206 diethylbenzene, 207 diethylene glycol dimethyl ether, 209 diethylene glycol ethyl ether, 211 diethylene glycol monoethyl ether, 211 diethylene glycol, 208 diethyleneglycol monobutyl ether acetate, 209-210 diethylenetriamine, 212 dietyl ether, 241 dietyl oxide, 241 diglycol monobutyl ether acetate, 210 diglycol monobutyl ether, 209 diglycol, 208 diheptyl ester, 212 diheptyl phthalate, 212 dihydroxydiethyl ether, 208 diisobutyl ketone, 214 diisobutylcarbinol, 213 diisobutylene, 214 diisodecyl ester, 215 diisodecyl phthalate, 215 diisopropanolamine, 216 diisopropyl ester, 273 diisopropyl ether, 271 diisopropyl oxide, 271 diisopropyl percarbonate, 273 diisopropyl peroxydicarbonate, 273 diisopropylamine, 217 dimethoxymethane, 284 dimethyl ether, 218 dimethyl sulfate, 218 dimethyl sulfide, 219 dimethyl sulfoxide, 220 dimethylcarbinol, 269 dimethylformal, 284 di-n-amyl phthalate, 194
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Industrial Solvents Handbook
di-n-butyl ether, 196 di-n-butyl ketone, 197 di-n-butylamine, 195 dioctyl adipate, 221 dioctyl phthalate, 222 dipentene, 222 dipentyl ester, 194 dipentyl phthalate, 194 diphenyl ether, 223 diphenyl ketone, 160 diphenyl methanone, 160 diphenyl oxide, 223 dipropylene glycol, 224 distillates, flashed feed stocks, 225 distillation, 16, 18 DMS, 219 DMSO, 92, 220 DOA, 221 dodecanol, 225, 274 dodecene, 226, 227 dodecyl alcohol, 225 dodecyltrichlorosilane, 228 OOP, 222 Dovanol EM, 249 Dovonol EB Glycol Butyl Ether, 247 Dowanol DB, 209 Dowanol DE, 211 Dowanol EE, 248 Downtherm E, 197 dyes, 9 Dytol S-91, 191
EB, 233 Ektasolve DB Acetate, 210 elastomers, 10 electropositive metals, 4 enanthic alcohol, 256 epichlorohydrin, 229 epoxypropane, 300 Eskimon 11, 307 esterification, 4 esters, 1, 34-38 ethanethiol, 245 ethanoic acid, 149 ethanoic anhydride, 149
ethanol plants, 18 ethanol, 3-6, 13, 14, 15, 17, 232 ethers, 1, 38-46 ethoxy diglycol, 211 ethoxyethane, 241 ethyl acetate, 229 ethyl acetoacetate, 230 ethyl acrylate, 231 ethyl alcohol, 15, 232 ethyl alpha-hydroxy-propionate, 244 ethyl alpha-methylmethacrylate, 246 ethyl butanoate, 235 ethyl butanol, 234 ethyl butyrate, 235 ethyl carbonate, 207 ethyl cellulose, 9 ethyl chloracetate, 237 ethyl chloride, 236 ethyl chloroacetate, 237 ethyl chloroethanoate, 237 ethyl chloroformate, 237 Ethyl DL-Lactate, 244 ethyl ester, 229, 230, 231, 235, 237, 243, 244, 246, 241 ethyl formate, 243 ethyl formic ester, 243 ethyl hexanol , 242 ethyl hexyl tallate, 243 ethyl lactate, 244 ethyl mercaptan, 245 ethyl methacrylate, 246 ethyl methacrylate-inhibited, 246 ethyl methanoate, 243 ethyl methyl ketone, 283 ethyl nitrite, 246 ethyl sulfhydrate, 245 ethylamine, 233 ethylbenzene, 233 ethylcarbinol, 299 ethyldichlorosilane. 238 ethylene chlorhydryn, 239 ethylene dichloride, 72-73 ethylene glycol dihydroxydiethyl ether, 312 ethylene glycol ethyl ether, 248
Index ethylene glycol monobutyl ether, 247, 248, 249 ethylene glycol, 4 ethylene oxide, 21 ethylenediamine, 240 ethyleneimine, 250 ethylhexyl alcohol, 242 ethylidene dichloride, 73-74 Eufm, 207 Exxsol solvents, 81 fermentation alcohol, 232, 262 fermentation, 15, 17 fiberglass-reinforced plastic, 20 formaldehyde dimethylacetate, 284 formaldehyde, 9-10, 12, 250 formalin, 250 formalith, methanal, 250 formic acid, 243 formic acid, methyl ester, 285 formic aldehyde, 250 formic ether, 243 Freon 11, 307 Frigen 11, 307 fuel oil, 274 Fumigrain, 152 furan resins, 20 furan, 20 furancarbinol, 251 furane resins, 20 furfuralcohol, 251 furfuryl alcohol derivatives, 20 furfuryl alcohol urea, 20 furfuryl alcohol, 6, 20, 251 furfuryl alcohol-based resins, 20 furfuryl amine, 20 furniture finishes, 20 furyl carbinol, 20 fusel oil, 262 Fyde, 250 gamma-chloropropylene oxide, 229 gas oil, 252 gasoline blending stocks, 254 gasolines, 253
341
Gemalgene, 306 Genetron 11, 307 glacial acetic acid, 149 glycerine, 255 glycerol, 4, 21, 255 glycol chlorohydrin, 239 glycol ethers, 1, 46-51 glycol monoethyl ether, 248, 249 glycols, 21 grain alcohol, 232 gum turpentine, 312 halogenated hydrocarbons, 1, 51-74 Hansen solubility parameters, 134141 Hansen solubility theory, 131-133 Hazardous and Solid Waste Amendments, 119-120 heat of reaction, 12 hendecanoic alcohol, 313 hendecanol, 313 hendecylenic alcohol, 313 heptane, 255 heptanol, 256 heptene, 257 heptyl alcohol, 256 heptylcarbinol, 293 heptylene, 257 heterocyclic amines, 1 hexahydric alcohol, 302 hexahydroazepine, 258 hexahydrobenzene, 186 hexahydrophenol, 187 hexalin, 187 hexamethylene, 186 hexamethyleneimine, 258 hexanal, 258
hexanaphthene, 186 hexane, 259 hexanol, 260 hexanone, 280 hexene, 261 hexone, 287 hexyl acetate, 278 hexyl alcohol, 260
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Industrial Solvents Handbook
hexylene glycol, 261 homopiperidine, 258 hot spray lacquers, 20 hydration, 15 hydrogen bonds, 3 Hydrosol series, 76-80 hydroxycyclohexane, 187 hydroxyheptane, 256 hydroxyhexane, 260 hydroxy 1 functional group, 3 hydroxymethylfuran, 251 hydroxytoluenes, 184 Hylene T, 304 Hytrol O, 188
isopropyl ester, 193, 268 isopropyl ether, 271 isopropyl mercaptan, 272 isopropyl percarbonate, 273 isopropyl peroxydicarbonate, 273 isopropylacetone, 287 isopropylamine, 270 isopropylcarbinol, 264 isopropylideneacetone, 275 isotridecanol, 308 isotridecyl alcohol, 308 Isotron 11, 307 Isovalerone, 214 kerosene, 1, 83-91, 274
illuminating oil, 274 intermolecular bonds, 3 Isceon 11, 307 isoamyl alcohol, 4-6, 262 isobutanol, 5-6, 264 isobutenyl methyl ketone, 275 isobutyl acetate, 263 iso-butyl acrylate, 169 isobutyl alcohol, 4, 264 isobutyl ester, 169, 263 isobutyl methyl carbinol, 286 isobutyl methyl ketone, 287 isobutyl methylmethanol, 278 isobutylaldehyde, 178 isobutylamine, 265 isobutylcarbinol, 262 isobutylmethyl carbinol, 278 isobutyraldehyde, 178 isobutyric aldehyde, 178 isodecyl alcohol, 265 isohexane, 266 isooctanol, 4 isooctyl alcohol, 262, 267 isophorone, 268 isopropanol, 4, 269 isopropenyl methyl ketone, 288 isopropyl 2,4-dichlorophenoxy acetate, 193 isopropyl acetate, 268 isopropyl alcohol, 6, 269
lacquers, 20 lactic acid, 244 lauryl alcohol, 225 Leucol, 301 levulic acid, 20 Limonene, 222 linear alcohols, 274 liquefaction, 17 liquefied phenol, 179 liquid petrolatum, 294 Lorol-22, 191 MAAc, 278 MAOH, 278 MAOH, 286 MEK, 86, 283 mercaptoethane, 245 mesityl oxide, 275 metal ethoxide, 15 metal-catalyzed hydrogenation, 20 methacrylic acid, 177, 246 methanethiomethane, 219 methanol, 3-9, 12, 277 methanol-based windshield antifreeze, 9 methyl acetate, 276 methyl alcohol, 10, 277, 286 methyl amyl acetate, 278 methyl amyl alcohol, 278
Index Methyl carbitol, 21 methyl chlorocarbonate, 281 methyl chloroformate, 63-67, 281 methyl cyclohexanol, 4 methyl cyclopentane, 282 methyl ether, 218 methyl formal, 284 methyl formate, 285 methyl isobutenyl ketone, 275 methyl isobutyl carbinol, 4, 6, 286 methyl isobutyl ketone, 287 methyl isopropenyl ketone, inhibited, 288 methyl methacrylate, 9 methyl n-butyl ketone, 280 methyl propyl benzene, 185 methyl sulfide, 219 methyl sulfoxide, 220 methyl tertiary-butyl ether (MTBE), 8,9 methylacetic anhydride, 299 methylal, 284 methylaniline, 279 methylated spirits, 14 methylbenzene, 303 methylbenzol, 303 methyldichlorosilane methyl ethyl ketone, 283 methylene chloride, 54-57, 202 methylene dichloride, 202 methylene dimethyl ether, 284 methylene di-para-phenylene diisococyanate (MDI), 10 methylethylcarbinol, 171 methylfuran, 20 methyl isobutyl carbinol, 278 methylisobutylcarbinyl acetate, 278 methyloxirane propene oxide, 300 methylphenols, 184 methylphenylamine, 279 methylpropyl ethanoate, 263 methylystyrene, 315 MIBC, 286 MIBK, 86, 287 MIC, 278
343
MIC, 286 middle oil, 179 MIK, 287 milling, 17 mineral spirits, 288 molecular sieve, 18 Mondur IDS, 304 monobromobenzene, 167 monochloracetic acid, 237 monochloretane, 236 monochlorethanoic acid, 237 monoethylamine, 233 monohydric alcohols, 1, 3, 13 monoisobutylamine, 265, 270 mono-n-butylamine, 173 motor gasoline oxygenate, 8 motor spirit, 253 multi-column distillation, 18 m-xylene, 316 Nacconate 100, 304 Nadone, 188 «-amyl alcohol, 5-6 naphtha, 288 naphthalane, 189 naph thane, 189 n-butanol, 4-6, 19 n-butyl acetate, 167 n-butyl acrylate, 170 n-butyl alcohol, 19, 171 n-butyl alpha-methyl acrylate, 177 n-butyl ether, 196 n-butyl mercaptan, 176 n-butyl methacrylate, 177 n-butyl methyl ketone, 280 n-butylamine, 173 n-butyraldehyde, 179 n-caproylaldehyde, 258 n-decyl alcohol, 191 n-decyl aldehyde, 190 n-decylbenzene, 192 n-dibutyl ether, 196; Necatorina, 180 n-heptane, 255 n-heptylethylene, 291
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Industrial Solvents Handbook
n-hexaldehyde, 258 fl-hexyl alcohol, 6 n-hexyl, 5 nitrocellulose, 9 nitroparaffins, 1 nitrous ether, 246 tt-methylaminobenzene, 279 rt-methylaniline, 279 n-octane, 292 /7-octyl alcohol, 6 nonanol, 289 nonene, 290, 291 nonilalcohol, 289 nonyl alcohol, 6 nonylcarbinol, 191 nonylene, 291 nonylethylene, 314 nonylphenol, 291 norvalamine, 173 n-propanol, 18 /i-propyl acetate, 299 n-propyl alcohol, 5-6, 18, 299 /i-propylcarbinol, 171 n-undecylbenzene, 315 octane enhancement, 8 octane, 292 octanol, 293 Octoil, 222 octyl alcohol, 293 octylcarbinol, 289 o-dichlorobenzene , 197 oil of bitter almond, 158 oils, 294-295 oleates, 19 omega-bromotoluene, 164 omega-chlorotoluene, 164 o-methylaniline, 305 organic chemicals, 1 organic liquids, 1 oriented strandboard (OSB) , 9 orthodichlorobenzene, 197 OSHA legislation, 1 OSHA, 95, 122-126 o-toluidine, 305
o-xylene, 317 oxytoluenes, 184 paint drier, 182 Paradi, 198 paradichlorobenzene, 198 Paradow, 198 Paramoth, 198 particle board, 9 p-cumene, 185 /?-dichlorobenzene, 198 pelargonic alcohol, 289 pentadecanol, 274 pentamethylene, 188 pentyl acetates, 155 perchloroethylene, 61-63 perchloromethane, 180 perhydronaphthlene, 189 peroxydicarbonic acid, 273 Petrohol, 269 petrol, 253 petroleum distillate, 225 petroleum spirits, 288 Phellandrene, 222 phenoxybenzene, 223 phenyl bromide, 167 phenyl ether, 223 phenylamine, 156 phenylcarbinol, 162 phenylcyanide, 159 phenylethane, 233 phenylmethanol, 162 phenylmethyl alcohol, 162 phenylmethyl amine, 163 phosphorus pentachloride, 4 phthalates, 19 phthalic acid, 194,212,215,222 physical properties, 7 pimelic ketone, 188 p-isopropyltoluene, 185 plasticizer DDP, 215 plasticizer-type esters, 19 plastics, 4, 9 pluracol polyol, 298 Poli-Solv EE, 248
Index
345
polybutene, 297 polyethylene glycol (PEG) , 21 polyhydric alcohols, 1, 21-22 polyisobutylene plastics, 297 polyisobutylene resins, 297 polyisobutylene waxes, 297 polymer compositions, 6 polyoxipropylene ether, PPG, 298 polyoxipropylene glycol, 298 polyproplene glycols P400 to P4000, 298 polypropylene glycol, 298 Poly-Solv DB, 209 Poly-SolvDE, 211 Poly-Solv EB, 247 Poly-Solv EM, 249 polyvinyl acetate, 9 potato-spirit oil, 262 propanoic anhydride, 299 propanol, 3, 299 propenamide, 151 propionyl oxide, 299 propyl alcohol, 18, 299 propyl ester, 299 propylene dichloride, 203 propylene oxide, 300 propylene tetramer, 226 propylene trimer, 290 propylethylene, 296 pseudohexyl alcohol, 234 p-xylene, 318
SARA Title III, 103-115 sec-amyl alcohol, 5-6 sec-butanol, 5-6 sec-butyl acetate, 168 sec-butyl alcohol, 171 sec-butyl ester, 168 sec-butylamine , 174 sec-he\yl alcohol, 234 sec-octyl alcohol, 6 sec-pentyl carbinol, 234 sec-propyl alcohol, 269 sextone, 188 shellacs, 9 silicochloroform, 307 sodium alkyl sulfates, 302 sodium hydrogen alkyl sulfate, 302 sodium, 4 solubility data, 8 solvent blends, 133-134 solvent, definition of, 1 Sorbitol, 302 spirit of ether nitrite, 246 spirit, 232 spirits of turpentine, 312 spirits of wine, 232 stearates, 19 straight chain alcohols, 3 sulfate turpentine, 312 sulfuric acid, 15 sulfuric ether, 241 surface tension, 6
quinoline, 301
tar acids, 184 TEA, 175 IDE, 304 TEG, 312 Telone, 204 ternary azeotrope, 13 Terpinene, 222 Terpodiene, 222 tert-amyl alcohol, 5 tert-amyl alcohol, 6 te/t-butanol, 5-6 tert-butyl alcohol , 172 tert-butylamine, 175
range oil, 274 RCRA, 115-119 reportable quantities, 104-115 resin, 6, 295 Retinol, 295 rosin oil, 295 Rosinol, 295 rubbing alcohol, 269 saccharification, 17 Santochlor, 198
346
Industrial Solvents Handbook
tertiary butyl alcohol, 6 tetrachloromethane, 180 tetradecanol, 274 tetrahydrofurfuryl alcohol, 6, 20 tetrapropylene, 226 Thanol PPG, 298 thinners, 20 thiobutyl alcohol, 176, 245 Threthylene, 306 toluene 2,4-diisocyanate, 304 toluene, 303 Toluol, 303 Toxic Substance Control Act, 121122 Trethylene, 306 trichloroethylene, 57-61, 306 trichlorofluoromethane, 307 trichloromethane, 181 trichloromonosilane, 307 trichlorosilane, 307 TriClene, 306 Tridecanol, 274, 308 Tridecene, 308 Trielene, 306 triethanolamine, 310 triethylbenzene, 311 triethylene glycol, 312 Triglycol, 312 Trihloran, 306 Trihloroethelene, 306 trihydric alcohols, 4 trihydroxypropane, 255 trihydroxytriethylamine, 310 Triline, 306 Trimar, 306 trimethylaminomethane, 175 trimethylcarbinol, 172 tripropylene, 290 tris(hydroxyethy)amine, 310 tungstic acid, 15 turpentine, 312 Turps, 312 Tyranton, 194 Ucon 11, 307
undecanol, 313 undecene, 314 undecyl alcohol, 313 undecylethylene, 308 undecylic alcohol, 313 underground storage tanks, 120 urea formaldehyde resins (UF), 9 urethane foams, 10 US EPA, 8 vinegar acid, 149 vinyl cyanide, 152 vinyltoluene, 315 water, 93-94 water-treatment chemicals, 9 white oil, 294 wood alcohol, 277 wood ether, 218 wood naphtha, 277 wood spirit, 277 wood turpentine, 312 xylenol, 319 xylol, 316 yeast, 17