Azeotropic Data-III (Advances in Chemistry Series 116)

Azeotropic Data—III

In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

Azeotropic Data—III

Compiled by Lee H . Horsley The Dow Chemical Co. Midland, Mich.

ADVANCES

IN

CHEMISTRY

SERIES

AMERICAN CHEMICAL SOCIETY

WASHINGTON,

D.

C.

1973

In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

116

ADCSAJ 116 1-628 (1973)

Copyright © 1973 American Chemical Society All Rights Reserved

Library of Congress Catalog Card 73-75991 ISBN 8412-0166-8 PRINTED I N T H E UNITED STATES O F AMERICA

In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

Advances in Chemistry Series Robert F . G o u l d , Editor

Advisory Board Bernard D . Blaustein Paul N . Craig Ellis K . Fields Louis Lykken Egon Matijević Thomas J. Murphy Robert W . Parry Aaron A . Rosen Charles N . Satterfield

In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

FOREWORD ADVANCES IN CHEMISTRY SERIES was

founded in 1949 by

the

American Chemical Society as an outlet for symposia and col­ lections of data in special areas of topical interest that could not be accommodated in the Society's journals. It provides a medium for symposia that would otherwise be fragmented, their papers distributed among several journals or not pub­ lished at all. Papers are referred critically according to ACS editorial standards and receive the careful attention and proc­ essing characteristic of ACS publications. Papers published in ADVANCES IN CHEMISTRY SERIES are original contributions

not published elsewhere in whole or major part and include reports of research as well as reviews since symposia may em­ brace both types of presentation.

In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

Table of Contents PREFACE LEE H. HORSLEY 1 Tables of Azeotropes and Nonazeotropes Table I. Binary Systems Table II. Ternary Systems Table III. Quaternary Systems Formula Index Bibliography 2 Prediction of Azeotropism and Calculation of Azeotropic Data

ix-x 1-613 3 448 496 503 589 615-622

3 Vapor-Liquid Equilibrium Diagrams of Alcohol-Ketone Azeotropes as a Function of Pressure E. C. BRITTON, H. S. NUTTING, and L. H. HORSLEY 623-625 4 Graphical Method for Predicting Effect of Pressure on Azeotropic Systems H. S. NUTTING and L. H. HORSLEY 626-628

PREFACE his volume is a complete revision of Azeotropic Data I and II pub±

-

lished as ADVANCES IN CHEMISTRY SERIES NO. 6 and No. 35, American

Chemical Society. It includes revised data on systems in the original tables plus new data on azeotropes, nonazeotropes, and vapor-liquid equilibria collected since 1962. No attempt has been made to evaluate the accuracy of the data. Where appreciable differences occur in the data from a single investigator, only the most recent data are recorded. Where differences in values from two different sources occur, both sets of data are recorded. To aid the reader in evaluating data on a given system, however, all references to that system are included. In general, data have been obtained from the original literature. Where the original litereature was not available, data have been taken from Chemical Abstracts. In a few instances, data have been taken from col­ lections of azeotropic data in handbooks, review articles, and so forth. The tables are arranged in the same manner as the previous volumes. This is based on empirical formula as in Chemical Abstracts except that all inorganic compounds are listed first, alphabetically by empirical formula. For a given binary system the lower order component according to empirical formula is chosen as the Α-component, and under each A-component the B-components are also arranged according to empirical for­ mula. For ternary and quarternary systems, the same arrangement is used, using the lowest order formula as Α-component, the next lowest order as B-component, and so on.

Abbreviations max. b.p. min. b.p. atm. mm. p.s.i.a. p.s.i.g. v-1 v.p.

Maximum boiling point azeotrope (negative azeotrope) Minimum boiling point azeotrope (positive azeotrope) Pressure in standard atmospheres Pressure in millimeters of Hg Pressure in pounds per square inch absolute Pressure in pounds per square inch gage Vapor-liquid equilibrium data are given in the original reference Vapor pressure ix

In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

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In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

620

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In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

Vapor-Liquid Equilibrium Diagrams of Alcohol-Ketone Azeotropes as a Function of Pressure 1

E. C. BRITTON, H. S. NUTTING, and L. H. HORSLEY The Dow Chemical Co., Midland, Mich.

Pressure has a marked effect on the azeotropic composition and vapor­ -liquid equilibrium diagrams of alcohol-ketone systems (1). This is due to the fact that the slopes of the vapor pressure curves of alcohols are appreciably greater than for ketones; it results in an unusually large change in the relative boiling points of the components of an alcohol­ -ketone system with change in pressure. As a result of the study of these systems, it has been found that the methanol-acetone azeotrope exhibits the unusual phenomenon of becom­ ing nonazeotropic at both low and high pressures—that is, below 200-mm. pressure the system is nonazeotropic with methanol as the more volatile product, while above 15,000 mm. the system is nonazeotropic with ace­ tone the more volatile component. Some of the equilibrium data for this system and two other alcohol­ -ketoneazeotropes are shown in Figures 1 and 2 on the following pages. The similarity of the diagrams for the different systems at suitable pres­ sures is of interest. For example, the diagram for methanol-acetone at 10,000 mm. corresponds approximately to the diagram for methanol­ -methyl ethyl ketone at 1000 mm. and for ethanol-methyl propyl ketone at 100 mm. Literature Cited (1) Britton, E. C., Nutting, H. S., Horsley, L. H. U.S. Patent 2,324,255 (July 13, 1943).

1

Deceased. 623

In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

624

200,

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In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

625

Alcohol-Ketone Azeotropes

METHANOL ACETONE

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Figure 2.

Difference in composition of vapor and liquid in equilibrium

Shown as a function of corresponding average composition of vapor and liquid for alcohol-ketone systems

In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

Graphical Method for Predicting Effect of Pressure on Azeotropic Systems H. S. NUTTING and L. H. HORSLEY The Dow Chemical Co., Midland, Mich.

A rapid and easily applicable method has been found for indicating the effect of pressure on the composition and boiling point of an azeo­ tropic system. The method is based on the use of the Cox vapor pressure chart (1) on which the log of vapor pressure is plotted as a function of 1/(t° C. + 230) to give a straight line over a wide range of pressures. Lecat (2) has considered the use of the vapor pressure curves of azeo­ tropes to indicate the pressure at which a system would become nonazeo­ tropic. However, he plotted in the conventional manner and could obtain the curves only by detailed experimental work. It has been found that the vapor pressure curves of azeotropes are straight lines when plotted on a Cox chart which permits determination of the complete vapor pressure curve from the data at two pressures. Since an azeotrope by definition has either a higher or a lower vapor pressure than that of any of the components, the azeotropic vapor pres­ sure curve will always lie above or below the curves of the components. This is indicated schematically in Figure 1 where A and Β are vapor

AZEOTROPE DISAPPEARS AT Ρ AND P

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COX SCALE l / ( T ° C . + 230)

Figure 1.

Schematic of vapor pressure curves of binary azeotropes 626

In Azeotropic Data—III; Horsley, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1973.

627

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