Admixtures in Crystallization

J. Njrvlt, J. Ulrich

Admixtures in Crystallization

0 VCH Verlagsgesellschaft mbH. D-69451 Weinheim (Federal Republic of Germany), 1995

Distribution: VCH, P. 0.Box 101161, D-69451 Weinheim, Federal Republic of Germany Switzerland: VCH, P. 0.Box, CH-4020 Basel, Switzerland United Kingdom and Ireland: VCH, 8 Wellington Court, Cambridge CBI lHZ, Great Britain USA and Canada: VCH, 220 East 23rd Street, New York, NY 10010-4606, USA

Japan: VCH. Eikow Building, 10-9 Hongo I-chome, Bunkyo-ku, Tokyo 113. Japan ISBN 3-527-28739-6

Jaroslav Nfvlt ,Joachim Ulrich

Admixtures in Crystallization

Weinheim - New York Base1 Cambridge - Tokyo

Dr. Sc. Ing. Jaroslav Syvlt Institute o f Inorganic Chemistry of thc Academy of Scicnces of the Czech Republic I’ellCova 24 16000 Prague 6 Czech Kcpublic

Priv.-Doz. Dr.-Ing. Joachim Ulrich Universitat I3remen Vcrfahrenstechnik/I;B 4 Postfach 330440 D-28334 Bremen Germany

I

1 This book wascarefully produced. Nevcrthelcss, authors and publisher do not warrant the information contained therein to be frec of errors. Readers are advised to kecp in mind that statements. data. illustrations, procedural details or other items may inadvertently be inaccurate.

Published jointly by VCH Verlagsgesellschaft, Weinheim (Fcderal Republic of Germany) VCII Publishers, New York, NY (USA) Editorial Director: D r . Barbara Bock Production Manager: Claudia Gross1

Library of Congress Card No. applied for A catalogue record for this book is available from the British Library

Die Deutsehe Bibliothek - CIP-Einheitsaufnahmc N+vlt, Jaroslav: Admixtures in crystallization I Jaroslav NCvlt ; Joachim Ulrich. Weinhcim : New York : Basel ; Cambridgk : Tokyo : VCH, 1995 ISBN 3-527-28739-6 KE: Ulrich. Joachim:

OVCH Verlagsgesellschaft mbH, D-69451 Weinheim (Federal Republic of Germany), 1995 Printed o n acid-free and low-chlorine paper

All rights reserved (including those of translation intoother languages). No part of this book may be rcproduccd in any form -by photoprinting, microfilm, or any other means -nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Printing: bctz-druck GmbH. 11-64291 I1armstadt 13ookbinding: CJroDbuchbinderei Josef Spinner, D-77833 Ottersweier Printed in the Federal Republic of Germany

Industrial crystallization has been considered for many years to be more a magic than a science. One of the reasons has certainly been the fact that additives or impurities even in the smallest amounts have tremendous effect on nucleation. crystal growth, crystal forms and dissolution rates. In recent years, not only has the level at which impurities are detectable decreased dramatically, but also the understanding of the interaction of substances has increased by the same extent. Although there is still not a complete understanding of the functioning of additives and impurities in crystallization, there are many interesting new approaches in this field which should lead t o helpful models soon. The authors want to contribute by gathering every piece of information together in this book to help to contribute for a better understanding of the whole matter. Data of crystallizing substances are presented here together with the examined admixtures and the found effects, extracted from the literature databases of both of the authors. The authors hope that the use of the tables presented wffl lead to a better design and understanding of crystallization processes, especially of the functioning of additives. and thus facilitate a proper choice of additives in order to obtain the required product properties. The authors would acknowledge the support of the Czech Grant Agency (Grant No. 203/93/0814) and of the Volkswagen Stiftung.

J . Njrvlt. J. Ulrich

December 1994

Contents ........................................

4

...........................

6

1.

Introduction

2.

Classification of Admixtures

3.

Influence of Admixtures on Nucleation . . . . . . . . . . . . . . . . . . .

3.1. Homogeneous Nucleation

4.

10

..............................

12

..................................

14

3.2. Heterogeneous Nucleation

3.3. Secondary Nucleation

...............................

9

Influence of Admixtures on Crystal Growth . . . . . . . . . . . . . . .

4.1. The Role of the Solid Surface

16

............................

16

....................

22

4.2. The Role of the Interphase Solid - Liquid

5.

Influence of Admixtures on Crystal Shape . . . . . . . . . . . . . . . .

6.

Influence of Solvents

.................................

30

7.

Distribution of Admixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . .

34

.......................................

34

.................................

37

..............................

41

7.1. Solid Solutions

7.2. Isomorphous Inclusion

7.3. Anomalous Mixed Crystals

..................................

7.4. Adsorption Inclusion

43

.................................

45

7.7. Materials Balance for Crystallization in Presence of Impurities

7.8. Cascade Purification

42

........................

7.5. Mechanism of Internal Adsorption 7.6. Mechanical Inclusions

24

...................................

...

45

51

Contents

. 9. 8

.

10

. 12. 11

3

Notations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

55

.........................................

57

.............................................

75

Formula Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

273

References to Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

287

.......................................

389

References Tables

SubjectIndex

Admixtures in crystallization

Jaroslav Njlvlt, Joachim Ulrich 0 VCH Verlagsgesellschaft mbH, 1995

1. Introduction Crystallization is one of the oldest separation operations in chemical industries. I t serves not only to separate and purify substances, but also to produce crystals with a required shape. Both of these aspects are closely connected with the presence of

admixtures in the solution. Among the

many factors affecting the process of crystallization

I1 72,2261, [e.g.,

temperature, supersaturation, agitation). admixtures often exhibit the most pronounced effect. Even traces of admixtures can influence the nucleation. crystal growth, shape and size of product crystals, and also other properties (caking. hygroscopicity. etc.). On the other hand, they may be entrained into crystals and lower their purity. A few years ago, a largely empirical approach was used to quantify

the effect of admixtures and solvents. A theoretical description of the effect of admixtures has been developed only rather recently. Nevertheless, a consistent theory of the effect of admixtures on individual aspects of the process of crystallization is still missing. Various admixtures probably operate with different mechanisms. Some of them are selectively adsorbed on crystal faces and

deactivate individual growth centers, others can

change the structural properties of the solution or of the interface; they may be incorporated into the crystal lattice or pushed away by the growing crystal

and sometimes there exists a chemical interaction between the

micro- and macrocomponents. I t is obvious that this situation enables u s to give subsequent explanations of individual effects but the prediction is

1. Introduction

5

still difficult. Computer simulations available in recent years [2.123.124] facilitate the choice of tailor-made admixture but their use is still limited. Although the literature on crystallization in the presence of admixtures is very extensive, most papers exhibit j u s t a n empirical character. Reasonably complete information on the effect of admixtures can be found in monographies on crystallization and in surveys. At this point we have to mention in particular the books by Buckley [32], Khamski [101.102]. Mug [ 1121. Kuznetsov [120], Matusevich [133j. M a t z 11341. Melikhov (1421. Mullin

[152]. Njrvlt [169.171.172] and Ohara and Reid 11791. and papers by Broul [30].Cabrera and Vermilyea (411. Chernov [46]. Davey [SO]. Garrett I711 and

Wirges [2421. The purity of crystals and distribution of impurities is dealt with in many papers, e.g. by Melikhov (1421. Stepin et al. [211] or Slavnova 12061. More detailed information can be found in the literature which exceeds 2000 papers; the aim of this book is to give a survey of the state of

the art of this subject and of a number of these papers i n appended tables. Before we continue we must mentlon the pioneering work of late Dr. Broul who started the work on survey of the effects of admixtures 1291.

Admixtures in crystallization

Jaroslav Njlvlt, Joachim Ulrich 0 VCH Verlagsgesellschaft mbH, 1995

2. Classification of Admixtures Crystallization from aqueous solutions can be understood as a physical process where a pure solid A precipitates from its solution in pure solvent B. Systems met in practice are usually more complex and in addition contain several non-crystallizing substances, often in low concentrations. Crystallization itself therefore proceeds in a multicomponent system and the result may be affected by these foreign substances - admixtures. An admixture may be defined I301 a s a substance present in a crys-

tallizing system that itself doesn’t precipitate a s a separated solid under given conditions. Such a broad definition comprises the solvent a s an admixture a s well. This affects the crystallization parameters in many cases encountered in crystallization from various pure or mixed solvents. Besides the general term admixture we shall use a more specific term impurity for substances, unintentionaly present in the solution (e.g.. coming from the raw materials. from dissociation and other reactions, from corrosion of the equipment). and addftlue for substances that we add to the solution in order to modify its crystallization properties. The amount of admixtures is very different in individual cases. Substances whose concentration is comparable to that of the crystallizing macrocomponents are called macroadmixtures. whereas those present in a concentration lower by two orders than that of the macrocomponent are called microadmixtures or microcomponents [ 10 11 .

2. Classification of Admixtures

7

Additives are put into the solution with the purpose of affecting the parameters of the process of crystallization and the product quality. Additives employed for aqueous solutions can be subdivided into several groups:

a) n e e acids and/or bases, adjusting the pH value of the solution. The pH

modifies the nature and the concentration of ions in solution. particularly when the latter contains salts of weak acids or bases 118).This pH value has a dramatic effect on the shape (40,1291 or size I1681 of product crystals and affects also the growth rate [148]. Acids or bases most frequently used usually have a common ion with the crystallizing substance. b) Inorganic additives can be subdivided into highly and less active ones.

High active additives include polyvalent cations such as Fe3+. Cr3+, A13+, Cd2+, Pb2+, a s well a s certain anions like W0,2-.

PO,3-. Very low

concentrations of these additives are sufficient t o exhibit a dramatic effect on crystallization (0.001 to 0.1 wt. %). In order to obtain a similar effect with less active additives we have to use much higher concentrations (1 - 10 wt. 96). Inorganic additives affecting the crystal growth rate often exhibit a similar influence on crystal dissolution 152.68.76.1991. c) The most frequently used organfc addftfues exhibiting high effectiveness are surface active substances and organic dyestuffs. It has been observed I461 that 1 molecule of such a n additive per

lo4 to lo6 molecules

of an or-

ganic macrocomponent decreases its growth rate. The effect of big orga-

8

2. Classifiatlon of Admixtures

nic molecules is usually not specific to that molecule: a substance can modify the growth of several macrocomponents and a similar modification can be obtained using very different organic additives 1411. This property may be ascribed to the fact that big organic molecules can be adsorbed a t any site on the crystal surface s o that their size is a deciding feature. Like in catalysis, the position of

substituents in the molecule should also be

very important [32]. The influence of organic substances on the growth rate of crystals is usually very dramatic but their effect on the dissolution rate can usually be neglected [41.46.240]. In many cases, where the additive is very active on crystal growth, even a 1000 fold concentration has no effect on dissolution 1321.

The effectiveness of a n admixture is closely bound to the given system and cannot be simply generalized. For the activity of additives on the crystal shape, Buckley 1321 defined the measure of the effectiveness of the additive a s the number of weight units of the crystallizing substance per one unit of the additive that causes a certain shape modification. Another way of measurement and evaluation of the effectiveness of admixtures has also been described in the literature I2191. The influence of admixtures drops with increasing temperature and growth rate 1321.

Admixtures in Crystallization

Jaroslav Njlvlt, Joachim Ulrich 0 VCH Verlagsgesellschaft mbH, 1995

3. Influence of Admixtures on Nucleation Several mechanisms of nucleation can be distinguished according to conditions in a supersaturated solution 11781: nucleation

- primary

- homogeneous - heterogeneous

- secondary - originatedfrom solid phase - originatedfrom the interphase solid-liquid

- collision breeding A basic criterion for this distinction I1 781 is the presence or absence of a

solid phase. While primary nucleation occurs in the absence of solid particles of the crystallized substance, secondary nucleation is dependent on the presence of crystals. For homogeneous nucleation. no solid phase is required, while heterogeneous nucleation is catalytically initiated by any foreign surface. Many details on the mechanisms of secondary nucleation can be found in the literature 1152,177,178,214,215,225j. Strong effects of the admixtures can be observed with primary nucleation and with secondary nuclcation due to mechanisms of the interphase. There are several papers dealing with the theory of the effect of admixtures on nucleation: in addition to those mentioned below, i.e. papers

(23.78.1571.

10

3. Influence of Admivtures on Nucleation

3.1. Homogeneous Nucleation

According to the theory of homogeneous nucleation. the nucleation rate increases a s the interfacial surface tension, asl decreases. As the surfactants dramatically lower the surface tension, their presence in solution strongly increases the nucleation rate [44.55.83.176]. We may expect, however, that other admixtures when present in higher concentrations raise the surface tension and thus decrease the nucleation rate. Very active inorganic admixtures characterized by a strong tendency to form coordination complexes decrease the nucleation rate: the stronger their influence, the higher the complex stability. One of the explanations tells that heteroclusters are formed in the bulk solution with the centre formed by the active ion 179.803. The number of these heteroclusters corresponds to the number of ions of the admixture, their size being given by the ratio of the supersaturation and the admixture concentration. The effect then consists in redistributing of the solute forming supersaturation to these heteroclusters s o that the supersaturation is effectively decreased. Clusters can grow only when the supersaturation is increased again. The effect of admixtures can here be explained by the electric field of the admixture affecting the behaviour of the macrocomponent [ 1551. The inhibiting effect of polyphosphates on the nucleation of sparingly soluble carbonates and sulphates is well known 186,1923. It can be explained thus: due to the geometric similarity of the active ion and the surface

3.1.Homogeneous Nucleation

11

structure of the macrocomponent. polyphosphate ions are adsorbed on the surface of undercritical embryi of the macrocomponent s o that these clusters cannot continue to grow (33.55.1891.The static adsorption model assumes that the embryo surface is covered by a monomolecular layer of admixture molecules [62,146.147.180]: the dynamic model of adsorption 1144,160.1611 is based on the probability of collisions of the particles of the macrocomponent with those of the admixture. Calculations of the Me time of embryi and the time elapsed between two collisions of the embryi with

the admixture show that the collision mechanism prevails in the initial periods of the nuclei formation, whereas later the adsorption mechanism with adsorption of the admixture on active centres of the macrocomponent prevails. The endothermic adsorption of the admixture decreases the stability of the surface and raises the energetic barrier of critical nucleus formation. For thts reason, the complex formed by adsorption dissociates before it could form a critical nucleus. This leads to increased stability of the system. Incorporation of admixture particles in the first period of precipitation is not expected by thts model. Nevertheless, experiments have shown 11801 that the first fractions of precipitated crystals contain much of the admixture. so that the assumptions of thts model are not completely

realistic. Admixtures belonging to the group of water-soluble wUoids (dextrin. gelatlne) raise the solution viscosity: the diffusion and mobility of particles are then decreased s o that their growth to a critical size is more difficult [ 133,1691.

12

3. Influence of Admixtures on Nucleation

There are also examples described in the literature 1167,1691 where the admixture accelerates the nucleation. This may be encountered in cases where the admixture reacts with the macrocomponent to form less soluble substances. Admixtures that have a common ion with the macrocomponent can decrease its solubility, this leading to a rise in supersaturation and thus to a decrease of induction periods of nucleation [ 10 1,102.2441. Another reason can be given in the case of admixtures with a significant hydration ability: they remove water from the hydration spheres of the macrocomponent [82.170,1741 and in this way decrease the solution stability 11331.

3.2. Heterogeneous Nucleation Using a droplet technique for investigations of the induction time of nucleation, Wen (2391 was able to differentiate between homogeneous and heterogeneous nucleation mechanisms. With pure NaCl solutions he found both the mechanisms but in the presence of Pb2+ ions the induction time measurements indicated no effect on the homogeneous nucleation. H e therefore concluded that impurities affected nucleation by working on the substrate rather than the nucleating crystal. Nevertheless, measurements carried out on only one system does not allow such a generalization. The additive may adsorb onto the heteroparticles making them either more or less active as catalysts [55].This would either

increase or decrease the

nucleation rate. Alternatively, the additive molecule may itself act

3.2.Heterogeneous Nucleation

13

as a heteroparticle providing a template 11961 for the precipitating substance. This would lead to an increase in nucleation rate proportional to the additive concentration. The heterogeneous nucleation can be treated as secondary nucleation with the mechanism of interphase layer. At the solid surface there are more or less oriented clusters that may be removed by fluid shear back into the bulk of solution 120.43.97.188.2161. These clusters, if they are of the critical size, can survive and form new nuclei. S@me mtlve substances deactivate heterogeneous particles and thus

increase the width of the metastable region 1165,1831. The extent of this action is given by the amount and catalytic activity of foreign particles. An opposite influence [203.204] can be explained by the fact that surface active substances decrease the surface energy so that the nucleation rate can increase. The shape of the curve of nucleation rate vs. the admixture concentration resembles the adsorption isotherms of surface active substances on solid surfaces so that there may be expected a direct link of the nucleation rate rise with the adsorption of the admixture on the surface.

14

3. Infruence of Adrnivtures on Nucleation

3.3. Secondary Nucleation One of the mechanisms of secondary nucleation is the mechanism of interphase layer. At the solid surface there are a more or less oriented clusters that may be removed b y w d shear back into the bulk of solution 143,188,2161. These clusters, if they are of the critical size, can survive and form new nuclei. Some admixtures call forth formation of rough surfaces or even

dendrltes

[loo]. Due

to fluid dynamic forces or due to partial dissolution

these dendrites can be removed back to the bulk of solution, where they serve a s new nuclei [61.1401. Active inorganic admixtures dilate the metastable zone in supersaturated solutions. In absence of admixtures, the probability of formation of stable aggregates at the solid surface is higher than that in the bulk of solution [177]. This is due to the physical adsorption of the particles of the macrocomponent and thus due to higher local supersaturation. In analogy with heterogeneous chemical reactions, adsorption occurs preferentially a t energetically advantageous active sites on the surface. If these advantageous sites are blocked by the admixture, however, then the probability of formation of a critical cluster diminishes and the nucleation rate decreases 1203,2041. In addition, adsorption of ions of an admixture that possesses higher charge than those of the macrocomponent damages the balance of electric charges o n the surface [156]and this leads also to a decrease in the nucleation rate 1203,2041.

3.3. Secondary Nucleation

15

In systems where the admixture can easily be incorporated into the growing crystals' lattice. the so-called impurity concentration gradient can be effective I22.611. Nucleation in the bulk of solution is hindered due to presence of the admixture a t high concentration. Incorporation of the admixture into the crystal lattice leads to a decrease of its concentration close to the surface so that spontaneous nucleation In the intermediate layer becomes possible again. Presence of growth-restrainers also exhibits an effect on nucleation I1261 (they enlarge the metastable zone width [ZlO]).

Admixtures in Crystallization

Jaroslav Njlvlt, Joachim Ulrich 0 VCH Verlagsgesellschaft mbH, 1995

4. Influence of Admixtures on Crystal Growth There exist a number of books and papers dealing with the theory of crystal growth [ 100,112.130.152.178,179,184.185.202.243]. Quantities, necessary for the application of these theories, are often not known s o several simplifications have to be adopted. Fundamental physical quantities then lose their physical meaning and become adjustable parameters. I n addition, experimental methods 172,1781 provide data of limited accuracy s o that the fit of experiments and theory often becomes a matter of statistics.

This must be kept in mind when discussing the effect of admixtures on the growth rate of crystals. Due to the different structures and energetical situations growth rate of individual crystal faces is also different. This also holds for the effect of admixtures on the growth rate of crystals and this is why individual crystal faces must be considered separately. The effect of growth rate dispersion can lead to different values on individual crystals, however, and this may be one of the reasons why the literature data are scattered and differ from those obtained by measurements in suspension [ 116. 2261.

4.1. The Role of the Solid Surface Kossel 1114.1 151 and Stranski 1212.2131 recognized the importance of atomic inhomogeneities of crystalline surfaces and its relevance to growth processes.

They

distinguished

three

different regions

on

a

crystal

4.1. The Role of Solid Surface

surface: a) frcct surfaces. which are atomically smooth: b)

17

steps, which

separate flat terraces: c) kinks. which are formed in incomplete steps. Kinks present the most probable position for solute integration because the highest bonding energy associated with integration occurs here. Flat surfaces are the least energetically probable sites for incorporation. Nevertheless. admixtures. according to their nature, can adsorb on different sites on the surface: they can affect the relative interfacial energy of individual faces or block the active growth centres [30,38J.The effect of admixtures is different if they are adsorbed o n different sites 1531.

Fig. 4.1: Surface growth sites

According to growth rate equations and considering that adsorption lowers the edge or surface energies and the size of the critical two-dimen-

18

4. Infruence of Admixtures on Crystal Growth

sional nucleus, we see I181 that the expected result of adsorption is a n increase in the crystal growth rate. Other parameters must then act in the opposite direction in order to explain the decrease of the growth rates generally observed in habit change phenomena: the slow down of the flux towards to the steps 1371, the decrease of the lateral advancement velocity of growth layers due to step pinning [41.66.186.187.1981. a decrease of number of kinks available for the growth [48,491. In general, admixtures can be subdivided into strongly adsorbed and weekly adsorbed ones. One can suppose that physical adsorption is characteristic for weekly adsorbed admixtures whereas chemical bonds are typical for strongly adsorbed substances 1491. Mechanism of strongly adsorbed admixtures [41.158.179,234]

assumes that immobile particles of

the admixture are spread over the crystal surface. When a moving growth step hits such a particle, its edge becomes deformed. In the case where the distance of two neighbourlng adsorbed particles is smaller than the size of two-dimensional critical nucleus, the movement of the step will cease [67], otherwise the step will be deformed and pushed through the slot between adsorbed particles and continue in its movement but with a reduced rate l'i [9.41,186,187].

(4.1)

where l', represents the growth rate in absence of a n admixture and n is

4.1. The Role of the Solid Surface

19

assumed to be the average density of admixtures on the ledge ahead of the step 1411. This equation indicates that the velocity of steps is reduced by a n amount proportional to the concentration of adsorbed admixtures on the terrace. If such a foreign particle is incorporated into the crystal lattice, it causes some deformation of the lattice. Joining of another particle of the macrocomponent to such a deformed lattice may be difficult (1691. The retardation of growth takes place only if the height of the adsorbed particle can be compared with that of the moving step 1461. Some inorganic admixtures can form complex substances (double salts) in combination with the macrocomponent: such complex nuclei are formed at the sites with strongly adsorbed admixture. These complex nuclei are not stable, they may redissolve b u t the admixture remains adsorbed on the surface [34]. Another mechanism is encountered with weakly adsorbed admixtures. Here, the retarding action is due to blocking of the active growth centres. The strength of bonds between the lattice particles and the admixture determines the mobility of the admixture. Weakly adsorbed admixture can diffuse two-dimensionally on the surface and can be expelled by the movlng step, b u t at the cost of growth rate reduction. If the growth is sufficiently slow and the amount of admixture is not too high, adsorption equilibrium

can be attained at the surface. The relationshlp between the linear growth rate of the face

r'

and the concentration of admixture wi can be described

I12.151 by

1'

=

Wl

1 6 - ( 1 6 -1'- ) . -

B +w,

(4.2)

20

4. Infruence of Admixtures on Crystal Growth

where lv0 and l',

represent respectively the growth rates in absence of

admixture and in presence of admixture when all of active growth centres are occupied 12341. The surface fraction covered by the admixture can be determined using, for example, the Langmuir adsorption isotherm with the constant B. The linearized form of this equation I531 allows us to obtain the value of free enthalpy of adsorption [ 13.16.171. The Langmuir isotherm has been used also by other authors I581 considering surface diffusion to be the rate-determining step. The equation above holds even here if we take l'=- 0 130.1121.

Another model is based on a n estimate of the probability of occurrence of free growth active sites and uses the Freundlich adsorption isotherm to predict the movement rate of a growth step 14,661. All of the models mentioned above have been experlmentally verified with a satisfactory result [53].A survey of adsorption models is given in several papers 153.55.58.1121.

When the growth of a crystal face is governed by the mechanism of two-dimensional nucleatton, then the effects of admixtures on nucleation that

are mentioned in the preceding chapter may come into consideration. The

size of a two-dimensional nucleus is [10.411

2a Q 21, =-

kTS

(4.3)

4.1. The Role of Solid S@me

21

where a is the lattice constant, o the surface energy and S relative supersaturation. Since the size Zc , which can be compared with the admixture spacing on the surface, determines whether the step can advance or not, this equation indicates a critical supersaturation that must be exceeded in order to allow growth. According to Glasner I79.801 the crystal growth is executed by deposltlon of heteronuckl on the crystalline surface. The effective supersatu-

ration is then given by the product of the number of heteronuclei (i.e. of the amount of molecules of the admixture) and of the average size of a heteronucleus as expressed by the number of molecules of the macrocomponent forming a n average heteronucleus. Su.@atants and organic d y e s b g s usually exhibit a very sensitive effect

on the crystal growth rate; their big molecules are attached to the crystal surface through their polar I301 or hydrocarbon Ill21 portions and prevent the access of the macrocomponent molecules to the surface 1361. Complexlng agents, e.g. EDTA. remove certain ionic admixtures from the solution and

therefore act in a n opposite direction I116.2101. Certain admixtures. when present in low concentrations. can accek-

rate the growth of crystals [121.148]. First, this are admixtures lowering the surtace energy; one can expect those crystal faces possessing higher specific surface energy adsorb more admixtures and thus grow faster (141. In some cases, when the admixture has a similar structure parameters or forms complexes with a structure close to the lattice of the macrocompo

22

4. Infieme of Admixtures on Crystal Growth

nent. adsorbed admixture molecules can form new active growth sites on the surface that are energetically more advantageous for further growth

I 12,1691. Available data thus clearly substantiates the necessity for geometric simflarlties between the additive and the crystal surface 1551. Whether adsorption occurs due to surface interaction between ionizable groups on the additive molecule and ions in the crystal surface or due to a surface replacement mechanism is unresolved 1551 and will probably be different in different cases. In the case of crystal growth such adsorption mechanisms are easily visualized to involve the blocking of key sites on the surface and hence reduction in growth rates. The effect of admixtures can be combined with other factors, like pH (acid or base can be considered a s a second admixture) or, if a higher amount of admixture affects the solubility of macrocomponent. we can speak of the combined effect of admixture and supersaturation I10 1,1341.

4.2. The Role of the Interphase Solid - Liquid The growth of a crystal can be represented as three successive steps: a) Transport of the substance from the bulk of solution to the crystal; b) transport of the substance through the layer close to the crystal surface: c) incorporation of the substance into the crystal lattice, either by surface diffusion a t the kink or by formation of a two-dimensional nucleus. The first step

is

largely

affected

by

the

fluid

dynamics

of

the

system

4.2. The Role of the Interphase Solid - Liquid

23

and its role is usually not too important. The last step has been discussed in detail in the preceding chapter; we shall thus pay attention to the second step. The interphase or the "interface phase" 1511 is understood to be the region between the "perfect" solid phase and the "perfect" liquid phase. It can be diffuse (1.e. there are layers a t the phase interface and it is impossible to say clearly whether they belong to the solid or to the liquid; the changes of physical quantities occur within the distance of several lattice constants) or it can consist of a quasi-liquid layer, which usually has

a higher concentration of the solute in the bulk of solution 128,1751. The structure of the interphase has been studied using the theory of fractals [42.127.128.194] with the result that different growth models led to the

formation of clusters in the interphase with different fractal dimensions. These characterize the shape of clusters or the roughness of the interphase. Transport of molecules through the layer adsorbed o n the crystal surface is reallzed through diffusion. The admixture can play different roles in this step. It can affect the viscosity of the solution. in particular a t higher concentrations. It has been shown 11131 that even small amounts of surface active substances can dramatically raise I1 13.1181 or decrease I1191 the viscosity.

Admixtures in Crystallization

Jaroslav Njlvlt, Joachim Ulrich 0 VCH Verlagsgesellschaft mbH, 1995

5. Influence of Admixtures on Crystal Shape Under conditions of extremely slow growth, the shape of a crystal is determined by thermodynamics: the crystal tends to grow to a shape of a polyhedron having rnfnirnum surface energy 1751: for i faces holds

a,A, = min.

(5.1)

Such equilibrium shape can be affected by admixtures in the case that they change the specific surface energy of individual faces in a different way.

This condition is. however, met only exceptionally, as crystals usually grow under highly non-equilibrium conditions. Crystal shape is usually determined by the growth rates of individual crystal faces. According to the principle ofouerlapplngfaces [ 1691 the faces

that grow more slowly remain in the final crystal shape whereas the

I

Fig. 5.1: Principle of overlapping faces

5. Influence of Admixtures on Crystal Shape

25

rapidly growing faces disappear 165,701. The condition necessary for changing the crystal shape is thus to change the relation in growth rates of individual faces. As was pointed out earller. additives may influence the crystal growth rate. If they

are preferentially adsorbed

on certain

crystallographic faces, the mode of growth is altered 1501. Parameters influencing the occurrence of adsorption include the steric arrangement of molecules in the additive and their charge and dipole moment, a s well a s the electric field on the crystal surface [l69]. The rather pronounced effect of oxygen anions on the crystallization of oxy-salts shows that not only dimensional similarities but also similarities of the fields of force are of importance here. The Hartman-Perdok I89.90.9 11 technique based on calculations of the attachment energy reduces crystal structures to chains of strong bonds: the slowest growing faces are those lying parallel to a t least two bond chains. The faces most likely to be influenced by a n additive are those for which the change of bond energy due to additive is minimized. Some assumptions have to be made for the conformation of the additive molecule in the lattice. s o best results can be obtained with tallormade addltlues [63.123.124.228,235] or lf crystallographic data is known for the

substance with additive [232]. Such organic additives are active in relatively large concentralons > 1% 12421.

As the interatomic spacings and electric fields are different for different crystal surfaces [82], selectlue adsorption of individual admixtures occurs on the most favoured ones [ 11.31.35.163.195]. It is therefore often

26

5. I n t n c e of Admixtures on Crystal Shape

possible to predict the effect of individual additives on the shape of crystals [ 18,168,2231 if relevant structural parameters are available. As calcu-lation

of the fields of force is generally possible only in the simplest cases, and even then a s a rule only with difficulty, it is advisable to base calculations of structural analogies not on the absolute sizes of the ions but on epitaxial considerations. i.e. on the crystallographic parameters of the lattices of the crystallizing and the admixed substances [55.168,193.217]. Whetstone 12411 suggested that the charge centres of the polar groups should coincide accurately with sites for similarly charged ions in the crystal surface and any such group should not cause a disturbance of the lattice about the sites in question. One may here consider both substances as having a common ion 1162,1681 or as forming a complex compound [120.168], The closer the lattice dimensions of the crystallizing and the admixed substances are the more effective will the admixture be. As a condition for the incorporation of the admixture into the lattice it is generally considered that the lattice dimensions of the two substances should not differ by more than 5 to 15 % [32.73,74.94,111.149.150.193.220].

Example: How would the addition of A13+ affect the habit of ammonlum sulphatc crystals? The lattice dlmensions of ammonium sulphate are 1.056 nm, c

-

a

=

0.595 nm. b

0.773 nm. and that of aluminium ammonium sulphate is a

=

-

1.22

nm. Each basal surface of arnmonlum sulphate cells contains two molecules. Their mean distances are as follows:

5.Influence of Admixtures on Crystal Shape

(100) corresponds to (a+c)/2

-

molecule (001) corresponds to

(0.77 + 0.59)/2

- 0.68 nm

or

27

0.34 nm per

(a+b)/2

-

(1.06+0.59)/2

-

0.82 nm

or 0.41 nm per

@+c)/2

-

(1.06 + 0.77) / 2

-

0.91 nm

or 0.46 nm per

molecule (010) corresponds to

molecule The mean for (110)planes is (h2 + k2 + l2)-li2 and is proportional to the particle density. Its value I s thus given by its relation to (001)

One thus obtains for the dimensions in nm Alum

Ammonium sulphate

0.611

Difference %

(110)

0.58

4.9

(100)

0.68

9.3

(001)

0.82

34.0

(0101

0.91

49.0

The results show that one should expect (110) and (100)faces to be retarded in growth

so

that flatter needle-like habits should result. This has been confirmed

experimentally I168l.

A more quantitative way I1221 consists in determination of atoms in the

upper layer of each crystal face from the crystallographic data of the s u b -

stance. These layers are then plotted in the scale of Stuart-Brlgleb mole-

28

5. Infruence of Admixtures on Crystal Shape

cule models. The additive molecules are also modelled with these models. I n this way, we get a two-dimensional model of the upper layers of the crystal and a three-dimensional model of the additives. Assuming, that the growth of a face may be influenced by a n adsorbed additive, we try to find a well fitting position of the admixture on the surface. A well fitting position is characterized a s a position, where the additive has a s much ease to build attractive interactions to the surface a s possible. One possibility is to make these fits with a computer program. If we find a n additive. which has a well fitting position on one specific face of the crystal. we may expect it will be a n effective habit modifier. Another mechanism described in literature 12221 assumes that the effectivity of the admixture depends only on its properties. The electric field of the admixture 11561. given by the ionic charge, diameter [191 and deformation ability of its electron envelope are responsible for the effectiveness of the admixture. Ions present In the interphase accelerate the orientation of nuclei or clusters, prevent their agglomeration and thus contribute to a regular crystal growth. There exists also a possibility of formation of complexes I1201 of various stability, contributing to a change in properties of the interphase as well a s of the bulk solution. Another factor that can play a role is the hydratron of ions 11531: hydrated ions come into the adsorbed layer, "dilute" the interphase. slow down the diffusion and s o retard the crystal growth. The reverse flow of the hydration water also acts against the growth.

5. Infzuence of Admixtures on Crystal Shape

29

Another theory 12011 supposes that admixtures can affect the shape of crystals only when they are incorporated into the crystalline body. An admixture particle adhering to a crystal face acts on the deposition of the macrocomponent independently of its position; if it is incorporated into the lattice, it can affect just particles lying very close to it. A s the admixtures are adsorbed on different faces in a different amount, they affect the growth of these faces in a different degree.

An important class of additives are the so-called "tallor-made"addltiues 1112.2361, which are designed to interact In very specific ways with

selected faces of the crystals. These compounds contain groups that are similar to the crystallizing substance and are thus readily adsorbed at growth sites of the crystal surface. These additives then expose the opposite side, which chemically or structurally differs from the macrocomponent molecule, thereby disrupting or retarding the growth of the affected face [ 11. The design of these molecules can be achieved (45,601with knowledge of the stereochemisb$

and structure of the substrate crystal. In particular.

existing studies have relied on hydrogen bonding and chirality a s powerful recognition factors.

Admixtures in Crystallization

Jaroslav Njlvlt, Joachim Ulrich 0 VCH Verlagsgesellschaft mbH, 1995

6. Influence of Solvents Close to the interface, transport is restricted to diffusion through the diffusion boundary layer. The width of the boundary layer is a function of the fluid dynamics, viscosity and other mass transport-related properties. After the solute molecules diffuse from the bulk liquid phase to the interfacial region, they adsorb onto the surface and/or diffuse two-dimensionally on the surface before being integrated into the crystal lattice I 1121. During the surface diffusion step, bonds between the solute and solvent molecules are broken. Depending on the ease in which desolvation occurs, this step can be rate-determining to crystal growth. A more quantitative approach is to analyze the solvent effect on the

molecular level 11591 . The solvent molecule can be divided into segments, where its group similar to the solute is adsorbed and becomes part of one of the crystal surfaces, while its other part emerges from that surface. Then, the energy calculated as a sum of van der Waals

and electrostatic

interactions and these calculations are then repeated for a number of lowindex faces. Besides the structural conditions imposed by the crystal, it. is known 1181 that the affinity of solvents for a given face may vary considerably 1125,2371. The higher

the number of PBC vectors piercing a face, the

stronger is the adsorption of the solvent [109.110].Like admixtures, strongly adsorbed solvents may cause noticeable changes in the crystalli-

6.ZnJuence of Solvents

31

zation behaviour of the macrocomponent 12301. Hydrogen bonding frequently plays a dominant role in the action of solvents on the growth of both inorganic and organic crystals. Especially illustrative is the importance of these interactions in the action of polar and nonpolar solvents on crystallization of many substances 12381. One may expect that polar solvents that form a hydrogen bond with polar faces of the crystal reduce growth rate of that face, thus increasing its relative area: conversely, nonpolar solvents do not exhibit such effects. Thus, large solvent effects are expected in crystalline systems having faces of significantly different pola-

rlty 18.1 121.This general rule may be one of the best indicators of the abllity to change crystal habit by the use of a n alternative solvent. An example of a solvent enabling laboratory investigation of the polarity effect is a n acetone/toluene mixture [ 1121. The knowledge of dielectric constants of various solvents can be extremely helpful 12241. It follows from the preceding paragraph that solvents which modify

the hterJbce structure can also alter the growth kinetics of the particular crystal face. One of the most important results of growth theories has been the quantification of the effect of solvents on crystal interface structure. A parameter, called the surface enb-opy a-factor. now allows identtfication of likely growth mechanisms based only on solute and solution properties [ 112.1781. Precise values

of a cannot be determined, b u t estimates may be

made from enthalpies or entropies of solution or of surface and edge energies 154,1511.Increasing deviations from solution ideallty tend to de-

32

6.Infruence of Soluents

press the a value. Such calculations have been made for the growth of hexamethylene tetramine from the vapour and from water, water/ethanol and water/acetone solutions by Bourne and Davey 125.261 who were able to postulate the appropriate growth mechanisms for various experimental conditions, e.g. the BCF dislocation growth from the vapour. surface nucleation limited growth from aqueous solution and surface integration controlled growth from mixed solvents [ 1511. Interfacial structures of crystals were first related to thermodynamics by Jackson [95].Bourne 1241. Bennema 15.61. Temkin

12181 and Davey 154.56.591. If s-s designates the

bond between solid species, f-fbonds between liquid specles and s-f bond between solid and liquid species, then in formation of an s-f bond. a n s-s and an frf bond must be broken. The energy contribution is given by [ 1781

The surface entropy factor is then

a=4 ~ / k T

(6.2)

or

a = Y(AH'+AW)/RT

(6.3)

where F is the ratio of numbers of nearest neighbours on the surface and

6.Infuence of Solvents

33

in the bulk 196,1121 and AHf and A k P are the enthalpies of fusion and of mixing. respectively. Another equation relates the a factor to the solubility xs 171 and communal entropyfsf:

2

a = ( l - x s ) .(q,-tnxs)

(6.41

Results obtained from simulations permit determination of the mechanism that will occur during growth [27.77,2051: For a 2 4. the growth occurs by the dislocation mechanism alone and the surface is very smooth. For 3.25 a < 4.0,growth follows the nucleation mechanism (Nuclei Above Nuclei or Birth and Spread) and the surface is somewhat rougher. For a < 3.2,growth occurs through the mechanism of direct species incorporation and the surface is very rough. This approach can eventually lead to methods of choosing optimal solvents.

Admixtures in Crystallization

Jaroslav Njlvlt, Joachim Ulrich 0 VCH Verlagsgesellschaft mbH, 1995

7. Distribution of Admixtures Increasing demands on the purity of product crystals, in particular in the production of ultra-pure chemicals and in the separation of radioisotopes, led in recent years t o an intensive study of the distribution of impurities between the liquid and the solid phases. Nevertheless, first studies on this subject have been published already at the end of the last century. During this time. various mechanisms of impurity incorporation have been described [30.85.166.202.211.221.2451: 1. Zsornorphous LncZusion

- true isomorphism (solid solutions) - isodimorphisrn - isomorphism of second type - anomalous mixed crystals

2. adsorption mechanisms - external adsorption - internal adsorption

3.mechanical inclusions - of coUoids - of liquid phase

7.1. Solid Solutions Let us consider a three-component system: the macrocomponent A, the admixture B and the solvent S . There exist three fundamental limiting cases [171]:a) the macrocomponent and the admixture are completely immiscible. b) the macrocomponent and the admixture are miscible in a

7.I , Solid Solutions

35

limited range of concentrations. c) the macrocomponent and the admixture

are completely miscible. As the admixture concentration is usually low, cases b) and c) can be discussed altogether, but if the solubility of the admixture is below 1 %, the substances cannot usually be considered isomorphous. The condition for isomorphous incorporation is the fit of ionic or molecular diameters within 10 to 15 940 [30]. These cases are schematically shown in Fig. 7.1.

I \ \

II \I \ \ solid S

I immiscible in s.lid B solution

-B

Fig. 7.1: Schematic representation of a ternary system with components a) immiscible in solid phase

b) miscible in solid phase

In the system of immiscible components (right) the diagram indicates that for any composition of the ternary system only pure component A can precipitate. If both the components are miscible (on the left) then they form

36

7. Distribution of Admixtures

solid solution. The relative amount of the impurity incorporated in the crystalline phase is related to the energy change upon binding the admixture relative to that upon binding the macrocomponent 181. 7Yu.e solid sohtions, t e .

true isomorphous incorporation. are expected where the macrocom-

ponent and the admixture are similar in size and shape i93.1121: they form a common lattice in a large interval of concentrations by mutual substitution in lattice centres - so they must have a n identical lattice type and very close lattlce dimensions. Isodimorphism is characterized by the ability of two substances, having different modifications under given conditions, to form a common crystal lattice identical with that of the macrocomponent: their structures must be similar, however. I t is interesting to note that when small mismatches in size occur, the solubility of small molecules in a host lattice of larger ones is more probable than the solubility of large molecules in a lattice of smaller ones [88,93,207]. The incorporation of ionic species was

directly

related

to

the

charge

and

molecular

size

and,

for

isodimorphous substances, also to the distance from the transition temperature of structures. There exist a number of studies quantitatively describing the distribution of the admixture in the formation of solid solutions 139.87.1 12,1901:the most frequent equations are

InK, =in[:]=>(---)

AH' R

1 1 T TB

(7.1)

7.2.Isomorphous Inclusion

37

where KB is the distribution constant, x ~ and , xBf ~ are mole fractions of the impurity in crystals and in the solution, AHH$ is the heat of fusion (or crystallization) of the admixture and TB is its melting point. The product purity can be improved from solvents in which the admixture has a high solubility. This also explains the effect of temperature on some separations through its direct effect on component solubilities I 1 121. There exists a close simllarity between the criteria for habit modification and solid solution formation 12,601.

7.2. Isomorphous Inclusion According to Hahn’s 1851 precipitation rule, coprecipitation of microimpurities in crystals of the macrocomponent always occurs when the microcomponent is included isomorphously into the crystal lattice of the macrocomponent or if it contributes to normal lattice formation. Two basic distribution laws have been formulated for isomorphous impurity incorporation I138.14 1,166,1711: Doerner and Hoskins I641 assume that a n exchange reaction between macrocomponent particles in the lattice and microcomponent particles in the solution occurs on the surface of each newly formed layer. Assuming that crystallization is very slow s o that equilibrium is established. they derived the so-called logmtthrnic disMbution law

log-

XO

xo -x

=

R log-

YO

Yo-Y

(7.2)

38

7.Distribution of Admixtures

where xo and yo are the initial concentrations of the microcomponent and the macrocomponent, respectively, x and y are the precipitated parts of both components and il is the logarithmic distribution coefficient. If h > 1. the solid phase is enriched in the microcomponent during

the crystallization. otherwise, it is depleted in the microcomponent. In addition, the logarithmic distribution law assumes that diffusion in solid phase is negligible. Therefore, the admixture distribution in the solid phase is inhomogeneous: for h > 1, the highest impurity concentration is in the

centre of the crystal and it decreases towards the surface, while for h < 1 this distribution is inversed.

The Nernst distribution assumes that the ions of the two components are in equilibrium with the ions inside the crystal. The microcomponent distribution is then homogeneous throughout the crystal and the homogeneous dIsMbution law holds [92.103,106.117.190~in the form

- Xxo -x

-

D- Y

(7.31

Yo-Y

where D is the homogeneous distribution coefficient. The homogeneous distribution law states that, when two substances separate in the form of isomorphous mixed crystals. the micro- and macrocomponents are dis-

7.2. Isornorphous Inclusion

39

tributed between the solid and liquid phases in a constant ratio. For D > 1. the solid phase is enriched in the microcomponent. while for D
> uR >> uT -0. Detailed analysis of this case 1391 confirmed that a homogeneous distribution of the admixture in the solid phase is not necessarily contingent on a multiple recrystallization. 3 ) Migration regime with vR >> up >> uT >> 0 assumes very slow crystal growth.

If the diffusion proceeds quicker than the growth, solution of these stationary conditions leads 147.1411 to the logarithmic distribution law.

This general solution led to the following conclusions: a) Homogeneous distribution holds for constant concentrations of the macro- and microcomponent in solution. b) Logarithmic distribution is obtained for constant concentration of the macrocomponent and a variable concentration of the microcomponent in solution. c) If neither the concentration of the macrocomponent nor that of the microcomponent is constant, complicated ex-

7.3.Anomalous Mived Crystals

41

pressions are obtained that can be solved for the condition of a very slow crystallization; applying several simplifications. both equations for homogeneous and logarithmic distribution can be obtained: this explains, why the logarithmic distribution has been found in several cases where the experimental conditions differed from those applied for the derivation of the law. A number of authors investigated the effect of temperature 1108.1451,

agitation I131.1321. and acidity of the solution 1841 on the isomorphous distribution of impurities.

7.3.Anomalous Mixed Crystals Sometimes (e.g.. in syncrystallization of heavy metal chlorides with ammonium chloride 1971). true mixed crystals cannot be formed a s the micro- and macrocomponent are not isomorphous owing t o their chemical nature and crystal structure parameters. The ions must have a similar diameter but their charges must be different (e.g., B a s 0 4 and KMnO, or CaCO, and NaNO,). True solid solution is not expected here. Adsorption is also not involved,

as the admixture is distributed

homogeneously

throughout the crystals and the distribution coefficient is Independent of external crystallization conditions and of the specific surface area of crystals. With this type of system, like PbSO, - RaS04 , a so-called lower Umff

42

7 . Distribution of Admtvhues

of miscibiilty can often be observed [104.105.107.164]: on decreasing the

concentration of admixture in the solution below a certain limit, syncrystallization of the two components suddenly stops. This phenomenon can be explained thus: while in isomorphous inclusion the crystallizing units of the macrocomponent are replaced with particles of the admixture in the lattice being formed, here whole sections of the lattice are replaced. At very low concentrations of the admixture, the formation of such lattice sections on the crystal surface is improbable and hence a lower miscibility limit appears.

7.4. Adsorption Inclusion

Coprecipitation of admixtures was first investigated by Paneth [ 1821 who formulated the following rule: The cation of a n admixture is the more strongly adsorbed on the precipitate, the less soluble the component formed together with the anion of the macrocomponent is. This rule was been later modified by Hahn [55].It is thus required that the charge of the adsorbed ion should be opposite to that of the adsorbing surface and that the solubility of the component combined from the ions of both admixture and macrocomponent should be low. In addition, the charge and the size of the adsorbed ion are also of importance [19,70.81]: the polarisation of the ion proportional to lonix charge / (bnic dlameter)2

7.5. Mechanism of Internal Adsorption

is decisive. Adsorption

43

of positively charged ions of the admixture can oc-

cur on a neutral or even on a n also positively charged surface [155]. however. In any event, a direct dependence between the amount of admixture adsorbed and the specific surface of crystals has been found.

7.5. Mechanism of Internal Adsorption Internal adsorption is intermediate between isomorphous inclusion and adsorption inclusion. In a similar manner to adsorption. it is characterized by the variability of the distribution coefficient with changes in the crystallization conditions. These anomalous mixed crystals exhibit a regular but discontinuous distribution of the admixture, owing to Selective adsorption on certain faces of the growing crystal I209). When the distribution of impurity in the crystal is monitored (e.g.. visually with coloured admixtures, or by autoradiographic methods I1671). the crystal is found to be subdivided into individual sectors, identical with bipyramids of faces that exhibit selective adsorption. This phenomenon is therefore also called sectorial crystalgrowth [11,166,171,195.2311. The existence of such selective

adsorption is also reflected in the change of crystal shapes. The term internal adsorption is also used for the adsorption occurring on the internal crystal surface, closely connected with various defects in crystal structure like breaches or microcavities formed in the block

44

7.Distribution of Admixtures

structure of real crystals. Admixtures trapped at such sites I2001 are covered by new crystal layers so that they cannot be removed by washing without substantial dissolution 1301.They can move, however, if a temperature gradient is present across the crystal body 1197.2291.

Fig. 7.2: Sectorial crystal growth

7.6. Mechanical Inclusions

45

7.6. Mechanical Inclusions

Under certain conditions. trace amounts of admixtures in solutions can form colloids, the centres of which can contain various impurities like dust particles. During crystallization of the macrocomponent. these substances can be deposited on crystal faces and covered by subsequent layers of the growing crystal. Another extreme case is inclusion of the other liquor inside the growing crystals which usually occurs when crys-tallization proceeds

rapidly

in unstirred

solutions

[30]. This

sort of

crystal

contamination can be avoided by slower crystallization, removal of colloidal particles from the solution and better stirring.

7.7. Materials Balance for Crystallizationin Presence of

Impurities Recycling of mother liquors is a frequently used method in crystalli-

zation that serves a] for minimalization of the amount of discharged mother liquors, b) for adjustment of a n optimal suspension concentration. As the feed usually contains impurities. these impurities may accumulate in the crystallizer and it would be advantageous to know the maximum recycling ratio, a t which the product would still contain impurities within allowed limits.

An

answer

can

give a

complex materials

balance

of

the

46

7.Distribution of Admixtures

crystallization and separation unit 11731. A simple block diagram of the unit is shown in Fig. 7.3. Material balances of individual blocks can be calculated in a usual way; the crystallizing macrocomponent and the solvent are considered. The impurity is incorporated into crystals according to the Nernst law

mcr Wor = D1fmcl

(7.8)

WOl

where ma and m,., represent the mass of i-th impurity and that of the macrocomponent in crystals, respectlvely. and

war:

and wOl are corres-

ponding concentrations in the solution. Another part of the impurity is trapped on the surface of crystals with adhering mother liquor, proportional to the liquid content withdrawn with the crystals of product crystals

(7.91

where the subscrlpt c represents crystals and f represents the mother liquor. Percentage of the impurity in crystals is then

7.7 Materials Balance

I

47

vapour recycIe

si product

Fig. 7.3: Block diagram of the crystallization / separation unit with recycle of mother liquor

(7.10)

Mother liquor is divided into recycled part and withdrawn part in a ratio given by the recycling ratio R:

R=

recycled mother liquor total mother liquor

(7.11)

7.DLstributionof admixtures

48

An example of typical results 11731 is shown in Figs 7.4 and 7.5.

The following conclusions can be drawn from the simulations 11 731:

a) The time necessary to reach the steady state depends on the recycling ratio. b) The effect of the distribution coefficient of the admixture prevails in the

region D,, > 0.1, whereas the effect of adhering mother liquors becomes very important a t D,, < 0.5. c] The impurity content in the product from a cooling crystallizer is almost independent of the mass of precipitated crystals and of the recycling ratio R.

In the products from evaporative crystallizers. the impurities increase with the recycling ratio, in particular for admixtures with D,, c 0.5. whereas for

D,,

-

1 the purity slightly increases.

Another paper 11431 deals with the optimization of conditions for improving the purity of crystals.

7.7. Materials Balance

49

1.0

0.8

0.6

0.4

0.2

0

0

1

2

3

4

log D, Fig. 7.4:Dependence of the impurity contents in a product from a cooling crystallizer as function of the distribution coefficient D,i and the humidity of product crystals. The curves correspond t o the liquid content withdrawn with the crystals wco(from the top) 0.20, 0.10, 0.05 and 0.01, respectively

50

7.Distribution of Admixtures

2.5

4

2.0

15 1.0

0.5 0

0.5

0.6

0.7

0.8

0.9

10

R Fig. 7.5: Impurity contents in a product from an evaporative crystallizer as a function of the recycling ratio R and the distribution coefficient D,, (with a constant liquid content withdrawn with the crystals).

Values ofDI1: 1 6

... 1.0

... 0.005,2 ... 0.01,3 ... 0.05,4 ... 0.1,5 ... 0.5,

7.8. Cascade M i a t i o n

51

7.8. Cascade Purification Crystal contamination can arise from a number of causes. This is a n undesirable phenomenon when high-purity products are required. In spite of the different mechanisms, the distribution of a microcomponent a t

equilibrium

can

frequently

be

approximated

by

the

homogeneous

distribution law 11381 that can be written as

Y=k,X

(7.12)

where X and Y are the relative masses of the microcomponent related to unit mass of the macrocomponent in the liquid and solid phases respectively. If the initial mass fraction of the microcomponent in crystals is yo and its final value is yf then [ 1371 Y and X are:

(7.13)

-

Wf - (Wf - weq)YO

X=

1-yo

Y'

1- yi

From the point of view of economy in discharge of solutions, the multistage

counter-current recrystallization seems t o be most advantageous (Fig. 7.61.

52

7.Distribution of Admixtures

t ,,k-I l c

Q

mktl sol xk+l

Fig. 7.6: Definition of streams in the k-th stage of a cascade with counter-current recrystallization

The balance of the microcomponent in the k-th stage can be written in the form [ 135) :

m, Y k-l

+ mL x”-’ + m,,

xk+l =

m, Y

+ (mL+ mso,)xk

(7.14)

where the subscripts c, L and sol represent the crystals, liquid adhering on crystals and solutlon respectively, and the superscripts express the serial number of the stage. The mass balance for the microcomponent over the whoIe n-stage recrystalhation system can be written as:

7.8.Cascade Puriatron

m, Yo + mL X o +mso,Xn+' = m, Y n + m, X"

+mso,X'

53

(7.15)

The aim in solving this equation is to find the microcomponent contents in the product, Y". and in the exit mother liquor. X1.For the condition

and after introduction of the dimensionless concentration parameters

zk

=

Yk/ Y o

(7.17)

and the recrystallization factor

~Ww K = mdmc -WL-W~ kH +mL I me kH+----

WL-

WW

1 - w ~ ~ ~

WLWeq

(7.18)

1- WLWeq

the equations above can be solved 1137.1393 with the result

z;

=(l+K-k,K)-l

l / Z , "= ( l + K - k , , K ) ( l + K )

(7.19)

-K

(7.20)

(7.21)

7 . Distribution of Admixtures

54

Example: A saturated solution of KAl(SO4)z at 6OoC has been cooled down to 2OoC.

The original salt contained yo dropped to 2

. lo-*

- 1.3

Na. After crystallization the Na content

Na. The respective solubilities are w1

-

- w (60)- 0.5585

, weq

-

w (20) 0.1127. The distribution coefficient found in independent experiments was

kH WL

-

0.035. Liquid content withdrawn with the crystals of separated crystals was

- 0.03.I t follows that the recrystallization coefflclent K - 6.50. We shall calculate

the number of stages necessary to obtain crystals with a Na content 100 tlmes lower. We obtain:

-

Zf! 0.1375

- 0.0208 9.” - 0.0032 Zy

< 0.01

The required purification can thus be achieved in three stages.

A n analogous solution has been found 11361 also for a cross-current

flow model with the result that this model requires higher solvent consumptlon and is thus less advantageous. In melt crystallization. additional purification steps like sweating and washing can reduce the number of stages. Sweating is a temperature induced process step which leads to a liquidizing of impurities in crystals due to the temperature increase to the melting point of the major component. Washing is a stripping of the crystals of the adhering residual mother liquid by rinsing with pure product or by a so-called diffusion washing.

Dzfusion washing is a purification due to a liquid - liquid diffusion of impurities out of the crystal (pores or cracks) into the surrounding purer melt [181.197.227,228.2331.

Admixtures in Crystallization

Jaroslav Njlvlt, Joachim Ulrich 0 VCH Verlagsgesellschaft mbH, 1995

8. Notations A

surface area

a

lattice constant

B

constant

C

concentration

D

homogeneous distribution coefficient enthalpy of fusion enthalpy of mixing

K

recrystallization factor

KB

distribution coefficient

k

k-th stage

k

Planck constant homogeneous distribution coefficient growth rate of a face in presence of admixture growth rate of a face in absence of admixture growth rate of a face in full coverage by admixture

mass of crystals n

total number of stages

n

average density of the admlxture on a surface

P

concentration (wt. %)

R

gas constant

R

recycling ratio

S

relative supersaturation

56

8.Notatlons

-T

temperature

TB

melting point of the impurity

UR

mass transport rate in the bulk of solution

UP

mass transport rate through the interface

UT

mass transport rate in the solid phase

W

concentration (mass fraction)

X

relative mass of microcomponent in liquid phase

X

mole fraction of microcomponent

Y

relative mass of microcomponent in solid phase

Y

mole fraction of the macrocomponent

z

dimensionless concentration parameter

a

surface entropy factor

6

energy

R

logarithmic distribution coefficient

PC

crystal density

0

surface energy

a

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12301van der Voort. E.. Hartman. P.: J. Crystal Growth 104 (1990) 450

50 (1927) 3266 12311Walter, L.. Schlundt, N.: J. Am. Chem. SOC. 1232) Wang. J.L., Berkovltch-Yellin, 2.. Leiserowitz. L.: Acta Cryst. B41 (1985) 34 1

12331 Wangnlck, K. : Das Waschen als Nachbehandlungsprozesse der Schicht-

kristallisation, Thesis, Univ. Bremen 1994, VDI Verlag, Dnsseldorf 1994 12341Weijnen. M.P.C.. van Rosmalen. G.M.. Bennema, P.: J. Crystal

Growth 82 (3)(1987) 528 [235] Weissbuch. I.. Shlmon. L.J.W.. Addadi. L.. Berkovitch-Yellin, 2..

Weinstein. S.. Lahav. M., Leiserowitz. L.: Israel J. Chem. 25 (1985) 353 12361 Weissbuch. I., Shimon, L.J.W., Landau, E.M., Popovitz-Biro. R..

Berkovitch-Yellin, 2.. Addadi. L.. Lahav. M.. Leiserowitz. L.: Pure Appl. Chem. 58 (61 (1986) 947 12371 Wells, A.F.: Phil. Mag. 37 (1946) 184 12381 Wells, A.F.: Disc. Faraday SOC. 5 (19491 197 (2391Wen, Fu-Chu: Kinetic study of crystal growthfrom supersaturated

droplets, PhD Thesis, Georgia Inst. Technol. 1975 I2401 Westwood. A.R.C.. Rubln. H.: J. Appl. Phys. 33 (1962) 2001 (2411Whetstone, J . : Nature 168 (1951) 663 12421 Wirges. H.P.. Scharschmldt. J.. Karbach. A., Reichel, F.: The lnfluen-

ce of addltives on crystallization processes, in: B M C ’ 94 (ed. J.Ulrlch1, p. 82, Verlag Mainz, Aachen 1994

74

9.References

[2431Yanson, Yu. A., Stekol'nikov. A.V.: Teplofiz. Krist. Veshch.1 mater., Novosibirsk (1987) 6 6 [2441 Yuan, J.J.. Stepanski, M., Ulrich. J.: Chem.-1ng.-Tech. 62 (8)(1990) 645 [2451 Zharikov. E.V.. Zavartsev. Yu.D.. Laptev. V.V., Samoilova. S.A.: Crystal Res. Technol. 24 (1989) 751

TABLES

Admixtures in Crystallization

Jaroslav Njlvlt, Joachim Ulrich 0 VCH Verlagsgesellschaft mbH, 1995

10. Tables It is almost impossible to record all the papers dealing with the effect of admixtures on the crystallization of substances from aqueous solutions. The aim of this compilation is to give a qualitative survey of literature, providing the

possibility of finding references dealing with individual systems. In order to give a uniform presentation,

every table is divided into two parts: the first part gives

fundamental crystallographic information that might be useful for structural considerations. The data include the molecular weight (g/mol), density (kg/m31, crystal system with lattice parameters a, b, c (pm). a, b. y, number of particles per unit cell of the crystal 2. The crystallographic characterization is limited to the crystal system; more detailed information can be found in specialized literature or

in solubility tables I1931.

Crystal system cubic

Characteristics a - b - c . a-B-t.-90°

tetragonal

a - b s c , a-/j-=y-90°

hexagonal

al-a2=a3sc,a-?-900

trigonal

a - b - c , a-b-yt:9O0

rhombic

asbgc, a-,6-r-90°

monoclinic

a s b s c , a-y-90°

triclinic

a L b s c , a ,/1 ,y s 90°

/is90°

1O.Tables

77

In the lower part of the tables are listed admixtures with a qualitative description

of their effect: N - nucleation, G

- crystal growth. H - crystal habit,

S - crystal size. D - distri-

bution of admixture and corresponding reference number. In addition. there exists a number of reviews and survey papers I7.58.59. 137,139,147.153.156.222.234.250,284,285,286,346,377.414.626,682,777.779, 799.8 16.856.9 19,920.925.932.948.1 123.1 129,1158.1 166.1223.1224,1257,1302. 1305,14051. Those dealing with the effect of various solvents are [136,154.155,

158.287.758,932.953.1216,1310,1338].

10. Tables

78

t

MBr

SILVER BROMIDE Molecular weight: 187.80

Density: 0470

System: cubic

a

-

Z=4

0.5755

Admixture

Effect

3D-, 4D-element complexes

Reference I8911

Cd2+

D

1712,13131

K+

coagulation

15651

H

I11191

NH,OH 10Y0.pyridine

favourable

14721

Pb2+

lower S and recryst. rate

[109,110.111]

NH,

. KBr

Pb2+. Cd2+

I2581

solvation

G

12581

I- and gelatine

H

12561

pH

H

(257,2591

p H . I-

G . H

12581

dyestuffs Methylene blue

[ 10921

H

I4391

S-containing agent

[ 13831

surfactants

18491

urea, tetraalkylammonium salts,

I2581

gelatine, Methylene blue

10. Tables

4m SILVER CHLORIDE Molecular weight: 143.34

Density: 5660

System: cubic a

-

2- 4

0.5545

Admixture

Effect

Reference

Ac/Cl ratio

G

12931

3D-. 4D-element complexes

G

I8911

HgCI, 0.005-0.25%

favourable

18 11

NH,OH, pyridlne

favourable

14723

C1-. CH,COOH. pH

benzvlalcohol

I6661 G

dyestuffs

12631 I10921

Methylene blue

H

I4391

Na-dodecylsulphonate. benzylal-

G

16041

Na-dodecylsulphonate, eosfne

G

I2941

polyvinylalcohol

G

19933

S-containic agent

I13831

surfactants

18491

79

10. Tables

80

&2cr04

SILVER CHROMATE Molecular weinht:

331.77

Admixture

Effect

Reference

Ag+/ Cr0,2- ratio

G

15633

glutamate, cltrate, tartrate,

N

I10151

&I

SILVER IODIDE Density: 6670

Molecular weight: 234.79

2-4

System: cubic a

-

0.647

Admixture

Effect

Mg2+

Reference

I6091

Na'. I-

recryst.

I1 2791

3 D - . 4D-element complexes

G

I89 11 I1 3321

Methylene blue, sodium dodecylsulphate surfactants

H

1303.369.3701

surfactants

N

13021

surfactants

S

I30 1.13151

surfactants

18491

AgNOS

SILVER NITRATE Molecular weight: 153.874 System: rhombic E

-

0.697

b

-

Density: 4350 2-8

0.734

Admixture

ethylene glycol

c

-

1.014

Effect

Reference

I I12371

IN

AlC~(S0412* 12 H2O

ALUMINIUM CESIUM SULPHATE dodecahydrate Molecular weight: 668.185

I-

System: cubic a

-

Density: 1870 2-4

1.2363

Admixture

Effect

Bismarck brown, dyestuffs

H - cube

Reference

117871

10.Tables

82

AlCl,

6 HZO

ALUMINIUM CHLORIDE hexahydrate Molecular weight: 241.432 System: hexagonal

a

-

1.1827

c

-

Density: 1664 216

1.1895

Admixture

Effect

Reference

I 1551.5521 I I 15531

IG

electrolytes

I electrolytes

ID

Ale, 3 HZO ALUMINIUM FLUORIDE trihydrate Molecular weight: 138.022 System: tetragonal a

-

0.7734

c

-

212 0.3665

Admixture

Effect

Reference

HF

N

16451

~ 0 ~ 3 -

1759,8261

surfactants

1120.1211

10. Tables

I

AlK(SO&

12 HZO

ALUMINIUM POTASSIUM SULPHATE dodecahydrate Density: 1760

Molecular weight: 474.377 System: cubic a

-

2- 4

1.2130 Reference

Admixture

Ag', Cd2+,Au3+. Cu2+

retard N. not G

12991

N3+.Fe3+

salting out, purification

14531

cationic admixtures

G

16221

Cr3+

19231

Cr3+

[1500.1502]

G. dissolution

16231

G

17251

Na,B,O,

H, G reduces growth

192.14891

Na,CO,

H

Fe2+ KC1. KBr, KI. (NH,),SO,.

NaC1,

NaBr. NaNO,

Na,SO,.

CuSO,, H2S04, KOH,

- cubeloctahedron

I891

G

I10511

D

1581

Na,B,O,, NaOH NH4+,T1' rare earth elements

16141

D

admixtures

(1187,14111 139,684,685, 725.951

83

84

1O.Tables

UK(S04)2. 12 HZ0

continued)

Admixture

Reference

+---

admixtures

H

[ 10521

I

admixtures admixtures HCl

H

Bismarck brown

- face /210/

110511 1921 11141

1198.7873

Bismarck brown

[4731

Bismarck brown

I13071

Diamine sky blue

18961

Direct blue 3B

[ 10521

Metanil yellow, Brilliant Congo

[213.2 151

red. Bordeaux blue, Orange 1 and other dyestuffs methanol, ethanol

[1510.15111

methanol, ethanol, propanol

I 14001

polyvinylalcohol Qulnollne yellow saccharides, dyestuffs

,,I

11041 [ 11331

10. Tables

AlNH,(SO,),

85

. 12 HZO

ALUMINIUM AMMONIUM SULPHATE dodecahydrate Molecular weight: 463.317

Density: 1640

System: cubic

Z=4

a - 1.2220

Admixture

Effect

Reference

Cr3+, Fe3+, K+.TI+

D

1581

Fe3+, Fez+, Mn2+, Zn2+

D

I4931

K+

D

[ 1500,15021

Na,CO,

H - cube/octahedron

I891

NaCl

D - C1-

18571

NH,Fe(SO,l,

D - Fe3+

(8571

D - Fe3+

[4873

admixtures

D

I 1 187.74.10541

admixtures

S

I13931

Oxamine blue B. Diamine sky blue

H - face

NH,Fe(SO,),.

NaC1. H,SO,

/loo/

1215,7873

86

10. Tables

Al(N03),

- 9 H20

ALUMINIUM NITRATE nonahydrate Molecular weight: 375.133 System: monoclinic

*

Admixture

Effect

alkali metals + HNO,

I

Also3 M,O

n SiO,

Reference 12831

m H20

ZEOLITES Admixture

Effect

Reference

NaOH

N. G

19961

propyl-substttuted amines

N, G

18981

surfactant

11011

triethanolamine

111931

1O.Tables

87

Density: 2420 2-8

I3

-

c

-

0.9699

85O26’ ~~~~

~~~~~~~

Admixture

Effect

Reference

co,2-

N inhibition

1681

cu2+

I1961

Li+

H - pseudoboehmite

I4091

I,1C1

S. defects

I5741

D. solub.

I 11851

G

[ 14491

G

[360.1390,353]

admixtures admixtures

11441

admixtures

G,NS

111781

pH

modif.

[ 14071

citrate

N

I 12761

oils

;

- recryst.

I

I151 I8281

88

10. Tables

Admixture

Effect

Reference

admixtures

H

12261

KF, NaOH

[ 10491

AlRb(S04),

1 [ 10491

I

HC1. HNO,

12 H 2 0

ALUMINIUM RUBIDIUM SULPHATE dodecahydrate Molecular weight: 520.747

Density: 1867

System: cubic B

2-4

= 1.2246

Admixture

Effect

Diamine Sky blue FF

H-

/loo/

Reference

12151

10. Tables

AlTl(S04)2

12 H 2 0

ALUMINIUM THALLIUM SULPHATE dodecahydrate Molecular weight: 483.19 294

System: cubic a = 1.221

Admixture

Al2(SO&

Effect

Reference

. 10 H2O

ALUMINIUM SULPHATE hexadecahydrate Molecular weight: 630.379 System: rhombic

Admixture

Effect

Reference

K,SO,

N, H

[ 14931

89

10. Tables

90

Ba(BO2l2

BARIUM BORATE

Admixture

Effect

Reference

NaCl

G

I1451

BaBr,

- 2 H20

BARIUM BROMIDE dihydrate Molecular weight: 333.178 Syetem: monoclinic

a

-

1.0449

b

-

Density: 3872 2=4

0.7204

c

-

0.8385

113O29' ~

Admixture

Effect

~~~

~

~~

Reference

10.Tables

BaCO,

BARIUM CARBONATE Molecular weight: 197.37

Density: 4350

System: rhombic

a

-

0.529

2=4

b * 0.888

c

-

0.641

Admixture

pH polyglutamic acid, polyvinylsul-

G

[ 11651

phonate polyglutamlc acid. polyvinylsul-

11 1671

phonate

BaC20,

BARIUM OXALATE Molecular weight: 225.382 Admixture

Effect

Reference

Ce4+,Th4+

D

12251

Ra(COO),

I [lo651

91

1O.Tables

92

BaC12 2 H 2 0

B A R I U M CHLORIDE dihydrate Molecular weight: 244.276 System: monoclinic L

3

-

0.6738

b

-

Density: 3106 2-4

1.0860

c

-

0.7136

90°67'

Admixture

Effect

Reference

Mn2+. Co2+, N@+,c$+

G

13743

Mn2+, Co2+, N12+, Cu2+, Na+

G. N. H

[1254]

RaC1,

D

I509.6651

admixtures

N

I5281

(C$35)$JI

TETRAETHYLAMMONIUM IODIDE Molecular weight: 267.166 Admixture

Effect

Reference I

solvents

H, G

D321

10.Tables

BaCrO,

BARIUM CHROMATE Molecular weight: 253.33

Density: 4498

System: rhombic

IAdmixture Ce3+. Sr2+,pH, EDTA

I

RaCrO,

Effect

Reference

D - Ce3+. Sr2+

1971 .-.

D decreases with tempera-

I8821

ture rise

RaCrO,

D - mixed crystals

[ 10651

RaCrO, + HNO,

D - Ra2+

16651

Sr2+

D - Sr2+

1951

pH

G. H. S

1961

pH

N

[lo141

CH2COONH4

1951

EDTA

G.H. S

1961

gluconate, tartrate, citrate.

N

[lo151

glutamate. EDTA

93

10. Tables

94

BaF2

BARIUM FLUORIDE Molecular weight: 175.36

Density: 4830

System: cubic a

-

2-4

0.6184

Admixttlre

Effect

Reference

Fe2". Fe3+

D

111801

dissol.

I5171

Admixture

Effect

Reference

Ra(IO&

D - mixed crystals

[lo651

polyphosphonates

10. Tables

Ba(NO&

BARIUM NITRATE Molecular weight: 261. S O

Density: 3222

Syetern: cubic a

-

2-4

0.8110

Effect

AdmiXilWe

Reference

inorg. a d d i t i v e s MnO;, Ni(NO,I,.

[ 10421

Fe(CNIe4-. Fe(CN),3Fe(NO,),,

NP+

HNO,. LiNO,

H - /loo/ + /lOl/ + /210/ 12001 N. G

16571

N

I6431

N12+. Fe3+. Li+

[lo411 18611 D

1663,665, 10841

pH

[ 13391

amine

16431

M e t h y l e n e blue

G,H-

M e t h y l e n e blue

D

/loo/

+/810/

12001

95

96

10. Tables

1 Admixture

Effect

Reference

D. H - cube

[431.432.437. 438.44 1.442, 961,1402, 14221

Methylene blue

G. H. D

11238.12391

Methylene blue

H

I6421

Methylene blue, Malachite green

N

16431

New blue

H

- /loo/

I2 151

quinine nitrate

H

- tetraeder

12001

Ba(OH),

8 H20

BARIUM HYDROXIDE octahydrate Molecular weight: 315.476 Syetem: monoclinic

n

-

0.9350

b

-

Density: 2180 2-4

c

0.9280

-

Admixture

Effect

C1- 0.5 Yo

S

1.1870

Reference

10.Tables ~

~~

~~

~

~~

BaSO,

BARIUM SULPHATE Molecular weight: 233.40 System: rhombic a

-

0.885

b

-

Density: 4600 2-4

c

0.644

Admixture

-

0.713

IEffect

additives, Ba2+/S0,2- ratio

IReference

N, G

[ 11051

KMnO,

D - mixed crystals

1504,14231

N a citrate

H - spheric crystals

19021

K+ K+.C1-

N a + . K+

18151

S I

I

Pb2+

D

17031

Pb2+.Sr2+

D

111761

RaSO

D

A

- logar. distr.

13101

RaSO, + H N 0 3

D

[6651

Sr2+

D

194,7763

Th4+

D

[ 12921

admixtures

H

admixtures

G. dissol.

18131

admixtures

D

18681

admixtures

S. H

13441

admixtures

N. G

1794.7951

- regular rounded cryst.

18461

97

98

10.Tables

BaSO,

I

Effect

Reference

G accel.

[ 11051

HQSO,

H. S

I14241

pH

S

[7601

G - maximum growth rate

18631

Admixture

pH

- 12.3

gelatine + p H

I14651

inhibitor

G, scales

11127,11281

nitrilomethylenephosphonate

G

14201

DhosDhonate

N

[ 10641

agglomeration. S

17971

G

[ 186.796.1 1261

G retard.

[ 11051

G ,N

[805]

polycarboxylic acids. polyphos-

17981 19731 N

I3271

1O.Tables

99

CaCO,

CALCIUM CARBONATE - calcite Molecular weight: 100.09

Density: 2710

System: trigonal

a

9

2-2

0.6361

Density: 2930

Molecular weight: 100.09

z=4

System: rhombic a

-

0.494

b

c ~0.572

= 0.794

CALCIUM CARBONATE - vaterite Molecular weight: 100.09 System: hexagonal a

-

0.4120

c

-

2-2 0.8556 -

~~

Admixture

Effect

Reference

(NaPO,),

S

110301

(NH4),S04

N. G

[ 14293

BaCI,

H

[ 14341

Ca2+. OH-

I8511

Ca2+/ c0 ?2- ratio

H

1668,6901

Fe2+.Fe3+

G

15291

~

100

I

10.Tables

I

CaCO,

(continued)

IAdmixture

Reference

KHVPO,

G

1560.5611

Mg2+

lnhibition

[ 10881

Mg2+

polymorph.

[998.13301

Mg2+

D. N

Ill811

G

131 1.348.562, 1088l

Mg2+

transformation

[611,630,6941

Mg2+

N.G

110311

Mg2+

Mg2+. Mn2+. Cr3+, Ni2+

I10681

G. H

Mg2+. Ni2', Co2+, Fe2+. Zn2+, Cu2+, modlf.

[ 12591

11 1301

Mn2+, Cd2+. Ca2+, Sr2+, Pb2+. Ba2+ Mg2+, Sr2+, Ba2+, Pb2+

G

17491

N - inhibited nucleation ol

[ 119,5051

calcite G, H

I12591

H

[ 14341

113851

1O.Tables

I

CaCO,

(continued)

I

Admixture

Effect

Reference

N - stabilized supersatura- I4231

tlon modif.

[2181

NH4+

G

I12581

NH,C1

N - low scale formation

I2461

NH4NOq

N

13661

Pb2+, Mn2", Mg2+,Co2+, NOq-

H

[6891

Sr2+

D

Sr2+

D

[1503]

Sr2+,Ba2+, Pb2+

modif.

[ 14661

uo,2+

modif.

11 164.13111

Zn2+

D

I13481

Zn2+

N. D

I4791

admixtures

D, H - aragonite

16731

admixtures

H, G

- aragonite/calcite

- aragonite

1674.7101

[ 11481

admixtures

I6101

admixtures

[ 14261

admixtures

(503,8841 [ 10301

101

102

10. Tables

I

CaCO, (continued)

I

Admixture

Effect

Reference

hexametaphosphate. pyro-

modif.

“2181

phosphate hexametaphosphate.

110931

pyrophosphate. dihydrogenphosphate. borate, tetraborate, vanadate inhibitor

G

I63 11

inhibitor

scale

[ 13331

lanthanides, Cd2+

G. D

114151

metaphosphates N a

N - stabilized supersat.

[lo721

oxalate

G inhib.

[4701

aH

[ 11861

pH

N. G

[682]

DhosDhates

H

1903.9761

G inhib.

15601

modif.

11 2361

Pod3-

[ 140 11

S042-

tripolyphosphate, surfactants

N

13 11,3481

acetate, gluconate. EDTA. tripoly-

G. N

110171

phosphate

10. Tables

c CaCOs

(continued)

Effect

Reference

albumine

G

[ 12461

benzenepolycarboxylic acid

G

1251 I10681

citrate, stearic acid Congo red, other dyestuffs

G - retardation

fatty acid

I7141 I491

G

I14141

glycerophosphate. PO,3-

inhibition G

[ 10861

organic colloids

G

[lo121

gluconate. borogluconate. tartrate, polyacrylate

organic polymers

[1406]

organophosphonic acid

[ 10481

- low scale formation

phenol. resorcinol, hydroquinone

N

phosphonates

G

1187,10871

phosphonates

G

I10871

12461

polyethylene oxide

I3941

polyglutamic acid, polyvinylsul-

[ 11651

Dhonate polyglutamic acid, DolwinvlsulDhonate

[ 11671

103

10. Tables

104

CaCO, (continued) Admixture

Effect

Reference

polymers

S

114061

stearic acid

N

[829,8301

surface active substances

H

[ 14341

surfactants

modif.

[ 1280l

tetrakis(phosphonomethy1)tetra-

G

114301

Admixture

Effect

Reference

KF

H

[ 1416,14171

azacyclododecane

Ba'NO,

BARIUM TITANATE Molecular weight: 233.26 System: cubic R

0.397 ~~

Nb,O,. Ta,O,,

~~

Sb,O,, Bi,O,

~

~~

114211

10.Tables

105

CaC20,. H 2 0

CALCIUM OXALATE monohydrate Molecular weight: 146.12 Effect

Reference

[SO1,802,12833 G

I4251

H

I551 11 171

G. N

[72.8851

G, aggreg.

111421 [841.994.1142, 12831

I

N a citrate

173,513.841.964. 10991

Na pyrophosphate

N

14191

Na,P20,. trlpolyphosphate.

N. G

19651

admixtures

inhibition

[ 11731

admixtures

H

1511

admixtures

G

[499.12343

admixtures

N

1413,12961

phosphonates. EDTA,KH2P0,. K,P,O,

admixtures

106

10.Tables

1

I

CaC204 H 2 0 (continued)

IAdmixture

Effect

phosphorus derivatives

G

pop

G inhibition

% G

pyrophosphate

N, G

pyrophosphate, citrate

G. aggreg.

pyrophosphate, phosphonate

transformation

I4181

amino acids

G , transform.

I 1681

amino acids

S. G. N

amino acids

transformation

carboxyglutamic acid

G

chondroitin sulphate, macro-

G

molecules chondroitinsulphate.

[73.419,512,1108,

I I1 1101

I161.365.4981

jentosansulphate citrate

G, N

citrate, pyrophosphate

G

dodecylammonium chloride

G

d u t a m i c acid

modif., G. aggreg.

hcparinc, polyglutamic acid

N

I

I

L!aC,04

H,O

'continuedl Admixture

mect

heparine inhibitors in urine

IReference [364.1107,11081

N. G

18181

Methylene blue

181

pH

15001

+

adenosine phosphates

phosphonate

G

I12331

phosphonates Dolvacrvlate polyacrylic acid polyacrylic acid, heparin, organic copolymers

1269,12831

I N. G

111721 12691

polyhydroxycarboxylic acids pyrophosphate, Methylene blue

N, G, S

13141

pyrophosphate, Methylene blue

N

I3 141

sodium dodecyl sulphate

inhob.

[ 12981

urea

N

[6591

uric acld

108

10. Tables _

ZaCl,

_

~

~

~

- 2 H20

ZALCIUM CHLORIDE dihydrate Molecular weight: 147.016 3ystem: rhombic L

-

0.7190

b

-

Density: 835

0.585 ~~

7

~

~~

Admixture

Effect

Reference

CaS04

N - unfavourable. scaling

19761

admixtures

G

16711

nucl. catalysts

N

1764,14351

polyethylene oxide

N

110701

Admixture

Effect

Reference

Nd3+

G

1461

CaC4H406

CALCIUM TARTRATE

1O.Tables

CaF,

CALCIUM FLUORIDE Molecular weight: 78.08

Density: 3180

system: cubic i

-

2-4

0.5451 Effect

Admixture

Reference

Fe2+,Fe3+

D

11 1801

NaCl + additives

dissolution

I5161

S

I1 0451

polyelectrolytes

G

I351

~ 0 ~ 3 -

G

I [ 12261

I polycarboxyllc acids.

G

I641

G

I34.9421

polyphosphates polyphosphonate

Admixture

glucose. arabonate

Effect

Reference

I7551

109

1 10

10.Tables

CaHP04 2 H,O

CALCIUM HYDROGEN PHOSPHATE dihydrate lYoleeular weight: 172.09

Density: 2306

System: trigonal Admixture

Effect

Reference

M @2+

N, G

I3621

Mg2'

1946.11501

Mg2'

N

121

Mg2+

G

I1 1501

Na'. NH.+

I8171

SnF,, SnCl,, NaF

19471

F-

N

I5411

I?-

S

111691

P,O,

N - retardation

12481

pH

modif.

I3991

pyrophosphate

G

1844.9411

U0,2+. SiF,2-. polyphosphates. F-.

S

11 1751

H

I12021

G, aggregation

11 1101

sio

1 carboxvlic acids

I

chondroitin sulphate. urinary

macromolecules ~~

citrate

[ 10041

di- and trlcarboxylic acids

11671

~~

10. Tables

I

ICaHPO,

111

2 H,O

(continued)

1 Admixture organic acid

I

P containing complexons

I3291

I

I6921

I

Effect

Reference

polycarboxylic acids surfactants

I J I tricarbo

Uc acid

H

I1671 I4861

urine inhibitors

CaHPO,

N. G

3/2 H,O

CALCIUM HYDROGEN PHOSPHATE sesquihydrate, BRUSHITE Molecular weiaht: 163.09 Admixture

casein

Effect

I

Reference II6361

112

10. Tables

Admixture

Effect

Reference

A13+,Fe3+, Mg2+

19151

Mg(N0Jp

I4561

NH,NO,

lower hygroscopicity

I9761

Admixture

Effect

Reference

Feso,. Ca Salt

H

15911

NaC1. NaC10,. KCl

G

I13311

ethyleneglycol. glycerol

H

I5911

10. Tables

Ca8H2(P0&

113

- 5 H,O

OCTACALCIUMPHOSPHATE Molecular weight: 982.581 I

Admixture

Effect

Reference

Mg2+

G

11 1501

Effect

Reference

Ca,(PO,),

TRICALCIUM PHOSPHATE Molecular weight: 310.20 Admixture

Be2+

112101

Mg2+

transform.

16671

citrate. pyrophosphate

transform.

11651

gelatine

transform.

I1661

polyacrylic acid

114

10.Tables

Effect di- and tricarboxylic acids

Reference 1261 1321

1301

Ca,(P04),

CaFz

FLUORAPATITE

Admixture

Effect

Mg2+

Reference I361

CaS03

CALCIUM SULPHITE

I

Molecular weieht: 120.15 Admixture

Effect

Reference

organic admixtures

S

18641

10.Tables

115

Molecular weight: 384.30 Reference

Admixture

12781 I7461 1361

G

1946.11501

Zn2+

G

12791

NaC1. LiCl. NH,Cl. CsCl. HCl

G

19451

c1-

H

I7451

F

precip. rate

I5411

F-

fluorapatite

17441

G

19101

DH

G

1542.8861

polyphosphates, polycarbaxylic acids

G

I271

biophosphonic acids

G

19431

I

glucose

, hydrolryhydroxyphosphonyl-ethane

12771 I2791

F

116

10. Tables

Ca3(PO4I2 Ca(OW2

Admixture

Effect

Reference

mellitic acid

G

I241

proteins

G

I9101

Casios

CALCIUM SILICATE Molecular weight: 116.17 System: monoclinic a = 1.531

b = 0.735

c = 0.708

p = 950 25'

1

Admixture

Effect

Reference

sr2+

D

I15031

BaSO,. BaF,. BaCl,

N. G

19241

10.Tables ~~

ZaSO,

~

~

~~

- 2 H20

XLCIUM SULPHATE dihydrate dolecular weight: 172.168

Density: 2310

jystem: monoclinic

2=4

L

= 1.047

c =0.659

b= 1.515

L = 151° 3 3 Admixture

Effect

Reference

M3+, Cr3+

H

114721

~ 1 3 +F .

NS

I1 1711

M3+,Fe3+.Mg2+

solubility

112811

A13+. Fe*, SPG2-

G

I1 5041

A13+, Na maleate

S, G. aggregation

12161

AlF,

N. D

I1 1711

AIF,

G. H

18451

Ca2+/so42-ratio

N

1635,8471

Cd2+

D

[ 13291

Cd2+

G

[ 1 1021

Cd2+

S

I1 1021

CdF,. AlF,

D

114611

Cu2+.Zn2+

G

[ 14401

F-modifiers, N3+

14151

Fe3+.Fe2+

[7351

117

118

10.Tables

CaSO,

- 2 H,O

[continued) Effect

Reference

H

13411

NaCl

G

11641

NaNO,

G

114601

Admixture

H+. Sr2+, Ag+. HSO;.

NO3-. N a + .

OH-

NH,, C G + , PO,^-.

co,2-, ~

0 0 ~ 2 -G

16081

10. Tables

119

I CaSO,

2 H,O

(continued)

I

Admixture

Effect

admixtures

G

admixtures

hvdration. G

admixtures

H

admixtures

G.

admixtures

N. hydration

I5101

admixtures

scaling

11851

Cd2++I-.Br-, S1032-

D

[ 14621

S

I12291

H

I

I [ 11981

F-.A13+

1 HPSOA

Reference

18 141

I4801 N, S . G

B24.98 11

HaSO, + H,P04

hydration

I5081

HQSO,. H,PO,

G. H

[ 15041

HqPOA

affects hydration

H3P04

pH

N

DH

G

pH

S. H

pH

G

[ 12491

p H , impurities

H. D

17181

[ 11841

120

10. Tables

CaS04 2 H,O [continued) Admixture

polyelectrolytes

Effect

Reference

D

15761

D. S

I5821

G

1371

surfactants + HNO, + H,PO,

114581

tripolyphosphate

G

1441

acrylates

H

I1 1151

acrylates

caking

112551

alkylbenzenesulfonic acid

G

Ill20l

aminomethylene phosphonic acid

N

111511

anionic organic polymers, tri-

precipitation

I12481

N. G -accelerate

1675)

polyphosphate calcium acetate and formiate, pentaerythritol carboxylic acids, phosphonates

H,

s

113031

carboxylic acids, phosphonic acids

G. H

113031

citrate

S. H

110791

citric acid, tartaric acid, gelatine

G

- retarding

12381

citric, succlnic. tartaric, polyacry-

precipitati on

12381

lic. polymethacrylic acid, gelatine

1O.Tables

-

CaS04 2

H,O

(continued) Admixture

Reference

gelatine. saponlne

H. S

gelatine. sulphite liquor

N. G

gelatinc. waste liquor of cellulose

N - retarding

1255,7371

gluconate. borogluconate. tartrate

precipitation

I14141

hydroxyethylidenbiphosphonic

G

[ 11251

[ 1204)

- retardation

I6751

sulphate

acid ~

hydroxyethylidene. diphosphonic

G

[ 1122.14401

N,G

[ 11521

acid. polycarbonates hydroxypropylene diamine impurities, alcohols naphtenate

I7191

H

organic phosphonates organophosphonic acid

I13971 I326.3281

N

[ 1155.1 156,

11571

phosphonates

G

[14391

phosphonates, phosphates, orga-

G

1311

N

I1153,11541

nic polymers phosphonic acid, acetate polyacrylamide

19601

121

122

1O.Tables

CaSO,

2 H,O

(continued)

IAdmixture polyacrylic acid

Effect

Reference

N

I285.12481

I 14401

polycarboxylates. hydroxyethylene bisphosphonic acid

~~

~

N. S

[1168]

polymers

G

1291

polyvinylsulphonate. polyglutamic

H. S

Ill681

S. H

11121

H - short Drlsms

I423.790.9761

N

13501

succinic acid. polyacrylic acid

H

12851

sulfonate

fflterabilitv

I13861

acid

surfactant

I10051 ~

~~

~

surfactants

N. G

I6371

surfactants

G

I11911

surfactants

precipitation

I11911

xylenediamintetraphosphonic acid

N

I3271

10. Tables

Ca(C5H3N4031,

CALCIUM URATE Molecular weight: 374.27

I

I Effect

Admixture

I Mg2+.K+

I

I Reference I

I [1308]

IN

CaWO,

CALCIUM TUNGSTATE Molecular weight: 288.00 System: tetragonal a

-

0.524

c

-

214

1.128

Admixture

Effect

Reference

pH

modif.

I471

123

124

10. Tables

I CdCO,

CADMIUM CARBONATE Density: 4250

Molecular weight: 172.42

z=2

System: trigonal a

-

0.6112

a = 470 24'

Admixture

Effect

Reference

Fe2+, Cu2+, Co2', Ni2+. Cr3+,

D

14911

WOd2-. Mn2+

Cd(HCOO),

2 HZO

CADMIUM FORMATE dihydrate

Admixture

Effect

Reference

Mn2+

D

158,601

10. Tables

CdS

CADMIUM SULPHIDE Density: 4820

Uolecular weight: 144.48 System: cubic L

-

2-4

0.582

Admixture

Effect

Reference

anionic polymers

coagulation

[ 10291

polymer, pH

N. G,S

[ 10321

proteins

G

I6031

Admixture

Effect

Reference

LlCl

anhydr.

I1391

COCl,

hydrate

I1391

125

126

10.Tables

Admixture

Effect

Reference

Mg2+. Mn2+

D

158.601

Co(CH,COO),

4 H2O

COBALT ACETATE tetrahydrate Density: 1705

Molecular weight: 249.09

IReference

Admixture

I Mg2'

I I1581

10.Tables

Co(NH,&(SO&

6 H2O

AMMONIUM COBALT SULPHATE hexahydrate Molecular weight: 395.216 System: monoclinic

a

-

0.923

b

-

Density: 1901 2-2

1.249

c

-

0.623

B = 106O 56' Admixture

Effect

Reference

Fe2+. Cu2+

D

[488,4891

Ni2+. Fe2+,Zn2+. Cu2+

D

(581

COSO,. 7 H,O

COBALT SULPHATE heptahydrate Molecular weight: 281.097 System: monoclinic

a

-

1.545

b

-

Density: 1948

2

1.308

c

-

-

16

2.004

B = 104O 42' Admixture

Effect

Reference

inorganic ions

H. adsorption potential

12751

Fe2+

D

(488,4891

127

128

10. Tables

CrK(SO,),

12 H,O

POTASSIUM CHROMIUM SULPHATE dodecahydrate Molecular weight: 499.43

Density: 1830

System: cubic a

rl

-

2-4

1.214

Admixture

Effect

Reference

Cr(V1)

N. G

19581

admixtures

D

1581

CrNH,(SO,),

12 H 2 0

AMMONIUM CHROMIUM SULPHATE dodecahydrate Molecular weight: 478.362

ISvstem: cubic Admixture

Effect

Reference

Cr3+

D. G

I15071

K+

D

1581

A13+. Fe3+

D

[581

10. Tables L

CsH&O,

CESIUM DIHYDROGEN ARSENATE Molecular weieht: 273.836 Admixture

Effect

Reference

CSI

CESIUM IODIDE Molecular weight: 259.810

Density: 4510

System: cubic a

-

Z=1

0.4562

Admixture

Effect

Reference

Cu2+,Co2+, Mn2+, Ni2+

H

[ 12531

129

130

10. Tables

CSNO,

CESIUM NITRATE Molecular weight: 194.910

Density: 3685

System: hexagonal a

-

1.074

CUCl,

c

-

2-9

0.768

2 HZO

CUPRIC CHLORIDE dihydrate Molecular weight: 170.482 System: rhombic a

-

0.744

b

-

Density: 2514 202

c = 0.3764

0.8126

~~

Admixture

Effect

admixtures polyethylene oxide

~

Reference

16971 N

I10711

1O.Tables

Admixture

Effect

Reference

gluconates. citrate. tartrate, EDTA

N

[ 10 151

Cu(HC0O)Z 2 HSO

CUPRIC FORMATE dihydrate

Admixture

Effect

Reference

Co2+, Cd2+

D, structure

I12751

Admixture

Effect

Reference

sulfanilic acid, metanilic acid

H

I3901

131

132

10. Tables

CUPRIC HYDROXIDE

CU~(OH)~CO,

BASIC CUPRIC CARBONATE

I

Molecular welght: 221.107 Admixture

Effect

Reference

H,O,

filtrability

[1399]

I

Molecular weight: 399.829

Density: 1926

System: monoclinic Admixture

Effect

Reference

Zn2+

D

I488.4891

Ni2+, Zn2+. Fe2+, Co2+, Mg2+

D

1581

.

10.Tables

CuSO,

133

5 H,O

CUPRIC SULPHATE pentahydrate

I-

Molecular weight: 249.680

syetem: Mclinic

a

b 82O 16'

j3

-

Density: 2286 2-2

-

1.070

c

0.597

107O 26'

y 11020 40'

Reference

[487,852.854] [8571 112121

19851 I9861 I621 I7161 [8531 [ 12871

19881 1423,9761 16321 [ l066]

I13411

134

10.Tables

Admixture

Effect

Reference

M3+. Cr3+

D

I581

rare earth elements

D

16141

Zn2+

D

[ 488,4891

Zn2+. C o 2 + ,Mg2+. Cu2+. Ni2+

D

1581

admixtures

D

1741

Admixture

Effect

Reference

I

c1-

1265.3121

I

I17111

1O.Tables

Fe(OH13

FERRIC HYDROXIDE

-

Density: 3400 3900

Molecular weight: 106.87

ISystem: hexagonal

2-1

Admixture

Effect

Reference

Cu2+, Ag+. Au3+. Ge4+.Sn4+.Pt4+,

D

I1971

intermediates

I701

Mn2+.Ca2+ EDTA. diaminocyclohexanetetra-

Fe203

FERRIC OXIDE (GOETHITE) Molecular weight: 159.70

Density: 5250

System: cubic a

-

0.830

Admixture

Effect

Reference

Ni2+

conversion of hydroxide

I2661

oxidizing agent

N. S

[ 11401

HC1

L9671

dioxyethylglycine, urea

I9671

organic anions

12671

135

1O.Tables

136

Fe304

FERROUS-FERRIC OXIDE (MAGNETITE)

-

Molecular weight: 231.55

Density: 5100 5200

System: cubic a

-

Z=8

0.837

Admixture

Effect

Reference

I

admixtures

I

FeSO, - 7 H20

FERROUS SULPHATE heptahydrate Molecular weight: 278.011 Syetem: monoclinic

a

fi

-

1.4020

b

-

Density: 1899 2=4

0.6600

c

-

1.1010

105O 34' Reference

ICd2+,Cu2+ I TiOSO, admixtures

S

I6501

10.Tables

137

I H2O

ICE Molecular weight: 18.016

Density: 917

System: hexagonal a

-

2-4

c = 0.734

0.462

I

Admixture

Effect

Reference

Ag halogenides

N

17431

AgI

N

I342.12511

impurities

N - retardina

[lo241

LiCl

N. H

13761

I LiI. CsF. K F

G

11 1431

G

15211

D

I14781

NaCl

G, D

I11901

NaCl, Agl. CuS

N

1355.41 11

admixtures

H

admixtures

N

110911

a-fenazine, floroglucine

N

13541

alcohols, org. acids

N

[4473

aliphatic alcohols

N

[lo501

amino acids

N

[4481

CXHROX.

G. D

I1 1901

l i

I6401

CliHgq011

glycoproteins

- dendrites

I1 1 13.11141

138

10.Tables

H2O [continued) Admixture

Effect

Reference

organic substances

N

[355,411]

starch

N

[396.397.9921

sucrose

H

[822l

sucrose

G

18231

ternene

N

111211

HSPO4

PHOSPHORIC ACID Molecular weight: 98.00

Density: 1870

I

Admixture

organic impurities

Effect

Reference 16911

10. Tables

H3BO3

BORIC ACID Density: 1435

Molecular weight: 61.832 System: triclinic

a a

-

0.704

b

9 2 O 30'

0

Admixture

-

-

2-4

0.704

c

1010 10'

Y

-

-

0.658

1200 00'

Effect

Reference

D

(13141

191

H,SiO,

G

KMnO,

H. S - favourable

sop

S.

N. G

flaking agents

I2151 16161 111821

gelatine. caseine

H - flakes

1423.9763

polyacrylamide.

S

[ 13881

polymethacrylamlde polyelectrolytes

I2201

139

140

10.Tables

HgBr2

MERCURIC BROMIDE Molecular weight: 360.398 System: rhombic a

-

0.4624

b

-

Density: 6053 2-4

0.6978

Admixture

c

-

1.2445

Effect

Reference

H€!(CN),

MERCURIC CYANIDE Molecular weight: 252.625 System: tetragonal

a

-

0.9670

Admixture

c

-

Density: 3996

I

Z = 8 0.8920

Effect

Reference

.

10. Tables

KBSO,

4

141

Ha0

POTASSIUM PENTABORATE tetrahydrate Molecular weight: 293.26 Syetem: rhombic a

-

1.108

b

-

2=4

1.114

Admixture

c

-

0.897

Effect

Reference I

pH

N

Molecular weight: 166.228

19401

Density: 2155

Syetem: monoclinic

I

Admixtare

Effect

Reference

admixtures

G

112871

polyethylene oxide

N

[ 10701

142

10. Tables

KBr

POTASSIUM BROMIDE Density: 2750

Molecular weight: 119.002 System: cubic a

-

2-4

0.0660

-~

Admixture

Effect G

- decrease

D

Reference I3401 12611

~

D

I3 181

G

t3223

' inorganic anions

1274,3191

,

- cube/octahedron

Pb2+

H

Dh2t

D

[1161]

D

I391

admixtures c1-

I2 15.4723

I3231

N

I10231

OH-

"7041

- retard growth of / l o o /

alifatic carbon acids

G

Brilliant Cro cein 9B

H

14101

G

[126.127,128.

I

phenol

I1311

1O.Tables

KBrO,

POTASSIUM BROMATE Density: 3270

Molecular weight: 167.000 System: trigonal L

3

-

Z=1

0.4403 8 6 O 00'

Admixture

Effect

Reference

NaNO,. Pb2+,Th4+.Te(1V). V

favourable

I4721

Pb(NO,),. NaNO,

G

[669l

Cr3+, Pb2+. Ca2+. Na+. K+,

N

[628l

admixtures

N

El91

KCN

POTASSIUM CYANIDE Density: 1520

Molecular weight: 65.1 1

2-4

System: cubic R

-

0.656

I

Admixture K,Fe(CN),

N(CH,CONH,),

Effect

H.caking

I

Reference

143

144

10. Tables

K2C2O4 * H a 0

POTASSIUM OXALATE monohydrate Molecular weight: 184.231 System: monoclinic a

-

0.9320

b

-

Density: 2145 2-4

0.6170

c

-

1.0650

Admixture

Effect

Reference

admixtures

G

I7821

Admixture

Effect

Reference

KC1

D - C1-

I8571

10. Tables

KCl

POTASSIUM CHLORIDE Molecular weight: 74.551

Density: 1989

System: cubic

2-4

a = 0.0293

.

Admixture

Effect

Reference

A13+,Ba2+,Cd2+. Cu+. Cu2+, Fe2+,

N. H. D

I7801

Fe3+,Hg2+. KCN. K3Fe(CN)6. K,Fe(CN)6, Mg2', M n 2 + , NH,+. Ni2+, Pb2+,Sn2+,Sr2+, Zn2+ ~

Ba2+

N, G. H

I7341

Ca2+,Sr2+,Ba2+

D

13 181

Cd2+

D, G. hardness, el. c o n d u -

[ 12671

I

2uvity

I

Cd2+

d n

[32 11

C02+

D

113201

hardness

I12681

D

11264.12651

D

[ 1265,1269,

12701

D. melt

12711

145

146

10.Tabbs

Effect

Reference

G,H

1956,9571

G

- retarding effect

H, caking K,Fe(CN),

13401 [ 1036,10551

G

K,Fe(CNIR. Pb2+. Co2+,Cu2+ K,Fe(CN)6. PbCl,, BeCl,, MgCl,,

I 1881

H

LiC1, ZnCl,.. CdCl,. NiC1,. SnC1, K,Fe(CNl,.

K,Fe(CN),

G,D

112631

D

12963

- strong retardation

KNO,

G

KPbCl,

H

18661

N

11 2881

G

113531

D

I13211

H

I12201

H - favourable

19261

H - favourable

19273

G

I1481

N. G

I 14571

18031

1O.Tables

147

KCl (continued)

Admixture

Effect

Reference

NaCl

G

I73 11

NaC1. MgC1,

I11831

NaC1. NH,Cl. MgC1,. AlCl,

17301

NaCl

I727.7293 ~

NH4Cl

D

I7321

NH,Cl + KBr [+K$X),)

D for creep crystallization

17201

N@+, C O ~ +C. U ~ +29'. , Mn2+.

D

I 1269,1270)

Sn2+,Cr3+, Fe3+, Cl-, NO,.,

sod2-

0-containing i o n s

[1461

Pb2+, Fe3+

Ipb2+

D

I11611

G. D

I149.150.151.

1521

D. G. N - retards nuclea-

i474.475.476,

tion

4781 ~~

~~

G.H - change growth rates 16071 of faces

N

1638,9831 I4771

148

10.Tables

Admixture

Effect

IPb2+

Ipb2+

Reference [917.1260, 12321

G. H

[149,1408. 1474.3203 1541

S - favourable

19761

S - favourable

[4231

D

14771

favourable

14723

N - retarding

19551

N. H

19541

I PbC12

H, caking

[ 1036,1055.

1095l

- retards /loo/

PbC12

G

PbC1,

H, D

I1 1961

PbCl,,, BaC1,. K,Fe(CN),

N. D

I7811

PbCl,. K,Fe(CN),, Cu2+,Cd2+.

N

[7781

Zn2+,Hg2+

111951

1O.Tables

149

Admixture

Effect

Reference

phosphate

caking

[ 10471

ZnC1,

G

17801

Rb+

D

1102.488.4891

RbCl

D. recrvstallization

18791

Sr2+

D

11 1 1 1,7681

admixtures

N

1528.771

admixtures

I705.7171

admixtures

11287,12741

admixtures

H

admixtures

I11701 13231

admixtures

agglomeration

114121

admixtures

D

1868.5141

admixtures

N, G

[11.121

admixtures

11 1121

Br-

[lo231

HC1

Lf. H

15641

HC1. KOH

La n

[go51

irn p urities

s

[50.5921

r7

J

17041

D

[695.721]

150

10. Tables

KCl (continued) AdmiXtUre

Effect

Reference

aliphatic amines (2OC)

caking

13851

aliphatic amines

N. G. S

I14941

amaranth

N. H. D

17801

amines

caking

I13951

bromobenzole, phenole. aniline

H - cube + octahedron

17401

G

I

- retardation

dyes

H

14101

ethyl-hexanoic acid, octanoic acid.

N, D, yield

17811

ethylenglycol. diethylenglycol

caking

113801

laurylaminoacetate

H

N(CH2CONH2)3,octadecylamine

H. caking

monochloracetic acid

acetate

I I3871 I

I

110361

octadecylamine

caking

I10551

octadecylamine hydrochloride, pH

H.G

110671

I

I

I I caking

I I10471 I

organic substances with free

caking

D

I451 I

I16811

I

1O.Tabks

151

KC1 (continued) ~~

~

~~~~~

Admixture

Effect

Reference

surfactants

Ostwald ripening

[ 14561

I123,1021,

surfactants

1022,14551

t

KC103

POTASSIUM CHLORATE Density: 2320

Molecular weight: 122.549 System: monoclinic a R

-

-

b

0.4647

-

2-2

0.5585

c

-

0.7086

10QO 38'

IAdmixture

Effect

Reference

H - /Oll/ + /001/

DO41

H

[205.2121

H

[2151

H

12141

Biebrich scarlet

H - /011/

14391

organic dyestuffs

H

[207.210,214.

s,o,~-, CrO,2-,

Cr,0,2-

2151 Ponceau red

D. H

13 15.8351

152

10.Tables

KCIO,

POTASSIUM PERCHLORATE Density: 2520

Holecular weight: 138.549 System: rhombic a

-

0.8834

b

-

2-4

0.6660

c

-

0.7240

Effect

Reference

D

I8921

H - /001/

I211.2151

sop

H

Bordeaux B. Chromotrope 8B.

H - /Oll/

- /llO/

I2141 I2 11,2151

Wool scarlet, Solochrome black.

Fast red extra ~

Brilliant Congo red, Chlorazol fast

H - /102/

1211.2151

orange, Brilliant &urine. Trypan red, Bordeaux B ~~

~

Chromotrope 2B

H -

/loo/

1211.2 151

Chromotrope 2R. Chromotrope 2B.

H-

/loo/

I2141

Acid magenta, Alizarin Delphinol, Alizarin cyanine ~~

Erio fast fuchsin. Cr,0,2-

H - /001/

Ponceau red sulphonated dyestuffs

12141 11281

H - /Oil/, /102/

12141

1O.Tables

153

K,CrO,

POTASSIUM CHROMATE Density: 2732

Molecular weight: 194.190 System: rhombic

a

-

0.6920

b

-

294

1.0400

c

7

Admixture +

KC1.

(NH4),Cr04+ K,S04 + KC1

s,o,2Trypan red, Acid green DD extra Water blue, Methyl blue, Wool green, Naphthol red S, Scarlet GR. Past acid magenta, Tartrazine

azo acld red. Acid yellow, and other dyestuffs

0.7610

+ Reference

1

(NH,J2Cr04 + K 2 S 0 4 . %SO4

-

H - /001/

[ 2 13.2 14.2151

H - /010/ - /Oll/

I213.214.2 15)

154

10. Tables

qCr2O7

POTASSIUM DICHROMATE Molecular weight: 294.184 System: triclinic a

a

0

0.7340

b

82O 00'

I3

-

Density: 2690

z=4 0.7490

c 11.3390

97" 56'

y

I

=90° 30'

Admixture

Effect

KMnO,

H

Scarlet 2R. Naphthol black B.

H - /010/. /111/

- /010/

Reference 1213.214.2 151 213.2 14.2 15

Bordeaux S, Ponceau S extra, and other dyestuffs Methyl orange, Chloramlne yellow

19761

KH2As04

POTASSIUM DIHYDROGEN ARSENATE Molecular weight: 180.033

Density: 2867

Syetem: tetragonal a

A

-

0.7610

c

-

Z=4

0.7150

Admixture

Effect

Reference

pH

G. H

I1221

10.Tables

155

I

POTASSIUM DIHYDROGEN PHOSPHATE Density: 2338 System: tetragonal

a

-

0.7430

c

-

2-4

0.6940 -~ ~

Admixture

Effect

Reference

AlWO,):,

dissolution

1911

G

[lo531

Al3 +

G

[931

Al3+

H. D

15371

Al(NO,),,

KOH

~~

1535,5393

Fe3+

N, G

[ 1344.13451

G

I1691

1171 12801

~ r 3 +

-

Cr3+

G . H, N. D

15401

Fe3+

H - dendrites

12151 18391

Fe3+

16211 optical properties

17751 I12711

156

10.Tables

IAdmixture

Effect

Reference

I8401

H

FeCl,, pH KAI(SO,),. A3+

18393

13951 G. H

15381

1 12081

KCIO, KOH. Ni2+, Fe3+

optical properties

1449,7751

Na,B407

favourable

14721

Na,B,07

G. H

Pb2+,KNO, pH > 4,Cr3+, Fe3+.A3+< 50 ppm

H - prisms without pyramids I 1207.12151

I

admixtures

admixtures

G

[281.989.1206, 14821

G. H

[536.1081]

D

12981 13431

IO.Tables

KIOS

POTASSIUM IODATE Density: 3930

Molecular weight: 214.001 System: cubic a

-

Z=1

0.8920

Admixture

Effect

Reference

pH

N

I9401

157

158

10. Tables

POTASSIUM HYDROGEN TARTRATE Molecular weight: 188.184 System: rhombic

-

a 0.7614

b

-

Density: 1956 2-4

1.070

c

-

0.780

I

Admixture

Effect

Reference

cu2+

H - /111/

1213,2141

KgS04

G

[ 10851

admixtures

G

17131

dyes

H - /010/

12 13.2 141

tannin, red polyphenol. pectin

G

[ 10851

~~

KHC8H404

POTASSIUM HYDROGEN PHTHALATE Kolecular weight: 204.23

Density: 1630

Admixtove

I Effect 1 Reference

Fe3+, Ce3+

D

admixtures

15591 14541

admixtures

G

[557.5581

glycerine, polyethylene glycol

G. H

19951

10.Tables

KI

POTASSIUM IODIDE Molecular weight: 166.002

Density: 3123

System: cubic

2-4

D = 0.7062

Admixture

Effect

KBr

D

N a + , Rb', Cs'. Cl-, Br-. NOR-

D

Pb2+

H

Pb2+.Ti4+,Sn4+. Bi3+, Pe3+

favourable

- mixed crystals

Reference 1421 1401

- octaeders

admixtures

D151 14723 I3231

OH-

G

17041

Fast acid magenta, Brilliant yellow

H

I4 101

surfactants

G-retard

17401

LiNH,C,H,O,

AMMONIUM LITHIUM TARTRATE Molecular weight: 173.056 Admixture

Effect

Reference

A3+,Mg2+. Ca2'. Pb2+, Si. pH

H

I8401

159

10. Tables

160

mo2 POTASSIUM NITRITE Molecular weight: 85.104 Syatem: monoclinic R

0

= 0.4450

-

b

-

Density: 1915 2=2

0.4990

c = 0.7310

114O 50'

_____~ ~

~~

Admixture

Effect

Reference

Fe2+

favourable

14721

KMnO,

POTASSIUM PERMANGANATE Molecular weight: 158.034

Density: 2738

System: rhombic

a

-

0.9099

2=4

b = 0.5707

c

-

0.7411

Admixture

Effect

Reference

Cr,O,2-

H - /001/

I20 1,2021

CrO,2-. Se0,2-. CO,~-

H-

/loo/

12151

H3.P04-

H-

/loo/ + /011/

I2 151

HP042-.HA SO,^-,

As0,3-

H - /011/+

/loo/

12151

HQAsOd-

pH, CO,

H,S

I979.9841

10. Tables

161

KNO,

POTASSIUM NITRATE Molecular weight: 101.103 System: rhombic a

I

-

0.5430

b

-

Density: 2110 2-4

0.9170

c

-

0.6450

Effect

Reference

D

16791

N. G . S

11222.12241

Cr3+

clusters

18251

Cr3.’, Na+

N

[12141

cs+

D

[ 12951

Fe3+, Ni2+. Li+

diel. permeability

[6431

isomorphous admixtures

G, D

[6781

K2Cr,0,. Cu(N0219

D

(6491

KC1

D-

Pb2+

H

(6421

Pb2”,Th4+. Bi3+

favourable

[4721

Sr2+

D

[6831

admixtures

H

16981

admixtures

G

I163.1116.

Admixture

c1-

18571

11171

I CH,NH,Cl, C , ?,H,f;NH,.HCl

N. G

r 12221

162

10. Tables

mo3 continued) Admixture

Effect

110981

dyestufs Fast red extra, Bordeaux S.

Reference

H - /001/ platelets

12241

H, caking

I14481

N. G. S

[ 12241

N

I8601

Tartrazine. and other dyestuff's Fast red extra, Naphthol red S, Tartrazine. 1.4-diaminoanthraquinon-2-sulphonate methylamine hydrochloride, dodecylamine hydrochloride, fluorocarbon surfactant surfactant

11231

KTiOPO,

POTASSIUM TITANYL PHOSPHATE Molecular weight: 197.975 Admixture

Effect

Reference

C9+

D

I1431

10. Tables

CNaC,H,O,

SODIUM POTASSIUM TARTRATE Nolecular weight: 210.167 Admixture

Effect

Reference

A P . cuco,

H

[ 12931

Cu2+. H,BO,

H - /210/

1213.2151

cuco,

H - retards /001/,shortening.

I901

decreases with decreasing pH cuso,

H

- retards /001/,effect rises

1901

with raising pH

H - retards /210/,stronger

I901

effect with decreasing pH MnCI,

H -retards / 1 1 1 / and /Oil/,

I901

alkalis - stronger effect (NH&M004. Na2Mo04. NH4Cl.

H

13473

H2B01, CuSO,, Cu acetate, MgSO&

- /LOO/

Na+

H

Na3B4O7

G - retards, H - /210/

NH4+

I213.2151 I891 I213.2151

163

164

10. Tables

OJaC4H,0, continued) Admixture

effect

ref.

admixtures

H

11334.13351

Crocein scarlet 3B. Diamine sky blue

H, D

18961

Admixture

Effect

Reference

C103-,B,0,2-

H

12151

10.Tables

165

K2S04

POTASSIUM SULPHATE Molecular weight: 174.254

Density: 2662

System: rhombic

2=4

a = 0.5731

c = 0.7424

b = 1.0008

Zeference

Admixture N3+

2, dissol.

11791

Ca2+,Sr2+.Ba2+.&+, Pb2+, C s + .

v

12131

Ni2+

Ce3+

.

D retards reaystalliza-tion

52,874,875,876l

N

762)

G

767.918.14971

dissol.

13571

G

I 13561

D

[5201

D

12401

H. caking

[182,1036]

N.G

I1 1311

D

[680,1499.1500. 15021

K,Cr04 + KC1

D - creep cryst.

17201

166

10. Tables

I

Admixture

Effect

K,Cr04. Pb2+

Reference 16 171

K,Fe( CN)

G. dissol.

114.95)

KCIO,, K9Cr0,

H, I)

12211

KCr(S04)?

G

[ 14951 ~

Li

N

[ 14331

Mn2+. U 0 2 2 + . V 0 2 2 + . Cd2+.

favourable

14721

(NH,),SO,

D

I2961

Ni2+, Cu2+, Co2+, Mn2+

D

I3 171

NiSO,, MnSO,

D

12391

PbCl,

N, H

19541

D

15721

+

Fez+, CS+. Cu2+,A13+,Mg2+, sio,2-

[11001

admixtures

N

1424.14321

G

1757,766,906. 1273,1274,1355, 1357.14981

2 D

inor anic anions

18731

10.Tables

167

I K2s04

(continued) Admixture

Effect

Reference

s,o,2-. s,o,2-

H - platelets /001/

1203.214.2153

Alizarin yellow

H-

Amaranth

H, caking

[182.1036]

Crystal Ponceau

D

[6001

dyestuffs

H

1209,210,214, 215.

/loo/

12081

391.14471 [ 12731

18341 solvents

19301

surfactants

G

[237,7721

LiCl H2O

LITHIUM CHLORIDE monohydrate Molecular weight: 60.409 System: tetragonal a

-

0.7669

Density: 1762 2-8

c = 0.7742

Admixture

Effect

Reference

Mn2’. Cd2+. Sn2+,Sn4+,Co2+,

favourable

14723

Ni2+, Fe3+.Ti4+.Cr3+.Th4+

168

10. Tables

Molecular weight: 26.94

Density: 2300

System: cubic

a

-

2=4

0.401

Admixture

Effect

Reference

M gF2

D

I8081

FeF,

G, N

111971

LiI 3 HzO

LITHIUM IODIDE trihydrate Molecular weight: 187.891

Density: 2290

System: hexagonal

a

-

0.7460

2x2

c

-

0.6460

Admixture

Effect

Reference

admixtures

D. H

[ 11371

10.Tables

169

LiIO,

LITHIUM IODATE Molecular weight: 181.85 System: hexagonal a

-

0.5469

c

-

Density: 2=2

0.5155 ~

~~

Admixture

Effect

Reference

MnO;

H

I9901

admixtures

D, G

I3631

pH

G

I2471

Mg(CH,C00)2

. 4 H2O

MAGNESIUM ACETATE tetrahydrate Molecular weight: 214.47

Density: 1450 ~

Admixture

Effect

~~

-

~

Reference

10. Tables

170

LizSO,

HZO

LITHIUM SULPHATE monohydrate Molecular weight: 127.955 Syetem: monoclinic a

B

-

0.5430

b

-

Density: 2051 212

0.4830

c

-

0.8140

107O 35'

Admixture

Effect

Reference

D

[ 13501

H

[ 10801

H,SO,

H

I11091

pH

lower pH - better crystals

[959]

pH

- 5.0

H

- shorter crystals

pH 6.0 - 6.5

H - longer crystals

DH 6.5 - 6.7

favourab le

M@,&SO&

[ 10571

110571

1 I4721

6 HzO

POTASSIUM MAGNESIUM SULPHATE hexahydrate

IMolecular weiaht: 402.742

I

Admixture

Effect D

I

Reference [1189]

10.Tables

171

Mgcos

MAGNESIUM CARBONATE ldolecular weight: 84.33

Deneity: 2980

System: trigonal L L

-

2-2

0.561

48O 12'

pH

Effect

Reference

S

[1035.1167]

complexons

IlO2Ol

H. precipitation

I6531

DhosDhonates

G

I8121

polyglutamic acid, polyvinylsul-

N

[ 11671

hydroxyethylenediphosphonic acid, EDTA

I Mgc204

MAGNESIUM OXALATE

Admixture

Effect

Reference

surfactants

G

19441

172

10. Tables

MgF2

MAGNESIUM FLUORIDE Molecular weight: 62.32 System: tetragonal a

-

0.466

c

-

2-2 0.308

7

Admixture

Effect

Reference

Ni2+. Co2+

D

I14961

admixtures

G

131

Molecular weight: 160.388

1

I

I

Admixture

Effect

Reference

Mn2+. Zn2+, Co2+, N12+

D

158,603

10.Tables

Molecular weight: 360.688 System: monoclinic

a

-

p-

0.9324

b

-

Deneity: 1723 2-2

1.2597

c

-

0.6211

107O 08'

Admixture

Effect

Reference

Ni(N134)2(S04)2

D

[9281

Ni2"-,Fe2+,Cu2+

D

1581

Effect

Reference

D

1621

173

174

10. Tables

Molecular weight: 58.34 System: hexagonal a

-

0.311

c

-

Density: 2400

z=1 0.474

Admixture

Effect

Reference

admixtures

periodic crystallization

1201

pH

S

17881

saccharides. glycerine

G - retarding

113091

MnCOS

MANGANOUS CARBONATE Molecular weight: 114.95

Density: 3400

System: trigonal a

a

-

252

0.584 470 45'

Admixture

Sod2-.Se0,2-.

Ni2+, Cu2+, c02+,

Effect

Reference

D

18381

1O.Table.s

I

MgSO,

7

HzO

MAGNESIUM SULPHATE heptahydrate

Molecular weight: 246.469

System: rhombic a

-

1.1940

b

-

Density: 1680 2-4

1.2030

c

-

0.6870

Admisture

Effect

Reference

cationic admixtures

G

16221

Co2+, Fe2+, Cu2+

H. D

1571

D

1621 191

H - shortening, H2S0,

I90.524.9761

decreases this effect

I

G

Na2B407

[907.908]

shortening

Ni2+, Zn2+ H,BO,

- retarding, H -

+ NaOH

H - needles

12331

D

1488,4891

G

19293

D

1581

H

pH

G

methanol, ethanol

N

- shortening

1901

p- phenylendiamine

tensides

G

1728.7331

175

176

1O.Tables

M n S 0 4 H,O

MANGANOUS SULPHATE monohydrate Molecular weight: 169.011

Density: 2950

System: monoclinic (rhombic)

a

-

b

0.6740

-

c

0.8100

Admixture

-

1.3300

IEffect

I Reference

I

I

-

Mn(HC00)2 2 H 2 0

MANGANOUS FORlMATE dihydrate Molecular wefPht: 181.007

Admixture

Effect

1O.Tables

177

UH,Br

WMONIUM BROMIDE dolecular weight: 97.942

Density: 2429

bystem: cubic L

2-1

= 0.4047

Admixture Cr3", Fe3+, Cu2+, Nl2+, Co2+,Fe2+.

Reference

H

11322.1323,

Zn2+.Mn2+. Cd2+.Be2+

13241

Cu2+ + Fe3+

I6021

Cu2+, Cd2+

D

I6011

Fe2+,N a +

caking

110431

admixtures

H

[ 11701

aliphatic monoamines

caking

I5901

hydrazlne and guanidine

caking

I4021

caking

110431

caking

[13721

derivatives lactame oil 0-

and p-vinylphenylmethan

sulfoaclds 1221.10971

10. Tables

178

NH,Cl

AMMONIUM CHLORIDE Molecular weight: 53.491

Density: 1527

System: cubic B

-

Z=1

0.3866

Admixture

Effect

Reference

Be2+

H

[ 1322.1323.

13261 Cd2+, Fe3+,A13+

16021

Cd2+

[5991

Cd2+

D. H

[ 1324.13261

CdCl,. K4Fe(CN)6. pectine.

H. caking

I10361

G, N

[1427j

Co2+, N12+, Mn2+, Cu2+

D

112691

Cu2+, Co2+, Ni2+

D

15811

N(CH,CONHY)? Co2+,Mn2+.Fe2+,Cr3+, NaSCN, CH3COONH4, (NaPO,),

cU2+,

Co2+, Ni2+, Zn2+, Mn2+, Sn2+ D

[ 1264,1269,

12701 CUCI,

D

13 161

cuso,

H - cube

I1131

D Fe3+,Cr3+, C u 2 + , Mn2+, ~ p + c02+, ,

I600.1322,

Cd2+

1323.13263

I

I

NHaC1

(continued)

I

Admixture

Effect

Reference

Fe3+.Cu2+

H

16421

Fe3+.Ni2+, Co2+,CuSO,

H - dendrites/cubes

1773,7741

FeCl,, CuSO,. CuC1,

H - transparent cubes

16601

KC1 + KqSO,

D for creep cryst.

17201

Mn2+,Mg2+,phosphatcs

H - favourable

19261

Mn2+. Zr4+,Cd2+. Fez+.Cuz+,

favourable

14721

H , anomalous mixed

12601

Co2+,Ni2+, Fe3+.Cr3+

Mn2+, Fe2+,Co2+,Ni2+. Cu2+

crystals Cd2+. Mn2+.Co2+,Cu2+,

H

14401

Ni2+, Fe3+. Sod2-. NO3-.

ammonium acetate a n d formate NaCl

I12911

NiCl,

H

18201

Pb2+

S - favourable

[4231

H - dendrites/cube

14231

I

C032-. SO,2-.

F-. I-.

favourable

180

10.Tables

m,c1 (continued)

I

Admixture

Effect

Reference

ZnC1,. AICl,, NiC1,. CoC1,. MnC1,.

H

[ 10961

FeCl,. CdC1,. (NH4),S0,. CuC1,. (NH,),MoO,. HgCl, admixtures

N

C0,2-. HCOR-.Na+.NH,

H

HC1

caking

inorganic anions

H ~~

~

phosphates

G

phosphates. CO,,-. SO,,-

H - dendrites/cube

alkylarninoacetate and -chloride

caklna

dyes

I12181 ~

~

extract of peanuts

favourable

I8041

laurylaminoacetate

H

13871

murexide

H ~~

I440.6421 ~~

octadecylamine hydrochloride

caking

I3391

pectine. pectinlc acid

H - prolongated trans-

13451

parent crystals pectine

N. S

18811

phenolsulphonic acid

S. caklna

15871

I solvents

I12051

10. Tables

NH,CI [continued) Admixture

Effect

Reference

urea

H

1221 I

urea

H - cube aggregates

1773.7743

urea

H

urea

H - cubes

I 1096.10971

urea, lactose

G

112191

urea, pectin

G. N

114271

Admixture

Effect

Reference

Cu2+,Ca2+,Fe2+,Th4+

favourable

14721

Zn2', Cd2+.Mn2+. Ca2+.Mg2+, Sc3+,Co2+, Ni2+

- dendrites/octahedron

19761

"7231

181

182

10.Tables

NH4ClOs

AMMONIUM CHLORATE Molecular weight: 101.50 Admixture

admixtures

H

surfactants

inclusions

Admixture

Effect

Reference

Ca,(PO,),

caking

114131

so,2-

H

dyes

H - /Oil/, /102/

surfactants

[ 11701

- /llO/

[2 14.2151

1214,2151 15323

10.Tables

System: rhombic a

-

0.7290

218

b = 1.0790

c = 0.8760

Admixture

Effect

Reference

dehydrating substances

stabilization

14631

NaHSO,. MgCl,, CaSO,

caking

14573

admixtures

I781

hydrocarbons

stabilization

14631

oil, sugar

13. favourable

14591

Admixture

Effect

Reference

dyes

I-I

[214.21 51

glycerine. Na,B40,. sucrose

favourable

14721

183

184

10. Tables

I

NH4HC4H40,

AMMONIUM HYDROGEN TARTRATE

1lKolecdar weinht: 167.124 Admixture

I

Effect

Reference

(NH,),HPO4

AMMONIUM HYDROGEN PHOSPHATE

I

Molecular weight: 132.056

I

Density: 1619

Svetem: monoclinic

lAd*ture

Imeet I H - platelets/cubes

IReference

I I

10. Tables

185

NH4H2P04

AMMONIUM DIHYDROGEN PHOSPHATE Density: 1803

Molecular weight: 116.026 System: tetragod

a

-

0.7610

Admixture

c

-

z=4 0.7630

Effect

Al3+

Reference

I5351

AlCI,, FeC1,. Cr3+

G.H

[289.2901

Ba2+,Sod2-

higher electric conduct.

14231

Co(NO2)q

G. D

[ 14431

cr3+

green prismatic faces

14233

H

1176,13361

H

15783

I Cr3+,N 3 + .Fe3+

I

Cr3', Fe3+

CrCI,

G

- retarding, N - wider

P763

metastable zone N. G

G

"2893

H. G - lower growth rate of

I5791

prismatic faces

H

13751

If - wedges

14231 ll6l 19743

186

10.Tables

NH,H,PO, (continued) lAd*e

Effect

Reference

G. H

12641 12951

G. H

17711

H, G

I15141

G fluctuations

I15141

D. H - wedges

1161

H

- thicker crystals

I161 I12943

pH. FeC13. CrPO,

D. H - rhombic shape

1161

H - prisms

I9211

G. H

1227,228,229,

I 2301

pH-3.9. Fe3+, Cr3+,A3+.Sn2+.

favourable

I4721

H - wedges

I7221

admixtures

D - purity

19341

admixtures

ti

1249,14823

admixtures

G. H

ll08ll

admixtures

H -platelets

NH,

Sn4+.Cr3+,Fe3+,Ti4+,Au3+. H 3 + , Be2+

10.Tables

(continuedl Admixture

Effect

Reference

H,P04

N - slowning

17221

PH

H - a t higher p H regular

11 1091

growth pH

G

19521

pH

S, H

I14181

p H > 3.6

H

pH. gel

G

PH. NH,OH. H 3 P 0 4

- shortening

H

EDTA

H

surfactant

N

surfactants

G

- lower rate

16061

187

Density: 1652

Molecular weight: 80.043 system: rhombic b

-

Z=4

c

0.7660

-

0.5800

Reference I

'D S. decreases

caking

'1

16521

'

[?I861

' [ 13 16.13 171

safety

16701

H. caking

(10361

lower hygroscopiclty. tight

13521

hygroscopicity

16481

coarsening of dendrites

13241

caking

[2971

stability

10.Tables

I

NH4NO3 (continued1 ~~

~

~~

Admixture

Effect

Reference

admixtures

N

I 13641

admixtures

H. stability

13251

Acid magenta, Bordeaux S.

caking

[ 14481

H. caking

[ 10361

H

I13471

Azofuchsine. Chromaeol yellow Acid magenta, N(CH2COONa)3. Bordeaux S alkylamines, Sod2-.sulphonates amine

16431

aminoalcane salts

I3881

dyes

H - /010/platelets

[224.1098]

dyes

noncaking platelets

W63

glycole. glycerine

caking

14621

laurylaminoacetates

H

13871

S

I6611

hosphate solids

I

salts of p-rosaniline disulphonic

I4001

acid

w

sodium ethylsiliconate

caking

I13941

sulphonates

caking

[ 1 376.13771

toluidine, azobenzole, anthranilic

hygroscopicity

if3581

acid

189

190

10. Tables

NH4NOs

[continued)

Admixture

Effect

Reference

toluidine. resorcin. azobenzene.

hygroscopicity

16431

malelc acid urea

[1391] cakina

wax. dves

I2971

“H412BeF4

AMMONIUM BERYLLIUM FLUORIDE Molecular weight: 121.263 System: rhombic

m

-

0.58

Admixture (NH4)&rO4

b

-

c

1.020

-

IEffect D

0.75

IReference

10. Tables

dolecular weight: 132.134

Density 1769

System: rhombic L

= 0.5951

191

2=4

b = 1.0560

c = 0.771 b I

Admixture

Effect

1 Reference

M,(SO,),

H

1114633

M 2 ( S 0 4 ) 3 150-200 ppm

H, decreasing mois-

I

18831

ture M3+

caking

15831

A13+. Cr3+,Fe3+

S. H. N

(1365,13661

A13+. Fe3+

S decreasing

I79 11

M3+.Fe3+,Cd2+,K+

H. S

13041

M3+.Mg2+. Fe2+,pH, urea

H - rice corn

1977,9821

A13+. Mn2+. Cu2+

N. G . S . H

11881

A13+, p H

H, noncaking flakes

14641

As5+

H

- needles

I48 11

As5+ 0.03 %

yellow crystals

15731

15271

Ca2+. Fe2+

cakin

1481

S. H. favourable

14811

192

10. Tables

I

Admixture

Effect

Reference

I181

caking

14031

cr3+

H

I7151

Cr3+

G

I6931

Cr3+

N. G. S

17861

cr3+

N

17631

Cr3+ + H,SO,

H - prisms

I661

Cr3+ >50 ppm

H - longer,

I661

decolorUed

Cr3+. Fe3+

G

[ 14731

Cr3+, H,PO,

S. colouring

15881

cu2+

N. G. S , H

I1951

Cu2+,A13+. Mn2+

192

Fe2+

113181

Fez+. A13’

1378,379,3801

Cu2+, Na+. pH

D

972

N. H. S

[ 977,9821

10.Tables

Effect

Reference

H. S. caking

12761

favourable

14821

at high conc. unfa-

I830al

193

vourable

H - prisms

[ 170.1711

D

19711 ~

- needles

(84,4291

H. S - needles

I482.5431

H

G. H

- needles

I14711

Fe3+,A13+. Cr3+,H,S04. P,O,

H. S

[105.106.107]

Fe3+,As+,Cr3+,Mn2+

S. caking

[ 13611

Fe3+,A3+,Mg2+.CaC,04

H

I14381

Fe3+.C1-

[ 13961

Fe3+,Co2+,Cr3+,Cu2+

D

14901

Fe3+.Fe2+

D

[969.970.9711

Fe3+.Fe2+.Na,S,03

S

13001

Fe3++, Fe2+.pH

D. H. N

19721

Fe3+,organic admixtures

H. colourlng

1706.7071

194

10. Tables

Admixture H,C,04.

Na3S,03. Mg2+

I Effect

Reference

H - shortening

13511

H - hexagonal rice

i3511

corn HqSO, 2g/L1A 1 9 0 3 8g/L

H - rice corn

1651

H,S04. A13+. Fe3+,Mg2+. Na,S,O,

H - rice corn

13821

H,S04, Fe3+.Cu2+,Mn2+,Na,S,03

H - rice corn

13811

isomorphous sulphates

H

14551

K 3 S 0 4 . K2Cr04

H. D

12211

Mg2+

H, S

Mg2+, Mn2+.Zn2+. Cr3+, NaC1.

N, H, S

sulphonlc acids

Mg2+. Mn2+,Zn2+,organic

H. S

14651

MgS04 + HqC,04

H - shortening

151

Mn2+

G,S

19751

Mn2+

N. G , S

11941

Mn2+, Cu2+, Al3+

H. S

11911

sulphonic acids

1O.Tables

I

(NH4)2s04

fcontinuedl Effect

Reference

N. 13. S . D

[189,1901

caking G

D H - rice corn

I977.9821

G.H

(13041

H

_____

pH, urea, A13+,Fe3+.Mg2+, Cu2+,

r9771 ~~

H - rice corn

[1200]

H. S

[ 10271

H. S

19761

D

15201

G. I3

[ 14701

admixtures

[307.1211, 14281 S

[7651 I40 11

195

196

1O.Tables

I

“H,),SO,

[continued]

I

Admixture

Effect

Reference

CN-.SCN-

unfavourable

17911

H,S04

minimum

[2701

H9S04

[ 172.5851

HSPOI

[ 9 7 7.98 2,1951

P,05 + 0.5 Yo H,SO,

H - favourable

PnOc. HnSO,

€1.

pH

S

I10341

G. H

[ 12873

s

I2331 I13591

113631 pH6-7

H. S

I3041

pH. C1-

G. S

[ 10691

cakinr!

14231

amines

caking

I2411

Bordeaux S

II - noncaking long

[2241

alkylarylsulphonates

’

brittle crystals Bordeaux S, Azofuchsine.

H. caking

[ 14481

Tartrazine. Diamine sky blue cyclohexanone oxime. hydroqli

amine sulphate. caprolactame

18331

10. Tables

I Admixture

I

Effect

Reference

dyes I I

I

dyes

1 caking

glucose, molasses

‘H.S

glycerine. urea, pectine

H. S

glycol, glycerine

caking

imidazoline salts

caking

I13671 I

impurities from caprolactam

I I

15061

nonionic surfactants

N

organic admixtures

H

1706,7071

organic dyes

H

13911

organic substances

G

organic sulphonic acid

H. S

14651

pectine. wood extract

S. H

14601

phenol, pyridine

G.H

15271

phenol, pyridine

H

[ 14381

polyacrylamide

S

I14041

- higher

polyvinylalcohol surfactant. dye

748

1661

I13961

caking

[ 13601

197

198

10.Tables

~~

Admixture

Effect

Reference

surfactants

caking

[789,1289]

tar

H

(4811

urea

S - favourable

1461.1 1921 [977.9 821

urea, phenol, glycerine, starch, glue

I

-

Admixture

Effect

H,S04. (NH4),S04

N. G

[6541

H 2 S 0 4 . (NH4)2S04. Nb205, Ta205

N. G Nb retards, Ta

1655,6561

I accelerates

Reference

10. Tables

Admixture

Effect

Reference

UO,Fq, F-

S , N. G

I2541

“H,),W04

AMMONIUM TUNGSTATE Molecular weight: 283.998

pods-,~

~ 0 , 3 sio,2- .

Iyield

I I3561

199

200

10.Tables

Na,AlF6

SODIUM HEXAFLUOROALUMINATE (CRYOLITE) Molecular weight: 209.941 Syetem: monoclinic

IBa

b

0.5460

Density: 2900

-

c

0.6610

-

2-2 0.7800

900 12'

Admixture

Effect

I

Reference

I 114831

I

YaBOs 4

H,O

SODIUM PERBORATE tetrahydrate blolecular weight: 153.87 ~~~~~~

~

~

Admixture

Effect

Reference

surfactants

G

133 1,3331

surfactants

1184,236,251. 253.330.3921

10. Tables

NaBO,

H202 3 H,O

SODIUM PEROXOBORATE trihydrate Molecular weight: 153.875 Admixture

Effect

ionic impurities, surfactants admixtures

Reference I3931

G

admixtures

I7821 13941

admixtures

N

I12501

surfactant

N

I3321

surfactant

G

I3331

surfactant

N, G. H

I2521

Admixture

Effect

Reference

201

10. Tables

202

Na2B407 10 H 2 0

SODIUM TETRABORATE decahydrate Molecular weight: 381 367 System: monoclinic

a

B

-

-

1.1820

b

Density: 1692

-

2-4

1.0610

c = 1.2300

106O 35'

I

Admixture

Effect

CUCI,, c u s o ,

H

admixtures

N. H

142 I, 10771

H,BO,

caking

113701

pH

H - cubes

[423,976]

H

[213,214.2151

oleic acid

S, H - favourable

1422,423,9761

sodium oleate, dodecylbenzene

N. G , S

[ 10771

H. N

[123, 10781

=

9.7

Azoflavine RS, Chrome fast yellow.

- /010/

Reference [213,214,2151

Ponceau 4. Acid brown R. Alizarin yellow, Orange 1, Naphtol black, Ponceau S extra, and other dyes

sulphonate surfactant

10. Tables

-

NaBr 2 H,O

SODIUM BROMIDE dihydrate Molecular weight: 138.924 System: monoclinic

a = 0.6590

b

Density: 2176

-

c = 0.6510

1.0200

p = 1120 05' Admixture

Effect

Reference

Na,Fe(CN16, CdBr2, PbBr2,

H, caking

110361

NaBrO,

SODIUM BROMATE Molecular weight: 150.892

Density: 3325

System: cubic

a

-

3-4

0.6705

Admixture

pH

I

Effect G

I

Reference

203

204

10. Tables

NaCHsCOO

3 H20

SODIUM ACETATE trihydrate Molecular weight: 136.080 Admixture

Effect

Reference

N a pyrophosphate

N

[ 14191

Na2HP04

N

[1420,1436]

Na2PO,

N

(14371

admixtures

G

[ 11381

cyclohexane

H

I3091

Admixture

Effect

Reference

CaO, pH

H - prisms. cubes

I13751

admixtures

H

[1159]

lysine

H - prisms

[ 13741

10. Tables

olecular weight: 286.141

b

Density: 1460

= 0.9009

c = 1.2597

Admixture

Effect

Reference

admixtures

N

[3051

205

206

10. Tables

NaCl

SODIUM CHLORIDE Molecular weight: 88.443

Density: 2163

System: cubic a

-

3-4

0.5627

Admixture

Effect

Reference

admixtures forming double salt

H

IlOOll

AgCl

D - ultrasound

I7411

A@C1

D, Ostwald ripening

I877.8781

caking

14061

H

[ 10391

Al3+

Ba2+

[ 14101

Ca2+, Sr2+.Ba2+. Cd2+

D

1381

Ca2+. Sr2+,Ba2+, Mg2+. pH

D

[ 10741

Ca2+, Sr2+,Cu2+, Ba2+,Zn2+, Fe2+ H - fibers

I5221

+ polyvinylalcohol

CaC1,

H - octahedrons

I8001

CaC1,

dissolution

[ 12251

CaCl,, Fe(CNIe4-

caking

15471

H

1141.1421

Cd2+,Pb2+,Mn2+, Mg2+, Hg2+,

H

10.Tables

207

: INaCl

(continued)

1 Admixture

Effect

[ 11361

Cd2+. Zn2+, Mn2+ CH2NH2CH2COOH, Cd2+,Mn2+,

Reference

G,H

I53 I1

cu2+

D

I13201

CllC1,

G , H, D

[699.700.70 11

Fe2+,Mg2+. alkaline carbonates

caking

14041

Hg2+

a n d hydroxides

- favourable

19761

Fe3+,A13+,Zn2+

S

HgC1,

H

25 inorganic cations

G

1n3+

D

18721

K,Ti0(C904),

caking

I5891

K,Fe(CN),

N, S

I7831

K,Fe(CN),

H

12821

K4Fe(CNI6 5 ppm

caking

11751

1138,10901

- decrease

K4Fe(CNI6, K,Fe(CN),

I3401

11401

K4Fe(CN)6,Mg2+

caking

[I 15,6721

KCaCl,

n

1411

208

10. Tables

I

NaCl (continued1 Reference

i2731

1391 [ 13531

[1481] [5481

I13811 (569,13211

14051

161 [ 10371

I423.9761

[1362]

11 1601 dendrites Na,Fe(CNj6, Na3Fe(CNjG

H. noncaking

11741

10. Tables

NaCl I continuedl

Admixture

Effect

209

Reference [lo101

NaOH NaOH

H

111941

NaOH. Na2C03

H. electrical

[ 11391

properties caking S

- favourable

113731 (423,9761

N, G. D

I4771

D

I9361 18271 Ill611

Pb2+. Cd2+,Ca2+,Mg2+

D

[1349]

Pb2+, H , S 0 4 Pb2+, K,Fe(CNIG

14771

N, G , H, solubility

Pb2+, Mn2+, Bi3+,Sn2+,Ti3+,Cd2+. favourable

"2601 14721

Fe2+, Hg2+

I

Pb2+. urea

I

Pb2+,urea, Cd2+

D on / 1 1 1 / and

16201

/loo/ H

[ 141,142,190.

530.53 11

2 10

10. Tables

NaCl

Admixture

Effect

PbC1,

D

PbC1,

G

PbCl,, CdClQ

D

1869,8711

PbC1, , K,Fe( CN),

G

[ 14951

ZrOC1,

caking

(13711

Rb+. Cs+

D

(12471

small ion admixture

G - rise

12731

sop

H

I1771

Ti K oxalate

caking

I8481

T1+

D

[870,87 11

water-containing substances

decrease caking

(3711

admixtures

H, low attrition

I1801

admixtures

H

11170,1221, 14801

admixtures

N

admixtures

D

10.Tables

21 1

I

NaCl

I(continued) Admixture

Effect

Reference

CH,COO-. CdCl,, CaCl,+MgCl,

H

I7363

complex cyanides, sfloxanes

caking

I5451

complex cyanides, urea

caking

I5461

OH-

G

I7041

pH

H

I13361

D

I7211

26 admixtures

H. caking

110361

alanine , glycine , CH,CO 0H

G. H. lower attrition

I12621

aliphatic amines

N. G. S

I14941

brornobenzene. phenol, aniline

H - cube +

I7401

octahedron citric acid. tartaric acid

caking

14061

cysteine. creatinine. pepsine, sodium glutamate, sodium phosphate glycine laurylaminoacetate

I116,138.10891

212

10.Tables

(continued) Admixture Methylene blue, Erythrosine N a salt of carboxymethyl-cellulose

organic acids phenol golysaccharides polyvinylalcohol golyvinylalcohol sodium dodecylsulphate sodium sulphonaphtalate surfactants surfactants surfactants surfactants surfactants synth. polyelectrolyte urea

10.Tables

213

~

Effect

Reference

H

IlOOO.1002. 1 1 18.1244. 1261,1487.

urea, aliphatic acids

caking

urea, CrCIR

H

urea, formamide, glycine

H

urea, pyridine. formamide

H - octahedrons

I

14711

NaC,H,O,N,

SODIUM PICRATE Molecular weight: 251.096 ~

~~~

~

~~

~

Admixture

Effect

Reference

Na,SO,

N - accelerates

13721

NO,-. Cl-, Br-. COS2-.

G

- accelerate

I3721

214

10.TabZes

NaClO,

SODIUM CHLORATE Molecular weight: 106.441 System: cubic a

-

0.6570

Admixture

Effect

Reference

cu2+

H - /llO/ - / 1 1 1 /

113361

N a dithionate

H. G

[1103,1104]

Na,B,07

H. G

I4851

Na2B,0,

N

11531

Na2Cr0,

D

16871

Na,S, 0

H - /loo/ - / 1 1 1 /

[ 1991

Na,SO,

G. H

[124.125.132]

Na,SO,

N. H

18621

H - /111/

15231

NaBO,

H,G

17261

NaBO,

N

I14091

S2062-,B4072-, S2032-. SO,^-,

H - /111/

12151

Na,SO,.

NaClO,

Cr,.0,2-. CrO,2-, C10,2-

admixtures

114901

admlxtures

I12821 19761

10. Tables

Admixture

Effect

Reference

Na,S04

G

11281

~~~~

SODIUM FLUORIDE Molecular weight: 41.988

Density: 2790

Z=4

System: cubic

Admixture

Effect

Ponceau 4GB. Solochrome black, H - cube/octahedron

Reference [4101

Alizarin red S polyacrylic acid

[4521

2 15

2 16

10. Tables

NaHCO,

SODIUM HYDROGEN CARBONATE Density: 221 1

Molecular weight: 84.007 System: monoclinic

a

B

-

-

0.7510

2-4

b

= 0.9700

c = 0.3530

930 19'

I Admixture Na,SO,

+ hexamethylenimine

Effect N. G

1

Reference

17501 [ 181.3841

NaCl NaCl

N

18421

NaC1, NaNO,, Na,SOd

N. G - accelerate

1861

admixtures

N

18421

admixtures

S

19761

admixtures

H

[ 13691

admixtures

[1217]

benzenesulp honates

[4071

carbamate surfactants

G

I3671

I I13921

10.Tables

2 17

NaCsH3N,0S

MONOSODIUM URATE

I

Molecular weight: 190.11 Admixture

Effect

Reference I

Mg2+. K+

N

[ 13081

Admixture

Effect

Reference

organic substances

S

_1

Na3H(CO3I2

TRONA Molecular weight: 190.448

- favourable

benzenesulphonates surfactants

I4211 I4071

G. H, S

I1368.13791

,

2 18

10. Tables

NaI 2 H,O

SODIUM IODIDE dihydrate Molecular weight: 185.925 System: triclinic

a a

-

Density: 2448 2-4

0.6850

b

-

98000'

0

= 119000'

0.5760

c = 0.7160 y

Admixture

Effect

Cu2+,Fe2+.Pb2+,SO,2-

D

~68~30'

NaNO,

SODIUM NITRITE Molecular weight: 68.995

Density: 2144

System: rhombic a

-

0.3550

b

-

292

c = 0.5380

0.6660

Admixture

Effect

Reference

Pb(NO,),. Hg(NO,),

H

[3731

Ca2+

favourable

I4721

surfactants

hydrophobization

[ 1464)

10. Tables

NaNO,

SODIUM NITRATE Molecular weight: 84.995

Density: 2257

System: trigonal

a a

-

3-2

0.6320 4 7 O 14'

Admixture

Effect

Reference

Ostwald riDenina

[ 14531

N

14121

n

I57 11

S. H

[ 10271

Pb2+,Ca2

N. G

[2721

solid impurities

unfavourable

19761

aniline sulphonate, Wool scarlet,

H - /001/faces on a

[2241

Chloramine sky blue FF, Acid

rhombohedron

Fe3+

I HN03, Na2C03,NaC1. NaN02, Fe,O,

green GG extra, Soluble blue, Induline, Gallophenine D Congo red, Oxamine blue B.

H

Magenta, Fuchsine. Methylene bllie caking hydrophobization

[ 1442)

219

220

10.Tables

-

NaOH H20

SODIUM HYDROXIDE monohydrate Molecular weight: 58.012

Density: 1750

System: rhombic B

-

0.6210

b

-

1.1720

c

-

Z=8

0.6050

NaOH

SODIUM HYDROXIDE Molecular weight: 39.997

Density: 2020

System: rhombic B

-

b

0.3397

-

0.3397

I

I

Effect

Admixture

Na,PO,

c = 1.1320 Reference

12 H 2 0

SODIUM PHOSPHATE dodecahydrate Molecular weight: 380.123

Density: 1589

System: hexagonal

a = 1.2020

2=2 c = 1.2660

Admixture

Effect

Reference

CH,COOH

N

I8871

s10,2-, VO;

16341

10. Tables

22 1

Admixture

Effect

Reference

surfactants

G

1549, 13461

~

Na2S20,

5 H20

SODIUM THIOSULPHATE pentahydrate Molecular weight: 248.174

Density: 1756

System: monoclinic a = 0.5944

2-4

b = 2.1570

c = 0.7525

Admixture

Effect

Reference

Na,S, p H > 8

D

1101

222

10. Tables

Na,S04

10 H,O

SODIUM SULPHATE decahydrate Density: 1468

Molecular weight: 322.189 System: monoclinic

a

-

1.1430

2=4

b = 1.0340

c = 1.2900

SODIUM SULPHATE Molecular weight: 142.037

Density: 2665

System: rhombic a = 0.5860

2-8

b = 1.2300

Admixture

Na9B,O7

c = 0,9820

I Effect N

admixtures

IReference I56.13121 I9141

admixtures

N, G

I5071

NOn-. sulphamate

H. G

I4831

impurities from caprolactam surfactants surfactants

I5061

H - rounded crystals

1423,9761 I8581

10.Tables

Na2SiF6

SODIUM HEXAFLUOROSILICATE Molecular weight: 188.056 System: hexagonal a

-

0.8860

c

Density: 2679

-

2=3 0.5020

Admixture

Mg2+, Ca2+, Pod3-

Effect N3+,H,PO,

Reference 18991

G

[lo591

Na2Si03 - 9 H 2 0

SODIUM SILICATE nonahydrate

Admixture

Effect

Reference

Ca2+. M3+

D

[531

223

224

10.Tables

Ni(HC0O)Z

2 H2O

NICKEL FORMATE dihydrate Molecular weight: 172.747 Admixture

Mg2+. Mn2+

Effect ID

Reference I[58.601

Ni(CH3COO)Z 4 H2O

NICKEL ACETATE tetrahydrate Molecular weight: 236.831 Admixture

Effect

Reference

Mg2+

D

I581

I

10. Tables

Ni(NO&

225

6 H2O

NICKEL NITRATE hexahydrate Molecular weight: 290.81 1 System: triclinic

a cc

-

-

0.5790

b

106" 38'

B

Density: 2050

=

z=2 0.7690

c = 1.1890

SOo 32'

y

=lolo27'

Admixture

Effect

Reference

Mg2+, Zn2+

D, H

IS21

I

Ni[OH),

NICKEL HYDROXIDE Molecular weight: 92,706

System: hexagonal

a

-

0.307

c

-

Z=1 0.4605

Admixture

Effect

Reference

H,O,

filterability

113991

226

10. Tables

Ni(OH),CO,

BASIC NICKEL CARBONATE Molecular weight: 152.717 Admixture

Effect

Reference

H,O,

filterability

[ 13991

NiSO,

7 H2O

NICKEL SULPHATE heptahydrate Molecular weight: 280.874 System: rhombic

a

-

1.1800

b

Density: 1948

-

2-4

1.2000

c = 0.6800

Admixture

Effect

Reference

Fe2+

D

[488,489]

inorganic ions

H. adsorption poten-

[2751

tial

Zn2+, Mg2+ gelatin

,

D

1581

H. dissolution

[2231

10.Tables

PbBr2

LEAD BROMIDE Molecular weight: 367.008

Density: 6667

System: rhombic

b = 0.8040

a = 0.4720 ~~~~~

~~

~~

Admixture

~

c

-

z=4 0.9520

~

Effect

Reference

[1235]

Ag+

gum arabic

I I2151

H

PbCOs

LEAD CARBONATE Molecular weight: 267.221 System: rhombic

2=4

Admixture

Effect

Reference

uo,2+

transform.

11 1641

polyglutamic acid, polyvinyl-

N

[1167]

sulphonate

227

228

10. Tables

I

Pb(CH3COO)z 3 H2O

LEAD ACETATE trihydrate

Admixture

Effect

Reference

pH

G.H

I8071

PbC1,

LEAD CHLORIDE Molecular weight: 278.106

Density: 5850

Syetem: rhombic a

-

0.4520

Z=4

b = 0.7610

IAdmixture

c = 0.9030 Effect

Reference

KC1, NH,C1, CdCl,, HC1

H

110191

Mn2+, Co2+, Ni2+, Cu2+

e .

I3741

Mn2+. Co2+, Ni2+, Cu2+,Na+

H, N. G

I 12541

PbFQ

D

16761

admixtures

N

I4131

dextrine

N,

large

metastable

zone

H - rounded crvstals

1894,8951

10.Tables

PbCrO,

LEAD CHROMATE Molecular weight: 323.22

Density: 6100

System: monoclinic x

-

0.682

b

-

0.748

c

-

2-4

0.716

3 = 1020 33’ Admixture

Effect

Reference

glutamate, gluconate,

N

I10151

N

I10171

citrate. tartrate, EDTA acetate, gluconate. EDTA, citrate. tripolyphosphate

Admixture

Effect

Reference

pH

G

[ 12773

pH

modif.

[1278]

229

230

10.Tables

Pb"O,),

LEAD NITRATE Molecular weight: 331.210

Density: 4535

System: cubic R

2=4

0.7810

Admixture

Effect

Reference

Ba(NO,),

D

(928.10461

Ba(NO,), + NaCl

D

I8571

RalNO,I,

D

[ 10841

Capri blue

H

I8671

Methylene blue

G ,H

I1241

Methylene blue

D

- pleochroism

[130.391,43 1, 597,598,664,

Methylene blue

H - cubes

[200,430,432, 437.44 1,442. 443,96 1,14021

Methylene blue

G

I1331

Methylene blue

G , D, H

[ 1238.1239,

1240.12431

10.Tables

231

Pb(N03)2 (continued) Admixture

Effect

Reference

Methylene blue

N

113411

Methylene blue, Bismarck brown

D

I3891

Methylene blue, Thionine blue

S

18571

Thionine blue

H. D

[ 1241.12421

i

Pb,(P04)2, PbHPO4, Pb2P20, LEAD PHOSPHATES Admixture

uo,2+

1 Effect

Reference [1164,13111

232

10.Tables

I

PbS

LEAD SULPHIDE Molecular weight: 239.28

Density: 7500

System: cubic a = 0.597

Admixture

Effect

Reference

EDTA

equilibrium, G

113511

I

_I

PbSO,

LEAD SULPHATE Density: 6200

Molecular weight: 303.28 System: rhombic a

-

0.845

b

-

0.538

c = 0.693

Admixture

Effect

Reference

RaSO, + HNO,

D

I6651

admixtures

G. H

[lOOSl

pyrophosphate, tetrameta-

precipitation

I8 101

acetate, gluconate, EDTA, citrate.

[lo171

tripolyphosphate alcohols

I10131

surfactants

I8101

10.Tables

RbCl

RUBIDIUM CHLORIDE Molecular weight: 120.921

Density: 2760

System: cubic

a

-

3=4

0.6540

Admixture

Effect

Reference

Pb2+.Sn2+,Zr4+, Ti4+

favourable

I4721

OH-

I G

I I7041

RUBIDIUM DIHYDROGEN PHOSPHATE

Admixture

Effect

I

Fe3+,Mg2+, SiOS2-, Ca2+,Ag+, BiS+, H

Fe3+,pH

H

Reference 118401

233

234

10.Tables

SrCO,

STRONTIUM CARBONATE Molecular weight: 147.64

Density: 3700

System: rhombic

a

-

0.513

2=4

0.842

b

c = 0.610

Admixture

Effect

Reference

p olyglutamic acid, polyvinyl-

N

[1165,1167]

sulphonate

Sr(HCOO),

2 H20

STRONTIUM FORMATE dihydrate Molecular weight: 213.686 ~

System: rhombic

a

-

0.7300

Admixture

cations

Density: 2255

b

-

1.1990

I

2-4

c = 0.7130 Effect G

I

Reference

10.Tables

235

~

3rF,

STRONTIUM FLUORIDE Holecular weight: 125.63 System: cubic L

-

0.586

Admixture

Effect

Reference

Fe2+,Fe3+

D

I11801

inhibitors, Mg2+, Zn2+

G. dissolution

13.41

Mg2+

G

I5151

phosphonates

G

I1351

SrHPO,, Sr,P,O,,

Sr,(PO,),

Admixture

Effect

Reference

F-

G

I36 11

I uo,2+

I transform.

I II1164.13111 1 164,131 11

I

236

10.Tables

Sr"O&

STRONTIUM NITRATE Molecular weight: 211.630

Density: 2930

System: cubic

a

-

364

0.7763

Admixture

Effect

Reference

Ba2+

D

[ 11451

r

I saphranine, wood extract

1H.D

[12011

-

ZnC204 2 H 2 0

ZINC OXALATE dihydrate Molecular weight: - 189.432 L

/

Admixture

Effect

Reference

Mn2+

D

(1031

cu2+

D

1277,10261

10.Tables

237

3rS0,

STRONTIUM SULPHATE Kolecular weight: 183.70 System: rhombic I

-

0.836

b

-

z=4 c = 0.684

0.536

Admixture

Effect

Reference

N a phosphates

H. G

[900,9011

N a phosphates

N - retarding

[950.951,10061

N a triphosphate

N

[ 12481

pH, phosphates, Fe3+, Cr3+

H

[g041

pH

S

18061

G - maximum

18631

pyrophosphate

G

13081

tripolyphosphate

H, aggregation

110071

tripolyphosphate

N. G

1904.949.950

pH

=

4.6

1007.10171 CVHSOH CH,OH

[ 12451

S

phosphonate

13411 (10631

polyvinylsulphonate

N

[1163.11681

polyvinylsulphonate

H. S

11162,11731

238

10. Tables

SrSO, (continued) Admixture

Effect

Reference

sodium cltrate. EDTA

H

(1006, 10091

surfactants. citrate. EDTA water soluble polymers

110061 H. inhibition N

11162, 11741

lmo2

TITANIUM DIOXIDE (anatase)

Admixture

Effect

Fe2+ alcohol + surfactant

Reference W301

N, G

I5931

10.Tables

Zn(HCOO),

239

2 H20

ZINC FORMATE dihydrate Molecular weight: 191.447 Admixture

Effect

Reference

Mg2+, Mn2+

D

[58,601

ZnC4H604

ZINC ACETATE Molecular weight: 183.48

I

IEffect

Admixture

Admixture

D

Effect

gluconate. tartrate, EDTA. N

I Reference I

I Co2+, Cd2+

I

I [63l

Reference I10151

II

240

10.Tables

I

ZnK2(S04),

6 H20

ZINC POTASSIUM SULPHATE hexahydrate

Admixture

Effect

Reference

Ni2+

D

[ 150 1,I5021

I

Zn(NH4)2(S04)2 6 H20

ZINC AMMONIUM SULPHATE hexahydrate

Molecular weight: 401.687 System: monoclinic a

-

0.920

b

= 1.247

c = 0.623

3! = 106O 52'

Admixture

Effect

Reference

D

11499,1500, 15021

Fe2+,Ni2+, Co2+,Cu2+

n

10. Tables

Zn(NO&

- 6 H,O

ZINC NITRATE hexahydrate Molecular weight: 297.481 System: rhombfc a = 1.2240

Admixture

ZINC SULPHIDE Molecular weight: 97.45 System: hexagonal

b

Density: 2067

-

z=4 c = 0.6290

1.2850 Effect

Reference

241

242

10.Tables

ZnSO, 7 H,O

ZINC SULPHATE heptahydrate Molecular weight: 287.544 System: rhombic

a

-

1.1850

b ~

~~

~~

Density: 1957

-

1.2090

c

-

2=4

0.6830

~

Admixture

Effect

Reference

co2+

D

[ 13431

CU2+

ID I

+ 162,9851

I9861

Cu2+, Fe2+,Co2+

[57,611

f488.4891

~

ZnWO,

ZINC TUNGSTATE Molecular weisht: 313.3 Admixture

Effect

Reference

11831

10. Tables

ORGANIC SUBSTANCES

I

Molecular weight: 60.06

Density: 1335

System: tetragonal

332

Effect

IReference

H

I991

caking

I9781

H

I991

H

- prisms

[2211

H

I4161

H

[ 11411

N

I6291

H

I4171

admixtures, solvents

H

113481

alkylamines, HCOOH

caking

[ 12891

biuret

H

I1001

biuret

G

12921

-biuret 3-5YO biuret, cyanuric acid biuret, formamide

13831 G. H - cubes

[ 10821

243

244

10.Tables

Admixture

Effect

Reference

dyes

I1781

solvents

capping growth

I5661

solvents

G

113421

surfactants

caking

19781

CH4NZS

THIOUREA Molecular weight: 76.12

Density: 1405

System: rhombic a = 0.550

Admixture

2-4

b

c = 0.857

= 0.708

Effect

I6273

NH,SCN I

CH,OH

Reference

N

I5191

10. Tables

Molecular weight: 123.075 Admixture

Effect

Reference

Methylene blue

D. H - prisms

1434.43 51

C2H204 2 HZO

OXALIC ACID dihydrate Molecular weight: 126.04

Density: 1653

System: monoclinic

a I3

-

-

0.612

b

-

c

0.361

-

3=2

1.203

106O 12'

Admixture

Effect

Reference

Ca2+

D

13591

Fe2+,Cu2+,Pb2+

D

14941

245

246

10.Tables

Z,HBO,N

WINOACETIC ACID aolecular weight: 75.07 Admixture

Effect

Trypan Red, Chloramine Sky Blue H - long needles FF. Chromotrooe 2B

/(Ill/

Methyl Blue MBJ

H - suppresses

Reference 12 151

[2151

needles aminoacids

N

1784,1444, 14461

CSH4O4N4

UREA OXALATE Molecular weight: 160.097

IAdmixture

Effect

Reference

H - /010/

14441

Neutral red

H - needIes

(4441

Victoria blue, Brilliant green,

H - /201/

I4441

Magenta, Fuchsine , Tartrazine , Eosine

Malachite green, Gentiana blue

10. Tables

247

C3H702N

AMINOPROPIONIC ACID (L-ALANINE)

Admixture

Effect

Brilliant yellow

Reference

I I7781 I I I7921

I G

I

IG, H

admixtures

C4H604

SUCCINIC ACID Molecular weight: 118.092 System: monoclinic

a = 0.506

b

-

2-2 0.881

c = 0.757

B = 133O 37'

Admixture

Effect

Reference

solvents

H

129 11

isopropanol

G, solubility

[ 14501

II

248

10. Tables

C ~ H ~ O HSO B

TARTARIC ACID monohydrate Molecular weight: 168.09

Density: 1697

System: triclinic

a a

-

0.809

b

8 2 O 20'

B

-

-

2=2

1.003

c

0.481

1180 0'

y =72O

58'

Admixture

Effect

Reference

Fe2+. Cu2+, Sb3+.S d + ,Co2+,

D

I4921

cuso,

H

I6051

admixtures

n

I 1 1471

so42-.c1-

C4H808N8

OCTOGENE (TETRANITRO-TETRAZA OCTANE)

Admixture

solvents

Effect

Reference I3381

1O.Tables

C4HQOSN

L-THREONINE Molecular weight: 119.124 Admixture

Effect

Reference

1-glutamlc acid

D

"7691

C4HeO4N

y-AMINOBUTYRIC ACID Molecular weirtht: 136.124

surfactants

I I8091

IN,H

I

CsH4OsN4

URIC ACID

Molecular weight: 168.11

Density: 1893 I

Admixture

Effect

Reference

Magenta, Fuchsine

H - width prolonga-

I4461

tion Bismarck brown. Neutral red.

H - length prolonga-

Safranlne, Methylene blue

tlon

I4461

249

250

10. Tables

C6H904N

L-GLUTAMIC ACID Molecular weight: 147.14 Admixture

Effect

Reference

amino acids

111141

1-aspartic acid, 1-valine, 1-leucine, N, G

I5181

I-phenylalanine 1- aspartic acid

N. G

[ 14751

CSH1006

XYLOSE Molecular weight: 150.13

Density: 1530

System: rhombic

a

-

0.921

b

-

Z=4 1.248

c

=

0.556

Admixture

Effect

Reference

Ca formiate and acetate

G - acceleration

19381

10.Tables

Admixture

Effect

admixtures

Reference 113891

Admixture

Effect

Reference

Ca[HCOO),

N. G

[ 15121

dipentaerythritol

N. S

115131

dipentaerythritol

N

I6181

dipentaerythritol

G. N. S

16191

251

252

10.Tables

CBH,OZNCl

m-CHLORONITROBENZENE Molecular weight: 157.663 Admixture

Effect

Reference

admixtures structurally similar additives

I2441

H

I2451

COHO

BENZENE

I

Molecular weight: 78.12

System: rhombic

Admixture

2=4

Effect

Reference

10.Tables

253

C6H602

RESORCINOL Density: 1285

Molecular weight: 110.12 System: rhombic a

-

0.966

2-4

b = 1.05

Admixture

c = 0.568 Effect

Reference

I

C6H603

PHLOROGLUCINE (1,3,5-TRIHYDROXYBENZENE)

1

IMolecular weight: 126.114 Admixture

Effect

Reference

Magenta, Fuchsine, Toluidine blue

H

14451

254

10. Tables

Molecular weight: 134.146 Admixture

IIEffect

surfactant

I

I

I

I Reference I

I [9161

C6HS06

ASCORBIC ACID Molecular weight: 176.13 Admixture

Effect

methanol

Reference

I8591

CITRIC ACID Molecular weight: 192.13

Density: 1542

Admixture

Effect

Reference

H,SO,

G

I9871

t

I

I

10. Tables

Admixture

Effect

Reference

amino acids

H

I6251

C6H 10°4N2

ETHYLENEDIAMINE TARTRATE Molecular weight: 174.162 I

Effect

Reference

Ca2+. Mg2+.Cu2+, A13+

H

18401

Fe3+.A13+, Ca2+, Mg2'

H - wedge

17091

pH

H

18401

Admixture r

9H

=

6.0

H, S favourable

pH

=

6.0

H - needles

pH

=

7.5

low sensibility to

255

256

10. Tables

C6H1004

ADIPIC ACID Molecular weight: 146.15

Density: 1366

System: monoclinic

a

0

-

1.027

b

-

z=2 0.516

c = 1.002

137O 5'

IAdmixture trimethyldodecylammonium

I Effect G - decreasing

I Reference [888,889,

chloride

8901

sodium dodecylbenzenesulphonate H - needles, thin

[888,889.

plates

8901

n-alkanoic acids

physical properties

I4961

n-alkanoic acids

G Inhibition

12881

related compounds

N, G

19661

succlnic acid, solvents, formic acid H

I9331

10.Tables

C6H110N

CAPROLACTAM Molecular weight: 113.162 Admixture

Effect

Reference

' cyclohexanone

D

I13521

cyclohexanone

G

I9621

H

I981

N, S . D

[ 13021

Admixture

Effect

Reference

Fe3+,Pb2+, As3+, SiOS2-, T1+.Cu2+

H

[8401

Ni2+. Cu2+, Fe3+

H. D

I9091

Tl+.Li+. Na', K+.Rb+.Cs+

H

[ 13821

HqSO,

H, G - retards

17241

pH

H

18401

1-alanine

G

I5961

' solvents trichlorethylene

C6H1104N3

' H2S04

FRIGLYCINE SULPHATE Yolecular weight: 287.26

257

258

10.Tables

c6H1206

GLUCOSE Molecular weight: 180.17

Density: 1544

System: rhombic

a

-

1.040

b

-

2=4

1.489

c = 0.499

Admixture

Effect

Reference

fructose

mutarotation

1751.7531

fructose

N

[980.7531

fructose

H, G

[752.753]

L

c6H1206

SORBITOL Molecular weight: 182.13 I

Admixture

_i

soap

Effect

Reference [7701

10.Tables

1

259

C6H12N4

HEXAMETHYLENETETMINE, (UROTROPIN) Molecular weight: 140.20

z=2

System: cubic

Admixture

Effect

Reference

benzylalcohol + Si02

caking

1831

Ca and Mg stearates

caking

[831

solvents

G

[ 159.1SO]

Admixture

Effect

Reference

surfactants

H

[ 1134,1508,

L-ISOLEUCINE Molecular weight: 131.178

15091

260

10. Tables

Admixture

Effect

Reference

admixtures

D

I6961

C7H602

BENZOIC ACID Molecular weight: 122.13

Density: 1266

System: monoclinic a

D

-

0.544

2=4

b

= 0.518

c = 2.16

970 5'

.

Admixture

Effect

Reference

ethylalcohol

G

I7381

admixtures

G

I10581

I

10. Tables

Ip-HYDROXYBENZOIC

26 1

ACID

Admixture

Effect

Reference

derivates of benzoic acid

N

[ 14451

Admixture

Effect

tailor-made additive

H

Reference

1

262

10. Tables

%*6O4

PHTHALIC ACID Molecular weight: 166.14

Density: 1593

System: monoclinic

a

B

-

0.933 94O

2-2

b = 0.713

c = 0.510

36'

~

Admixture

Effect

Li, Na. K, C s halides

a-naphtylamine sulphonate,

Reference I7391

H - thin plates /010/

I2151

H

14333

Effect

Reference

Bismarck brown, Fuchsine diphenylamine. Methylene blue, Malachite Preen

Admixture I

admixtures

193 11

10.Tables

Admixture

Effect

dyes

H-

/loo/

Reference

>> /llO/

[215]

C1oHs

NAPHTHALENE Molecular weight: 128.17

Density: 1145

System: monoclinic a

-

0.834

Z=2

b

= 0.598

c = 0.868

D * 122044' Admixture

Effect

Reference

fenantrene, anthracene

G. H

I10401

biphenyl

G

I9633

263

264

1O.TabZes

C12HlO

ACENAPHTHENE Molecular weight: 154.21

Density: 1024

System: rhombic

a

-

0.892

3=4

b

= 1.415

c = 0.726 =

~~~

Admixture

Effect

Reference

solvents

N

I8361

solvents

IG

I I8371

ClZHlO

BIPHENYL Density: 1180

Molecular weight: 154.21 System: monoclinic

m

-

0.811

b

-

2=2 0.567

c = 0.957

Admixture

Effect

Reference

solvents

G. H

I5671

10.Tables

C12H1,OTNdP2S

265

HCl

COCARBOXYLASE HYDROCHLORIDE

I

Molecular weight: 460.789 Admixture

Effect

Reference

acetone

S

D171

Admixture

Effect

Reference

C a C I , , AlCl,, FeCI,

G

I3131

Cl2H22Oll

H2O

LACTOSE monohydrate Molecular weight: 360.31

L

266

10. Tables

C12H22O11

SUCROSE Molecular weight: 342.31

Density: 1588

System: monoclinic a

-

1.065

2=2

b

0.870

c

= 0.800

p = 105O 44' Admixture

Effect

Reference

Ca2+, Na+, K+

I14841

CaCl,, Na,C03

[ 14861

inorganic salts KC1, CaCl,, MnSO,. NH,NO,.

H CdI?

[6 131 13371

I [1284.1285,

MnSO,

12861

Na+. K+, Ca2+, Fe2+.Cu2+

N. G, H. S

NaCl, KCI, CaCl,, CaSO,, CaHPO,

W41 19971

admixtures

G

11 188,13401

admixtures

G.H

1451

admixtures

H

13061

10. Tables

C,2€€2,0,,

267

(SUCROSE)

(continued) ~

Admixture

Effect

Reference

amino acids

c,

12191

betaine

I83 11

colouring impurities

I14921

dextrose

I131

dextrose

G, H

[3361

impurities

D

(525.5261

impurities, colouring substances

G

11485,149 11

G

I14.334.335.

I

raffinose

33 7,554. 12521 ~

H

I337.568. 8321

raffinose. glucose

Isaccharides starch, dextrine

G. H

[555,556]

G. H

I3371

c,

[ 14861

268

10.Tables

C14H14

DIBENZYL Molecular weight: 182.266 System: monoclinic a

-

1.282

b

-

Z=2 c = 0.774

0.618

0 = llSO 0'

i

Admixture

Effect

Reference

tolan

D periodicity

I7541

Effect

Reference

I

C15H1202N2

PHENYTOIN Molecular weight: 252.277 Admixture

I

p o p , ci-

G

115061

.

10. Tables

C16H3202

PALMITIC ACID Molecular weight: 256.432 2=4

System: monoclinic

-

a

-

B

0.941

c = 4.59

b = 0.500

50° 50'

Admixture

~~

Effect

~

~~~~~

C18H3602

STEARIC ACID Density: 941

Molecular weight: 284.49 System: monocIinic a

-

0.5546

2=4

b = 0.7381

c = 4.884

3 = 63O 38'

I

Admixture

Effect

solvents

H. polymorphs

14271

surfactants

H

[4281

butanone + emulsifier

G. H

[761

unsaturated homologues solvents, sorbitone monostearate

Reference

[lo611 G. H

I I751

269

270

10. Tables

CnH2n+2

PARAFFIN Admixture

Effect

admixtures inhibltors

G

polymers

N, G

solvents

H. G

Admixture

Effect

Reference

hydrocarbon solvents

N

I2431

15501

10. Tables

271

I

C27H460

CHOLESTEROL

Admixture

Effect

Reference

solvents

H

[4261

Effect

Reference

C32H60

N-DOTRIACONTANE Molecular weight: 450.88 Admixture

polymers

I

I [801

I

272

10.Tables

%*74

HEXATRIACONTANE Molecular weirrht: 506.988 Admixture

Effect

Reference

G, H

I12311

I

PROTEINS I

Admixture phospholipids

EXfect

Reference 18651

L

FORMULA INDEX

Inorganic substances

AgBr

silver bromide

78

AgCl

silver chloride

79

silver chromate

80

4 1

silver iodide

80

AgN0,

silver nitrate

81

AlCs(S04)2 * 12 H2O

aluminium cesium sulphate

81

aluminium chloride

82

AlF3 . 3 H2O

aluminium fluoride

82

AlK(SO4)2. 12 H 2 0

aluminium potassium sulphate

83

AlNH,(SO4)2

aluminium ammonium sulphate

85

aluminium nitrate

86

aluminium hydroxide

87

AlCl,

. 6 H20

Al(NO,),

*

*

12 H2O

9 H2O

Al(OH),

A1203.M20.n SiO,

m H20 zeolites

86

aluminium phosphate

88

aluminium rubidium suIphate

88

aluminium thallium sulphate

89

Alz(SO4)3 . 16 H20

aluminium sulphate

89

Ba(B0&

barium borate

90

BaBr2 2 H 2 0

barium bromide

90

BaC0,

barium carbonate

91

BaC204

barium oxalate

91

AlPO,

AlRb(SO,), AITl(SO,),

-

*

12 H2O

. 12 H 2 0

274

10.Tables

BaC12 - 2 H20

barium chloride

92

BaCr04

barium chromate

93

BaF,

barium fluoride

94

Ba(I0312 H20

.

barium iodate

94

Ba(N0312

barium nitrate

95

barium hydroxide

96

BaS04

barium sulphate

97

BaTiOQ

barium titanate

104

Be(NH412F4

ammonium beryllium fluoride

190

(C2H,I4NI

tetraethylammonium iodide

92

CaC03

calcium carbonate

99

. 8 H,O

Ba(OH),

CaCz04 H20

-

calcium oxalate

105

CaC4H,0,

calcium tartrate

108

Ca(C&,

calcium gluconate

109

CaC12. 2 H20

calcium chloride

108

CaFz

calcium fluoride

109

CaHP04. 2 H20

calclum hydrogen phosphate

110

CaHPOq. 3/2 H 2 0

calcium hydrogen phosphate

111

Ca(N0312 4 H20

calcium nitrate

112

Ca(OH12

calcium hydroxide

112

Ca3(P04)2

tricalcium phosphate

113

dicalcium phosphate

114

ffuorapatite

114

10712

.

Ca2P20,

- 2 H20

Ca3(PO4l2 CaF2

10. Tables

-

275

Ca3(PO4I2 Ca(OHI2

hydroxyapatite

115

CaSO,

calcium sulphite

114

CaS04 2 H20

calcium sulphate

117

CaSi03

calcium silicate

116

Ca(C5H3N403),

calcium urate

123

CaWO,

calcium tungstate

123

octacalcium phosphate

113

CdCOs

cadmium carbonate

124

Cd(CHO2)2* 2 H,O

cadmium formate

124

CdS

cadmium sulphide

125

C0C03

cobalt carbonate

125

Co(CH02)Z 2 H2O

cobalt formate

126

Co(CH,C02)2

cobalt acetate

126

ammonium cobalt sulphate

127

cobalt sulphate

127

potassium chromium sulphate

128

ammonium chromium sulphate

128

-

Ca,H2(P04),

- 5 H20

*

4 H2O

* 6 H2O CO(NH~)~(SO&

-

C0S04 7 H 2 0

- 12 H20 CrNH4(S04)2. 12 H20

CrK(S04),

C~Al(SO4)121* 12 H2O

aluminium cesium sulphate

81

CSH~ASO,

cesium dihydrogen arsenate

129

CSI

cesium iodide

129

CsN0,

cesium nitrate

130

CUClz * 2 H2O

cupric chloride

130

Cu(CH02)2 * 2 HZO

cupric formate

131

276

10. Tables

cupric acetate

13 1

cupric chromate

131

ammonium cupric sulphate

132

cupric hydroxide

132

basic cupric carbonate

132

cupric sulphate

133

ammonium ferrous sulphate

134

ferric oxide hydroxide

134

ferric hydroxide

135

ferric oxide

135

magnetite

136

ferrous sulphate

136

ice

137

boric acid

137

phosphoric acid

138

mercuric bromide

140

mercuric cyanide

140

aluminiumpotassium sulphate

83

potassium pentaborate

141

potassium bromide

142

potassium bromate

143

potassium cyanide

143

potassium carbonate

141

1O.TabZes

277

potassium oxalate

144

KC1

potassium chloride

145

KClO,

potassium chlorate

151

KCIO,

potassium perchlorate

152

K2Cr04

potassium chromate

153

%,cr207

potassium dichromate

154

KCr(S0412 12 H,O

potassium chromium sulphate

128

K4Fe(CN16 * 3 H,O

potassium ferrocyanide

144

KH2As04

potassium dihydrogen arsenate

154

KH2PO4

potassium dihydrogen phosphate

155

KHC,H,O6

potassium hydrogen tartrate

158

KHCSH404

potassium hydrogen phthalate

158

KI

potassium iodide

159

uo3

potassium iodate

157

potassium magnesium sulphate

170

KMn0,

potassium permanganate

160

KNO2

potassium nitrite

160

KNo3

potassium nitrate

161

KNaC4H40,

sodium potassium tartrate

163

K2s04

potassium sulphate

165

K2s206

potassium dithionate

164

KTiOPO4

potassium titanyl phosphate

162

K2Zn(S04)2 6 H,O

zinc potassium sulphate

240

QcZ04

'

H2°

-

K2Mg(SO,l2

*

6 H2O

278

10. Tables

lithium chloride

167

lithium fluoride

168

lithium iodide

168

lithium iodate

169

ammonium lithium tartrate

159

lithium sulphate

170

magnesium carbonate

171

magnesium acetate

169

magnesium fluoride

172

magnesium formate

172

magnesium oxalate

171

potassium magnesium sulphate

170

ammonium magnesium sulphate

173

magnesium nitrate

173

magnesium hydroxide

174

magneslum sulphate

175

manganous carbonate

174

manganous formate

176

manganous sulphate

176

aluminium ammonium sulphate

85

ammonium beryllium fluoride

190

ammonium bromide

177

ammonium oxalate

181

10. Tables

279

ammonium chloride

178

ammonium chlorate

182

ammonium perchlorate

182

ammonium cobalt sulphate

127

ammonium chromium sulphate

128

ammonium cupric sulphate

132

ammonium ferrous sulphate

134

ammonium hydrogen carbonate

183

ammonium hydrogen oxalate

183

ammonium hydrogen tartrate

184

ammonium dihydrogen phosphate

185

ammonium hydrogen phosphate

184

ammonium lithium tartrate

159

ammonium magnesium sulphate

173

ammonium nitrate

188

ammonium nickel sulphate

190

ammonium sulphate

191

ammonium titanyl sulphate

198

ammonium uranate

199

ammonium tungstate

199

zinc ammonium sulphate

240

sodium hexafluoroaluminate

200

sodium perborate

200

280

10. Tables

N a B 0 2 . H20,

- 3 H20

sodium peroxoborate

20 1

sodium tetraborate

202

NaB508. 5 H20

sodium pentaborate

20 1

NaBr . 2 H20

sodium bromide

203

NaBr03

sodium bromate

203

NaC2H302 3 H 2 0

sodium acetate

204

Na2C03 10 H 2 0

sodium carbonate

205

NaC5H804N H 2 0

sodium glutamate

204

NaC6H20,N3

sodium picrate

2 13

NaCl

sodium chloride

206

NaClO,

sodium chlorate

2 14

NaC10,. H20

sodium perchlorate

215

NaHCO,

sodium hydrogen carbonate

216

NaC5H3N403

sodium urate

217

NaF

sodium fluoride

215

Na3H(CO3I2

trona

217

NaI 2 H20

sodium iodide

218

NaKC4H406

potassium sodium tartrate

163

NaN02

sodium nitrite

218

NaN0,

sodium nitrate

219

NaOH

sodium hydroxide

220

sodium phosphate

220

sodium triphosphate

22 1

Na2B40,

- 10 H,O

-

-

.

Na3PO4

I

12 H20

Na5P3OI0 6 H 2 0 a

10. Tables

281

sodium sulphate

222

sodium thiosulphate

22 1

sodium hexafluorosilicate

223

sodium silicate

223

sodium zincate

205

nickel formate

224

nickel acetate

224

ammonium nickel sulphate

190

nickel nitrate

225

nickel hydroxide

225

basic nickel carbonate

226

nickel sulphate

226

lead bromide

227

lead carbonate

227

lead acetate

228

lead chloride

228

lead chromate

229

lead fluoride

229

lead nitrate

230

lead phosphates

23 1

lead sulphide

232

lead sulphate

232

aluminium rubidium sulphate

88

282

10.Tables

RbCl

rubidium chloride

233

RbH2P04

rubidium dihydrogen phosphate

233

SrC03

strontium carbonate

234

Sr(CHO2I2. 2 H,O

strontium formate

234

SrFz

strontium fluoride

235

Sr(N0312

strontium nitrate

236

SrHP04

strontium phosphates

235

SrS04

strontium sulphate

237

7302

titanium dioxide

238

TlAl(S04)2. 12 H2O

aluminium thallium sulphate

Tio(NH&(S0412

ammonium titanyl sulphate

198

ZnC204 2 H20

zinc oxalate

236

Zn(CHO2I2 2 H20

zinc formate

238

ZnC4H604

zinc acetate

238

ZnCrO,

zinc chromate

238

zinc potassium sulphate

240

Zn(NH412(S0412. 6 H20

zinc ammonium sulphate

240

Zn(N0312. 6 H20

zinc nitrate

241

ZnS

zinc sulphide

24 1

ZnS04. 7 H20

zinc sulphate

242

ZnWO,

zinc tungstate

242

-

ZnK2(S0,),

a

6 H20

89

10. Tables

Organic substances

urea

243

thiourea

244

urea nitrate

245

oxalic acid

245

aminoacetic acid

246

urea oxalate

246

L-alanine

247

succinic acid

247

tartaric acid

248

octogene

248

L-threonine

249

y-aminobutyric acid

249

uric acid

249

L-glutamic acid

250

xylose

250

trimethylolethane

25 1

pentaerythritol

25 1

m-chloronitrobenzene

252

benzene

252

allopurinol

254

resorcinol

253

phloroglucine

253

283

10. Tubks

284

C6H806

ascorbic acid

254

C6H807

citric acid

254

C6H902N3

L- histidine

255

C6H 10'4

adipic acid

256

C6H 10°4N2

ethylenediamine tartrate

255

caprolactam

257

C6H1104N3 ' HzS04

triglycine sulphate

257

C6H1206

glucose

258

C6H1206

sorbitol

258

C6H12N4

hexamethylenetetramine

259

C6H 1 3°2N

L-isoleucine

259

C6H16N2

hexamethylenediamine

260

C7H602

benzoic acid

260

C7H603

p-hydroxybenzoic acid

26 1

C7H7ON

benzamide

26 1

C8H604

phthalic acid

262

C8H604

terephthalic acid

262

C9H9'3N

hippuric acid

263

'loH,

naphthalene

263

C12HlO

acenaphthene

264

C12H10

biphenyl

264

loN

C1,Hl,O,N4P,S

*

HCl

cocarboxylase hydrochloride

265

10. Tables

lactose

265

c 12H22O 1 1

sucrose

266

C14H14

dibenzyl

268

C15H1202N2

phenytoin

268

C16H3202

palmitic acid

269

C18H3602

stearic acid

269

CnH2n+2

paraffin

270

C24H50

tetracosane

270

C27H460

cholesterol

271

C32H66

N-dotriacontane

271

C36H74

hexatriacontane

272

proteins

272

C12H22Oll

*

H2O

285

Admixtures in Crystallization

Jaroslav Njlvlt, Joachim Ulrich 0 VCH Verlagsgesellschaft mbH, 1995

11. References t o Tables [ 11 Abakumov.

V.I., Diarov. M.D., Kardashina. L.F., Kalacheva. V.G.: Izv.

Akad. Nauk Kaz. SSR. Ser. Khim. 4 (1988) 3 [2] Abbona. F.. Madsen. H.E.L., Boistelle. R.: J. Crystal Growth 74 (1986)581

[31Abdul-Rahman, A.: Unlv. Microfilms No. DA8824030 :CA 110 (26) 40426 [4]Abdul-Rahman, A.. Hamza. S.M.. Nancollas. G.H.: AICHE Symp. Ser.

83,253 F u n d a m . Aspects Cryst. Precip. Processes (1987)36

[51Abram, T.: G a s World 136,No. 3559 (1952) 71 [6] Acharya. C.S., Tandon. S.P.: J. Sci. Ind. Res. (India) 200 (1961)464 [7] Addadi. L.. Berkovitch-Yellln, 2.. Weissbuch. I., Lahav. M.. Leiserowitz, L.: Mol. Cryst. Liq. Cryst. 96 (1-4) (1983) 1 [81Ahmed, K.. Tawashi. R.: Urol. Res. 6 (1978) 77 [9] Akakumov, V.I.. Kardashina. L.F.. NedopeMna. V.A.: Obogashch.

Rud (Leningrad) 5 (1989) 16

[lo] Akhmetov. T.G.,

Kuznetsov-Fetisov. L.I.: Tr. Kazan. Khim.-Tekhnol.

Inst. 34 (1965)25 1111 Akl. M.M.. Nassar. M.M.. Sayed. S.A.: Chem.-1ng.-Tech. 63 (1991) 935

I121 Akl. M.M.. Nassar. M.M.. Sayed. S.A.: Chem.-1ng.-Tech. 63 (1991) 939 [13]Albon, N., Dunning. W.J.: Proc. Int. Conf. Growth and Perfection of

Crystals, p. 450. New York 1958

288

11. References to Tables

[14] Albon. N.. Dunning, W.J.: Acta Cryst. 15 (1962) 474 I151 Aldcroft. D.. Bye, G.G., Hughes, C.A.: J. Appl. Chem. 19 (1969) 167 [16] Alemaikin. F.M.: Uch. Zapiski Mordovsk. Gos. Univ., Saransk 16 (1962) 20 I171 Alfimova. L.D.. Velikhov. Yu.N.. Demirskaya. O.V.: Vysokochist.

Veshch. 5 (1991) 153 I181 Alkashi, H., Kagaku. N.R.: J. Japan Chem. Soc. 2.(1948) 212 [ 191 Alybakov. A.A.. Umurzakov, B.S.: Tezisy Dokl. Vses. Soveshch.

Rostu Krist. 5th 1 (1977) 206 1201Ambrose. S., Kanniah. N.. G n a n a m , F.D., Ramasamy. P.: Crystal Res.

Technol. 17 (1982) 299 I2 11Amelina. E.A., Vaganov. V.P., Shchukin. E.D.: Kolloidn. Zhur. 42 (4) (1980) 611 1221Ameneiro Perez, S.: Rev. C u b a n a Fis. 4 (1) (1984) 129 1231Amin, A.B., Larson. M.A.: Ind. Eng. Chem., Process Des. Devel. 7 (1) (1968) 133 1241Amjad, 2.: Roc. Symp. Adsorpt. Surface Chem Hydroxyapatite (1984) 1-11; CA 100 18347.7

I251 Amjad. 2.: Langmuir 3 (2) (1987) 224 [26] Amjad, 2.:J. Colloid Interface Sci. 117 (1) (1987) 959 I271 Amjad, 2.: Langmuir 3 (6)(1987) 1063 I281 Amjad, 2.: J. Colloid Interface Sci. 11 7 (1987) 98 I291 Amjad, 2.: Can. J. Chem. 66 (6)(1988) 1529 1301 Amjad. 2.: Can. J. Chem. 66 (9) (1988) 2181

11. References to Tables

I311 Amjad. 2.:J. Colloid Interface Sci. 123 (1988)523 I321 Amjad. 2.:Langmuir 5 (5)(1989)1222 1331 Amjad. 2.:Colloids and Surfaces 48 (1990)95 I341 Amjad. 2.:Langmuir 7 (3)(1991)600 1351 Amjad. 2.:Langmuir 7 (10)(1991)2405 I361 Amjad. 2.. Koutsoukos, P.G.. Nancollas. G.H.: J. Colloid. Interface Sci. 101 (1) (1984)250

I371 Amjad, Z., Mooley. J.: J. Colloid Interface Sci. 111 (2) (1986)496 I381 Andreev, G.A.: Rz. Tverd. Tela 7 (1965)1653 I391 Andreev, G.A.: Kristallografiya 12 (1967)104 I401 Andreev. G.A.: Kristallografiya 13 (1968)872 l411 Andreev, G.A.. Buritskova. L.G., Hartmanova. M.: Krist. Tech. 13 (1978)805 I421 Annede Cugnac. H.J.. Pouradier. J.: Compt. rend. 264 (1967)1149 I431 Antinozzi, P.A.. Brown, C.M.. Purlch. D.L.: J. Crystal Growth 125 (1-2)(1992)215 I441 Aoki. S..Yoshida. M.. Aral, Y.: Gypsum Lime 178 (1982)129 I451 Aquilano, D.. Rubbo. M.. Vaccari, S.. Mantovani, G.. Squaldino, G.: Growth mechanisms of sucrose from face-by-face kinetics and crystal habit modifications from impurities effect, in: Industrial Crystallization '84 (eds. JanW, S.J.. de Jong. E.J.),p. 91,Elsevier,

Amstardam 1984

I461 Armington, A.F., et al.: U S Govt Res. Dev. Rept 68 (1968)100

289

290

11. References to Tables

1471 Atademir. M.R.. Kitchener, J.A., Shergold, H.L.: J. Colloid Interface

Sci. 71 (1979) 466 (481Austrian Pat. 248 479 (1963)

1491 Austrian Pat. 343 597 (1978) 1501 Autenrieth. H., et al.: Chem. Ing. Tech. 29 (1957) 709

1511 Azoury. R.. Garside. J.. Robertson. W.G.: J. Crystal Growth 76 (2) (1986) 259 1521 Babayan. S.G.. et al.: Radiokhimiya 4 (1962) 521

(531Babayan. S.G.. Isakhanyan. S.S.: Armen. Khim. Zhur. 22(2) (1969) 119 1541 Babich. S.A.. Soifer, L.M., Chubenko, A.I., Shakhnovich, M.I.: Sb. Nauch. Tr. VNII Monokr., Otd. Mater. i Osobo Chist. Khim. Veshch.

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North-Holland, Amsterdam 1982 12861 Davey. R.J.: Curr. Top. Mater. Sci. 8 (1982) 429 I2871 Davey. R.J.: J. Crystal Growth 76 131 (1986) 637 [288] Davey. R.J.. Black, S.N.. Logan, D., Maginn, S.J.. Fairbrother J.E.. Grant, D.J.W.: Chem. SOC.,Faraday Trans. 88 (23)(1992) 3461 I2891 Davey. R.J.. Mullin. J.W.: J. Crystal Growth 26 (1974) 45

306

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I2901 Davey. R.J.. Mullin, J.W.: The effect of ionic impurities o n the

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[2921 Davey, R.J., Fila. W.. Garside, J.: J. Crystal Growth 79 (1-3, Pt. 2) (1986) 607.

12931 Davies. C.W., Nancollas. G.H.: Trans. Faraday SOC. 51 (1955)818

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I3031 Despotovie, R.. Filipovie-VincekoviC. N., Subotie, B.: in Roc. 50th Int.

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308

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13191 Draganova, D.: Godish. Sofii. Univ.. Khim. Fak. 73 (1983)157 I3201 Draganova. D.: Izv. Khim. 14 (2)(1981)229 I3211 Draganova. D., Koleva. R.: Izv. Khim. 13 (4)(1981)631 13221 Draganova. D., Koleva. R.: Godish. Sofii. Univ.. Khim. Fak. 74 (1984) 300 I3231 Draganova. D. Koleva. R.: ICCG-A. Sendai (1989)21A C 0 8 (3241v a n Driel. C.A., v a n der Heijden. A.E.D.M.. v a n Rosmalen. G.M.: Granule structure formation by isothermal coarsening of dendritic

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(3261Driker. B.N., Protsakov. S.M.. Rempel. S.I.,Vakulenko. V.A.. Samborskii, I.V.: Zhur. Prikl. Khim. 54 (1981)1006

13271 Driker, B.N., Belyaeva. N.A., Vakulenko. V.A., Prostakov, S.M.: VINITI Depos. Doc. 2991 (1983);CA 101 046479

13281 Driker. B.N.. Prostakov. S.M..Rempel. S.I.. Vakulenko. V.A.. Samborskii. I.V.: Kompleksn. Ispol'zov. Miner. Syr'ya 12 (1981)22

I3291 Druker. B.N.. Belyaeva. N.A.: Zhur. Prikl. Khim. 61 (1988)610 I3301 Dugua, J.: Thesis, Univ. Aix-Marseille 1977 13311 Dugua, J.. Simon, B.: CEPAS 78, Abstract book (ed. A.E. Nielsen).

p.5. Univ. Copenhagen 1978

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309

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I3581 McFadyen. P., Matijevie, E.: J. Inorg. Nucl. Chem. 35 (1973)1883 I3591 Falin, V.A.. Tatarenko. N.P.. Serebrennikova. G.M.: Massov. Krist. 3 (1977)121 [360]Fedorova. L.L.. Volokhov, Yu.: Depos. Doc. VINITI 3995 (1984) I3611 Feenstra, T.P.. van Straten, H.A.. de Bruyn, P.L.: J. Colloid Interface Sci. 80 (1981)255 I3621 Feenstra. T.P.. Hop, J., de Bruyn. P.L.: J. Colloid Interface Sci. 83 (2) (1981) 583 13631 Feliksinski, T..Szewczyk. J.: Mater. Res. Bull. 16 (1981)1505

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13641 Felix. R., Monod, A.. Broge. L., Hansen, N.M.. Fleisch, H.: Urol. Res.

5 (1977)21 I3651 Fellstroem. B., Danielson, B.G.. Linsjoe, G. et al.:Fortschr. Urol. Nephrol. 23 (1985)24 I3661 Fillpescu, L.. Cretu. M.. Mocioi. M.. Zaharia. A.: Rev. Chim. [Bucharest) 32 (4)(1981) 347 I3671 Fillpescu, L., Meghea. A., Mociol. M.: Rev. Chim. (Bucharest) 34 (1983)1000 I3681 Filipescu, L.. Meghea. A., Zaharia. A.: Rev. Roum; Chim. 37 (8) (1992)927 13691 FilipoviC-VincekoviC. N.: Tensides, Surfact., Deterg. 26 (6)(1989) 417 I3701 Filipovie-VincekovlC, N.. Despotovie. R.: h-oc. 34th Meeting SOC.Chim. Phys., p. 197,Paris 1981

I3711 Finch, G.I.: J. Sci. Ind. Res. A 15 (1956)539 I3721 Fisher, V.M.: Issledovania nad peresyshchennymi rastvorami solei. Riga 1913 I3731 Fock. A.: 2. Krist. 17 (1890)177 I3741 Font-Altaba. M.. Solans-Huguet, J.: Acta Cryst. 21 (1966)267 13751 Fontcuberta. J., Rodriguez. R.. Tejada. J.: Mossbauer studies of the Fe(II1) effect o n the morphology of ADP, in: Industrial CystaZlization’78 (eds. de Jong. E.J.. Janeiie, S.J.),p. 523,North-Holland,

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I4151 Gabryel, H.: Effect of fluorine modifiers on phosphogypsum

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Franc. Mineral. Crist. 38 (1915) 149 I4401 Gaubert, P.: Bull. SOC. I4411 Gaubert, P.: Compt. rend. 167 (1918) 491 14421 Gaubert. P.: Compt. rend. 180 (1925) 378 14431 Gaubert. P.: Bull. SOC. Franc. Mineral. Crist. 53 (1930) 157 I4441 Gaubert, P.: Compt. rend. 192 (1931) 965 I4451 Gaubert. P.: Compt. rend. 200 (1935) 1120 (4461 Gaubert. P.: Compt. rend. 202 (1936) 1192 14471 Gavish. M., Popovitz, R., Lahav. M.. Leiserowitz, L.: Science 250 (1990) 973 (4481Gavish, M., Wang, J.L.. Eisenstein, M.. Lahav. M.. Leiserowitz. L.:

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3 15

3 16

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14541 Gerasimov, Y.M., Distler. G.I., Kanevskii, V.M.. Kortukova. E.I., Suvorova, E.I., Okhrimenko, T.M.. Belikova, G.S.: Crystal Res. Technol. 18 (1983)1283

(4551Gerhart. H.:Tschermaks Min. Petr. Mitt. 24 (1906)359;ibid. 28 (1910)347 I4561 Ger. Pat. 56 713 (1914) 14571 Ger. Pat. 336 100 (1918) 14581 Ger. Pat. 425 335 14591 Ger. Pat. 485 054 (1925) 14601 Ger. Pat. 519 597 (1927) (4611Ger. Pat. 612 744 (1935) (4621Ger. Pat. 621 739 (1935) 14631 Ger. Pat. 622 876 (1935) 14641 Ger. Pat. 636 057 (1936) (4651Ger. Pat. 648 539 (1937) [4661Ger. Pat. 651 311 (1937) (4671Ger. Pat. 666 546 (1938) 14fj81 Ger. Pat. 693 986 (1940) 14691 Getsinger: J. Agr. Food Chem. 5 (1955)433 14701 Giannimaras, E.K..Koutsoukos, P.G.: Langmuir 4 (1988)855 14711 Gille, F.,Spangenberg. K.: 2. Krist. Miner. Petrograd A 65 (1927)204 1

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14731 Girolami, M.W.. Rousseau, R.W.: J. Crystal Growth 71 (1985)220

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3 17

(4741Glasner, A.,Skurnik. S.: J. Chem. Phys. 47 (1967)3687 (4751Glasner, A.,Skurnik, S.: Israel J. Chem. 6 (1968)69 (4761Glasner, A..Kenat, J.: J. Crystal Growth 2 (1968)119 (4771Glasner. A.. Skurnik, S., Zidon. N.: Israel J. Chem. 7 (1969)649 (4781Glasner, A.. Kenat, J.: J. Crystal Growth 6 (1970)135 (4791Glasner, A.,Weiss, D.: J. Inorg. Nucl. Chem. 42 (5) (1980)655 (4801Glazyrina, L.N., Savinkova. E.I., Desyatnik, V.N.. Cherepanova, I.S. Zhur. Prikl. Khim. 56 (2) (1983)241

[481]Gluud, W.,Ritter, H.: Ber. Ges. Kohlentech. 3 (1931)208 (4821Gluud, W.,et al.: Ber. Ges. Kohlemtech. 3 (1931)371 1483)Goatln, C.: ICP 16 (11) (1988)140 [484]Gomez, R.A.: Effect of some metallic impurities on sugar crystal formation a n d growth, in: Industrial CrystaZlization'78 (eds. de Jong, E.J., JanEiC S.J.). p. 519. North-Holland, Amsterdam 1979

(4851Gonzales, M.A., de Andres. A., Balcazar, J.L.: Estud. Geol. (Madrid) 38 (3-4)(1982)27

I4861 Gorecki, H.,Hoffmann, J., Schroder, J.: Pr. Nauk. Akad. Ekon. Wroclaw 200 (1982)141

14871 Gorshtein, G.I.: Tr. Vsesoy. Nauch.-Issl. Inst. Khim. Reaktivov 20 (1951)3, 44 (4881Gorshtein, G.I.: Zhur. Neorg. Khim. 3 (1958)51 14891 Gorshtein, G.I.: Radiokhimiya 1 (1959)497 (4901Gorshtein, G.I., Tyutyueva, N.N.: Radiokhimiya 5 ( l ( (1963)1 1 14911 Gorshtein, G.I., Tyutyueva, N.N., Puzyreva, A.I.: Kristallizatsiya 2 (1976)55

3 18

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14921 Gorshtein, G.I., Dmitrieva. N.S.: Zhur. Prikl. Khim. 36 (1963)1725 I4931 Gorshtein, G.I.: Tr. Vsesoy. Nauch.- Issl. Inst. Khim. Reaktivov 25 (1963)123 I4941 Gorshtein. G.I.. Bashkina. N.F.: Tr. Vsesoy. Nauch.-Issl. Inst. Khim. Reaktivov 26 (1964)369

I4951 Gracheva, R.A., Syzdykbaeva. M.B.. Kozhakova, A.A.: Depos. Doc. SPSTL 865 KHP-D81 (1981)

I4961 Grant, D.J.W., Chow, K.Y., Chan. H.K.: AICHE Symp. Ser. 87 (284). Part. Des. Cryst., 38

I4971 Grases. F., Genestar. C.. Palou, J.: Colloids Surf. 44 (1990)29 I4981 Grases. F.,Gil, J.J.. Conte. A.: Colloids Surf. 36 (1989)29 14991 Grases. F.,March, J.G.. Bibfloni, F., Amat. E.: J. Crystal Growth 87 (2-3)(1988)299

[500]Grases. F.,March, J.G.. Costa-Bauza, A.: J. Colloid Interface Sci. 128 (2)(1989)382

15011 Grases. F., March. P.: J. Crystal Growth 96 (41(1989)993 15021 Grases. F., Millan. A., Garcia-Raso. A.: J. Crystal Growth 89 (1988) 496 [503]Gratz, A.J., Hfllner. P.E.: J. Crystal Growth 129 (3-4)(1993)789 15041 Grimm, Wagner.: 2. physik. Chem. 132 (1928)131 15051 de Groot, K.. Dyuvis, E.M.: Nature 12 (5058) (1966)183 15061 Gufaro, G.. Goatin. G., Zanetti. R.: Process Technol. Proc. 2, Ind. Cryst. (1984)333

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3 19

I5071 Gufaro. G., Goatln, C.. Petrone, A., Talamini. G.: J. Crystal Growth 66 (1984) 621

I5081 Haas. K.. Jager, L., N@lt. J.: Collect. Czech. Chem. Commun. 37 (1972) 744 Sltzung Preuss. Akad. 30 (1930) 3 15091 Hahn, 0.: I5101 el Hagouji, A., Murat. M.: Compt. rend. Acad. Sci.. ser. 2. 303 (8) (1986)657

I5111 Haley. V.. Mattloll, T.A., Wiles, D.R.: Can. J. Chem. 63 (1985)2290 15121 Hallson. P.I.. Rose, G.A., Sulalman, S . : Urol. Res. 11 (1983) 151

I5131 Hallson. P.I.. Rose, G.A.. Sulaiman. S . : Urol. Int. 38 (1983) i 7 9 I5141 Hamidanl, A.U.. et al.: Res. Ind. 36 (4)(1991) 283

15151 Hamza, S.M., Abdul-Rahman, A., Nancollas, G.H.: J. Crystal Growth 73 (2)(1985) 245

I5161 Hamza. S.M.. Hamdona. S.K.: J. Phys. Chem. 95 (81 (1991) 3149 I5171 Hamza. S.M..EIHamouly: J. Chem. SOC..Faraday Trans. 1 85 (1989) 3725

I5181 Harano. Y.. Yamamoto. H.: Impurity effect of some amino acids on formation and growth of L-glutamlc acid nuclei by secondary nucleation in agitated solution, in: Industrial Crystallization '81(eds. J a n W S.J., de Jong. E.J.). p. 137, North-Holland, Amsterdam 1982 [519] Harano. Y.. Matsul. T.: Metastable zone width and nucleation rate effects of agitation and impurity for KBr0,/H20 and (H,N),CS/ MeOH, in: Industrial Crystallization '84 (eds. JanEie, S.J., de Jong. E.J.), p. 249, Elsevier, Amsterdam 1984

320

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[5291 Herzog, R.E.. Shi. 9..Patil. J.N..Katz. J.L.: Langmuir 5 (1989) 861 15301 Hille, M., Jentsch. Ch.: 2. Krist.118 (1963) 283 I5311 Hflle, M.. Jentsch. Ch.: 2. Krist. 120 (1964) 323 I5321 Hiquily, N.,Canselier, J.P.: ref. 31 in: Canselier, J.P.: Dispers. Sci. Technol. 14 (6) (1993) 625 [533] Hiquily, N.,Couderc, J.P., LaguCrie, C.: Chem. Eng. J. 30 (1985) 1 I5341 Hiquily, N.,Laguerie,,,C,: Inclusion formation in the ammonium perchlorate crystals - influence of surfactants. in: Industrial

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I5361 Hirota, S.,Nakajima, M.: Chem. Eng. J a p a n Symp. Ser. 18 (1988) 151 [5371Hirota, S.:Inclusion of aluminium ion a n d I t s effect on crystal growth of KDP. Intern. Syrnp. o n Repar. of F'unct. Mat. and Crystall.. , Osaka 1988

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15391 Hirota, S.:Kagaku Kogaku Ronbunshu 15 (6)(1989)1195 15401 Hirota. S.,Setoguchl, K.: Effect and incorporation of chromic ion when KDP crystallizes. in: Industrial Crystallization '93, VoL I, (ed. Rojkowski, 2.). p. 3-087.Warsaw 1993

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137 [6341 Kazov. M.N.. Trebukhova. T.A., Kazova. R.A.: Depos. Doc. VINITI 523 (1979) I6351 Keller. D.M., Massey, R.E., Hlleman, O.E.: Can. J. Chem. 56 (1978) 83 1 16361 van Kemenade, M.J.J.M., de Bruyn, P.L.: Colloids Surf. 36 (3)(1989) 359 16371 Kempe, G., Netimann, H., Winzer, A.: Mezhvuz. Sb. Nauch. Tr. Leningrad. Teknol. Inst. 6 (1982) 146 16381 Kenat, J.: The crystallizationofKC2 in solutions containing small amounts of lead, Thesis, The Hebrew Univ. Jerusalem 1962

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16391 Kern, R.,Dassonvflle, R.: J. Crystal Growth 116 (1-2)(1992) 191 16401 Kerr. W.L., Osuga, D.T..Feeney. R.E.. Yeh, Y.: J. Crystal Growth 85 (3)(1987) 449

16411 Khamskii, E.V.: Zhur. Prikl. Khim. 32 (1959) 948 (6421 Khamskii, E.V.: Some problems of crystal habit modification, in: Industrial CrystalUzation fed. Mullin. J.W.), p. 215, Plenum Press. New York 1976 16431 Khamskii, E.V.: The role of impurities in crystallization, in: Industrial Crystallization '78 (eds. de Jong, E.J.. JanEie. S.J.). p. 105, NorthHolland, Amsterdam 1979 16441 Khamskii. E.V.: Kristallizatsia t 2 rastuorou, Nauka. Leningrad 1967. I6451 Khamskii. E.V., Bogatyrenko. A.S.: Zhur. Prikl. Khlm. 54(21 (1981) 392 16461 Khamskii. E.V..Bondarenko, S.I., Smirnova, O.M., Shkarupa. L.N.: Ukr. Khim. Zhur. 51 (91 (1985) 920 16471 Khamskii. E.V., Bykova, A.N.: Zssledouania u oblasti khimii i tekhrwlogii mineralnykh solei i okislou, p. 79, Nauka. Moscow 1965 16481 Khamskii, E.V., Kondrashenko. T.A.: Zhur. Prikl. Khim. 36 (1963) 263 1 16491 Khamskii, E.V., Kozina. Z.A.: Dokl. AN SSSR 149 (1963) 915 I6501 Khamskii, E.V., Maidurova. O.E.: Zhur. Prikl. Khim. 65 (8) (1992) 1681 16511 Khamskii, E.V., Marcenko, L.I.: Ukr. Khim. Zhur. 49 (3)(1983) 236 16521 Khamskii, E.V., Nazarova, E.G.: Zhur. Prikl. Khim. 35 (1962) 1206

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329

(6531Khamskii. E.V., Panfilov, V.V., Shakitskaya, N.A.: Ukr. Khim. Zhur.

50 (1) (1984) 2 6 [654] Khamskii, E.V., Podozerskaya, E.A.: Zhur. Prikl. Khim. 41 (1968)

245

I6551 Khamskii. E.V.. Podozerskaya. E.A.: Zhur. Prikl. Khim. 41 (1968) 252

16561 Khamskii. E.V., Podozerskaya. E.A.: Krist. Tech. 3 (1968) 6 0 5 [657]Khamskii. E.V., et al.: KristaZUzatsfyaf_fiziko-khirnicheskiesuofstua laistallichesklkh ueshchestu. Nauka. Leningrad 1969 (6581Khamskii. E.V.. Yagodkina. G.N.: Zhur. Prikl. Khim. 36 (1963)2620

16593 Khamskii. E.V., Zelenkova, L.V., Novikova, E.P.: Zhur. Prikl. Khim. 63 (9)(1990) 1976

(6601 Khartanovich, A.Z.: Kristallizatsiya i fazouye perekhody. p. 118, AN SSSR, Minsk 1962 [661]Khausankhodzhaev. M.G., Khairullaev. Ch.K.. Tadzhiev. S.M.:

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(6651 Khlopin. V.G.: Izbrannye Trudy I, Izd. AN SSSR. MOSCOW1957 I6661 Kholakova, I.: God. Vissh. Khim.-Tekhnol. Inst., Sofia, 23 (1) (1977) 297 16671 Klbalczyc, W.. Bondarczuk, K.: J. Crystal Growth 71 (1985)751 [668] Klbov, V.K., Veselinov, I., Cherneva, 2.: Krist. Tech. 7 (1972) 497

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I6691 Kidyarov. B.I.. Nevyantseva, R.R., Dandaron. N.D., Zaitseva. L.F.:

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Sibir. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk 5 (1984) 51 I6701 Kil’man. Ya.1.. Usachev. V.A.. Vakhrushev. Yu.A.: Zhur. Prikl. Khim. 58 (1985) 7

[6711 Kimura. H.: J. Crystal Growth 73 (1985) 53 16723 McKinnon, C.E.: 2nd Symp. Salt, Cleveland 1965. 1 (1966) 365 I6731 Kinsman, D.J.J., Holland, H.D.: Geochim. Cosmochim. Acta 33 (1969) 1 16741 Kinsman. D.J.J.: Sediment. Petrology 39 (1969) 486 I6751 Kinzhalov. A.A.. et al.: Zhur. Prikl. Khim. 42 (1969) 2700 I6761 Kirgintsev. A.N.. et al.: Zhur. Neorg. Khim. 9 (1964) 1025 I6771 Kirgintsev, A.N., Nikashina. T.A.: Zhur. Neorg. Khim. 9 (1964) 1450 I6781 Kirgintsev. A.N.. Avyakumov, E.G.: Fiz. Tverdogo Tela 6 (1964) 1167 16791 Kirgintsev, A.N.. Avyakumov, E.G.: Zhur. Neorg. Khim. 10 (1965) 2187

[680lKirkova, E., et al.: Godish. Sofii. Univ.. Fiz. Mat. Fak. 53 (3)(1958/59) 37 I6811 Kirkova, E.. et al.: Godish. Sofii. Univ., Fiz. Mat. Fak.. 53 (3) (1958/59) 43 [682] Kirkova, E., Bllznakov. G.. Nikolaeva, R.: Godish. Sofii. Univ., Khim.

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533

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33 1

I6851 Kirkova. E.. Nikolaeva, R.: Kristall u. Tech. 8 (1973) 463 (6861 Kirkova. E.. Pencheva. J.: On the mechanism of incorporation of

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1989 I6871 Kirkova, E.. Yaneva. S.B.: Krist. Tech. 2 (1967) 21 I6881 Kirov. G.: Geokhlm. Mineral. Petrol. 12 (1980) 18 I6891 Kirov, G.K.. Filizova. L.: Krist. Tech. 5 (1970) 387 I6901 Kirov, G.K., Vesselinov. I.. Chernova. 2.: Krist. Tech. 7 (5) (1972) 497 I6911 Kir’yanova. E.V.: Neorg. Mater. 28 (6)(1992) 1236 I6921 Kir’yanova, E.V., Franke. V.D., Kopyleva, B.B.: Zhur. Prikl. Khim. 64 (11) (1991) 2233 L6931 Kitamura. M.. Ikemoto, K.. Kawamura, Y., Nakai. T.: Kagaku

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332

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[7031KIein, D.R., Fontal, B.: Talanta 12 (11 (1965)35 17041 Klein. M.V., et al.: Mater. Res. Bull. 3 (1968)677 17051 Kleinert. P.: Freiberger Foreschungsh. A 267 (1961)281 I7061 Klempt. W.:Ber. Ges. Kohlentech. 4 (1933)191 17071 Klempt. W.: Brennstoff-Ch. 33 (1952)114 17081 Klepetsanis. P.,Koutsoukos, P.G.: Crystal growth and inhibition of calcium sulfate in aqueous solutions, in: Industrial Crystallization '90 (ed. A. Mersmann). p. 261,Munich 1990

17091 Klier, E..Shaki. M.: eeskosl. Easop. fyz . 4 (6)(1954) 17101 Kloatzer, D.,Levi. H.W.: Radiochim. Acta 6 (2) (1966)81 I7111 Knight, R.J.. Sylva. R.N.: J. Inorg. Nucl. Chem. 36 (1974)591 17121 Koch, E., Wagner, C.: 2. physik. Chem. 381 (1937)295 17131 Koch, J., Schiller. H.: 2. Lebensmittel- Unters. Forsch. 124 (1964) 180 I7141 Kohlschfitter, V.,Egg, C.: Helv. Chim. Acta 8 (1925)697 17151 Kokubo. R., Sasaki. S.: Chem. Eng. J a p a n 28 (5((1964)386 17161 Kolarov. N.: Compt. rend. Acad. Sci. Bulgar. 3 (1950)21 17171 Kolarov. N., Boncheva, 2.: Monatsh. 93 (1962)1254 17181 Kolarov. N..et al.: Zhur. Neorg. Khim. 9 (1964)760 17191 Kolarov, N., Kolarova, M.: Godish. Khim.-Tekhnol. Inst. Sofia 13 (2) (1966)217 17201 Kolarov. N.. Dobreva. R.: Monatsh. 99 (1968)409 [7211Kolarov. N., Shopova, R.: Godlsh. Vissh. Khim. Tekhnol. Inst.. Sofia, 24 (1) (1981)147

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333

17221 Kolb. H.J., Comer. J.J.: J. Am. Chem. SOC.67 (1945) 894 I7231 Kolb, H.J., Comer, J.J.: J. Am. Chem. SOC.68 (1946) 719 I7241 Koldobskaya. M.F.. Gavrilova, I.V.: Rost Kristallov 3 (1961) 278 I7251 Komarova. T.A.: Issledovanie kinetiki kristallizatsii solei iz rastvorov.

Thesis, Mosk. Gos. Univ.. Moscow 1953 [7263 Komatsu, H.. Shigematsu, K.: Koen Yoshibu-Jinko Kobutsu Koronkai

24th. (1979) 5-6 I7271 Konag, A., Emons, H.H.: Freiberger Forschungsh. A 683 (1983) 46 17281 Konig, A., Emons. H.H.: The influence of tensides on crystallization

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Amsterdam and Academia Prague, 1989 (7291Konig, A., Emons, H.H.. Njvlt. J.: The effect of electrolyte

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admixtures in high concentration on the crystal growth of highly soluble salts, in: Industrial Crystallization '87 (eds. N p l t , J., ZaCek, S.), p. 285, Elsevier Amsterdam and Academia Prague. 1989 I7311 Konig. A., Ernons, H.H.. Nyvlt. J.: Crystal Res. Tcchnol. 22 (1987)

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W.:Ukr. Fiz. Zhur. 23 (8)(1978)

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17351 Kopylev, B.A., et al.: Zhur. Prikl. Khim. 42 (1969) 2429 17361 Korbe, A.: Beobachtungen iiber Variation der Kristalltracht des

Chlomatriurns, Leipzig 190 7 17371 Korolkov, I.I., Q g u n o v a . Z.A.: Gidroliz. Lesokhim. Prom. 8 (1956) 8 (7381 Korovkina, E.K.. Komarova, T.A.: Vest. Moskov. Univ.. ser. I1 - khlm. 20 (5) (1965) 34

17391 Korovkina. E.K.. Komarova. T.A.: Vest. Moskov. Univ.. ser. 11 - kNm. 21 (2) (1966) 39

17401 Korshunov, G.S.. Mokievskii. V.A.: Zhur. Obsch. Khim. 18 (19481 569 17411 Korshunov, I.A., Polikarpov, J.S.: Radiokhimiya 3 (196 1) 50 1 I7421 Kosevich, V.M.. et al.: Dokl. AN SSSR 180 (1968) 341 17431 Koutsky, J.A., et al.: Surface Sci. 3 (2) (1965) 165 17441 Koutsoukos, P.G., Amjad. Z., Tomson, M.B., Nancollas, G.H.: J. Am.

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Khim. Tekhnol. Dvuokisi Titana i Zhelezosoder. Pigmentov. M 69 (7481 Koziol. K.. Pujanek, M.: The dependence of nonionic s u r f a c t a n t s o n

the metastable zone, in: Industrial Crystallization '81 (eds. Janeii., S.J., d e Jong. E.J.). p. 319, North-Holland, Amsterdam 1982 17491 Kranz, M., Domka, L.: Cem.-Wapno-Gips 32 (3) (1978) 89

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110641 Prostakov, S.M.. Driker, B.N., Rempel, S.I.. Belyaeva. N.A.: Deposited doc. SPSTL 339 KHP-D8 1 (1981)

110651 Przytycka, R.:Nukleonika 12 (1967)747 [lo661Punin, Yu.0.: Uch. Zap. Leningr. Gos. Univ. 409 (1982)143 110671 Punin, Yu.0.. Petrov, T.G.: Kristallografiya 13 (1968)922 [lo681Pytkowicz. R.M.: h e r . J. Sci. 273 (1973)515 ll0691 Rabkin, M.A.. et al.: Zhur. Prfkl. Khim. 24 (1951)1257

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111151 Rolfe, P.F.: Desalination 1 (1966)359

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[11531 Samakaev, R.Kh., Dyatlova, N.M., Driker. B.N., Dyutyuk. L.T.:

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111571 Samakaev. R.Kh., Nikolaeva, L.S.. Dyatlova. N.M., Evseev, A.M.: Zhur. PriM. Khlm. 57 (1984)2237

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111801 Sattarov, S.A.,Yuldashev, U.Y., Reiterov. V.M.. Trofimova, L.M.: Fiz. Tverdogo Tela 32 (4)(1990)1256

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1965 I12651 Steinike. U.: Krist. Tech. 1 (1966) 113 I12661 Steinike, U.: Krist. Tech. 1 (1966) 285 I12671 Steinike, U.: Krist. Tech. 3 (1968) K 5 I12681 Steinike, U.: Krist. Tech. 5 (1970) K19 [12691 Steinike. U.: Krist. Tech. 6 (1971) 7 I12701 Steinike. U.: Krist. Tech. 6 (19711 17 112711 Stepanova. N.S.. Belyustin, A.V.: Fiz. Krist. (19791 107 I12721 Stepanova. N.S.. Portnov, V.N.. Fridman. S . S . . Fishman. Yu.M..

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I12941 Shterberg, A.A.. Pozdnyakov, P.G.: Avtor. svid. 101 179 (1952) I12951 Shvarcvald. A.I.: Zhur. Prikl. Khim. 40 (1967) 2452 I12961 Skrtie. D.. FSlredi-Milhofer. H., Markovie. M.: J. Crystal Growth 80

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380

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38 1

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I14551Winzer. A.. Emons, H.H.: Freiberger Forschungsh. A600 (1979) 73 [ 14561 Winzer, A., Emons, H.H.. Jugel, B.: Freiberger Forschungsh. A600

(1979) 3 1 [ 14571 Winzer. A., Emons, H.H.. Burger, V.: Freiberger Forschungsh.

A 600

(1979) 6 1 I14581 Winzer. A., Quasdorf. G.. Kemp. G.: Mezhvuz. Sb. Nauch. Tr.

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Xuebao 17 (2) (1991) 129 114681Xyla. A.G.. Koutsoukos, P.G.: J. Chem. SOC.,Faraday Trans. I, 83 (1987) 1477

114691 Xyla, A.G., Koutsoukos, P.G.: J. Chem. SOC..Faraday Trans. I, 85 (1989) 3165 [14701 Yamada, T., et al.: Nagoya Kogyo Daigaku Gakuho 10 (1958) 176 I14711Yamada. T., Hiyama. E.: Nagoya Kogyo Daigaku Gakuho 13 (1961) 295 I14721 Yamada, T., et al.: Sekko To Sekkai 78 (1965) 440 [ 14731 Yamakami, T.: Tohoku Daigaku Kagaku Keisoku Kenkyusho

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383

114751 Yamamoto. H.,Hasegawa. H.. Harano. Y.: J. Chem. Eng. J a p a n 14

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111

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(1909) 1

384

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329

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385

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Admixtures in Crystallization

Jaroslav Njlvlt, Joachim Ulrich 0 VCH Verlagsgesellschaft mbH, 1995

12. Subject Index 6,7.10,13,15,19.2 1,

concentration

A

active site 11.14.17.19.20,21

23.25.35.35.36.38,

activity 8.13

39.40.41.42.45

additive 6.7.8.12.13.22.25.27.28

coordination complexes 10

adhering mother liquor 45.46.49.53

counter-current recrystallization 50

adsorption

critical nucleus 11.13,14,17.18

11,13.17,18,19,20.22,25. 30.34,41.42,43

adsorption isotherm 13.20

cross-current flow 53 crystalgrowth 4.8.11.16,18,19.20,

agglomeration 20

21.22.23.24.28.29,

agitation 4.41

30.3 1,32.33.40

anomalous mixed crystals 34.43

crystal lattice 4.15.19.20.2 1.22.23,

attachment energy 25

25.26.29.30.36.37.

B

4 1.42

bond 19.25.29.30.32

crystal surface 8.11,13,14,15.16,17.

- chain 25

18,19.20.2 1.22.25,

- energy 17.25

26.28.29.30.32.33,

boundary layer 30

37.38.41.42.43.46

C

D

chirality 29

dielectric constant 3 1

collision 9.1 1

diffusion 11.19.20,22,23.28,30,38.

collision breeding 9

39.40

colloids 11.34,44,45

diffusional regime 40

computer simulation 5.28.33.48

diffusion washing 54

12. SuQJectIndex

388

dislocation 32

growth rate 7.8,16,17,18,20.21.22,

- mechanism 32.33

24.3 1

- restrainer 15.19

dissolution 7.8,14,19.43

- rate

- site 17.20.21.29

8

distribution 5,10.34.36,37,38,39,40. 41,43

H habit 18.28.3 1,37

- coefficient see d. constant

heteroclusters 10

- constant 37.38.39.43.47.48,

heterogeneous nucleation 9.12,13

49

heteronucleus 2 1

dust particles 44

heteroparticles 13

dyestuffs 7.2 1

homogeneous dfstribution 38.40.41

E

- coefficient 38,41

effectiveness 7.8.28

-law 38.49

electric

homogeneous nucleation 9,10,11

- charge 14

hydration 12,28

- field 10.25.28

hydrogen bonding 30.31

embryo 1 1

I

equilibrium 19,24,37.38.49

impurities 5,6,12.34.37.38.4 1,43.44.

F

45.48.47.48.49.53.54

fractals 23

impurity concentration gradient 15

G

induction period 12

geometric similarity 10.22

inhibiting effect 10

growth center 4,17,19,20, see also

inorganic additives 7.10,14,19

growth site

interface 4.23,30,31

12. SubjectIndex

389

interphase 9,13,14.22.23.28,39

miscibility 34,35.36,41.42

isodimorphism 34.36

mother liquors 44.45,46.49,52,53

Isomorphous inclusion 34.35.36.37.

N

38,41,43

Nernst distribution 38.45

K

non-stationary precipitation 40

Kinetic regime 39

nucleatton 4.9.10.12.13,14,15,19.

L

20.28,32

lattice 4.15.19.20.21.22,23,25,26,

- mechanism 12.13.14.33 - rate 10.12,13.14

29.30.36.37.41.42

- dimensions 21,23,26,36

nucleus

logarithmic distribution 37.38.40

- critical 11.13.17.18

M

- two-dimensional 18,20,22

macroadmixture 6

0

macrocomponent 5.6.7.8.10.1 1.12.

organic additives 7.8.21.25

14,19.21,22.29.

overlapping faces 24

3 1.34.35.36.37.38.

P

39.40.41.42,44.45.

pHvalue 7.22

49

polarity 31

materials balance 45

polyvalent cations 7

mechanical inclusions 34.44

primary nucleation 9

melt crystallization 54

purification 4.4953

melting point 37

purity 4,5,34.37.49

microcomponent 5.6.37,38,39.40,

R

41.49.52 migration regime 40

recycling 45.46

- ratio 45,46,48,49

390

12. Subject Index

roughness 14.23.33

surface 8,9.11,13,14.15,16.17,18.

S

19.20.22.25.26.28.29.30.32,

secondary nucleation 9.13,14

33.37.38.42.46

- active substances 7.13,22

sectorial crystal growth 43.44 semistationary coprecipitation 39

surface - diffusion 19,20,22,30

separation 4.6.34.37.38.45.48

- energy 13.17,20.21,24.31

shape 4,7,8.23.25.29,36.43,31,37

- entropy factor

size 4.7,8.10.11,13.14.17,18,20,21,

- integration 22.32

3 1.32

- nucleation 32

26.36.42

- tension 10

solid phase 9.23,34,35,38,39,40,49 solid solution 34,36.37.41

sweating 53

solubility 12.22.32.35.3 6.37.42 solvent 4.6.30.3 1,32,33.34.37,45.

T

tailor-made admixtures 5.25,29

53 -mixed 31.32 stationary coprecipitation 39 steric arrangement 25

temperature 4.8.36,37,41.43,53

V

viscosity 11,23.30

structure 11,16,21,23.25,29,31,32, 36.41.43 supersaturation 4,9,10,12,14,20,2 1, 22

W

washing 43,53.54 well fitting position 28