[Jaroslav nyvlt, joachim_ulrich]_admixtures_in_cry(book_zz.org)

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

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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

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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 detec-

table 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 to helpful models soon.

The authors want to contribute by gathering every piece of informa-

tion 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

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

2. Classification of Admixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

3. Influence of Admixtures on Nucleation . . . . . . . . . . . . . . . . . . . 9

3.1. Homogeneous Nucleation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3.2. Heterogeneous Nucleation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

3.3. Secondary Nucleation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

4. Influence of Admixtures on Crystal Growth . . . . . . . . . . . . . . . 16

4.1. The Role of the Solid Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

4.2. 22 The Role of the Interphase Solid - Liquid . . . . . . . . . . . . . . . . . . . .

5. Influence of Admixtures on Crystal Shape . . . . . . . . . . . . . . . . 24

6. Influence of Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

7. Distribution of Admixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

7.1. Solid Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

7.2. Isomorphous Inclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

7.3. Anomalous Mixed Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

7.4. Adsorption Inclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

7.5. Mechanism of Internal Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 43

7.6. Mechanical Inclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

7.7. Materials Balance for Crystallization in Presence of Impurities . . . 45

7.8. Cascade Purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 1

Contents 3

8 . Notations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

9 . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

10 . Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

Formula Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273

11 . References to Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287

12 . SubjectIndex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389

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 sti l l 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 sti l l limited.

Although the literature on crystallization in the presence of admix-

tures is very extensive, most papers exhibit just an 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. Matz 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 in 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


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 concen-

trations. Crystallization itself therefore proceeds in a multicomponent

system and the result may be affected by these foreign substances - ad-

mixtures.

An admixture may be defined I301 as a substance present in a crys-

tallizing system that itself doesn’t precipitate as a separated solid under

given conditions. Such a broad definition comprises the solvent as an

admixture as 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. Addi-

tives employed for aqueous solutions can be subdivided into several groups:

a) nee 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+, as well as certain anions like W0,2-. PO,3-. Very low

concentrations of these additives are sufficient to 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. I t has been observed

I461 that 1 molecule of such an 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 at

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 an admixture is closely bound to the given sys-

tem 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 as 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


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 as the interfacial surface tension, asl decreases. As the sur-

factants 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 cor-

responds 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 ad-

mixture 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 explai-

ned thus: due to the geometric similarity of the active ion and the surface

3.1. Homogeneous Nucleation 1 1

structure of the macrocomponent. polyphosphate ions are adsorbed on the

surface of undercritical embryi of the macrocomponent so that these clus-

ters cannot continue to grow (33.55.1891. The static adsorption model as-

sumes 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 so 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 sta-

bility 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 sub-

stance. This would lead to an increase in nucleation rate proportional to the

additive concentration.

The heterogeneous nucleation can be treated as secondary nuclea-

tion 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 as new nuclei [6 1.1401.

Active inorganic admixtures dilate the metastable zone in super-

saturated 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 advanta-

geous 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 on 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 at high concentration. Incorporation of the ad-

mixture 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]).



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 so

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 so

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 17

surface: a) frcct surfaces. which are atomically smooth: b) 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. Never-

theless. 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 on 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 an in-

crease 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 an 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 an

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 re-

tardation of growth takes place only if the height of the adsorbed particle

can be compared with that of the moving step 1461. Some inorganic admix-

tures 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 but 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, but 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 Wl 1' = 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

130.1 121.

Another model is based on a n estimate of the probability of occur-

rence of free growth active sites and uses the Freundlich adsorption iso-

therm to predict the movement rate of a growth step 14,661. All of the

models mentioned above have been experlmentally verified with a satisfac-

tory result [53]. A survey of adsorption models is given in several papers

153.55.58.1 121.

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

kTS 21, =- (4.3)

4.1. The Role of Solid S@me 21

where a is the lattice constant, o the surface energy and S relative super-

saturation. 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 macrocom-

ponent forming an average heteronucleus.

Su.@atants and organic dyesbgs 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 an 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 ad-

sorption 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 as 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 at 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 on 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 at higher

concentrations. It has been shown 11 131 that even small amounts of surface

active substances can dramatically raise I1 13.1181 or decrease I1 191 the

viscosity.



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, as well as

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. so 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 dif-

ferent crystal surfaces [82], selectlue adsorption of individual admixtures

occurs on the most favoured ones [ 11.31.35.163.195]. I t 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 as 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 a = 0.595 nm. b - 1.056 nm, c - 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 27

(100) corresponds to (a+c)/2 - (0.77 + 0.59)/2 - 0.68 nm or 0.34 nm per

molecule

(001) corresponds to (a+b)/2 - (1.06+ 0.59)/2 - 0.82 nm or 0.41 nm per

molecule

(010) corresponds to @+c)/2 - (1.06 + 0.77) /2 - 0.91 nm or 0.46 nm per

molecule

The mean for (110) planes is (h2 + k2 + l2)-l i2 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 Difference %

0.61 1 (1 10) 0.58 4.9

(100) 0.68 9.3

(001) 0.82 34.0

(0 101 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 sub-

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 an adsorbed additive, we try to find a well

fitting position of the admixture on the surface. A well fitting position is

characterized as a position, where the additive has as much ease to build

attractive interactions to the surface as possible. One possibility is to make

these fi ts with a computer program. If we find an additive. which has a well

fitting position on one specific face of the crystal. we may expect it will be

an 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 effec-

tiveness of the admixture. Ions present In the interphase accelerate the

orientation of nuclei or clusters, prevent their agglomeration and thus con-

tribute 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 as 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 so

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 ad-

mixture 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. As 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" addlti-

ues 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 (45,601 with knowledge of the

stereochemisb$ and structure of the substrate crystal. In particular.

existing studies have relied on hydrogen bonding and chirality as powerful

recognition factors.



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-dimen-

sionally on the surface before being integrated into the crystal lattice I1 121.

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 low-

index 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 3 1

zation behaviour of the macrocomponent 12301. Hydrogen bonding fre-

quently 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 sol-

vents that form a hydrogen bond with polar faces of the crystal reduce

growth rate of that face, thus increasing its relative area: conversely, non-

polar 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 an alternative solvent. An example of a

solvent enabling laboratory investigation of the polarity effect is an

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

[ 1 12.1781. Precise values of a cannot be determined, but 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 nu-

cleation limited growth from aqueous solution and surface integration

controlled growth from mixed solvents [ 1511. Interfacial structures of crys-

tals 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-f bonds between liquid specles and s-f bond

between solid and liquid species, then in formation of an s-f bond. an s-s

and an frf bond must be broken. The energy contribution is given by [ 1781

The surface entropy factor is then

or

a = 4 ~ / k T

a = Y(AH '+AW) /RT

(6.2)

(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 -xs) . (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 3.2 5 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 incor-

poration and the surface is very rough.

This approach can eventually lead to methods of choosing optimal solvents.



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 radio-

isotopes, led in recent years to 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 3 5

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 \ \ I immiscible in s.lid

I \ \ B I I \ solid solution

S - 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 admix-

ture relative to that upon binding the macrocomponent 181. 7Yu.e solid soh-

tions, 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 sub-

stitution in lattice centres - so they must have an 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 solu-

tions 139.87.1 12,1901: the most frequent equations are

InK, =in[:]=>(---) AH' 1 1 R 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 micro-

impurities 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 in-

corporation I1 38.14 1,166,17 11:

Doerner and Hoskins I641 assume that an 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 so that equilibrium is established. they

derived the so-called logmtthrnic disMbution law

log- X O = R log- Y O

x o - x Y o - Y (7.2)


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 ho-

mogeneous dIsMbution law holds [92.103,106.117.190~ in the form

X Y - - - D- x o - x Y o - Y

(7.31

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 < 1 it is

depleted, compared with the microcomponent contained in the solution.

A general solution of the distribution law [99.138.141.154.1911

originates from a general form of the equation

d x - = R ( x , y) . f ( a ) dY

(7.4)

where x and y are amounts of the micro- and macrocomponent in crystals, 12

k y ) is the differential distribution coefficient in time t andflcJ is the ad-

mixture concentration in the interphase. The shape of the function above is

determined by the relation between the rates of three subsequent steps: a)

transport of the microcomponent from the bulk of solution to the crystal

(uR), b) passage of the admixture through the interphase (up) and c) trans-

port of the admixture through the solid phase (vT). For very different rates

simple solutions can be found:

1) Kinetic reglme where uR s up s uT -0: intensive stirring and diifusion

guarantee a regular distribution of the admixture in solution so that NcA - c

. If the concentrations of the admixture and of the macrocomponent remain

constant, statlonary copreclpltation is described by the equation

X - = js4.c Y

(7.5)


If the concentration of the macrocomponent remains constant whereas the

concentration of the admixture decreases (semistatbnary copreclpitatfon), an

exponential equation 123 11 is obtained

X

x o - = 1 - expCf(n,y)]

Finally, if both the concentrations of components change during the crys-

tallization (non-statbnury precipitation). one obtains the logarithmic distri-

bution law derived by Doerner and Hoskins (641.

2) Di_oirsional regime is characterized by the condition up >> uR >> uT -0.

Detailed analysis of this case 1391 confirmed that a homogeneous distri-

bution 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 statio-

nary 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 micro-

component 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 macro-

component nor that of the microcomponent is constant, complicated ex-

7.3. Anomalous Mived Crystals 4 1

pressions are obtained that can be solved for the condition of a very slow

crystallization; applying several simplifications. both equations for homo-

geneous and logarithmic distribution can be obtained: this explains, why

the logarithmic distribution has been found in several cases where the ex-

perimental 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 mi-

cro- and macrocomponent are not isomorphous owing to their chemical

nature and crystal structure parameters. The ions must have a similar

diameter but their charges must be different (e.g., Bas04 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 crys-

tals. 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, syncrys-

tallization 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]. I t 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 43

is decisive. Adsorption of positively charged ions of the admixture can oc-

cur on a neutral or even on an also positively charged surface [155]. how-

ever. 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 charac-

terized 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 distri-

bution 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 occur-

ring on the internal crystal surface, closely connected with various defects

in crystal structure like breaches or microcavities formed in the block


structure of real crystals. Admixtures trapped at such sites I2001 are cove-

red by new crystal layers so that they cannot be removed by washing with-

out 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 sub-

stances 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 Crystallization in 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 an 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


crystallization and separation unit

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

11731. A simple block diagram of the

mcr Wor

mcl W O l - = D1f- (7.8)

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 47

I vapour recyc I e

product si 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:

recycled mother liquor total mother liquor

R = (7.11)

48 7. DLstribution of admixtures

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 to the liquid content withdrawn with the

crystals wco (from the top) 0.20, 0.10, 0.05 and 0.01, respec-

tively


4 2.5

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:

6 ... 1.0 1 ... 0.005, 2 ... 0.01, 3 ... 0.05, 4 ... 0.1, 5 ... 0.5,

7.8. Cascade M i a t i o n 5 1

7.8. Cascade Purification

Crystal contamination can arise from a number of causes. This is an

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)

Y O Y' Wf - - (Wf - weq)- 1-yo 1 - yi X =

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

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


t ,,,k-I l c

m k t l sol

x k + l Q

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 53

m, Yo + mL X o + mso, Xn+' = m, Y n + m, X" + mso, X' (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 = Y k / Y o (7.17)

and the recrystallization factor WW ~- Ww WL-

m d m c - W L - W ~ 1 - w ~ ~ ~ K = - WLWeq

kH+---- 1 - WLWeq

kH +mL I me

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 ) - K

(7.18)

(7.19)

(7.20)

(7.21)

54 7 . Distribution of Admixtures

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

The original salt contained yo - 1.3 Na. After crystallization the Na content

dropped to 2 . lo-* Na. The respective solubilities are w1 - w (60) - 0.5585 , weq - w (20) - 0.1127. The distribution coefficient found in independent experiments was

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

WL - 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

Zy - 0.0208

9.” - 0.0032 < 0.01

The required purification can thus be achieved in three stages.

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

flow model with the result that this model requires higher solvent con-

sumptlon 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 compo-

nent. 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.



8. Notations

A

a

B

C

D

K

KB

k

k

n

n

P

R

R

S

surface area

lattice constant

constant

concentration

homogeneous distribution coefficient

enthalpy of fusion

enthalpy of mixing

recrystallization factor

distribution coefficient

k-th stage

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

total number of stages

average density of the admlxture on a surface

concentration (wt. %)

gas constant

recycling ratio

relative supersaturation

56 8. Notatlons

-T

TB

UR

UP

UT

W

X

X

Y

Y

z

a

6

R

P C

0

a

temperature

melting point of the impurity

mass transport rate in the bulk of solution

mass transport rate through the interface

mass transport rate in the solid phase

concentration (mass fraction)

relative mass of microcomponent in liquid phase

mole fraction of microcomponent

relative mass of microcomponent in solid phase

mole fraction of the macrocomponent

dimensionless concentration parameter

surface entropy factor

energy

logarithmic distribution coefficient

crystal density

surface energy

ratio of number of nearest neighbours



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[ l66] Novobilsky. V.. N@lt. J., Jager. L.: Chem. prfimysl 18 (1968) 14

[ 1671 Novobilsky. V.. N@lt. J,.. JBger. L.: Chem. prfimysl 18 (1968) 180;

ibid. 459

9. References 69

I1681 N j v l t , J.: Chem. prhmysl 12 (1962) 170

[ 1691 Njvlt, J.: IndusLTLal Crystallizationfrom solutions. Butterworth. London

1971

11701 Njvlt. J.: Chem. prhmysl29 (1979) 238

[ 1711 Nyvlt, J.: Solid - Lquid Phase Equilibria, Elsevier Amsterdam and

Academia Prague 1977

[ 1721 Njvlt. J.: Industrial Crystallization - Me Present State of the Art.

2nd. ed.. Verlag Chemie, Weinheim 1982

I1731 Njvl t . J.. Broul, M.: Chem. p r ~ m y s l 27 (1977) 597

I1741 Njvlt . J.. Eysseltovh, J.: Collect. Czech Chem. Commun. 59 (1994)

191 1

[175] Njvl t . J.. Gotffried, J.: Collect. Czech. Chem. Commun. 32 (1967)

3459

[ 1761 N j v l t , J., Gotffried. J., KilCkova. J.:Chem. prhmysl 14 (1964) 242

I1771 Njvl t . J.. Gottfried. J., KflEkova., J . : Collect. Czech. Chem.

Commun. 29 (1964) 2283

[ 1781 Njvlt . J., Sdhnel. 0.. MatuchovB. M.. Broul, M.: The Kinetics of

Industrial Crystallization, Elsevier Amsterdam and Academia Prague

1985

[ 1791 Ohara, M., Reid, R.C.: Modeling Crystal GrowthRatesfrom Solution.

Prentice Hall, Englewood Cliffs, N.J. 1973

I1801 Otant, S.: Bull. Chem. SOC. J a p a n 33 (1960) 1549

[ 18 11 ozoguz, Y: Zur Schichtkristalllsatn als SchmeIzkristalllsatio~ve~a~en,

Thesis. Unlv. Bremen 1991, VDI Verlag. Diisseldorf 1992

70 9. References

[ 1821 Paneth. F.: Radio-Elements as Indicators. New York 1928

[ 1831 Panov, V.I., Novikov. A.N., Prisyazhniuk, V.A.: Promyshlennaya

KristalUzatsia, Rudy MOKHLM 20 (1969) 72

11841 Potapenko. S.Yu.: Poverkhnost 8 (1988) 28

[185] Potapenko, S. Yu.: Rost Krist. 18 (1990) 31

[I861 Potapenko. S.Yu.: J. Crystal Growth 133 (1-2) (1993) 141

(1871 Potapenko. S.Yu.: J. Crystal Growth 133 (1-2) (1993) 147

11881 Powers, H.E.C.: Ind. Chemist 39 (1963) 351

[ 1891 Raistrick. B.: Disc. Faraday SOC. 5 (1949) 234

(1901 Ratner, A.P.: J. Chem. Phys. 1 (1933) 789

(1911 Riehl. N.. Kading. H.: 2. Physik. Chem. A 149 (1930) 180

11921 Rosenstein. L.: USP 2 038 316 (1936)

[193] Royer. L.: Bull. SOC. Franc. Mineral. 51 (1928) 7

11941 Sander, L.M.: in: Kinetics ofAggregatlon and Gelation, (eds. Landau,

D.P.. Family, F.). p.13. North-Holland, Amsterdam 1984

11951 Sangwal. K.. Owczarek. I.: J. Crystal Growth 129 13-41 (1993) 640

11961 Sarig. S., Ginio, 0.: J. Phys. Chem. 80 (1976) 256

I1 971 Scholz. R.: Die Schichtkristallisation als thermisches Trennuerfahren,

Thesis, Univ. Bremen 1993. VDI Verlag, Dfisseldorf 1993

[ 1981 Sears, G.W.: J. Chem. Phys. 29 (1958) 1045

(1991 Sears, G.W.: J. Chem. Phys. 33 (1960) 1068

(2001 Senol. D.. Myerson, A.S.: AICHE Symp. Ser. 78 (215) (1982) 37

12011 Sheftal. N.N.: Rost kristallov 1 (1957) 5

9. References 7 1

[202] Sheftal, N.N.: Protsessy Realnogo Kristalloobraz. 101 (1977); CA 91

047479

I2031 Shor. S.M.: Thesis. Iowa State Univ., Ames. Iowa 1970

I2041 Shor, S.M.. Larson. M.A.: Chem. Eng. Progr., Symp. Ser. 67

(110) (1971) 32

12051 Simon. B., Boistelle. R.: Crystal Growth from Low-Temperature

Solutions, ZCCG-6, Moscow 1980

12061 Slavnova, E.N.: Rost kristallov 2 (1959) 223

12071 van der Sluls. S . . Witkamp, G.J., van Rosmalen, G.M.: J. Crystal

Growth 70 (1 986) 620

12081 Spangenberg, K.: Z Krist. 59 (1924) 383

12091 Stelnike. U.: Krls ta l l u. Technik 6 (1971) 7

12 101 Stepanski. M.: Zur Wachstumskinetik in der LlfsungskristaUisation.

Thesis, Univ. Bremen 1990

I2 1 11 Stepin, B.D.. Gorshtein. I.G.. Blyum, G.Z., Kudryumov, G.M..

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ueshchesiu. Khlmia, Leningrad 1969

I2121 Stranski. I.N.: 2. Physik. Chem. B11 (1931) 342

I2131 Stranski. I.N.: Naturwiss. 19 (1931) 689

(2 141 Strickland-Constable, R.F.: Ktnetics and mechanism of crystafiation,

Acad. Press, London 1968

I2151 Strickland-Constable, R.P.: AIChE, Symp. Ser. 121 (1972) 1

12161 Sung, C.Y.. Estrin. J.. Youngquist. G.R.: AIChE J. 19 (1973) 957

72 9. References

12171 Tadros, M.E.. Mayes. I.: J. Colloid Interface Sci. 72 (19791 245

[2 181 Temkin. D.E.: in: CystalUzatIon Processes. p. 15. Consultants Bureau,

New York 1964

12191 Terkhin. S.N. . Zherebovich. A.S.. Volkova. N.A.: Vysokochlst.

Veshchestva 1 (1989) 20

12201 Thomson. G.: Proc. Phys. Soc. 61 (19481 403

I2211 Tiller, W.A.: J. Crystal Growth 75 (1) (1986) 132

[222] Tilmans. Yu. Ya.: KristaUizatsiya Solei iz Vodnykh Rastoorov v Prisutstvii

PrimeseiRaznykhZonov, Izd. AN Kirg. SSR. Frunze 1957

[223] Titiloye, J.O., Parker, S.C., Dsuguthorpe, D.J.. et al.: J. Chem. Soc..

Chem. Commun. 20 (1991) 1494

12241 Treivus. E.B.: Kristallografiya 27 (1) (1982) 165

12251 Ulrich. J.: Zur Kristallkeimbildung durch mechanischen Abrieb, Thesis,

RWTH Aachen 1981

(2261 Ulrich, J.: Kristallwachsturnsgeschwfndigkeiten bei der KomkristaUisa-

tion. Einfihrl ikn und Mepechniken. Reihe Verfahrenstechnik,

Shaker, Aachen 1993

(2271 Ulrich, J., Kallies. B.: Developments in crystallization processes from

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Trends, Trivandrum (India) (1994)

12281 Ulrich. J.: Chem.-1ng.-Tech. 66 (1994) 1341

[229] Ulrich. J., Scholz. R.. Wangnick. K.: J. Phys. D: Appl. Phys. 26 (1993)

B168

9. References 73

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

12311 Walter, L.. Schlundt, N.: J. Am. Chem. SOC. 50 (1927) 3266

1232) Wang. J.L., Berkovltch-Yellin, 2.. Leiserowitz. L.: Acta Cryst. B41

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

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1994

12341 Weijnen. M.P.C.. van Rosmalen. G.M.. Bennema, P.: J. Crystal

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[235] Weissbuch. I.. Shlmon. L.J.W.. Addadi. L.. Berkovitch-Yellin, 2..

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353

12361 Weissbuch. I., Shimon, L.J.W., Landau, E.M., Popovitz-Biro. R..

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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

(2391 Wen, 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

(2411 Whetstone, 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

[2431 Yanson, Yu. A., Stekol'nikov. A.V.: Teplofiz. Krist. Veshch.1 mater.,

Novosibirsk (1987) 66

[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



Crystal system

cubic

tetragonal

hexagonal

trigonal

rhombic

monoclinic

triclinic

10. Tables

Characteristics

a - b - c . a-B- t . -90°

a - b s c , a - / j - = y - 9 0 °

a l - a 2 = a 3 s c , a - ? - 9 0 0

a - b - c , a-b-y t :9O0

a s b g c , a - , 6 - r - 9 0 °

a s b s c , a - y - 9 0 ° / i s 9 0 °

a L b sc , a ,/1 ,y s 90°

I t 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.

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].

78 10. Tables

t MBr SILVER BROMIDE Molecular weight: 187.80

System: cubic

a - 0.5755

Admixture

3D-, 4D-element complexes

Cd2+

K+

NH, . KBr

NH,OH 10Y0. pyridine

Pb2+

Pb2+. Cd2+

solvation

I- and gelatine

pH

p H . I-

dyes tuffs

Methylene blue

S-containing agent

surfactants

urea, tetraalkylammonium salts,

gelatine, Methylene blue

Density: 0470

Z = 4

Effect

D

coagulation

H

favourable

lower S and recryst. rate

G

H

H

G . H

H

Reference

I8911

17 12,13 131

15651

I11191

14721

[109,110.111]

I2581

12581

12561

(257,2591

12581

[ 10921

I4391

[ 13831

18491

I2581

10. Tables 79

4m SILVER CHLORIDE Molecular weight: 143.34

System: cubic

a - 0.5545

Density: 5660

2 - 4

Admixture

Ac/Cl ratio

3D-. 4D-element complexes

HgCI, 0.005-0.25%

NH,OH, pyridlne

C1-. CH,COOH. pH

benzvlalcohol

dyestuffs

Methylene blue

Na-dodecylsulphonate. benzylal-

Na-dodecylsulphonate, eosfne

polyvinylalcohol

S-containic agent

surfactants

Effect

G

G

favourable

favourable

G

H

G

G

G

Reference

12931

I8911

18 11

14723

I6661

12631

I10921

I4391

16041

I2941

19933

I13831

18491

80 10. Tables

Admixture

&2cr04

SILVER CHROMATE

Effect

Molecular weinht: 331.77

Ag+/ Cr0,2- ratio

glutamate, cltrate, tartrate,

G 15633

N I10151

Reference

&I

SILVER IODIDE Molecular weight: 234.79

System: cubic

a - 0.647

Admixture

Mg2+

Na'. I-

3D- . 4D-element complexes

Methylene blue, sodium dodecyl-

sulphate

surfactants

surfactants

surfactants

surfactants

Density: 6670

2 - 4

Effect

recryst.

G

H

N

S

Reference

I6091

I1 2791

I89 11

I1 3321

1303.369.3701

13021

I30 1.13 151

18491

AgNOS

SILVER NITRATE

Molecular weight: 153.874 Density: 4350

System: rhombic 2 - 8

E - 0.697 b - 0.734 c - 1.014

Admixture Effect Reference

ethylene glycol IN I I12371

- Admixture Effect Reference

AlC~(S0412 * 12 H2O

ALUMINIUM CESIUM SULPHATE dodecahydrate


System: cubic I a - 1.2363

2 - 4

Bismarck brown, dyestuffs H - cube 117871

82 10. Tables

Admixture

AlCl, 6 HZO

ALUMINIUM CHLORIDE hexahydrate


System: hexagonal 2 1 6

a - 1.1827 c - 1.1895

Effect Reference

Admixture

H F

~ 0 ~ 3 -

surfactants

electrolytes I G I 1551.5521 I I

Effect Reference

N 16451

1759,8261

1120.12 11

electrolytes I D I 15531

Ale, 3 HZO

ALUMINIUM FLUORIDE trihydrate

Molecular weight: 138.022

System: tetragonal 2 1 2

a - 0.7734 c - 0.3665

10. Tables 83

AlK(SO& 12 HZO

ALUMINIUM POTASSIUM SULPHATE dodecahydrate I Molecular weight: 474.377

System: cubic

a - 1.2130

Admixture

Ag', Cd2+, Au3+. Cu2+

N3+. Fe3+

cationic admixtures

Cr3+

Cr3+

Fe2+

KC1. KBr, KI. (NH,),SO,. NaC1,

NaBr. NaNO,

Na,B,O,

Na,CO,

Na,SO,. CuSO,, H2S04, KOH,

Na,B,O,, NaOH

NH4+, T1'

rare earth elements

admixtures

Density: 1760

2- 4

Reference

retard N. not G

salting out, purification

G

G. dissolution

G

H, G reduces growth

H - cubeloctahedron

G

D

D

12991

14531

16221

19231

[1500.1502]

16231

17251

192.14891

I891

I10511

1581

16141

(1187,141 11

139,684,685,

725.951

84 1O.Tables

UK(S04)2. 12 HZ0

continued)

Admixture

admixtures

admixtures

admixtures

HCl

Bismarck brown

Bismarck brown

Bismarck brown

Diamine sky blue

Direct blue 3B

Metanil yellow, Brilliant Congo

red. Bordeaux blue, Orange 1 and

other dyestuffs

methanol, ethanol

methanol, ethanol, propanol

polyvinylalcohol

Qulnollne yellow

saccharides, dyestuffs

H I +--- H - face /210/

I,,,

Reference

[ 10521

110511

1921

11 141

1198.7873

[4731

I13071

18961

[ 10521

[2 13.2 151

[1510.15111

I 14001

11041

[ 11331

10. Tables 85

Admixture

Cr3+, Fe3+, K+. TI+

Fe3+, Fez+, Mn2+, Zn2+

K+

Na,CO,

NaCl

NH,Fe(SO,l,

NH,Fe(SO,),. NaC1. H,SO,

admixtures

admixtures

Oxamine blue B. Diamine sky blue

AlNH,(SO,), . 12 HZO

ALUMINIUM AMMONIUM SULPHATE dodecahydrate

Effect Reference

D 1581

D I4931

D [ 1500,15021

H - cube/octahedron I891

D - C1- 18571

D - Fe3+ (8571

D - Fe3+ [4873

D I 1 187.74.10541

S I 13931

H - face / l o o / 1215,7873


System: cubic

a - 1.2220

Density: 1640

Z = 4

86 10. Tables

Al(N03), - 9 H 2 0

ALUMINIUM NITRATE nonahydrate


System: monoclinic * Admixture Effect

alkali metals + HNO,

Also3 M,O n SiO, m H 2 0 I ZEOLITES

Reference

12831


NaOH

propyl-substttuted amines

surfactant

triethanolamine

N. G 19961

N , G 18981

11011

111931

1O.Tables 87

I3 - 85O26’ ~~~~ ~~~~~~~

Effect

N inhibition

H - pseudoboehmite

S. defects

D. solub.

G

G

G , N S

modif.

N

Density: 2420

2 - 8

c - 0.9699

Reference

1681

I1961

I4091

I5741

I 11851

[ 14491

[360.1390,353]

11441

111781

[ 14071

I 12761

Admixture

co,2-

cu2+

Li+

I,1C1

admixtures

admixtures

admixtures

pH

citrate

oils ; - recryst. I I151 I8281

88 10. Tables

Admixture

admixtures

KF, NaOH

Effect Reference

H 12261

[ 10491

HC1. HNO, I 1 [ 10491

Admixture

Diamine Sky blue FF

AlRb(S04), 12 H20

ALUMINIUM RUBIDIUM SULPHATE dodecahydrate


System: cubic 2 - 4

B = 1.2246

Effect Reference

H - /loo/ 12 151

10. Tables 89

Admixture

AlTl(S04)2 12 H 2 0

ALUMINIUM THALLIUM SULPHATE dodecahydrate


System: cubic 2 9 4

a = 1.221

Effect Reference

Admixture

K,SO,

Al2(SO& . 10 H2O

ALUMINIUM SULPHATE hexadecahydrate


System: rhombic

Effect Reference

N, H [ 14931

90 10. Tables

Admixture

NaCl

Ba(BO2l2

BARIUM BORATE

Effect Reference

G I1451

Admixture

BaBr, - 2 H 2 0

BARIUM BROMIDE dihydrate


Syetem: monoclinic 2 = 4

a - 1.0449 b - 0.7204 c - 0.8385

- 113O29' ~ ~~~ ~ ~~

Effect Reference

10. Tables 91

BaC20,

BARIUM OXALATE

BaCO,

BARIUM CARBONATE


System: rhombic

a - 0.529 b * 0.888


Density: 4350

2 = 4

c - 0.641

Admixture

Ce4+, Th4+

Admixture

Effect Reference

D 12251

pH

polyglutamic acid, polyvinylsul-

phonate

polyglutamlc acid. polyvinylsul-

phonate

G [ 11651

11 1671

Ra(COO), I [lo651

92 1O.Tables

Admixture

Mn2+. Co2+, N@+, c$+ Mn2+, Co2+, N12+, Cu2+, Na+

RaC1,

admixtures

BaC12 2 H 2 0

BARIUM CHLORIDE dihydrate


System: monoclinic 2 - 4

L - 0.6738 b - 1.0860 c - 0.7136

3 - 90°67'

Effect Reference

G

G. N. H [1254]

D

N

13743

I50 9.66 51

I5281

(C$35)$JI

TETRAETHYLAMMONIUM IODIDE



solvents H, G D321

I

10. Tables 93

BaCrO,

BARIUM CHROMATE Molecular weight: 253.33

System: rhombic

Density: 4498

I Admixture

Ce3+. Sr2+, pH, EDTA

RaCrO, I RaCrO,

RaCrO, + HNO,

Sr2+

pH

pH

CH2COONH4

EDTA

gluconate, tartrate, citrate.

glutamate. EDTA

Effect

D - Ce3+. Sr2+

D decreases with tempera-

ture rise

D - mixed crystals

D - Ra2+

D - Sr2+

G. H. S

N

G. H. S

N

Reference

1971 .- - . I8821

[ 10651

16651

1951

1961

[lo141

1951

1961

[lo151

94 10. Tables

Admixttlre

Fe2". Fe3+

polyphosphonates

BaF2

BARIUM FLUORIDE Molecular weight: 175.36

System: cubic

a - 0.6184

Effect Reference

D 11 1801

dissol. I5 171

Density: 4830

2 - 4

Admixture

Ra(IO&

Effect Reference

D - mixed crystals [lo651

10. Tables 95

Ba(NO&

BARIUM NITRATE Molecular weight: 261 . S O

Syetern: cubic

a - 0.8110

Density: 3222

2 - 4

AdmiXilWe

inorg. a d d i t i v e s

MnO;, Fe(CNIe4-. Fe(CN),3-

Ni(NO,I,. Fe(NO,),, HNO,. LiNO,

NP+

N12+. Fe3+. Li+

pH

amine

Methylene blue

Methylene blue

Effect

H - /loo/ + /lOl/ + /210/

N. G

N

D

G , H - / loo/ +/810/

D

Reference

[ 10421

12001

16571

I6431

[lo411

18611

1663,665,

10841

[ 13391

16431

12001

96 10. Tables

1 Admixture

Methylene blue

Methylene blue

Methylene blue, Malachite green

New blue

quinine nitrate

Effect

D. H - cube

G. H. D

H

N

H - / l o o /

H - tetraeder

Reference

[43 1.432.437.

438.44 1.442,

961,1402,

14221

11238.12391

I6421

16431

I2 151

12001

Ba(OH), 8 H 2 0

BARIUM HYDROXIDE octahydrate Molecular weight: 315.476 Density: 2180

Syetem: monoclinic 2 - 4

n - 0.9350 b - 0.9280 c - 1.1870


C1- 0.5 Yo S

10.Tables 97

N, G

~ ~~ ~~ ~ ~~

BaSO,

BARIUM SULPHATE



a - 0.885 b - 0.644 c - 0.713

[ 11051

Admixture

D - mixed crystals

H - spheric crystals

I Effect I Reference

1504,14231

19021

additives, Ba2+/S0,2- ratio

K+

D

D

D - logar. distr.

D

D

D

H - regular rounded cryst.

G. dissol.

K+. C1-

17031

111761

13101

[6651

194,7763

[ 12921

18461

18131

KMnO,

N a citrate

Na+ . K+

D

Pb2+

18681

Pb2+. Sr2+

S . H

N. G

RaSO A

13441

1794.7951

RaSO, + H N 0 3

Sr2+

Th4+

admixtures

admixtures

admixtures

admixtures

admixtures

S 18151 I I

98 10.Tables

BaSO,

I Admixture

HQSO,

pH

pH - 12.3

gelatine + pH

inhibitor

nitrilomethylenephosphonate

DhosDhonate

polycarboxylic acids. polyphos-

Effect

G accel.

H . S

S

G - maximum growth rate

G, scales

G

N

agglomeration. S

G

G retard.

G, N

N

Reference

[ 11051

I 14241

[7601

18631

I14651

11127,11281

14201

[ 10641

17971

[ 186.796.1 1261

[ 11051

[805]

17981

19731

I3271

1O.Tables 99

Admixture

(NaPO,),

(NH4),S04

BaCI,

Ca2+. OH-

Ca2+ / c 0 ?2- ratio

Fe2+. Fe3+

CaCO,

CALCIUM CARBONATE - calcite Molecular weight: 100.09 Density: 2710

System: trigonal 2 - 2

a 9 0.6361

-

Effect

S

N. G

H

H

G


System: rhombic

a - 0.494 b = 0.794

Density: 2930

z = 4

c ~0 .572

CALCIUM CARBONATE - vaterite Molecular weight: 100.09

System: hexagonal 2 - 2

a - 0.4120 c - 0.8556 ~~ ~

Reference

110301

[ 14293

[ 14341

I8511

1668,6901

15291

100 10. Tables

I CaCO, I (continued)

I Admixture

KHVPO,

Mg2+

Mg2+

Mg2+

Mg2+

Mg2+

Mg2+

Mg2+. Mn2+. Cr3+, Ni2+

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

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

Mg2+, Sr2+, Ba2+, Pb2+

G

lnhibition

polymorph.

D. N

G

transformation

N.G

G. H

modlf.

G

N - inhibited nucleation ol

calcite

G, H

H

Reference

1560.56 11

[ 10881

[998.13301

Ill811

131 1.348.562,

1088l

[611,630,6941

110311

I10681

[ 12591

11 1301

17491

[ 119,5051

I12591

[ 14341

113851

1O.Tables 101

CaCO, I (continued)

I Admixture

NH4+

NH,C1

NH4NOq

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

Sr2+

Sr2+

Sr2+, Ba2+, Pb2+

uo,2+

Zn2+

Zn2+

admixtures

admixtures

admixtures

admixtures

admixtures

Effect

N - stabilized supersatura-

tlon

modif.

G

N - low scale formation

N

H

D - aragonite/calcite

D

modif.

modif.

D

N. D

D, H - aragonite

H, G - aragonite

Reference

I4231

[2181

I12581

I2461

13661

[6891

1674.7 101

[1503]

[ 14661

11 164.13 111

I13481

I4791

16731

[ 11481

I6101

[ 14261

(503,8841

[ 10301

102 10. Tables

CaCO, I (continued)

I Admixture

hexametaphosphate. pyro-

phosphate

hexametaphosphate.

pyrophosphate. dihydrogenphos-

phate. borate, tetraborate,

vanadate

inhibitor

inhibitor

lanthanides, Cd2+

metaphosphates N a

oxalate

aH

pH

DhosDhates

Pod3-

S042-

tripolyphosphate, surfactants

acetate, gluconate. EDTA. tripoly-

phosphate

Effect

modif.

G

scale

G. D

N - stabilized supersat.

G inhib.

N. G

H

G inhib.

modif.

N

G. N

Reference

“2181

110931

I63 11

[ 13331

114151

[lo721

[4701

[ 11861

[682]

1903.9761

15601

11 2361

[ 140 11

13 11,3481

110171

10. Tables 103

CaCOs

(continued) c albumine

benzenepolycarboxylic acid

citrate, stearic acid

Congo red, other dyestuffs

fatty acid

gluconate. borogluconate. tartrate,

polyacrylate

glycerophosphate. PO,3-

organic colloids

organic polymers

organophosphonic acid

phenol. resorcinol, hydroquinone

phosphonates

phosphonates

polyethylene oxide

polyglutamic acid, polyvinylsul-

Dhonate

polyglutamic acid,

DolwinvlsulDhonate

Effect

G

G

G - retardation

G

inhibition G

G

N - low scale formation

G

G

Reference

[ 12461

1251

I1 0681

I7141

I491

I14141

[ 10861

[lo121

[1406]

[ 10481

12461

1 187,10871

I10871

I3941

[ 11651

[ 11671

104 10. Tables

Admixture

polymers

stearic acid

surface active substances

surfactants

tetrakis(phosphonomethy1)tetra-

azacyclododecane

CaCO,

(continued)

Effect Reference

S 114061

N [829,8301

H [ 14341

modif. [ 1280l

G 114301

~~ ~~ ~ ~~

Admixture

KF

Nb,O,. Ta,O,, Sb,O,, Bi,O,

Ba'NO,

BARIUM TITANATE


System: cubic

R 0.397

Effect Reference

H [ 1416,14171

114211

10. Tables 105

CaC20,. H 2 0

CALCIUM OXALATE monohydrate


N a citrate I Na pyrophosphate

Na,P20,. trlpolyphosphate.

phosphonates. EDTA, KH2P0,.

K,P,O,

admixtures

admixtures

admixtures

admixtures

admixtures

Effect

G

H

G. N

G, aggreg.

N

N. G

inhibition

H

G

N

Reference

[SO 1,802,12833

I4251

I551

11 171

[72.8851

11 1421

[841.994.1142,

12831

173,513.84 1.964.

10991

14191

19651

[ 11731

1511

[499.12343

1413,12961

10 6 10. Tables

1 CaC204 H 2 0 I (continued)

I Admixture

phosphorus derivatives

p o p

% pyrophosphate

pyrophosphate, citrate

pyrophosphate, phosphonate

amino acids

amino acids

amino acids

carboxyglutamic acid

chondroitin sulphate, macro-

molecules

chondroitinsulphate.

j en tosansulphate

citrate

citrate, pyrophosphate

dodecylammonium chloride

dutamic acid

hcparinc, polyglutamic acid

Effect

G

G inhibition

G

N, G

G. aggreg.

transformation

G , transform.

S . G . N

transformation

G

G

G, N

G

G

modif., G. aggreg.

N

[73.419,512,1108,

I4181

I 1681 I

I1 1101 I1 1101 I I161.365.4981

I

L!aC,04 H,O

'continuedl

N. G

G

Admixture

[364.1107,11081

18181

181

15001

I12331

heparine

inhibitors in urine

Methylene blue

p H + adenosine phosphates

phosphonate

phosphonates

Dolvacrvlate N. G

polyacrylic acid

polyacrylic acid, heparin, organic

copolymers

polyhydroxycarboxylic acids

pyrophosphate, Methylene blue

pyrophosphate, Methylene blue

sodium dodecyl sulphate

urea

1269,12831

uric acld

N, G, S

N

inhob.

N

mect I Reference

13 141

I3 141

[ 12981

[6591

11 1721 I 12691

108 10. Tables

7 ~~ ~ ~~

Admixture Effect

CaS04 N - unfavourable. scaling

admixtures G

nucl. catalysts N

polyethylene oxide N

_ _ ~ ~ ~

ZaCl, - 2 H 2 0

ZALCIUM CHLORIDE dihydrate


3ystem: rhombic

L - 0.7190 b - 0.585

Reference

19761

16711

1764,14351

110701

Admixture Effect

Nd3+ G

CaC4H406

CALCIUM TARTRATE

Reference

1461

1O.Tables 109

Effect

D

dissolution

S

CaF,

CALCIUM FLUORIDE

Reference

11 1801

I5 161

I1 0451


system: cubic

i - 0.5451

Admixture

Fe2+, Fe3+

NaCl + additives

polyelectrolytes

~ 0 ~ 3 -

polycarboxyllc acids.

polyphosphates

polyphosphonate

G

Density: 3180

2 - 4

I351

G I641

G I [ 12261 I

Admixture

glucose. arabonate

Effect Reference

I7551

G I34.9421

1 10 10. Tables

CaHP04 2 H,O

CALCIUM HYDROGEN PHOSPHATE dihydrate lYoleeular weight: 172.09

System: trigonal

Admixture

M @2+

Mg2'

Mg2'

Mg2+

Na'. NH.+

SnF,, SnCl,, NaF

F-

I?-

P,O,

pH

pyrophosphate

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

sio

1 carboxvlic acids

chondroitin sulphate. urinary I macromolecules

citrate

di- and trlcarboxylic acids

Density: 2306

Effect

N, G

N

G

N

S

N - retardation

modif.

G

S

H

G, aggregation

Reference

I3621

1946.1 1501

121

I1 1501

I8 171

19471

I54 11

111691

12481

I3991

1844.94 11

11 1751

I12021

11 1101

~~ ~~

[ 10041

11671

10. Tables 111

I

(continued)

1

ICaHPO, 2 H,O

CaHPO, 3/2 H,O

CALCIUM HYDROGEN PHOSPHATE sesquihydrate, BRUSHITE

Molecular weiaht: 163.09

Admixture

organic acid

Admixture

P containing complexons

Effect Reference

polycarboxylic acids

surfactants

tricarbo Uc acid JI urine inhibitors

Effect

H

N. G

Reference I I3291 I

I6921 I I1671 I I4861 I

casein I II6361

112 10. Tables

Admixture Effect

A13+, Fe3+, Mg2+

Mg(N0Jp

NH,NO, lower hygroscopicity

Reference

19151

I4561

I9761

Admixture Effect

Feso,. Ca Salt H

NaC1. NaC10,. KCl G

ethyleneglycol. glycerol H

Reference

15911

I13311

I5911

10. Tables 113

Ca8H2(P0& - 5 H,O

OCTACALCIUMPHOSPHATE



Mg2+ G 11 1501

I

Effect

transform.

transform.

transform.

Ca,(PO,),

TRICALCIUM PHOSPHATE

Reference

112101

16671

11651

I1661


Admixture

Be2+

Mg2+

citrate. pyrophosphate

gelatine

polyacrylic acid

114 10.Tables

Effect Reference

di- and tricarboxylic acids 1261

1321

1301

Admixture Effect

Mg2+

Ca,(P04), CaFz

FLUORAPATITE

Reference

I361

Admixture

organic admixtures

CaS03

CALCIUM SULPHITE

Effect Reference

S 18641

Molecular weieht: 120.15 I

10. Tables 1 15


F

polyphosphates, polycarbaxylic acids

biophosphonic acids

glucose

, hydrolryhydroxyphosphonyl-ethane

Admixture

Zn2+

NaC1. LiCl. NH,Cl. CsCl. HCl

c1-

F

F-

I DH

G

G

G

H

precip. rate

fluorapatite

G

G

G

G

Reference

12781

I7461

1361

1946.11501

12791

19451

I7451

I5411

17441

19 101

1542.8861

I271

19431

12771

I2791

116 10. Tables

Ca3(PO4I2 Ca(OW2


mellitic acid G I241

proteins G I9101

Casios

CALCIUM SILICATE


System: monoclinic

a = 1.531 b = 0.735 c = 0.708

p = 950 25' 1

Admixture Effect

sr2+ D

BaSO,. BaF,. BaCl, N. G

Reference

I1 5031

19241

10. Tables 117

Effect

H

N S

solubility

G

S, G. aggregation

N. D

G . H

N

D

G

S

D

G

~~ ~ ~ ~~

ZaSO, - 2 H20

XLCIUM SULPHATE dihydrate

Reference

114721

I1 1711

112811

I1 5041

12 161

I1 1711

18451

1635,8471

[ 13291

[ 1 1021

I1 1021

114611

[ 14401

14 151

dolecular weight: 172.168

jystem: monoclinic

L = 1.047 b= 1.515

L = 151° 33

Admixture

M3+, Cr3+

~ 1 3 + . F

M3+, Fe3+. Mg2+

A13+. Fe*, SPG2-

A13+, Na maleate

AlF,

AIF,

Ca2+/so42- ratio

Cd2+

Cd2+

Cd2+

CdF,. AlF,

Cu2+. Zn2+

F-modifiers, N3+

Fe3+. Fe2+

Density: 2310

2 = 4

c =0.659

[7351

118 10. Tables

Admixture

H+. Sr2+, Ag+. HSO;. NO3-. Na+ .

OH-

CaSO, - 2 H,O

[continued)

Effect Reference

H 13411

NaCl

NaNO,

NH,, CG+, PO,^-. co,2-, ~ 0 0 ~ 2 -

G 11641

G 114601

G 16081

10. Tables 119

I CaSO, 2 H,O

(continued)

1 HPSOA

HaSO, + H,P04

HQSO,. H,PO,

HqPOA

I Admixture

admixtures

admixtures

admixtures

admixtures

admixtures

admixtures

Cd2++I-. Br-, S1032-

F-. A13+

H3P04

pH

DH

p H

pH

pH, impurities

Effect

G

hvdration. G

H

G. H

N. hydration

scaling

D

S

N, S . G

hydration

G. H

affects hydration

N

G

S. H

G

H. D

Reference I I [ 11981

18 141

I5101

11851

[ 14621

I12291

I4801

B24.98 11

I5081

[ 15041

[ 11841

[ 12491

17181

120 10. Tables

CaS04 2 H,O

[continued)

Admixture

polyelectrolytes

surfactants + HNO, + H,PO,

tripolyphosphate

acrylates

acrylates

alkylbenzenesulfonic acid

aminomethylene phosphonic acid

anionic organic polymers, tri-

polyphosphate

calcium acetate and formiate,

pentaerythritol

carboxylic acids, phosphonates

carboxylic acids, phosphonic acids

citrate

citric acid, tartaric acid, gelatine

citric, succlnic. tartaric, polyacry-

lic. polymethacrylic acid, gelatine

Effect

D

D. S

G

G

H

caking

G

N

precipitation

N. G -accelerate

H, s G. H

S. H

G - retarding

precipitati on

Reference

15761

I5821

1371

114581

1441

I1 1151

112551

Ill20l

111511

I1 2481

1675)

113031

113031

110791

12381

12381

1O.Tables 121

CaS04 - 2 H,O

(continued)

Admixture

gelatine. saponlne

gelatine. sulphite liquor

gelatinc. waste liquor of cellulose

sulphate

gluconate. borogluconate. tartrate

hydroxyethylidenbiphosphonic

acid

hydroxyethylidene. diphosphonic

acid. polycarbonates

hydroxypropylene diamine

impurities, alcohols

naphtenate

organic phosphonates

organophosphonic acid

phosphonates

phosphonates, phosphates, orga-

nic polymers

phosphonic acid, acetate

polyacrylamide

H. S

N. G - retardation

N - retarding

precipitation

G

~

G

N,G

H

N

G

G

N

Reference

[ 1204)

I6751

1255,7371

I14141

[ 11251

[ 1122.14401

[ 11521

I7191

I13971

I326.3281

[ 1155.1 156,

11571

[14391

1311

I 1153,11541

19601

122 1O.Tables

CaSO, 2 H,O

(continued)

I Admixture

polyacrylic acid

polycarboxylates. hydroxyethy-

lene bisphosphonic acid

polymers

polyvinylsulphonate. polyglutamic

acid

succinic acid. polyacrylic acid

sulfonate

surfactant ~ ~~ ~

surfactants

surfactants

surfactants

xylenediamintetraphosphonic acid

Effect

N

N. S

G

H. S

S . H

H - short Drlsms

N

H

fflterabilitv

N. G

G

precipitation

N

Reference

I285.12481

I 14401

~~ ~

[1168]

1291

Ill681

11 121

I423.790.9761

13501

12851

I13861

I10051

I6371

I11911

I11911

I3271

10. Tables 123

Admixture

pH

Ca(C5H3N4031,

CALCIUM URATE


I I

Effect Reference

modif. I471

Admixture I Effect I Reference I I

Mg2+. K+ I N I [1308]

CaWO,

CALCIUM TUNGSTATE


System: tetragonal 2 1 4

a - 0.524 c - 1.128

124 10. Tables

I

Admixture

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

WOd2-. Mn2+

CdCO,

CADMIUM CARBONATE


System: trigonal

a - 0.6112

a = 470 24'

Effect

D

Density: 4250

z = 2

Admixture Effect

Mn2+ D

Reference

158,601

Reference

14911

Cd(HCOO), 2 HZO

CADMIUM FORMATE dihydrate

10. Tables 125

Admixture Effect

LlCl anhydr.

COCl, hydrate

CdS

CADMIUM SULPHIDE

Reference

I1391

I1391

Uolecular weight: 144.48

System: cubic

L - 0.582

Admixture

anionic polymers

polymer, pH

proteins

Density: 4820

2 - 4

Effect

coagulation

N. G, S

G

Reference

[ 10291

[ 10321

I6031

126 10. Tables

Admixture Effect

Mg2+. Mn2+ D

Reference

158.601

Co(CH,COO), 4 H2O

COBALT ACETATE tetrahydrate


Admixture I Reference I I

Mg2' I1581

10. Tables 127

Admixture

Fe2+. Cu2+

Ni2+. Fe2+, Zn2+. Cu2+

Co(NH,&(SO& 6 H2O

AMMONIUM COBALT SULPHATE hexahydrate



a - 0.923 b - 1.249 c - 0.623

B = 106O 56'

Effect Reference

D [488,4891

D (581

Admixture

inorganic ions

Fe2+

COSO,. 7 H,O

COBALT SULPHATE heptahydrate



a - 1.545 b - 1.308 c - 2.004

B = 104O 42'

Effect Reference

H. adsorption potential 12751

D (488,4891

128 10. Tables

Admixture

CrK(SO,), 12 H,O

POTASSIUM CHROMIUM SULPHATE dodecahydrate


System: cubic 2 - 4

a - 1.214 Effect Reference

Cr(V1) N. G 19581

rl admixtures D 1581

Admixture

Cr3+

K+

A13+. Fe3+

CrNH,(SO,), 12 H20

AMMONIUM CHROMIUM SULPHATE dodecahydrate


Effect Reference

D. G I15071

D 1581

D [581

I Svstem: cubic

10. Tables 129

L

CsH&O,

CESIUM DIHYDROGEN ARSENATE

Molecular weieht: 273.836


CSI

CESIUM IODIDE


System: cubic Z=1

a - 0.4562

Admixture

Cu2+, Co2+, Mn2+, Ni2+

Effect Reference

H [ 12531

130 10. Tables

Admixture

admixtures

polyethylene oxide

CSNO,

~~ ~

Effect Reference

16971

N I10711

CESIUM NITRATE


System: hexagonal

a - 1.074 c - 0.768

Density: 3685

2 - 9

CUCl, 2 HZO

CUPRIC CHLORIDE dihydrate


System: rhombic 2 0 2

a - 0.744 b - 0.8126 c = 0.3764

1O.Tables 131

Admixture Effect

gluconates. citrate. tartrate, EDTA N

Reference

[ 10 151

Cu(HC0O)Z 2 HSO

CUPRIC FORMATE dihydrate

Admixture Effect

Co2+, Cd2+ D, structure

Reference

I12751

Admixture Effect

sulfanilic acid, metanilic acid H

Reference

I3901

132 10. Tables

Admixture

CUPRIC HYDROXIDE

Effect Reference

CU~(OH)~CO,

BASIC CUPRIC CARBONATE

Molecular welght: 221.107 I

H,O, filtrability [1399] .

Admixture

Zn2+

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

Molecular weight: 399.829 I System: monoclinic

Effect Reference

D I488.4891

D 1581

Density: 1926

10. Tables 133

CuSO, 5 H,O

CUPRIC SULPHATE pentahydrate


syetem: Mclinic I Density: 2286

2 - 2

b - 1.070 c - 0.597

a - 82O 16' j3 - 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

M3+. Cr3+

rare earth elements

Zn2+

Zn2+. Co2+, Mg2+. Cu2+. Ni2+

admixtures

Effect Reference

D I581

D 16141

D [ 488,4891

D 1581

D 1741

I

Admixture

c1-

I I17111

Effect Reference

1265.3 121

1O.Tables 135

Admixture Effect

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

Mn2+. Ca2+

EDTA. diaminocyclohexanetetra- intermediates

Fe(OH13

FERRIC HYDROXIDE


Reference

I1971

I701

I System: hexagonal

Admixture

Ni2+

oxidizing agent

HC1

dioxyethylglycine, urea

organic anions

Density: 3400 - 3900

2-1

Effect Reference

conversion of hydroxide I2661

N. S [ 1 1401

L9671

I9671

12671

Fe203

FERRIC OXIDE (GOETHITE)


System: cubic

a - 0.830

Density: 5250

136 1O.Tables

Admixture

Fe304

FERROUS-FERRIC OXIDE (MAGNETITE) Molecular weight: 231.55

System: cubic Z = 8

a - 0.837

Density: 5100 - 5200

Effect Reference

admixtures I

FeSO, - 7 H20

FERROUS SULPHATE heptahydrate I Molecular weight: 278.011

Syetem: monoclinic

a - 1.4020

f i - 105O 34'

b - 0.6600

I Cd2+, Cu2+

I TiOSO,

admixtures

Density: 1899

2 = 4

c - 1.1010

Reference

S I6501

10. Tables 137

I H2O ICE Molecular weight: 18.016

System: hexagonal

a - 0.462 c = 0.734

Density: 917

2 - 4

I Admixture

Ag halogenides

AgI

impurities

LiCl

LiI. CsF. KF I NaCl

NaCl, Agl. CuS

admixtures

admixtures

a-fenazine, floroglucine

alcohols, org. acids

aliphatic alcohols

amino acids

CXHROX. CliHgq011

glycopro teins

Effect

N

N

N - retardina

N. H

G

G

D

G , D

N

H - dendrites

N

N

N

N

N

G. D

l i

Reference

17431

I342.12511

[lo241

13761

11 1431

15211

I 14781

I11901

1355.41 11

I 1 1 13.1 1141

110911

13541

[4473

[lo501

[4481

I1 1901

I6401

138 10. Tables

Effect

N

H2O

[continued)

Reference

[355,411]

Admixture

N

H

G

N

organic substances

[396.397.9921

[822l

18231

111211

starch

sucrose

sucrose

ternene

HSPO4

PHOSPHORIC ACID



organic impurities 16911

I

10. Tables 139

H3BO3

BORIC ACID Molecular weight: 61.832

System: triclinic

a - 0.704 b - 0.704

a - 9 2 O 30' 0 - 1010 10'

Density: 1435

2 - 4

c - 0.658

Y - 1200 00'

Admixture

H,SiO,

KMnO,

s o p

flaking agents

gelatine. caseine

polyacrylamide.

polymethacrylamlde

polyelectrolytes

Effect

D

G

H. S - favourable

S. N. G

H - flakes

S

Reference

(13141

191

I2151

16161

11 1821

1423.9763

[ 13881

I2201

140 10. Tables

Admixture

HgBr2

MERCURIC BROMIDE

Effect Reference


Admixture


a - 0.4624 b - 0.6978 c - 1.2445

Effect Reference .

H€!(CN),

MERCURIC CYANIDE Molecular weight: 252.625 Density: 3996

System: tetragonal Z = 8

a - 0.9670 I c - 0.8920

10. Tables 141

Admixture

pH

KBSO, 4 Ha0

POTASSIUM PENTABORATE te trahydrate Molecular weight: 293.26

Syetem: rhombic 2 = 4

a - 1.108 b - 1.114 c - 0.897

Effect Reference

N 19401

I


Syetem: monoclinic I Admixtare Effect

admixtures G

polyethylene oxide N

Reference

112871

[ 10701

142 10. Tables

-~

Admixture

KBr

POTASSIUM BROMIDE Molecular weight: 119.002

System: cubic

a - 0.0660

' inorganic anions , Pb2+

Dh2t

admixtures

c1-

OH-

alifatic carbon acids

Brilliant Cr o cein 9 B

phenol I

Density: 2750

2 - 4

Effect

G - decrease

D ~

D

G

H - cube/octahedron

D

D

N

G - retard growth of / l o o /

H

G

Reference

I3401

12611

I3 181

- t3223

1274,3191

I2 15.4723

[1161]

I391

I3231

I10231

"7041

I1311

14101

[126.127,128.

1O.Tables 143

Admixture

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

Pb(NO,),. NaNO,

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

admixtures

KBrO,

POTASSIUM BROMATE Molecular weight: 167.000

System: trigonal

L - 0.4403

3 - 8 6 O 00'

Effect Reference

favourable I4721

G [669l

N [628l

N El91

Density: 3270

Z = 1

KCN

POTASSIUM CYANIDE Molecular weight: 65.1 1 Density: 1520

System: cubic 2 - 4

R - 0.656

Admixture I Effect I Reference

K,Fe(CN), N(CH,CONH,), H. caking

144 10. Tables

Admixture

admixtures

K2C2O4 * H a 0

POTASSIUM OXALATE monohydrate



a - 0.9320 b - 0.6170 c - 1.0650

Effect Reference

G I7821

Admixture

admixtures

Effect Reference

G I7821

Admixture

KC1

Effect Reference

D - C1- I8571

10. Tables 145

Admixture

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

Fe3+, Hg2+. KCN. K3Fe(CN)6.

K,Fe(CN)6, Mg2', Mn2+ , NH,+.

Ni2+, Pb2+, Sn2+, Sr2+, Zn2+

Ba2+

Ca2+, Sr2+, Ba2+

.

KCl

POTASSIUM CHLORIDE Molecular weight: 74.551

System: cubic

a = 0.0293

I Cd2+

I Cd2+

C02+

Density: 1989

2 - 4

Effect

N. H. D

~

N, G. H

D

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

2uvity

n d

D

hardness

D

D

D. melt

Reference

I7801

I7341

13 181

[ 12671

[32 11

113201

I12681

11264.12651

[ 1265,1269,

12701

12711

146 10.Tabbs

G, D

D

G - strong retardation

H

N

G

D

H

H - favourable

H - favourable

G

N. G

K,Fe(CN),

K,Fe(CNIR. Pb2+. Co2+, Cu2+

K,Fe(CN)6. PbCl,, BeCl,, MgCl,,

LiC1, ZnCl,.. CdCl,. NiC1,. SnC1,

112631

12963

18031

18661

11 2881

113531

I13211

I12201

19261

19273

I1481

I 14571

K,Fe(CNl,. K,Fe(CN),

KNO,

KPbCl,

Effect Reference

G, H 1956,9571

G - retarding effect 13401

H, caking [ 1036,10551

G

H I 1881

1O.Tables 147

KCl

(continued)

Admixture

NaCl

NaC1. MgC1,

NaC1. NH,Cl. MgC1,. AlCl,

NaCl

NH4Cl

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

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

Sn2+, Cr3+, Fe3+, Cl-, NO,., sod2-

0-containing ions

Pb2+, Fe3+

I pb2+

Effect

G

~

D

D for creep crystallization

D

D

G. D

D. G. N - retards nuclea-

tion ~~ ~~

G.H - change growth rates

of faces

N

Reference

I73 11

I11831

17301

I727.7293

I7321

17201

I 1269,1270)

[1461

I11611

I149.150.15 1.

1521

i474.475.476,

4781

16071

1638,9831

I4771

148 10. Tables

Admixture

I Pb2+ I pb2+

PbC12 I PbC12

PbC1,

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

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

Zn2+, Hg2+

Effect

G. H

S - favourable

S - favourable

D

favourable

N - retarding

N. H

H, caking

G - retards /loo/

H , D

N. D

N

Reference

[917.1260,

12321

[149,1408.

1474.3203

1541

19761

[4231

14771

14723

19551

19541

[ 1036,1055.

1095l

111951

I1 1961

I7811

[7781

1O.Tables 149

Admixture

phosphate

ZnC1,

Rb+

RbCl

Sr2+

admixtures

admixtures

admixtures

admixtures

admixtures

admixtures

admixtures

admixtures

admixtures

Br-

HC1

HC1. KOH

irn p urities

Effect

caking

G

D

D. recrvstallization

D

N

H

agglomeration

D

N , G

Lf. H

n La

s

r 7 J

D

Reference

[ 10471

17801

1102.488.4891

18791

11 1 1 1,7681

1528.771

I705.7171

11287,12741

I11701

13231

114121

1868.5 141

[11.121

11 1121

[lo231

15641

[go51

[50.5921

17041

[695.721]

150 10. Tables

caking

KCl

(continued)

AdmiXtUre

aliphatic amines (2OC)

aliphatic amines

amaranth

13851

amines

N. G. S

N. H. D

bromobenzole, phenole. aniline

I14941

17801

dyes

ethyl-hexanoic acid, octanoic acid.

monochloracetic acid

ethylenglycol. diethylenglycol

laurylaminoacetate

N(CH2CONH2)3, octadecylamine

acetate

octadecylamine

octadecylamine hydrochloride, pH

caking

H - cube + octahedron

G - retardation

H

N, D, yield

caking

I organic substances with free

I13951

17401

14101

17811

113801

Effect Reference I

H I I3871 I I

I 110361 I H. caking H. caking 110361

caking I10551

H.G 110671

I10551

110671

caking I I10471 I I

caking I45 1 I

D I16811 I

1O.Tabks 151

~~

Effect

Ostwald ripening

KC1

(continued)

Admixture

surfactants

surfactants

~ ~~~~~

Reference

[ 14561

I 123,102 1,

1022,14551

Effect

H - /Oll/ + /001/

H

H

H

H - /011/

H

D. H

t

Reference

DO41

[205.2 121

[2151

12141

14391

[207.2 10,2 14.

2151

13 15.8351

KC103

POTASSIUM CHLORATE Molecular weight: 122.549

System: monoclinic

a - 0.4647

R - 10QO 38' b - 0.5585

Density: 2320

2 - 2

c - 0.7086

I Admixture

s,o,~-, CrO,2-, Cr,0,2-

Biebrich scarlet

organic dyestuffs

Ponceau red

152 10.Tables

KCIO,

POTASSIUM PERCHLORATE Holecular weight: 138.549

System: rhombic

a - 0.8834 b - 0.6660

sop Bordeaux B. Chromotrope 8B.

Wool scarlet, Solochrome black.

Fast red extra

Brilliant Congo red, Chlorazol fast

orange, Brilliant &urine. Trypan

red, Bordeaux B

Chromotrope 2B

Chromotrope 2R. Chromotrope 2B.

Acid magenta, Alizarin Delphinol,

Alizarin cyanine

Erio fast fuchsin. Cr,0,2-

Ponceau red

sulphonated dyestuffs

Density: 2520

2 - 4

c - 0.7240

Effect

D

H - /001/

H - / l l O /

H - / O l l /

H - /102/

~~ ~

H - / loo /

H - / l o o /

~~

H - /001/

H - /Oil/, /102/

Reference

I8921

I211.2151

I2141

I2 11,2151

~

121 1.2151

12 11.2 151

I2141

12141

11281

12141

1O.Tables 153

7

Admixture

(NH,J2Cr04 + K 2 S 0 4 . %SO4 + KC1.

(NH4),Cr04 + K,S04 + KC1

1

s,o,2-

Trypan 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

K,CrO,

POTASSIUM CHROMATE Molecular weight: 194.190

System: rhombic

a - 0.6920 b - 1.0400

Density: 2732

2 9 4

c - 0.7610

Reference

H - /001/ [ 2 13.2 14.2 151 + H - /010/ - /Oll/ I213.214.2 15)

154 10. Tables

KH2As04

POTASSIUM DIHYDROGEN ARSENATE


Syetem: tetragonal Z = 4

a - 0.7610 c - 0.7150 A

qCr2O7

POTASSIUM DICHROMATE

Admixture Effect

pH G . H


System: triclinic

a - 0.7340

a 0 82O 00'

b - 0.7490

I3 - 97" 56'

Reference

I1221

Density: 2690

z = 4

c 11.3390

y =90° 30'

I Admixture

KMnO,

Scarlet 2R. Naphthol black B.

Bordeaux S, Ponceau S extra, and

other dyestuffs

Methyl orange, Chloramlne yellow

Effect

H - /010/

H - /010/. /111/

Reference

1213.214.2 151

213.2 14.2 15

19761

10. Tables 155

System: tetragonal

a - 0.7430 c - 0.6940

Admixture

AlWO,):,

Al(NO,),, KOH

Al3+

Al3+

I POTASSIUM DIHYDROGEN PHOSPHATE

Fe3+

~ r 3 + -

Cr3+

Fe3+

Fe3+

Density: 2338

2 - 4

Effect

dissolution

G

G

H. D ~~

N, G

G

G . H, N. D

H - dendrites

optical properties

-~ ~

Reference

1911

[lo531

[931

15371

1535,5393

[ 1344.13451

I1 691

1171

12801

15401

12151

18391

16211

17751

I12711

156 10. Tables

I Admixture

FeCl,, pH

KAI(SO,),. A3+

KCIO,

KOH. Ni2+, Fe3+

Na,B407

Na,B,07

Pb2+, KNO,

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

admixtures I admixtures

Effect

H

G. H

optical properties

favourable

G . H

H - prisms without

pyramids

G

G. H

D

Reference

I8401

18393

13951

15381

1 12081

1449,7751

14721

I 1207.12 151

[281.989.1206,

14821

[536.1081]

12981

13431

IO.Tables 157

Admixture

pH

KIOS

POTASSIUM IODATE Molecular weight: 214.001

System: cubic

a - 0.8920

Effect Reference

N I9401

Density: 3930

Z = 1

158 10. Tables

H - /111/

G

G

H - /010/

G

POTASSIUM HYDROGEN TARTRATE



a - 0.7614 b - 1.070 c - 0.780

1213,2141

[ 10851

17131

12 13.2 141

[ 10851

Admixture

cu2+

K g S 0 4

admixtures

dyes

tannin, red polyphenol. pectin

D

G

G. H

Effect I Reference

15591

14541

[557.5581

19951

~~

KHC8H404

POTASSIUM HYDROGEN PHTHALATE

Kolecular weight: 204.23

Admixtove

Fe3+, Ce3+

admixtures

admixtures

glycerine, polyethylene glycol

Density: 1630

I Effect 1 Reference

10. Tables 159

Admixture

KBr

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

Pb2+

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

admixtures

KI

POTASSIUM IODIDE


System: cubic 2 - 4

D = 0.7062

Reference Effect

D - mixed crystals 1421

D 1401

H - octaeders D151

favourable 14723

I3231

OH-

Fast acid magenta, Brilliant yellow

surfactants

G 17041

H I4 101

G-retard 17401

LiNH,C,H,O,

AMMONIUM LITHIUM TARTRATE


Admixture

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

Effect Reference

H I8401

160 10. Tables

_ _ _ _ _ ~ ~ ~~

Admixture

Fe2+

mo2 POTASSIUM NITRITE

Effect Reference

favourable 14721


Syatem: monoclinic 2 = 2

R = 0.4450 b - 0.4990 c = 0.7310

0 - 114O 50'

KMnO,

POTASSIUM PERMANGANATE


System: rhombic 2 = 4

a - 0.9099 b = 0.5707 c - 0.7411


Cr,O,2- H - /001/ I20 1,2021

CrO,2-. Se0,2-. CO,~- H - / l o o / 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 - 0.5430 b - 0.9170

Density: 2110

2 - 4

c - 0.6450 I Admixture

Cr3+

Cr3.’, Na+

cs+

Fe3+, Ni2+. Li+

isomorphous admixtures

K2Cr,0,. Cu(N0219

KC1

Pb2+

Pb2”, Th4+. Bi3+

Sr2+

admixtures

admixtures

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

Effect

D

N. G . S

clusters

N

D

diel. permeability

G , D

D

D - c1-

H

favourable

D

H

G

N. G

Reference

16791

11222.12241

18251

[12141

[ 12951

[6431

[6781

(6491

18571

(6421

[4721

[6831

16981

I163.1116.

11 171

r 12221

162 10. Tables

Admixture

C9+

mo3 continued)

Admixture

dy estufs

Fast red extra, Bordeaux S.

Tartrazine. and other dyestuff's

Fast red extra, Naphthol red S,

Tartrazine. 1.4-diaminoanthra-

quinon-2-sulphonate

methylamine hydrochloride,

dodecylamine hydrochloride,

fluorocarbon

surfactant

surfactant

Effect

D

Effect

H - /001/ platelets

H, caking

N. G. S

N

Reference

110981

12241

I14481

[ 12241

I8601

11231

KTiOPO,

POTASSIUM TITANYL PHOSPHATE


Reference

I1431

10. Tables 163

CNaC,H,O,

SODIUM POTASSIUM TARTRATE

Nolecular weight: 210.167

Admixture

A P . cuco,

Cu2+. H,BO,

cuco ,

cuso ,

MnCI,

(NH&M004. Na2Mo04. NH4Cl.

H2B01, CuSO,, Cu acetate, MgSO&

Na+

Na3B4O7

NH4+

Effect

H

H - /210/

H - retards /001/, shortening.

decreases with decreasing pH

H - retards /001/, effect rises

with raising pH

H - retards /210/, stronger

effect with decreasing pH

H -retards /111/ and /Oil/,

alkalis - stronger effect

H

H - /LOO/

G - retards, H - /210/

Reference

[ 12931

12 13.2 151

I901

1901

I901

I901

13473

I2 13.2 151

I891

I213.2151

164 10. Tables

Admixture Effect

C103-, B,0,2- H

OJaC4H,0,

continued)

Admixture

admixtures

Crocein scarlet 3B. Diamine sky blue

Reference

12151

effect

H

H, D

ref.

1 1334.13351

18961

10. Tables 165

K2S04

POTASSIUM SULPHATE


System: rhombic

a = 0.5731 b = 1.0008

Admixture

N3+

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

Ni2+

Ce3+

K,Cr04 + KC1

Density: 2662

2 = 4

c = 0.7424

2, dissol.

v

D . retards reaystalliza-tion

N

G

dissol.

G

D

D

H. caking

N.G

D

D - creep cryst.

Zeference

11791

12131

52,874,875,876l

762)

767.918.14971

13571

I 13561

[5201

12401

[182,1036]

I1 1311

[680,1499.1500.

15021

17201

166 10. Tables

I Admixture

K,Cr04. Pb2+

K,Fe( CN)

KCIO,, K9Cr0,

KCr(S04)?

Li +

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

Fez+, CS+. Cu2+, A13+, Mg2+,

sio,2-

(NH,),SO,

Ni2+, Cu2+, Co2+, Mn2+

NiSO,, MnSO,

PbCl,

admixtures

2 inor anic anions

Effect

G. dissol.

H, I)

G ~

N

favourable

D

D

D

N, H

D

N

G

D

Reference

16 171

114.95)

12211

[ 14951

[ 14331

14721

I2961

I3 171

12391

19541

15721

[11001

1424.14321

1757,766,906.

1273,1274,1355,

1357.14981

18731

10. Tables 167

I K2s04

(continued)

Admixture Effect

s,o,2-. s,o,2- H - platelets /001/

Alizarin yellow H - /loo/

Amaranth H, caking

Crystal Ponceau D

dyestuffs H

solvents

surfactants G

Reference

1203.2 14.2 153

12081

[182.1036]

[6001

1209,210,214, 215.

391.14471

[ 12731

18341

19301

[ 23 7,7 721

LiCl H2O

LITHIUM CHLORIDE monohydrate


System: tetragonal 2-8

a - 0.7669 c = 0.7742


Mn2’. Cd2+. Sn2+, Sn4+, Co2+, favourable 14723

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

168 10. Tables


M gF2 D I8081

FeF, G, N 111971


System: cubic 2 = 4

a - 0.401

LiI 3 HzO

LITHIUM IODIDE trihydrate Molecular weight: 187.891 Density: 2290

System: hexagonal 2 x 2

a - 0.7460


admixtures D. H [ 11371

c - 0.6460

10. Tables 169

~ ~~

Admixture Effect

MnO; H

admixtures D, G

pH G

LiIO,

LITHIUM IODATE

Molecular weight: 181.85 Density:

System: hexagonal 2 = 2

a - 0.5469 c - 0.5155

Reference

I9901

I3631

I2471

- ~ ~~ ~


Mg(CH,C00)2 . 4 H2O

MAGNESIUM ACETATE tetrahydrate


170 10. Tables

Effect

D

H

H

lower pH - better crystals

H - shorter crystals

H - longer crystals

LizSO, HZO

LITHIUM SULPHATE monohydrate

Reference

[ 13501

[ 10801

I1 1091

[959]

[ 10571

110571


Syetem: monoclinic

a - 0.5430

B - 107O 35'

b - 0.4830

Density: 2051

2 1 2

c - 0.8140

Admixture

H,SO,

pH

pH - 5.0

pH 6.0 - 6.5

DH 6.5 - 6.7 favo urab le 1 I4721

M@,&SO& 6 HzO POTASSIUM MAGNESIUM SULPHATE hexahydrate

I Molecular weiaht: 402.742

I Admixture Effect I Reference

D [1189]

10.Tables 171

Effect

Mgcos MAGNESIUM CARBONATE

ldolecular weight: 84.33

System: trigonal

L - 0.561

L - 48O 12'

Reference

Deneity: 2980

2 - 2

S

H. precipitation

G

N

p H

complexons

hydroxyethylenediphosphonic

acid, EDTA

DhosDhonates

[1035.1167]

IlO2Ol

I6531

I8121

[ 11671 polyglutamic acid, polyvinylsul-

Admixture

surfactants

Effect Reference

G 19441

I

Mgc204

MAGNESIUM OXALATE

172 10. Tables

Molecular weight: 160.388 I I

MgF2

MAGNESIUM FLUORIDE Molecular weight: 62.32

System: tetragonal 2-2

1

a - 0.466 c - 0.308

Admixture

Mn2+. Zn2+, Co2+, N12+

Admixture

Effect Reference

D 158,603

Ni2+. Co2+

admixtures

Effect

D

G

7

Reference

I 14961

131

10. Tables 173

Effect

D

Molecular weight: 360.688 Deneity: 1723

Reference

1621


a - 0.9324 b - 1.2597 c - 0.6211

p - 107O 08'


Ni(N134)2(S04)2 D [9281

Ni2"-, Fe2+, Cu2+ D 1581

174 10. Tables

Admixture

admixtures

pH

saccharides. glycerine


Effect Reference

periodic crystallization 1201

S 17881

G - retarding 113091

System: hexagonal z=1 a - 0.311 c - 0.474

Admixture

Sod2-. Se0,2-. Ni2+, Cu2+, c02+,

Effect Reference

D 18381

MnCOS

MANGANOUS CARBONATE Molecular weight: 114.95

System: trigonal

a - 0.584

a - 470 45'

Density: 3400

2 5 2

1O.Table.s 175

MgSO, 7 HzO

MAGNESIUM SULPHATE heptahydrate I Molecular weight: 246.469

System: rhombic

a - 1.1940 b - 1.2030 Density: 1680

2 - 4

c - 0.6870

Admisture

cationic admixtures

Co2+, Fe2+, Cu2+

Na2B407 I

Ni2+, Zn2+

H,BO, + NaOH

pH

methanol, ethanol

p- phenylendiamine

tensides

Effect

G

H. D

D

H - shortening, H2S0,

decreases this effect

G - retarding, H - shortening

H - needles

D

G

D

H - shortening

G

N

G

Reference

16221

1571

1621

191

I90.524.9761

[907.908]

12331

1488,4891

19293

1581

1901

1728.7331

176 1O.Tables

MnS04 H,O

MANGANOUS SULPHATE monohydrate


System: monoclinic (rhombic)

a - 0.6740 b - 0.8100 c - 1.3300

Admixture I Effect 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 2-1

L = 0.4047

Admixture

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

Zn2+. Mn2+. Cd2+. Be2+

Cu2+ + Fe3+

Cu2+, Cd2+

Fe2+, Na+

admixtures

aliphatic monoamines

hydrazlne and guanidine

derivatives

lactame oil

0- and p-vinylphenylmethan

sulfoaclds

H

D

caking

H

caking

caking

caking

caking

Reference

11322.1323,

13241

I6021

I60 11

110431

[ 11701

I5901

I4021

110431

[13721

1221.10971

178 10. Tables

NH,Cl

AMMONIUM CHLORIDE Molecular weight: 53.491

System: cubic

B - 0.3866

Density: 1527

Z = 1

Admixture

Be2+

Cd2+, Fe3+, A13+

Cd2+

Cd2+

CdCl,. K4Fe(CN)6. pectine.

N(CH,CONHY)?

Co2+, Mn2+. Fe2+, Cr3+, NaSCN,

CH3COONH4, (NaPO,),

Co2+, N12+, Mn2+, Cu2+

Cu2+, Co2+, Ni2+

c U 2 + , Co2+, Ni2+, Zn2+, Mn2+, Sn2+

CUCI,

c u s o ,

Fe3+, Cr3+, Cu2+, Mn2+, ~ p + , c02+,

Cd2+

Effect

H

D. H

H. caking

G , N

D

D

D

D

H - cube

D

Reference

[ 1322.1323.

13261

16021

[5991

[ 1324.13261

I10361

[1427j

112691

15811

[ 1264,1269,

12701

13 161

I1 131

I600.1322,

1323.13263

I

NHaC1 I (continued)

I Admixture

Fe3+. Cu2+

Fe3+. Ni2+, Co2+, CuSO,

FeCl,, CuSO,. CuC1,

KC1 + KqSO,

Mn2+, Mg2+, phosphatcs

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

Co2+, Ni2+, Fe3+. Cr3+

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

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

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

ammonium acetate and formate

NaCl

NiCl,

Pb2+

C032-. SO,2-. F-. I-. I

Effect

H

H - dendrites/cubes

H - transparent cubes

D for creep cryst.

H - favourable

favourable

H , anomalous mixed

crystals

H

H

S - favourable

H - dendrites/cube

favourable

Reference

16421

1773,7741

16601

17201

19261

14721

12601

14401

I12911

18201

[4231

14231

180 10. Tables

m,c1

(continued)

I Admixture

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

FeCl,. CdC1,. (NH4),S0,. CuC1,.

(NH,),MoO,. HgCl,

admixtures

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

HC1

inorganic anions

phosphates

phosphates. CO,,-. SO,,-

alkylarninoacetate and -chloride

dyes

extract of peanuts

laurylaminoacetate

murexide

octadecylamine hydrochloride

pectine. pectinlc acid

pectine

phenolsulphonic acid

I solvents

Effect

H

N

H

caking

H ~~ ~

G

H - dendrites/cube

caklna

~ ~

favourable

H

H ~~ ~~

caking

H - prolongated trans-

parent crystals

N. S

S. caklna

Reference

[ 10961

I12181

I8041

13871

I440.6421

I3391

13451

18811

15871

I12051

10. Tables 181

Admixture

urea

urea

urea

urea

urea, lactose

urea, pectin

NH,CI

[continued)

Effect Reference

H 122 1 I

H - cube aggregates 1773.7743

H - dendrites/octahedron 19761

H - cubes

G 112191

G . N 114271

I 1096.1 0971

Admixture

Cu2+, Ca2+, Fe2+, Th4+

Zn2', Cd2+. Mn2+. Ca2+. Mg2+,

Sc3+, Co2+, Ni2+

Effect Reference

favourable 14721

"7231

182 10. Tables

Admixture Effect

Ca,(PO,), caking

so,2- H - /llO/ dyes H - /Oil/, /102/

surfactants

NH4ClOs

AMMONIUM CHLORATE

Reference

114131

[ 2 14.2 151

1214,2151

15323


Admixture

admixtures H [ 11701

surfactants inclusions

10. Tables 183


a - 0.7290 b = 1.0790 c = 0.8760

Admixture

dehydrating substances

NaHSO,. MgCl,, CaSO,

admixtures

hydrocarbons

oil, sugar

Effect Reference

stabilization 14631

caking 14573

I781

stabilization 14631

13. favourable 14591

Admixture

dyes

glycerine. Na,B40,. sucrose

Effect Reference

I-I [2 14.2 1 51

favourable 14721

184 10. Tables

Admixture

NH4HC4H40,

AMMONIUM HYDROGEN TARTRATE I Effect Reference

1lKolecdar weinht: 167.124

(NH,),HPO4

AMMONIUM HYDROGEN PHOSPHATE I I Molecular weight: 132.056 Density: 1619 I Svetem: monoclinic

lAd*ture I meet I Reference I I H - platelets/cubes I

10. Tables 185

NH4H2P04

AMMONIUM DIHYDROGEN PHOSPHATE Molecular weight: 116.026

System: tetragod

a - 0.7610 c - 0.7630

Density: 1803

z = 4

Admixture

Al3+

AlCI,, FeC1,. Cr3+

Ba2+, Sod2-

Co(NO2)q

cr3+

I Cr3+, N 3 + . Fe3+

Cr3', Fe3+ I CrCI,

Effect

G.H

higher electric conduct.

G. D

green prismatic faces

H

H

G - retarding, N - wider

metastable zone

N. G

G

H. G - lower growth rate of

prismatic faces

H

If - wedges

Reference

I5351

[289.2901

14231

[ 14431

14233

1176,13361

15783

P763

"2893

I5791

13751

14231

ll6l

19743

186 10.Tables

NH,H,PO,

(continued)

lAd*e

pH. FeC13. CrPO,

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

NH,

Sn4+. Cr3+, Fe3+, Ti4+, Au3+. H3+,

Be2+

admixtures

admixtures

admixtures

admixtures

Effect

G. H

G. H

H, G

G fluctuations

D. H - wedges

H - thicker crystals

D. H - rhombic shape

H - prisms

G. H

favourable

H - wedges

D - purity

ti

G. H

H -platelets

Reference

12641

12951

17711

I15141

I15141

1161

I161

I12943

1161

I9211

1227,228,229,

2301

I4721

I7221

19341

1249,14823

ll08ll

10. Tables 187

Admixture

H,P04

PH

pH

p H

p H > 3.6

pH. gel

PH. NH,OH. H3P04

EDTA

surfactant

surfactants

(continuedl

Effect

N - slowning

H - at higher pH regular

growth

G

S , H

H - shortening

G

H

H

N

G - lower rate

Reference

17221

11 1091

19521

I14181

16061


system: rhombic

b - 0.7660

Density: 1652

Z = 4

c - 0.5800

I

' D

S. decreases

caking

safety

H. caking

lower hygroscopiclty. tight

hygroscopicity

coarsening of dendrites

caking

stability

Reference

' 16521

1 ' [ 13 16.13 171

' [?I861

16701

(10361

13521

16481

13241

[2971

10. Tables 189

acid

sodium ethylsiliconate

sulphonates

toluidine, azobenzole, anthranilic

acid w

NH4NO3 I (continued1

Admixture

admixtures

admixtures

Acid magenta, Bordeaux S.

Azofuchsine. Chromaeol yellow

Acid magenta, N(CH2COONa)3.

Bordeaux S

alkylamines, Sod2-. sulphonates

amine

aminoalcane salts

dyes

dyes

glycole. glycerine

laurylaminoacetates

hosphate solids

salts of p-rosaniline disulphonic I

~~ ~

Effect

N

H. stability

caking

H. caking

H

H - /010/ platelets

noncaking platelets

caking

H

S

caking

caking

hygroscopicity

~~

Reference

I 13641

13251

[ 14481

[ 10361

I13471

16431

I3881

[224.1098]

W63

14621

13871

I6611

I4001

I13941

[ 1 3 76.1 3 771

if3581

190 10. Tables

Admixture

toluidine. resorcin. azobenzene.

malelc acid

urea

wax. dves

NH4NOs

[continued)

Effect Reference

hygroscopicity 16431

[1391]

cakina I2971

“H412BeF4

AMMONIUM BERYLLIUM FLUORIDE


System: rhombic

m - 0.58 b - 1.020 c - 0.75


(NH4)&rO4 D

10. Tables 191

dolecular weight: 132.134 Density


L = 0.5951 b = 1.0560 c = 0.771

Admixture Effect

M,(SO,), H

M2(S04)3 150-200 ppm H, decreasing mois-

ture

M3+ caking

A13+. Cr3+, Fe3+ S. H. N

A13+. Fe3+ S decreasing

M3+. Fe3+, Cd2+, K+

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

A13+. Mn2+. Cu2+

A13+, p H H, noncaking flakes

As5+ H - needles

H. S

H - rice corn

N. G . S . H

As5+ 0.03 % yellow crystals

Ca2+. Fe2+

cakin

S. H. favourable

1769

b

I

1 Reference

1114633

I 18831

15831

(1365,13661

I79 11

13041

1977,9821

11881

14641

I48 11

15731

15271

1481

14811

192 10. Tables

I Admixture

cr3+

Cr3+

Cr3+

cr3+

Cr3+ + H,SO,

Cr3+ >50 ppm

Cr3+. Fe3+

Cr3+, H,PO,

cu2+

Cu2+, A13+. Mn2+

Fe2+

Fez+. A13’

Cu2+, Na+. pH

Effect

caking

H

G

N. G. S

N

H - prisms

H - longer,

decolorUed

G

S. colouring

N. G. S , H

D

N. H. S

Reference

I181

14031

I7151

I6931

17861

17631

I661

I661

[ 14731

15881

I1951

192

113181

1378,379,3801

972

[ 977,9821

10. Tables 193

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

Fe3+, As+, Cr3+, Mn2+

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

Fe3+. C1-

Fe3+, Co2+, Cr3+, Cu2+

Fe3+. Fe2+

Fe3+. Fe2+. Na,S,03

Fe3++, Fe2+. pH

Fe3+, organic admixtures

Effect

H. S. caking

favourable

at high conc. unfa-

vourable

H - prisms

D ~

H - needles

H. S - needles

G. H - needles

H. S

S. caking

H

D

D

S

D. H. N

H. colourlng

Reference

12761

14821

I830al

[ 170.17 11

19711

(84,4291

I482.5431

I14711

[105.106.107]

[ 13611

I14381

[ 13961

14901

[969.970.9711

13001

19721

1706.7071

194 10. Tables

sulphonlc acids

Mg2+. Mn2+, Zn2+, organic

sulphonic acids

MgS04 + HqC,04

Mn2+

Mn2+

Mn2+, Cu2+, Al3+

Admixture I Effect

H. S

H - shortening

G, S

N. G, S

H. S

H,C,04. Na3S,03. Mg2+ H - shortening

HqSO, 2g/L1 A1903 8g/L

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

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

isomorphous sulphates

K 3 S 0 4 . K2Cr04

Mg2+

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

H - hexagonal rice

corn

H - rice corn

H - rice corn

H - rice corn

H

H. D

H, S

N, H, S

Reference

13511

i3511

1651

13821

13811

14551

12211

14651

151

19751

11941

11911

1O.Tables 195

(NH4)2s04 I fcontinuedl

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

admixtures

Effect

N. 13. S . D

caking

G

D

H - rice corn

G . H

H _____ ~~

H - rice corn

H. S

H. S

D

G. I3

S

Reference

[189,1901

I977.9821

(13041

r9771

[1200]

[ 10271

19761

15201

[ 14701

[307.1211,

14281

[7651

I40 11

196 1O.Tables

Bordeaux S, Azofuchsine.

Tartrazine. Diamine sky blue

cyclohexanone oxime. hydroql-

amine sulphate. caprolactame i

“H,),SO, I [continued]

I Admixture

CN-. SCN-

H,S04

H 9 S 0 4

HSPOI

P,05 + 0.5 Yo H,SO,

PnOc. HnSO,

pH

p H 6 - 7

pH. C1-

alkylarylsulphonates ’

amines

Bordeaux S

Effect

unfavourable

minimum

H - favourable

€1. s

S

G. H

H. S

G. S

cakinr!

caking

II - noncaking long

brittle crystals

H. caking

Reference

17911

[2701

[ 172.5851

[ 9 7 7.98 2,19 51

I2331

I13591

I10341

[ 12873

113631

I3041

[ 10691

14231

I2411

[2241

[ 14481

18331

10. Tables 197

I13671 I

I 15061

748 I

I Admixture

dyes

I dyes

glucose, molasses

glycerine. urea, pectine

glycol, glycerine

imidazoline salts

impurities from caprolactam

nonionic surfactants

I

organic admixtures

organic dyes

organic substances

organic sulphonic acid

pectine. wood extract

phenol, pyridine

phenol, pyridine

polyacrylamide

polyvinylalcohol

surfactant. dye

I Effect

I

1 caking

‘ H . S

H. S

caking

caking

N

H

H

G - higher

H. S

S. H

G. H

H

S

caking

Reference

1706,7071

13911

1661

14651

14601

15271

[ 14381

I14041

I13961

[ 13601

198 10. Tables

~~

Effect Admixture

surfactants

tar

urea

urea, phenol, glycerine, starch,

glue

Reference

caking

H

S - favourable

[789,1289]

(4811

1461.1 1921

[ 9 7 7.9 821

I

Admixture Effect

H,S04. (NH4),S04

H2S04. (NH4)2S04. Nb205, Ta205

N. G

N. G Nb retards, Ta

I accelerates

- Reference

[6541

1655,6561

10. Tables 199


UO,Fq, F- S , N. G I2541

“H,),W04

AMMONIUM TUNGSTATE


pods-, ~ ~ 0 , 3 - . sio,2- I yield I I3561

200 10. Tables

Admixture Effect Reference I

Na,AlF6

SODIUM HEXAFLUOROALUMINATE (CRYOLITE)


Syetem: monoclinic 2 - 2

a - 0.5460 b - 0.6610 c - 0.7800

I B - 900 12'

~~~~~~ ~ ~

Effect

G

Reference

133 1,3331

1184,236,251.

253.330.3921

I I 114831

YaBOs 4 H,O

SODIUM PERBORATE tetrahydrate

blolecular weight: 153.87

Admixture

surfactants

surfactants

10. Tables 201

Admixture

ionic impurities, surfactants

admixtures

admixtures

admixtures

surfactant

surfactant

surfactant

NaBO, H202 3 H,O

SODIUM PEROXOBORATE trihydrate


Effect Reference

I3931

G I7821

13941

N I12501

N I3321

G I3331

N, G. H I2521


202 10. Tables

Na2B407 10 H 2 0

SODIUM TETRABORATE decahydrate

Molecular weight: 381 367 Density: 1692


a - 1.1820 b - 1.0610 c = 1.2300

B - 106O 35'

I Admixture

CUCI,, c u s o ,

admixtures

H,BO,

pH = 9.7

Azoflavine RS, Chrome fast yellow.

Ponceau 4. Acid brown R. Alizarin

yellow, Orange 1, Naphtol black,

Ponceau S extra, and other dyes

oleic acid

sodium oleate, dodecylbenzene

sulphonate

surfactant

Effect

H - /010/

N. H

caking

H - cubes

H

S, H - favourable

N. G, S

H. N

Reference

[213,214,2151

142 I, 10771

113701

[423,976]

[213,214.2151

1422,423,9761

[ 10771

[123, 10781

10. Tables 203

NaBr - 2 H,O

SODIUM BROMIDE dihydrate Molecular weight: 138.924 Density: 2176

System: monoclinic

a = 0.6590 b - 1.0200 c = 0.6510

p = 1120 05'


Na,Fe(CN16, CdBr2, PbBr2, H, caking 110361

NaBrO,

SODIUM BROMATE


System: cubic 3 - 4

a - 0.6705


pH G

204 10. Tables

Admixture

N a pyrophosphate

Na2HP04

Na2PO,

admixtures

cyclo hexane

NaCHsCOO 3 H 2 0

SODIUM ACETATE trihydrate


Effect Reference

N [ 14191

N [1420,1436]

N (14371

G [ 11381

H I3091

Admixture Effect

CaO, pH

admixtures H

lysine H - prisms

H - prisms. cubes

Reference

I13751

[1159]

[ 13741

10. Tables 205

Admixture Effect

admixtures N

olecular weight: 286.141 Density: 1460

b = 0.9009 c = 1.2597

Reference

[3051

206 10. Tables

NaCl

SODIUM CHLORIDE Molecular weight: 88.443

System: cubic

a - 0.5627

Density: 2163

3 - 4

Admixture

admixtures forming double salt

AgCl

A@C1

Al3+

Ba2+

Ca2+, Sr2+. Ba2+. Cd2+

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

Ca2+, Sr2+, Cu2+, Ba2+, Zn2+, Fe2+

+ polyvinylalcohol

CaC1,

CaC1,

CaCl,, Fe(CNIe4-

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

Effect

H

D - ultrasound

D, Ostwald ripening

caking

H

D

D

H - fibers

H - octahedrons

dissolution

caking

H

H

Reference

I l O O l l

I7411

I877.8781

14061

[ 10391

[ 14101

1381

[ 10741

I5221

I8001

[ 12251

15471

1141.1421

10. Tables 207

I NaCl

(continued) : 1 Admixture

Cd2+. Zn2+, Mn2+

CH2NH2CH2COOH, Cd2+, Mn2+,

Hg2+

cu2+

CllC1,

Fe2+, Mg2+. alkaline carbonates

and hydroxides

Fe3+, A13+, Zn2+

HgC1,

25 inorganic cations

1n3+

K,Ti0(C904),

K,Fe(CN),

K,Fe(CN),

K4Fe(CNI6 5 ppm

K4Fe(CNI6, K,Fe(CN),

K4Fe(CN)6, Mg2+

KCaCl,

Effect

G, H

D

G , H, D

caking

S - favourable

H

G - decrease

D

caking

N, S

H

caking

caking

n

Reference

[ 11361

I53 I1

I13201

[699.700.70 11

14041

19761

1138,10901

I3401

18721

I5891

I7831

12821

11751

11401

[I 15,6721

1411

208 10. Tables

Na,Fe(CNj6, Na3Fe(CNjG

I

dendrites

H. noncaking

NaCl

(continued1

Reference

i2731

1391

[ 13531

[1481]

[5481

I13811

(569,132 11

14051

161

[ 10371

I423.9761

[1362]

11 1601

11741

10. Tables 209

NaCl

I continuedl

Admixture

NaOH

NaOH

NaOH. Na2C03

Pb2+. Cd2+, Ca2+, Mg2+

Pb2+, H,S04

Pb2+, K,Fe(CNIG

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

Fe2+, Hg2+

Pb2+. urea I Pb2+, urea, Cd2+ I

Effect

H

H. electrical

properties

caking

S - favourable

N, G. D

D

D

N, G , H, solubility

favourable

D on /111/ and

/loo/

H

- Reference

[lo101

111941

[ 11391

113731

(423,9761

I4771

I9361

18271

Ill611

14771

[1349]

"2601

14721

16201

[ 14 1,142,190.

530.53 11

2 10 10. Tables

Admixture

PbC1,

PbC1,

PbCl,, CdClQ

PbC1, , K,Fe( CN),

ZrOC1,

Rb+. Cs+

small ion admixture

s o p

NaCl

Effect

D

G

D

G

caking

D

G - rise

H

Ti K oxalate

T1+

caking

D

water-containing substances

admixtures

admixtures

admixtures

admixtures

1869,8711

[ 14951

(13711

(12471

12731

I1 771

decrease caking

H, low attrition

H

N

D

I8481

[870,87 11

(37 11

I1801

11 170,1221,

14801

10. Tables 2 1 1

Effect

H

caking

caking

G

H

D

H. caking

G. H. lower attrition

N. G. S

H - cube +

octahedron

caking

I NaCl

Reference

I7363

I5451

I5461

I7041

I13361

I7211

110361

I12621

I 14941

I7401

14061

I (continued)

Admixture

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

complex cyanides, sfloxanes

complex cyanides, urea

OH-

pH

26 admixtures

alanine , glycine , CH,CO 0 H

aliphatic amines

brornobenzene. phenol, aniline

citric acid. tartaric acid

cysteine. creatinine. pepsine,

sodium glutamate, sodium

phosphate

glycine

laurylaminoacetate

I1 16,138.10891

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 2 13

~ ~~~ ~

Admixture

urea, aliphatic acids

urea, CrCIR

urea, formamide, glycine

urea, pyridine. formamide

~ ~~

Effect Reference

~

Effect

Na,SO,

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

H

N - accelerates 13721

G - accelerate I3721

caking

H

H

H - octahedrons

Reference

IlOOO. 1002.

11 18.1244.

1261,1487.

14711 I

NaC,H,O,N,

SODIUM PICRATE


214 10.TabZes

Admixture

cu2+

Na dithionate

Na,B,07

Na2B,0,

Na2Cr0,

Na,S, 0

Na,SO,

Na,SO,

Na,SO,. NaClO,

NaBO,

NaBO,

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

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

NaClO,

SODIUM CHLORATE


System: cubic

a - 0.6570

Effect

H - /llO/ - /111/

H. G

H. G

N

D

H - /loo/ - /111/

G. H

N. H

H - /111/

H, G

N

H - /111/

admixtures

admlxtures

Reference

113361

[1103,1104]

I4851

11531

16871

[ 1991

[124.125.132]

18621

15231

17261

I14091

12151

114901

I12821

19761

10. Tables 2 15

Admixture Effect

Na,S04 G

Reference

11281

~~~~

SODIUM FLUORIDE


System: cubic

Admixture Effect

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

Alizarin red S

polyacrylic acid

Density: 2790

Z = 4

Reference

[4101

[4521

2 16 10. Tables

N. G

N

N. G - accelerate

N

S

H

G

NaHCO,

SODIUM HYDROGEN CARBONATE Molecular weight: 84.007 Density: 221 1


a - 0.7510 b = 0.9700 c = 0.3530

B - 930 19'

17501

[ 18 1.3841

18421

1861

18421

19761

[ 13691

[1217]

[4071

I3671

I Admixture

Na,SO, + hexamethylenimine

NaCl

NaCl

NaC1, NaNO,, Na,SOd

admixtures

admixtures

admixtures

admixtures

benzenesulp honates

carbamate

surfactants

Effect 1 Reference

I I13921

10. Tables 2 17


Mg2+. K+ N [ 13081

I

_1

NaCsH3N,0S

MONOSODIUM URATE

Molecular weight: 190.11 I

Na3H(CO3I2

TRONA



organic substances S - favourable I4211

benzenesulphonates I4071

surfactants G. H, S I1368.13791 ,

2 18 10. Tables

Admixture

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

Ca2+

surfactants

NaI 2 H,O

SODIUM IODIDE dihydrate Molecular weight: 185.925 Density: 2448

System: triclinic 2 - 4

a - 0.6850 b - 0.5760 c = 0.7160

a - 98000' 0 = 119000' y ~68~30'

Effect Reference

H [3731

favourable I4721

hydrophobization [ 1464)

Admixture Effect

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

NaNO,

SODIUM NITRITE



a - 0.3550 b - 0.6660 c = 0.5380

10. Tables 219

NaNO,

SODIUM NITRATE Molecular weight: 84.995

System: trigonal

a - 0.6320

a 4 7 O 14'

Density: 2257

3-2

Admixture

Fe3+

I HN03, Na2C03, NaC1. NaN02,

Fe,O,

Pb2+, Ca2

solid impurities

aniline sulphonate, Wool scarlet,

Chloramine sky blue FF, Acid

green GG extra, Soluble blue,

Induline, Gallophenine D

Congo red, Oxamine blue B.

Magenta, Fuchsine. Methylene

bllie

Effect

Ostwald riDenina

N

n

S . H

N. G

unfavourable

H - /001/ faces on a

rhombohedron

H

caking

hydrophobization

Reference

[ 14531

14121

I57 11

[ 10271

[2721

19761

[2241

[ 1442)

220 10. Tables

Admixture

CH,COOH

s10,2-, VO;

NaOH - H20 SODIUM HYDROXIDE monohydrate


System: rhombic Z = 8

B - 0.6210 b - 1.1720 c - 0.6050

Effect Reference

N I8871

16341

NaOH

SODIUM HYDROXIDE


System: rhombic

B - 0.3397 b - 0.3397 c = 1.1320


Na,PO, 12 H 2 0

SODIUM PHOSPHATE dodecahydrate



a = 1.2020 c = 1.2660

10. Tables 22 1

Admixture

surfactants

Effect Reference

G 1549, 13461

~

Na2S20, 5 H20

SODIUM THIOSULPHATE pen tahydrate



Admixture Effect

Na,S, pH > 8 D

a = 0.5944 b = 2.1570 c = 0.7525

Reference

1101

222 10. Tables

Na,S04 10 H,O

SODIUM SULPHATE decahydrate


System: monoclinic

a - 1.1430 b = 1.0340

SODIUM SULPHATE


System: rhombic

a = 0.5860 b = 1.2300

Density: 1468

2 = 4

c = 1.2900

Density: 2665

2 - 8

c = 0,9820


Na9B,O7 N I56.13121

admixtures I9141

admixtures N, G I5071

NOn-. sulphamate H. G I4831

impurities from caprolactam I5061

surfactants H - rounded crystals 1423,9761

surfactants I8581

10. Tables 223

Admixture

Mg2+, Ca2+, N3+, H,PO,

Pod3-

Na2SiF6

SODIUM HEXAFLUOROSILICATE



a - 0.8860 c - 0.5020

Reference

18991

Effect

G [lo591

Admixture Effect

Ca2+. M3+ D

Na2Si03 - 9 H 2 0

SODIUM SILICATE nonahydrate

Reference

[531

224 10. Tables

Admixture

Ni(HC0O)Z 2 H2O

NICKEL FORMATE dihydrate


Effect Reference


Mg2+ D I581

Mg2+. Mn2+ I D I[58.601 I

Ni(CH3COO)Z 4 H2O

NICKEL ACETATE tetrahydrate


10. Tables 225

Admixture

Mg2+, Zn2+

Ni(NO& 6 H2O

NICKEL NITRATE hexahydrate

Molecular weight: 290.81 1 Density: 2050

System: triclinic z = 2

a - 0.5790 b - 0.7690 c = 1.1890

cc - 106" 38' B = SOo 32' y =lolo 27'

Effect Reference

D, H IS21

Admixture

H,O,

Ni[OH),

NICKEL HYDROXIDE I Effect Reference

filterability 113991

Molecular weight: 92,706

System: hexagonal Z = 1

a - 0.307 c - 0.4605

226 10. Tables

Admixture

Fe2+

Ni(OH),CO,

BASIC NICKEL CARBONATE



H,O, filterability [ 13991

Effect Reference

D [488,489]

NiSO, 7 H2O

NICKEL SULPHATE heptahydrate



a - 1.1800 b - 1.2000 c = 0.6800

inorganic ions

Zn2+, Mg2+ ,

gelatin

H. adsorption poten- [2751

tial

D 1581

H. dissolution [2231

10. Tables 227

~~~~~ ~~ ~~ ~

Admixture

Ag+

PbBr2

LEAD BROMIDE

~

Effect Reference

[1235]


System: rhombic z = 4

Admixture

uo,2+

polyglutamic acid, polyvinyl-

sulphonate

a = 0.4720 b = 0.8040 c - 0.9520

Effect Reference

transform. 11 1641

N [1167]

gum arabic H I I2151

PbCOs

LEAD CARBONATE



228 10. Tables

Admixture Effect

pH G. H

Pb(CH3COO)z 3 H2O

LEAD ACETATE trihydrate I Reference

I8071

PbC1,

LEAD CHLORIDE


Syetem: rhombic Z = 4

a - 0.4520 b = 0.7610 c = 0.9030

I Admixture

KC1, NH,C1, CdCl,, HC1

Mn2+, Co2+, Ni2+, Cu2+

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

PbFQ

admixtures

dextrine

Effect

H

e.

H, N. G

D

N

N, large metastable

zone

H - rounded crvstals

Reference

110191

I3741

I 12541

16761

I4131

1894,8951

10.Tables 229

Admixture

glutamate, gluconate,

citrate. tartrate, EDTA

acetate, gluconate. EDTA,

citrate. tripolyphosphate

PbCrO,

LEAD CHROMATE


System: monoclinic

x - 0.682

3 = 1020 33’

b - 0.748

Effect Reference

N I10151

N I10171

Density: 6100

2 - 4

c - 0.716

Admixture

pH

pH

Effect Reference

G [ 12773

modif. [1278]

230 10. Tables

Effect

D

D

D

H

G, H

D - pleochroism

Pb"O,),

LEAD NITRATE


System: cubic

R 0.7810

Reference

(928.10461

I8571

[ 10841

I8671

I1241

[130.391,43 1,

597,598,664,

Density: 4535

2 = 4

H - cubes

G

G, D, H

Admixture

Ba(NO,),

Ba(NO,), + NaCl

RalNO,I,

[200,430,432,

437.44 1,442.

443,96 1,14021

I1331

[ 1238.1239,

1240.12431

Capri blue

Methylene blue

Methylene blue

Methylene blue

Methylene blue

Methylene blue

10. Tables 231

Pb,(P04)2, PbHPO4, Pb2P20,

LEAD PHOSPHATES

Pb(N03)2

(continued)


Methylene blue N 113411

Methylene blue, Bismarck brown D I3891

Methylene blue, Thionine blue S 18571

Thionine blue H. D [ 124 1.12421 i

1 Admixture Effect

uo,2+

Reference

[1164,13111

232 10. Tables

I PbS

Admixture Effect Reference I

EDTA equilibrium, G 113511 _I

LEAD SULPHIDE


System: cubic

a = 0.597

PbS

LEAD SULPHIDE


System: cubic

a = 0.597

PbSO,

LEAD SULPHATE


System: rhombic

a - 0.845 b - 0.538

Density: 6200

c = 0.693

Admixture

RaSO, + HNO,

admixtures

pyrophosphate, tetrameta-

acetate, gluconate, EDTA, citrate.

tripolyphosphate

alcohols

surfactants

Effect

D

G. H

precipitation

Reference

I6651

[ l O O S l

I8 101

[lo171

I10131

I8101

10. Tables 233

Admixture

Pb2+. Sn2+, Zr4+, Ti4+

RbCl

RUBIDIUM CHLORIDE


System: cubic 3 = 4

a - 0.6540

Effect Reference

favourable I4721

Admixture Effect

OH- I G I I7041

Reference

RUBIDIUM DIHYDROGEN PHOSPHATE

Fe3+, Mg2+, SiOS2-, Ca2+, Ag+, BiS+, I H 118401

Fe3+, pH H

234 10. Tables

Admixture

p olyglutamic acid, polyvinyl-

sulphonate

SrCO,

STRONTIUM CARBONATE



a - 0.513 b 0.842 c = 0.610

Effect Reference

N [1165,1167]

Sr(HCOO), 2 H 2 0

STRONTIUM FORMATE dihydrate

Molecular weight: 213.686 Density: 2255 ~


a - 0.7300 b - 1.1990 c = 0.7130


cations G

10.Tables 235

Admixture

Fe2+, Fe3+

inhibitors, Mg2+, Zn2+

Mg2+

phosphonates

~

3rF,

STRONTIUM FLUORIDE

Holecular weight: 125.63

System: cubic

L - 0.586

Effect Reference

D I 11801

G. dissolution 13.41

G I5 151

G I1351

I uo,2+ I transform. I I1164.13111 I

SrHPO,, Sr,P,O,, Sr,(PO,),

Admixture Effect

F- G

Reference

I36 11

Admixture Effect

F- G

Reference

I36 11

uo,2+ transform. I 1 164,13 1 11

236 10. Tables

System: cubic 3 6 4

a - 0.7763

Sr"O&

STRONTIUM NITRATE

Molecular weight: 21 1.630

Admixture Effect r

Density: 2930

Ba2+ D

- L


Mn2+ D (1031

cu2+ D 1277,10261 /

I saphranine, wood extract 1 H . D

Reference

[ 11451

[12011

ZnC204 - 2 H20

ZINC OXALATE dihydrate


10. Tables 237

Admixture

N a phosphates

N a phosphates

N a triphosphate

pH, phosphates, Fe3+, Cr3+

3rS0,

STRONTIUM SULPHATE Kolecular weight: 183.70

System: rhombic

I - 0.836 b - 0.536

Effect

H. G

N - retarding

N

H

p H

pH = 4.6

pyrophosphate

tripolyphosphate

tripolyphosphate

S

G - maximum

G

H, aggregation

N. G

z = 4

c = 0.684

Reference

[900,9011

[950.951,10061

[ 12481

[g041

18061

18631

13081

110071

CVHSOH

CH,OH

phosphonate

polyvinylsulphonate

polyvinylsulp honate

S

N

H. S

1904.949.950

1007.10 171

[ 12451

13411

(10631

[1163.11681

11 162,11731

238 10. Tables

Admixture Effect

SrSO,

(continued)

Reference


sodium cltrate. EDTA H (1006, 10091

surfactants. citrate. EDTA 110061

water soluble polymers H. inhibition N 11162, 11741

Fe2+

alcohol + surfactant

TITANIUM DIOXIDE (anatase) lmo2 W301

N, G I5931

10.Tables 239


Mg2+, Mn2+ D [58,601

Zn(HCOO), 2 H 2 0

ZINC FORMATE dihydrate


Admixture Effect

gluconate. tartrate, EDTA. N

Reference

I10151

ZnC4H604

ZINC ACETATE


I I Admixture I Effect I Reference

I I I Co2+, Cd2+ D I [63l I

240 10. Tables


Ni2+ D [ 150 1, I5021

ZnK2(S04), 6 H20 I ZINC POTASSIUM SULPHATE hexahydrate

Zn(NH4)2(S04)2 6 H20 ZINC AMMONIUM SULPHATE hexahydrate I Molecular weight: 401.687

System: monoclinic

a - 0.920

!3 = 106O 52'

b = 1.247 c = 0.623

Admixture

Fe2+, Ni2+, Co2+, Cu2+

Effect

D

n

Reference

11499,1500,

15021

10. Tables 241


Zn(NO& - 6 H,O

ZINC NITRATE hexahydrate


System: rhombfc z = 4 a = 1.2240 b - 1.2850 c = 0.6290

ZINC SULPHIDE


System: hexagonal

242 10. Tables

~ ~~ ~~ ~

Admixture

co2+

ZnSO, 7 H,O

ZINC SULPHATE heptahydrate Molecular weight: 287.544 Density: 1957


a - 1.1850 b - 1.2090 c - 0.6830

Effect

D

Admixture

CU2+ I D I

Effect

+ Cu2+, Fe2+, Co2+

Reference

[ 13431

162,9851

I9861

[57,611

f488.4891

~

ZnWO,

ZINC TUNGSTATE Molecular weisht: 313.3

Reference

11831

10. Tables 243

H

ORGANIC SUBSTANCES

I

I991


System: tetragonal

caking

H

H - prisms

H

H

N

H

H

caking

H

G

G. H - cubes

admixtures, solvents

I9781

I991

[22 11

I4 161

[ 11411

I6291

I4 171

113481

[ 12891

I1001

12921

13831

[ 10821

alkylamines, HCOOH

biuret

biuret

- biuret 3-5 YO

biuret, cyanuric acid

biuret, formamide

Density: 1335

332

Effect I Reference

244 10. Tables

Admixture Effect

dyes

solvents capping growth

solvents G

surfactants caking

Reference

I1781

I5661

113421

19781

CH4NZS

THIOUREA



a = 0.550 b = 0.708 c = 0.857


NH,SCN I6273

CH,OH N I5191 I

10. Tables 245



Methylene blue D. H - prisms 1434.43 51

Admixture

Ca2+

Fe2+, Cu2+, Pb2+

C2H204 2 HZO

OXALIC ACID dihydrate Molecular weight: 126.04

System: monoclinic

a - 0.612

I3 - 106O 12'

b - 0.361

Effect Reference

D 13591

D 14941

Density: 1653

3 = 2

c - 1.203

246 10. Tables

Z,HBO,N

WINOACETIC ACID

aolecular weight: 75.07

Admixture

Trypan Red, Chloramine Sky Blue

FF. Chromotrooe 2B

Methyl Blue MBJ

aminoacids

Effect

H - long needles

/(Ill/

H - suppresses

needles

N

Reference

12 151

[2151

1784,1444,

14461

CSH4O4N4

UREA OXALATE


I Admixture

Magenta , Fuchsine , Tartrazine ,

Eosine

Neutral red

Victoria blue, Brilliant green,

Malachite green, Gentiana blue

Effect

H - /010/

H - needIes

H - /201/

Reference

14441

(4441

I4441

10. Tables 247

Admixture

C3H702N

AMINOPROPIONIC ACID (L-ALANINE)

Effect Reference

Brilliant yellow I G I I7781 I I I

admixtures I G , H I I7921 I

C4H604

SUCCINIC ACID


System: monoclinic

a = 0.506

B = 133O 37'

b - 0.881

2-2

c = 0.757

Admixture

solvents

isopropanol

Effect

H

G, solubility

Reference

129 11

[ 14501

248 10. Tables

Admixture

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

so42-. c1-

cuso,

admixtures

C ~ H ~ O B HSO

TARTARIC ACID monohydrate Molecular weight: 168.09

System: triclinic

a - 0.809

a - 8 2 O 20'

b - 1.003

B - 1180 0'

Effect Reference

D I4921

H I6051

n I 1 1471

Density: 1697

2 = 2

c - 0.481

y =72O 58'

Admixture

solvents

Effect Reference

I3381

C4H808N8

OCTOGENE (TETRANITRO-TETRAZA OCTANE)

1O.Tables 249

Admixture

1-glutamlc acid

C4HQOSN

L-THREONINE


Effect Reference

D "7691

Admixture

Magenta, Fuchsine

Bismarck brown. Neutral red.

Safranlne, Methylene blue

C4HeO4N

y-AMINOBUTYRIC ACID

Molecular weirtht: 136.124

Effect

H - width prolonga-

tion

H - length prolonga-

tlon

surfactants IN, H I I8091

CsH4OsN4

URIC ACID I Molecular weight: 168.11 Density: 1893

I

Reference

I4461

I4461

250 10. Tables

Admixture

amino acids

1-aspartic acid, 1-valine, 1-leucine,

I-p henylalanine

1- aspartic acid

C6H904N

L-GLUTAMIC ACID


Effect Reference

111141

N, G I5181

N. G [ 14751

Admixture

Ca formiate and acetate

CSH1006

XYLOSE Molecular weight: 150.13 Density: 1530

System: rhombic Z = 4

a - 0.921 b - 1.248 c = 0.556

Effect Reference

G - acceleration 19381

10. Tables 251

Admixture

admixtures

Effect Reference

113891

Admixture

Ca[HCOO),

dipentaerythritol

dipentaerythritol

dipentaerythritol

Effect Reference

N. G [ 15121

N. S 115131

N I6181

G. N. S 16191

252 10. Tables

CBH,OZNCl

m-CHLORONITROBENZENE



admixtures I2441

structurally similar additives H I2451

COHO

BENZENE

Effect Admixture


System: rhombic I Reference

2 = 4

10. Tables 253

Admixture

C6H602

RESORCINOL


System: rhombic

a - 0.966 b = 1.05

Effect Reference

Density: 1285

2 - 4

c = 0.568

Admixture

Magenta, Fuchsine, Toluidine blue

Effect Reference

H 14451

C6H603

PHLOROGLUCINE (1,3,5-TRIHYDROXYBENZENE) I IMolecular weight: 126.114 1

254 10. Tables


I I t

C6HS06

ASCORBIC ACID



methanol I8591

Admixture I Effect I Reference I I I

CITRIC ACID


surfactant I I [9161 I


H,SO, G I9871

10. Tables 255

Admixture Effect

amino acids H

Reference

I6251

C6H 10°4N2

ETHYLENEDIAMINE TARTRATE


I Admixture Effect r

Ca2+. Mg2+. Cu2+, A13+ H

Fe3+. A13+, Ca2+, Mg2' H - wedge

pH H

9 H = 6.0

pH = 6.0

pH = 7.5

H, S favourable

H - needles

low sensibility to

Reference

18401

17091

18401

256 10. Tables

G - decreasing

H - needles, thin

plates

physical properties

G Inhibition

N, G

H

C6H1004

ADIPIC ACID Molecular weight: 146.15 Density: 1366

System: monoclinic z = 2

a - 1.027 b - 0.516 c = 1.002

0 - 137O 5'

[888,889,

8901

[888,889.

8901

I4961

12881

19661

I9331

I Admixture I Effect I Reference trimethyldodecylammonium

chloride

sodium dodecylbenzenesulphonate

n-alkanoic acids

n-alkanoic acids

related compounds

succlnic acid, solvents, formic acid

10. Tables 257


' cyclohexanone D I13521

cyclo hexanone G I9621

' solvents H I981

trichlorethylene N, S . D [ 13021

C6H110N

CAPROLACTAM

Admixture

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

Ni2+. Cu2+, Fe3+

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

HqSO,

p H

1-alanine


Effect Reference

H [8401

H. D I9091

H [ 13821

H, G - retards 17241

H 18401

G I5961

C6H1104N3 ' H2S04

FRIGLYCINE SULPHATE

Yolecular weight: 287.26

258 10. Tables

Admixture Effect Reference L

c6H1206

GLUCOSE Molecular weight: 180.17

System: rhombic

a - 1.040 b - 1.489

fructose

fructose

fructose

Density: 1544

2 = 4

c = 0.499

mutarotation 1751.7531

N [980.7531

H, G [752.753]

c6H1206

SORBITOL



soap [7701 _i

10. Tables 259

1 C6H12N4

HEXAMETHYLENETETMINE, (UROTROPIN)


System: cubic

Admixture Effect

z = 2

Reference

benzylalcohol + Si02

Ca and Mg stearates

solvents

caking 1831

caking [831

G [ 159.1 SO]

L-ISOLEUCINE



surfactants H [ 1134,1508,

15091

260 10. Tables

Admixture

admixtures

Effect Reference

D I6961

C7H602

BENZOIC ACID

I Molecular weight: 122.13 Density: 1266


ethylalcohol G I7381

admixtures G I10581

.

System: monoclinic

a - 0.544 b = 0.518

D - 970 5'

2 = 4

c = 2.16

10. Tables 26 1

Admixture Effect

derivates of benzoic acid N

I p-HYDROXYBENZOIC ACID

Reference

[ 14451


tailor-made additive H 1

262 10. Tables

~


Li, Na. K, C s halides I7391

a-naphtylamine sulphonate, H - thin plates /010/ I2151

Bismarck brown, Fuchsine

diphenylamine. Methylene blue, H 14333

Malachite Preen

%*6O4

PHTHALIC ACID



a - 0.933 b = 0.713 c = 0.510

B - 9 4 O 36'


admixtures 193 11

I

10.Tables 263

Admixture Effect

dyes H - / l o o / >> /llO/

Reference

[215]

C1oHs

NAPHTHALENE Molecular weight: 128.17

System: monoclinic

a - 0.834

D * 122044'

b = 0.598

Admixture

fenantrene, anthracene

biphenyl

Density: 1145

Z = 2

c = 0.868

Effect Reference

G. H I10401

G I9633

264 1O.TabZes

~~~

Admixture Effect

solvents N

C12HlO

ACENAPHTHENE Molecular weight: 154.21 Density: 1024


a - 0.892 b = 1.415 c = 0.726 =

Reference

I8361

Admixture

solvents

solvents I G I I8371

Effect Reference

G. H I5671

ClZHlO

BIPHENYL

Molecular weight: 154.21 Density: 11 80

System: monoclinic 2 = 2

m - 0.811 b - 0.567 c = 0.957

10. Tables 265


acetone S D171

C12H1,OTNdP2S HCl

COCARBOXYLASE HYDROCHLORIDE


Admixture

CaCI, , AlCl,, FeCI,

Effect Reference

G I3131

Cl2H22Oll H2O

LACTOSE mono hydrate Molecular weight: 360.31

L

266 10. Tables

C12H22O11

SUCROSE


System: monoclinic

a - 1.065 b 0.870

p = 105O 44'

Admixture

Ca2+, Na+, K+

CaCl,, Na,C03

inorganic salts

KC1, CaCl,, MnSO,. NH,NO,. CdI?

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

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

admixtures

admixtures

admixtures

Density: 1588

2 = 2

c = 0.800

Effect

H

N. G, H. S

G

G.H

H

Reference

I14841

[ 14861

[6 131

13371

[1284.1285,

12861

W 4 1

19971

11 188,13401

1451

13061

10. Tables 267

C,2€€2,0,, (SUCROSE)

(continued) ~

Admixture

amino acids

betaine

colouring impurities

dextrose

dextrose

impurities

impurities, colouring substances

raffinose I raffinose. glucose

I saccharides

starch, dextrine

Effect

c,

G, H

D

G

G

~

H

G. H

G. H

c,

Reference

12 191

I83 11

I14921

I131

[3361

(525.5261

11485,149 11

I14.334.335.

33 7,554.

12521

I337.568.

8321

[555,556]

I3371

[ 14861

268 10. Tables


i tolan D periodicity I7541

C14H14

DIBENZYL


System: monoclinic Z = 2

a - 1.282 b - 0.618 c = 0.774

0 = llSO 0'



pop, ci- G 115061

I

.

C15H1202N2

PHENYTOIN I

10. Tables 269

H. polymorphs

H

G . H

C16H3202

PALMITIC ACID Molecular weight: 256.432

System: monoclinic 2 = 4

a - 0.941 b = 0.500 c = 4.59

B - 50° 50'

14271

[4281

[761

[lo611

Admixture Effect

~~ ~ ~~~~~

C18H3602

STEARIC ACID Molecular weight: 284.49

System: monocIinic

a - 0.5546 b = 0.7381

3 = 63O 38'

Density: 941

2 = 4

c = 4.884

Admixture

solvents

surfactants

butanone + emulsifier

unsaturated homologues

solvents, sorbitone monostearate

Effect I Reference

G. H I I751

270 10. Tables

Admixture

hydrocarbon solvents

CnH2n+2

PARAFFIN

Admixture Effect

admixtures

inhibltors G

polymers N, G

solvents H. G

Effect Reference

N I2431

15501

10. Tables 271

Admixture

solvents

C27H460

CHOLESTEROL I Effect Reference

H [4261

Admixture

C32H60

N-DOTRIACONTANE

Effect Reference


polymers I I [801 I

272 10. Tables

PROTEINS I I Admixture EXfect Reference

phospholipids 18651 L

%*74

HEXATRIACONTANE

Molecular weirrht: 506.988


G , H I12311

FORMULA INDEX

Inorganic substances

AgBr

AgCl

4 1

AgN0,

AlCs(S04)2 * 12 H2O

AlCl, . 6 H 2 0

AlF3 . 3 H2O

AlK(SO4)2. 12 H 2 0

AlNH,(SO4)2 * 12 H2O

Al(NO,), * 9 H2O

Al(OH),

A1203.M20.n SiO, m H20

AlPO,

AlRb(SO,), * 12 H2O

AITl(SO,), . 12 H 2 0

Alz(SO4)3 . 16 H20

Ba(B0&

BaBr2 - 2 H 2 0

BaC0,

BaC204

silver bromide

silver chloride

silver chromate

silver iodide

silver nitrate

aluminium cesium sulphate

aluminium chloride

aluminium fluoride

aluminium potassium sulphate

aluminium ammonium sulphate

aluminium nitrate

aluminium hydroxide

zeolites

aluminium phosphate

aluminium rubidium suIphate

aluminium thallium sulphate

aluminium sulphate

barium borate

barium bromide

barium carbonate

barium oxalate

78

79

80

80

81

81

82

82

83

85

86

87

86

88

88

89

89

90

90

91

91

274 10. Tables

BaC12 - 2 H20

BaCr04

BaF,

Ba(I0312 . H20

Ba(N0312

Ba(OH), . 8 H,O

BaS04

BaTiOQ

Be(NH412F4

(C2H,I4NI

CaC03

CaCz04 - H20

CaC4H,0,

Ca(C&, 10712

CaC12. 2 H20

CaFz

CaHP04. 2 H20

CaHPOq. 3/2 H 2 0

Ca(N0312 . 4 H20

Ca(OH12

Ca3(P04)2

Ca2P20, - 2 H 2 0

Ca3(PO4l2 CaF2

barium chloride

barium chromate

barium fluoride

barium iodate

barium nitrate

barium hydroxide

barium sulphate

barium titanate

ammonium beryllium fluoride

tetraethylammonium iodide

calcium carbonate

calcium oxalate

calcium tartrate

calcium gluconate

calcium chloride

calcium fluoride

calclum hydrogen phosphate

calcium hydrogen phosphate

calcium nitrate

calcium hydroxide

tricalcium phosphate

dicalcium phosphate

ff uorapatite

92

93

94

94

95

96

97

104

190

92

99

105

108

109

108

109

110

111

112

112

113

114

114

10. Tables 275

Ca3(PO4I2 - Ca(OHI2

CaSO,

CaS04 - 2 H20

CaSi03

Ca(C5H3N403),

CaWO,

Ca,H2(P04), - 5 H20

CdCOs

Cd(CHO2)2 * 2 H,O

CdS

C0C03

Co(CH02)Z 2 H2O

Co(CH,C02)2 * 4 H2O

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

C0S04 - 7 H 2 0

CrK(S04), - 12 H20

CrNH4(S04)2 . 12 H20

C~Al(SO4)121 * 12 H2O

CSH~ASO,

CSI

CsN0,

CUClz * 2 H2O

Cu(CH02)2 * 2 HZO

hydroxyapatite

calcium sulphite

calcium sulphate

calcium silicate

calcium urate

calcium tungstate

octacalcium phosphate

cadmium carbonate

cadmium formate

cadmium sulphide

cobalt carbonate

cobalt formate

cobalt acetate

ammonium cobalt sulphate

cobalt sulphate

potassium chromium sulphate

ammonium chromium sulphate

aluminium cesium sulphate

cesium dihydrogen arsenate

cesium iodide

cesium nitrate

cupric chloride

cupric formate

115

114

117

116

123

123

113

124

124

125

125

126

126

127

127

128

128

81

129

129

130

130

131

276 10. Tables

cupric acetate

cupric chromate

ammonium cupric sulphate

cupric hydroxide

basic cupric carbonate

cupric sulphate

ammonium ferrous sulphate

ferric oxide hydroxide

ferric hydroxide

ferric oxide

magnetite

ferrous sulphate

ice

boric acid

phosphoric acid

mercuric bromide

mercuric cyanide

aluminiumpotassium sulphate

potassium pentaborate

potassium bromide

potassium bromate

potassium cyanide

potassium carbonate

13 1

131

132

132

132

133

134

134

135

135

136

136

137

137

138

140

140

83

141

142

143

143

141

1O.TabZes 277

QcZ04 ' H2°

KC1

KClO,

KCIO,

K2Cr04

%,cr207

KCr(S0412 - 12 H,O

K4Fe(CN16 * 3 H,O

KH2As04

KH2PO4

KHC,H,O6

KHCSH404

KI

uo3

K2Mg(SO,l2 * 6 H2O

KMn0,

KNO2

KNo3

KNaC4H40,

K2s04

K2s206

KTiOPO4

K2Zn(S04)2 6 H,O

potassium oxalate

potassium chloride

potassium chlorate

potassium perchlorate

potassium chromate

potassium dichromate

potassium chromium sulphate

potassium ferrocyanide

potassium dihydrogen arsenate

potassium dihydrogen phosphate

potassium hydrogen tartrate

potassium hydrogen phthalate

potassium iodide

potassium iodate

potassium magnesium sulphate

potassium permanganate

potassium nitrite

potassium nitrate

sodium potassium tartrate

potassium sulphate

potassium dithionate

potassium titanyl phosphate

zinc potassium sulphate

144

145

151

152

153

154

128

144

154

155

158

158

159

157

170

160

160

161

163

165

164

162

240

278 10. Tables

lithium chloride

lithium fluoride

lithium iodide

lithium iodate

ammonium lithium tartrate

lithium sulphate

magnesium carbonate

magnesium acetate

magnesium fluoride

magnesium formate

magnesium oxalate

potassium magnesium sulphate

ammonium magnesium sulphate

magnesium nitrate

magnesium hydroxide

magneslum sulphate

manganous carbonate

manganous formate

manganous sulphate

aluminium ammonium sulphate

ammonium beryllium fluoride

ammonium bromide

ammonium oxalate

167

168

168

169

159

170

171

169

172

172

171

170

173

173

174

175

174

176

176

85

190

177

181

10. Tables 279

ammonium chloride

ammonium chlorate

ammonium perchlorate

ammonium cobalt sulphate

ammonium chromium sulphate

ammonium cupric sulphate

ammonium ferrous sulphate

ammonium hydrogen carbonate

ammonium hydrogen oxalate

ammonium hydrogen tartrate

ammonium dihydrogen phosphate

ammonium hydrogen phosphate

ammonium lithium tartrate

ammonium magnesium sulphate

ammonium nitrate

ammonium nickel sulphate

ammonium sulphate

ammonium titanyl sulphate

ammonium uranate

ammonium tungstate

zinc ammonium sulphate

sodium hexafluoroaluminate

sodium perborate

178

182

182

127

128

132

134

183

183

184

185

184

159

173

188

190

191

198

199

199

240

200

200

280 10. Tables

NaB02 . H20, - 3 H20

Na2B40, - 10 H,O

NaB508. 5 H20

NaBr . 2 H20

NaBr03

NaC2H302 - 3 H20

Na2C03 10 H 2 0

NaC5H804N - H 2 0

NaC6H20,N3

NaCl

NaClO,

NaC10,. H20

NaHCO,

NaC5H3N403

N a F

Na3H(CO3I2

NaI . 2 H20

NaKC4H406

N a N 0 2

NaN0,

NaOH

Na3PO4 I 12 H20

Na5P3OI0 a 6 H20

sodium peroxoborate

sodium tetraborate

sodium pentaborate

sodium bromide

sodium bromate

sodium acetate

sodium carbonate

sodium glutamate

sodium picrate

sodium chloride

sodium chlorate

sodium perchlorate

sodium hydrogen carbonate

sodium urate

sodium fluoride

trona

sodium iodide

potassium sodium tartrate

sodium nitrite

sodium nitrate

sodium hydroxide

sodium phosphate

sodium triphosphate

20 1

202

20 1

203

203

204

205

204

2 13

206

2 14

215

216

217

215

217

218

163

218

219

220

220

22 1

10. Tables 281

sodium sulphate

sodium thiosulphate

sodium hexafluorosilicate

sodium silicate

sodium zincate

nickel formate

nickel acetate

ammonium nickel sulphate

nickel nitrate

nickel hydroxide

basic nickel carbonate

nickel sulphate

lead bromide

lead carbonate

lead acetate

lead chloride

lead chromate

lead fluoride

lead nitrate

lead phosphates

lead sulphide

lead sulphate

aluminium rubidium sulphate

222

22 1

223

223

205

224

224

190

225

225

226

226

227

227

228

228

229

229

230

23 1

232

232

88

282 10.Tables

RbCl

RbH2P04

SrC03

Sr(CHO2I2. 2 H,O

SrFz

Sr(N0312

SrHP04

SrS04

7302

TlAl(S04)2. 12 H2O

Tio(NH&(S0412

ZnC204 2 H20

Zn(CHO2I2 - 2 H20

ZnC4H604

ZnCrO,

ZnK2(S0,), a 6 H 2 0

Zn(NH412(S0412 . 6 H20

Zn(N0312 . 6 H20

ZnS

ZnS04. 7 H20

ZnWO,

rubidium chloride

rubidium dihydrogen phosphate

strontium carbonate

strontium formate

strontium fluoride

strontium nitrate

strontium phosphates

strontium sulphate

titanium dioxide

aluminium thallium sulphate

ammonium titanyl sulphate

zinc oxalate

zinc formate

zinc acetate

zinc chromate

zinc potassium sulphate

zinc ammonium sulphate

zinc nitrate

zinc sulphide

zinc sulphate

zinc tungstate

233

233

234

234

235

236

235

237

238

89

198

236

238

238

238

240

240

24 1

24 1

242

242

10. Tables 283

Organic substances

urea

thiourea

urea nitrate

oxalic acid

aminoacetic acid

urea oxalate

L-alanine

succinic acid

tartaric acid

octogene

L-threonine

y-aminobutyric acid

uric acid

L-glutamic acid

xylose

trimethylolethane

pentaerythritol

m-chloronitrobenzene

benzene

allopurinol

resorcinol

phloroglucine

243

244

245

245

246

246

247

247

248

248

249

249

249

250

250

25 1

25 1

2 52

252

254

253

253

284 10. Tubks

C6H806

C6H807

C6H902N3

C6H 10'4

C6H 1 0°4N2

loN

C6H1104N3 ' HzS04

C6H1206

C6H1206

C6H12N4

C6H 1 3°2N

C6H16N2

C7H602

C7H603

C7H7ON

C8H604

C8H604

C9H9'3N

'loH,

C12HlO

C12H10

C1,Hl,O,N4P,S * HCl

ascorbic acid

citric acid

L- histidine

adipic acid

ethylenediamine tartrate

caprolactam

triglycine sulphate

glucose

sorbitol

hexamethylenetetramine

L-isoleucine

hexame thylenediamine

benzoic acid

p-hydroxybenzoic acid

benzamide

phthalic acid

terephthalic acid

hippuric acid

naphthalene

acenaphthene

biphenyl

cocarboxylase hydro-

chloride

254

2 54

255

256

255

257

257

258

258

259

259

260

260

26 1

26 1

262

262

263

263

264

264

265

10. Tables 285

C12H22Oll * H2O

c 12H22O 1 1

C14H14

C15H1202N2

C16H3202

C18H3602

CnH2n+2

C24H50

C27H460

C32H66

C36H74

lactose

sucrose

dib enzyl

phenytoin

palmitic acid

stearic acid

paraffin

tetracosane

cholesterol

N-dotriacontane

hexatriacontane

proteins

265

266

268

268

269

269

270

270

271

27 1

272

272



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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

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288 11. References to Tables

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I151 Aldcroft. D.. Bye, G.G., Hughes, C.A.: J. Appl. Chem. 19 (1969) 167

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I171 Alfimova. L.D.. Velikhov. Yu.N.. Demirskaya. O.V.: Vysokochist.

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I181 Alkashi, H., Kagaku. N.R.: J. Japan Chem. Soc. 2.(1948) 212

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1201 Ambrose. S., Kanniah. N.. Gnanam, F.D., Ramasamy. P.: Crystal Res.

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I2 11 Amelina. E.A., Vaganov. V.P., Shchukin. E.D.: Kolloidn. Zhur. 42 (4)

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1221 Ameneiro Perez, S.: Rev. Cubana Fis. 4 (1) (1984) 129

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1241 Amjad, 2.: Roc. Symp. Adsorpt. Surface Chem Hydroxyapatite (1984)

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I251 Amjad. 2.: Langmuir 3 (2) (1987) 224

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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 289

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

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I371 Amjad, Z., Mooley. J.: J. Colloid Interface Sci. 111 (2) (1986) 496

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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

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I421 Annede Cugnac. H.J.. Pouradier. J.: Compt. rend. 264 (1967) 1149

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I441 Aoki. S.. Yoshida. M.. Aral, Y.: Gypsum Lime 178 (1982) 129

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


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

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(481 Austrian Pat. 248 479 (1963)

1491 Austrian Pat. 343 597 (1978)

1501 Autenrieth. H., et al.: Chem. Ing. Tech. 29 (1957) 709

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1521 Babayan. S.G.. et al.: Radiokhimiya 4 (1962) 521

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1541 Babich. S.A.. Soifer, L.M., Chubenko, A.I., Shakhnovich, M.I.: Sb.

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1551 BabiC- IvanEiC, Ftiredi-Milhofer. H.. PurgariC, B.. BrniceviC, N..

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I561 Babin. L., Clausse, D., Sifrini. I., Broto. F.. Clausse, M.: J. Phys.

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I581 Balarew. Khr.: Inclusion of isomorphous admixtures in crystal

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12. Subject Index

A

active site 11.14.17.19.20,21

activity 8.13

additive 6.7.8.12.13.22.25.27.28

adhering mother liquor 45.46.49.53

adsorption 11,13.17,18,19,20.22,25.

30.34,41.42,43

adsorption isotherm 13.20

agglomeration 20

agitation 4.41

anomalous mixed crystals 34.43

attachment energy 25

B

bond 19.25.29.30.32

- chain 25

- energy 17.25

boundary layer 30

C

chirality 29

collision 9.1 1

collision breeding 9

colloids 11.34,44,45

computer simulation 5.28.33.48

concentration 6,7.10,13,15,19.2 1,

23.25.35.35.36.38,

39.40.41.42.45

coordination complexes 10

counter-current recrystallization 50

critical nucleus 11.13,14,17.18

cross-current flow 53

crystalgrowth 4.8.11.16,18,19.20,

21.22.23.24.28.29,

30.3 1,32.33.40

crystal lattice 4.15.19.20.2 1.22.23,

25.26.29.30.36.37.

4 1.42

crystal surface 8.1 1,13,14,15.16,17.

18,19.20.2 1.22.25,

26.28.29.30.32.33,

37.38.41.42.43.46

D

dielectric constant 3 1

diffusion 11.19.20,22,23.28,30,38.

39.40

diffusional regime 40

diffusion washing 54

388 12. SuQJectIndex

dislocation 32

- mechanism 32.33

dissolution 7.8,14,19.43

- rate 8

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

41,43

- coefficient see d. constant

- constant 37.38.39.43.47.48,

49

dust particles 44

dyestuffs 7.2 1

E

effectiveness 7.8.28

electric

- charge 14

- field 10.25.28

embryo 1 1

equilibrium 1 9,24,3 7.38.49

F

fractals 23

G

geometric similarity 10.22

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

growth site

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

24.3 1

- restrainer 15.19

- site 17.20.21.29

H

habit 18.28.3 1,37

heteroclusters 10

heterogeneous nucleation 9.12,13

heteronucleus 2 1

heteroparticles 13

homogeneous dfstribution 38.40.41

- coefficient 38,41

-law 38.49

homogeneous nucleation 9,10,11

hydration 12,28

hydrogen bonding 30.31

I

impurities 5,6,12.34.37.38.4 1,43.44.

45.48.47.48.49.53.54

impurity concentration gradient 15

induction period 12

inhibiting effect 10

inorganic additives 7.10,14,19

interface 4.23,30,31

12. SubjectIndex 389

interphase 9,13,14.22.23.28,39

isodimorphism 34.36

Isomorphous inclusion 34.35.36.37.

38,41,43

K

Kinetic regime 39

L

lattice 4.15.19.20.21.22,23,25,26,

29.30.36.37.41.42

- dimensions 21,23,26,36

logarithmic distribution 37.38.40

M

macroadmixture 6

macrocomponent 5.6.7.8.10.1 1.12.

14,19.21,22.29.

3 1.34.35.36.37.38.

39.40.41.42,44.45.

49

materials balance 45

mechanical inclusions 34.44

melt crystallization 54

melting point 37

microcomponent 5.6.3 7,38,39.40,

41.49.52

migration regime 40

miscibility 34,35.36,41.42

mother liquors 44.45,46.49,52,53

N

Nernst distribution 38.45

non-stationary precipitation 40

nucleatton 4. 9.10.12.13,14,15,19.

20.28,32

- mechanism 12.13.14.33

- rate 10.12,13.14

nucleus

- critical 11.13.17.18

- two-dimensional 18,20,22

0

organic additives 7.8.21.25

overlapping faces 24

P

pHvalue 7.22

polarity 31

polyvalent cations 7

primary nucleation 9

purification 4.4953

purity 4,5,3 4.3 7.49

R

recycling 45.46

- ratio 45,46,48,49

390 12. Subject Index

roughness 14.23.33

S

secondary nucleation 9.13,14

sectorial crystal growth 43.44

semistationary coprecipitation 39

separation 4.6.34.37.38.45.48

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

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

26.36.42

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

solid solution 34,36.37.41

solubility 1 2.22.32.35.3 6.3 7.42

solvent 4.6.30.3 1,32,33.34.37,45.

53

-mixed 31.32

stationary coprecipitation 39

steric arrangement 25

structure 11,16,21,23.25,29,31,32,

36.41.43

supersaturation 4,9,10,12,14,20,2 1,

22

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

19.20.22.25.26.28.29.30.32,

33.37.38.42.46

- active substances 7.13,22

surface - diffusion 19,20,22,30

- energy 13.17,20.21,24.31

- entropy factor 3 1.32

- integration 22.32

- nucleation 32

- tension 10

sweating 53

T

tailor-made admixtures 5.25,29

temperature 4.8.36,3 7,4 1.43,53

V

viscosity 11,23.30

W

washing 43,53.54

well fitting position 28

Engineering

[Jaroslav nyvlt, joachim_ulrich]_admixtures_in_cry(book_zz.org)