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Ostwald ripening of precipitates

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You are on page 1of 35

and Interface Science. 5 (1975) 1-35 Publishing Company, Amsterdam - Printed in The Netherlands

OSIWALD

RIPENING

OF PRECIPITATES

M. KAHLWEXT Max-Planck-Institut fiir biophysikalische D-34 GtTttingen (W. Germany) Chemie (Karl-fiiedr-ich-Bonhoeffer-lnstitutj.

CONTENTS

A. B. C. D. E. F. G. H. I. K. Introduction . . . . . . . . . . _ _ . . . . . . . . . . The size distribution of the precipitate and its development with time . . . Aging of particles under diffusion controlled growth in systems with convection Aging of particles under diffusion controlled growth in systems without . . . . . . . . . . _ . . . . . convection . . . . . . Aging of particles with secondorder growth kinetics . . . . . . . . . Comparison with the LSW theory . . . . . . . . . . . . . _ . . . The size distribution of the precipitate at the maximum of the aging rate . . . . . . . . _ . . , . . . Comparison with experiment , Ripening with periodic tempera&e changes . . . . _ . . . . . _ _ Further considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . _ . 1 .I 7 11 14 16 19 25 27 30

A. INTRODUCTION

Any system is unstable in the thermodynamic sense until its free energy has reached a minimum. Therefore a two-phase system consisting of a polydisperse precipitate within a parent phase is not stable, since the large interfacial area is a source of free energy arid further stabilization may be reached by decreasing this area. This conclusi-m is one which can be drawn from the celebrated paper of Gibbs On the Equilibrium of Heterogeneous Substances [I]. In this paper, in the paragraph following the condition for mechanical equilibrium eqn. (663), Gibbs then made the far-sighted statement: The obstacles to an exact realization of these relations are very great, _ . _ , but it may be easy to verify the general tendency toward diminution of surface, which is implied in the foregoing equations. Indeed, the coarsening of a precipitate was at that time already a well known technique in analytical chemistry. Ostwald 121 seems to have given the first correct qualitative description of the process, for which reason Liesegang [3] caLled it Ostwald ripening*_ Its driving force is the difference in solubility between the polydisperse particles of the precipi-

2 tate, as given by the well known Gibbs-Thomson c&-)-c_ =c_ [exp (a/r)

l] * c, - a/r

equation

(Al)

a = 2aV,/vRT Here, c,(r) denotes the solubility of a particle of size r, c, = c, (r = 00)) a the interfacial tension between the particles and the parent phase, V, the molar volume of the precipitate, v the number of its dissociation products, R the gas constant and T the absolute temperature. This solubility difference establishes a concentration gradient between the smaller and the larger particles, which leads to the growth of the larger particles at the expense of the smaller ones, the substance being transported through the parent phase. The rate of this aging process will thus be determined by the size distribution of the precipitate, its growth kinetics and the transport properties of the parent phase. As an example, we shall consider a system consisting of spherical particles precipitating from a stirred solution, We assume that the growth kinetics of the particles is diffusion controlled, i.e., that their growth rate is determined by the diffusion of the solute from the smaller particles to the larger ones. For the growth rate, we can then write i = kV, [F-cc,(r)] ; k =0/s

(A21

Here, c denotes the mean concentration of the solute in the parent phase, D its diffusion coefficient and 6 the thickness of the diffusion layer around the particles. If we replace c,(r) by eqn. (Al), we obtain

;=kVm

(AC-C_

a/r)

Ac~=F--c_.

(A3)

Since the concentration difference AC is always positive during the precipitation process, the sign of the bracket will be determined by the radius of the particle under consideration: All particles larger than r,(t) = ac, jAc (A4)

will grow while all particles smaller than r, will dissolve_ This situation leads to a continuous increase of the mean radius of the particles accompanied by a continuous decrease of their number per unit volume. Of course, r, is identical with the so-called critical radius of a nucleus. Thus, this critical radius plays a role not only during the nucleation period but also during the entire precipitation process, To discuss this point in further detail, we consider Fig_ 1 which illustrates the course of a precipitation. The upper part of the figure shows a schematic plot of the supersaturation II 5 (C/c_ ) versus time, while the lower part shows r, as well as the growth paths of a few particles. As the equilibrium line ll = 1 is crossed, r, decreases rapidly from infinity to small values and reaches its minimum at the maximum of ll,As thesubstance precipitates,thesupersaturationdecreases, and r, increases again. Each of the growth paths represents the life story of a particle

l-l

t __-_-_-_-___-_

0 ts 1

I

-t

i(t=co)

-----

=&(t=oD)

c----_---_

I

1 /

r-

:

I t \\I -

I

3

/! , , I I I t t

I l

lrlll

; ,

I

r;lItfltl

t lllltll

Fig. 1. (above) Supersaturation II vs. time t during a precipitation. re and radii r of precipitating particles vs. time t.

(below)

Critical radius

of the precipitate. As r, decreases, the first particles are formed (intersections between r and re). The nuclea\;ion rate reaches its maximum at the minimum of r, and then decreases again with increasing ;. until it becomes negligible. As each growth path crosses the r, curve, the particle enters a race with r,. During this race, all particles except one will sooner or later be overtaken by rC, because after very long times, in complete equilibrium, the new phase will consist of one single particle_ All growth paths except the highest one will, therefore, intersect the re cume for a second time, reaching their maxima at these intersections and then decrease again. The final radius of the largest particle, being identical with the final value of F,, is given by the mass balance. If we denote the properties of the largest particle by a star (*), then

r-q

t =oo)3<(t=oo)=3~[n-~

(t=ou)*Vl

WV

where n denotes the total number of moles of the precipitating substance in _ the (closed) system of volume V. One may express C (t = 00) in terms of r, (t = -) = r* (t = -), using eqn, (A4)

p(t = 00) = 32 -I+, (l+r*(tll__))]

;Y =n/V. to approximate Z( t = -) by

W6)

B. THE TIME SIZE DISTRIBUTION OF THE

PRECIPITATE

AND

ITS DEVELOPMENT

WITH

For the quantitative treatment we shall now introduce the size distribution N(r,t) of the precipitate, which at time t may have the shape shown in Fig. 2. N-dr then is the number of particles per unit volume at time t with sizes between r and (T + dr). The number of growing particles (r 2 rc) per unit is

then given by

Z(t) =

r

rC

N(r,t)

031)

Consequently,

i=

OaN s

N t

kinetics

of the particles.

If one assumes

grow

by reactions

with monomers only, one may introduce a flux J of particles from r to (r + dr) and write for the change of the size distribution with time

anr/at + aJ/ar

J=-

= 0,

033)

f -AL

8

l

(iUV/ar)

VW

Here, 0 deno%es a *diffusion coefficient which is defined as the number incorporated into the surface of a particle in unit time, multiwhere i is the number of monomers of which the particle plied by (dr/di)2, 1 consists. Inserting eqns. (B3) and (B4) into eqn. (B2), it follows that

of monomers

=-(0

= rc)

- i,

l aN/ar),,=-_(r=r,)=~,.

V35)

When, during the nucleation period at the beginning of the precipitation (t < t < t in Fig. l), the supersaturation R reaches its maximum, i.e. when i, = 0, then eqn. (B5) gives the (stationary) nucleation rate i (P, = 0) = Jsrat= (e - anr/ar),,, > 0. (B6)

When, on the other hand, after the nucleation period (t > t in Fig. l), the size distribution becomes increasingly flat so that I8 iHT/arl Cg i i NI, one may set (to be confirmed later)

l l

J=

i--N.

Equation aN/at+&

while eqn. (B5) reduces to i =-_N(r= J-&&C 0 (B9) giving the number of particles per unit time overtaken by r,. A quantitative treatment of the aging process based on the assumption (B7) has been published by Lifshitz and Slezov [5] and independently by Wagner [6] for the case in which the growth velocity of the particles is controlled by diffusion in an unstirred solution or by a first order reaction at their surface, respectively. Although the procedure taken in the two papers is quite different, the results are identical. We shall, therefore, abbreviate the theory as LSW theory. The procedure of Lifshitz and Slezov was later applied by Hanitzsch and Kahlweit [7] to the case in which the growth velocity of the particles is controlled by a second order reaction. From the latter calculations, these authors concluded that the change of

c with time asymptotically d (r,Q)/dt + l/r, while the size distribution can write

approaches a constant value (B10) approaches a time independent shape so that one

Wr.0

+ fWg(d

are

r/r,

(BT

The index of power Q, the time constant T, as well as the characteristic of the corresponding growth kinetics. However, in view of Fig. 1, the statement given in eqn. (BlO) can only be correct, if at all, for a limited time, since for t + -, f, will approach zero. The question then is whether the range of validity of eqn. (BlO) is longer than, comparable to or shorter than the duration of an experiment. To discuss this matter and also to reconsider the LSW theory, we shall recast Fig. 1 into Fig. 3 by plotting the quantity p (t) = r/r, versus t.

shape g (p)

Again, each of the p curves represents the life story of a particle. As p

the line p = I, the particle becomes a body of the new phase (nucleation) and enters the race with r,. During this race, all p curves except the one for the largest particle (denoted by p*) will pass through a maximum to decrease again and finally, after having crossed the line p = 1 for the second time, return to p = 0, Only the p * curve will, after passing its maximum, approach the line p = 1 asymptotically. The extremes of each p curve are given by

crosses b=O Since (B13) the solution of eqn. (B12) is determined by the growth kinetics of the parU312)

-s t -t

titles which expresses itself in 1;. For further discussion one therefore has to introduce at this point an equation which describes the growth kinetics of the particles under consideration. C. AGING OF PARTICLES UNDER DIFFUSION CONTROLLED WITH CONVECTION GROWTH IN SYSTEMS

As a first example, we shall consider the case of spherical particles precipitating from a stirred solution. We assume that the growth kinetics of the particles is diffusion controlled, i.e. that eqn. (AZ) holds. If we rewrite eqn. (A3) in terms of p, we find

;_

h-1 -rc P

bEkV,ac_, that

(Cl)

The term 6 will be called the aging rate. To find the extremes of the differ. ent p curves in Fig. 3. eqn. (CZ) has to be set equal to zero. Since b and @ are always positive and finite, it follows that

where the aging rate 6 has to be taken at that time at which the p curve under consideration reaches its extreme. For all particles except the largest one, this equation has only one physical meaningful solution, while for the largest particle, there are two solutions, namely the one for the maximum and, further, the one for t = 00: IimP

p=1

-1

=F=: P2

a=

(C4)

With respect to the solutions for the maxima, we now have to distinguish between the solution for the largest particle and those for the smaller ones. For this purpose, we consider the roots of the quadratic equation (C3), wherein for physical reasons 4 is positive. The solutions read:

For physical reasons, we exclude the complex roots and shall, therefore, only accept roots, the coefficients of which obey the relation 0 < 4 <, b/2 K-W

P

-1< P2

1 3.

(C7)

In Fig. 4, we have plotted (p - I)/p* versus p . The maximum at p = 2 corresponds to 6 = b/2, while the two branches on each side of p = 2 correspond to the two different roots given by eqn. (C5). Since the problem has to have a unique solution, and, further, since we have defined the p l curve to represent the largest particle, the branch 1 < p < 2 represents the admissible set of solutions. This branch corresponds to the minus sign in eqn. (C5). We may then conclude that p = 2 represents the solution for the largest particle, while the branch p < 2 represents the solution for all the smaller particles. In other words, we conclude that the heights of the maxima of the different p curves increase with time - as can also be seen in Fig. 3 - and reach the value 2 for the maximum of the highest p curve. The corresponding times at which these maxima are reached are determined by eqn. (C3), wherein 4 is a measure for the time. The curves of the smaller particles reach their maxima at times for which 6 < b/2 (eqn. C6), while the curve of the largest particle reaches its maximum at that time t at which 4 (t = t* ) = d (rz)/dtl,_,, = b/2 : p- (t = t) = 2 (C8)

We note that in this derivation we have nowhere made the assumption dc/dt = 0. The results are thus valid as long as the linearization of the Gibbs-

Thomson equation (Al) is a sufficient approximation. We further note that the aging rate as given by eqn. (CS) is claimed by the

LSW theory (see Wagner, eqn. VIII. 20) to be the asymptotic aging rate of

However, our derivation shows that this statement is incorrect. Instead, this aging rate attains this value only at the instant at which the p curve for the largest particle reaches its maximum. This contradiction would be irrelevant if t* was long compared with the duration of an experiment because one could then treat the maximum of the p* curve as a quasistationary value which was approached in times long compared with experimental times. If, however, t l was comparable with experimental times, then the contradiction would indeed be relevant. The problem is thus to determine t l . Clearly the answer to this question cannot be found from the above derivation since the aging rate will depend on the initial size distribution of the particles, i.e. on the experimental conditions under which the precipitate was formed. These conditions, however, do not enter the above derivation. Consequently, the answer has to be found experimentally, namely from

(ClW

Figure 5 shows a schematic plot of d versus t. The value of 6 is zero at the maximum of the supersaturation at the beginning of the precipitation process (compare Fig. I) and passes through a maximum during the early stages of precipitation to approach zero again for t - -. From this result it follows that 6 attains the value given by eqn. (CQ) twice during the precipitation process, once before and once after its maximum. To distinguish between these

10

two solutions,

From eqn. (B13),

(Cll)

At the maximum

of the p* curve, one has d = 0, i.e.

b 1 -r- - _rf+---_

.

re

rc p*

(C13)

i.e. (Cl4) Att=t*,onehasb=2&andp= (C14) that 2. It then follows from eqns. (C12) and

Sincep(t

= t)

has to be negative

and @ is always

positive,

it follows

that

(d$/dt) has to be positive at t = t . We thus find that the p curve of the largest particle reaches its maximum before the aging rate 6 itself reaches its maximum. Only if

is sufficiently

4 reaches

its maxi-

mum and if further this maximum is sufficiently broad, can one consider the value given by eqn. (C9) as a quasistationary value attained by the aging rate for a rather limited time interval during the first stages of the precipitation process. In general, however, the value of 4 at its maximum gives an upper limit for 4 (t = t ), while the time at which this maximum is reached gives an upper limit for t . For further comparison with the earlier theories, we now consider the derivative of b with respect to p _ From eqn. (C2), we find

If we set this equation equal to zero, we find the value of p for which b has a maximum. Denoting this value by pm, it follows from eqn. (C16) that Pit = 2b/tj At t = t, we have4 = b/2, thusp,(f = t-1

= p*(t = t) =

11

!,___ Y+rI-dL

----------I /

--------_-------

I I

same time at which p* reaches its maximum, /;* has a maximum with respect topFigure 6 shows a schematic plot of pm versus t. As 6 increases (Fig. 5), p ,,, decreases, passes through a minimum at the maximum of d and increases to infinity as 6 approaches zero. Also shown is the p curve for the largest particle. As one can see, there are two intersections between the two curves, the first one of which coincides with the maximum of p * .

D. AGING OF PARTICLES UNDER WITHOUT CONVECTION DIFFUSION CONTROLLED GROWTH IN SYSTEMS

In the last section we have considered the ripening of particles in a parent phase with either natural or artificial convection. This case is realized in a system consisting of droplets or solid particles dispersed in the vapor phase or a liquid solution. In the case of solid particles, one should ensure that their growth kinetics is indeed diffusion controlled, which might not be true for ionic crystals in aqueous solutions. Their growth rate seems to increase with the square of (C - c,); see Section E, Another case of interest is the ripening of particles in a solid solution, i.e. in a parent phase without convection. Such a system, as a matter of fact, was the original subject of the LSW theory. The authors assumed that the aging process was so slow that the steady state solution of the diffusion equation might be used as a sufficient approximation:

i

one obtains

=D+(Ac-aoe,/r)

032)

12

. Bp-1 r=--

;

p2

B=DV,ac,

rZ

(D3)

The application of the steady state solution runs into several problems. The first one arises from the fact that this solution is strictly valid only for systems, in which the mean concentration C does not change with time. During a precipitation, however, C decreases with time, although rather slowly during the

later stages. The second problem is that the steady state solution only holds if the mean distance between the particles is large compared with their diffusion spheres. In systems with a high volume fraction of the precipitate, how-

ever, it may happen that a large particle gets shielded by many small particles in such a way that the actual concentration gradient towards the large particle is higher than for other particles which can see the mean concentration C.

In spite of these reservations, we shall now proceed to determine the aging is applicable. For this purpose we insert eqn, (D3) into eqn, (B13) and obtain

.

,tg

IL [ P2

--spl

p-1 P3

;

6 _-0

3/Er3

(D4)

Again we find the positions of the maxima of the p curves by setting this equation equal to zero:

P_

= 0 for - -1

-3B

(D5)

where

&=a3 dt (~e,~_)~

(J36)

has to be taken at that time at which the corresponding p curve reaches its maximum. To distinguish between the maximum of the p* curve and those of all the other curves, we now have to cpnsider the roots of the cubic equation (D5), wherein for physical reasons $Jand B are positive_

The nature of the roots depends on the relationship between the coeffi-

cients. Namely, one has the following roots for \t > 4 B/G 2 complex and 1 negative, for & < 4 B/G 2 differen& positive and 1 negative, for 8j = 4 B/9

2 identical positive and 1 negative.

For physical reasons, we exclude the complex as well as the negative roots and shall, therefore, only accept solutions of eqn. (D5), the coefficients of

13

Fig.

7. For

the discussion

of eqn.

(D8).

which

obey

the relation

CP -

we obtain (D8)

l)/p3

G 4127

P = 3/2

In Fig_ 7 (p - 1)/p 3 is plotted versus p . The maximum of this curve at corresponds to the two identical positive roots, while the two branches on either side of p = 3/Z correspond to the two different positive roots. As in Section C, we conclude that the maximum in Fig. 7 represents the solution for the largest particle, while the branch on the lefthand side of the maximum represents the solutions for all the smaller particles. In other words, we conclude that the heights of the maxima of the different p curves increase with time and reach the value 3/2 for the highest p cume. The p curves of the smaller particles reach their maxima at times for which $ < 423/g, while the p curve reaches its maximum at a time t* at which (D9) that these equation equation (Dl) are rate \Las given by

Note

Thomson

of the Gibbs-

sufficient approximations. We further note that the aging eqn. (D9) is identical with what the LSW theory (see

obtained

as asymptotic

aging rate:

(DlW

Again we claim that instead, this aging rate is reached at that instant r = t

at which the p curve for the largest particle attains its maximum_ To consider the second derivative of the p l curve with respect

to t at t = t,

011)

Att=t,wehaveR=9&/4andp= and (Dll) that 3/2_ It then follows from eqns. (C12)

CD121

Again we conclude the following: Since i;* (t = t ) has to be negative and # is always positive, it follows that d@/dr has to be positive at t = t*. The p curve of the largest particle thus reaches its maximum before the aging rate reaches i+ maximum. Thus, again the value of $ at its maximum is an upper limit for #I/( t = t* ), while the time at which the maximum is reached is an upper limit for t* _ The maximum of b with respect to p follows from

%_.o=B_

dp 9

2-p

--c_

&

p3

3x3

(Dl3)

. Since for physical reasons 4 2 0, all solutions must satisfy p G 2. For I&= 0, we have t+e well known solution pm = 2, while for $ > 0, pm decreases with increasing 9 ,_reaches pm = 3/2 at t = t, passes through a minimum at the maximum of 9 and approaches pm = 2 as I) approaches zero. So, as in the case treated in Section C, there are two intersections between the pm curve and the p* curve, the first one of which coincides with the maximum of the p* curve. Before we proceed to discuss the reasons for the discrepancy between our results and those of the LSW theory, we shall first complete our analysis by considering the aging of particles whose growth is determined by a second order reaction at the interface.

E. AGING OF PARTICLES WITH SECOND ORDER GROWTH KINETICS

The growth kinetics of most ionic crystals in aqueous solutions close to equilibrium can be described by the equation

15

Wl)

For larger deviations from equilibrium, the parabolic dependence merges into a linear one, the point of intersection of the straight line with the abscissa not being c, , however. Compared with the growth, the dissolution of the crystals in general takes place much faster, indicating a diffusion controlled process. Hence, the observed dependence of growth and dissolution, respectively, may be drawn as shown schematically in Fig, 8. The region of parabolic dependence varies from system to system. With some systems (e.g. BaSO,), the parabolic region is rather wide, while with other systems (e.g. KClO*), the parabolic region is hardly measurable. In general, one may state that the lower the solubility of the crystals, the wider the parabolic region. When studying the aging of such systems, it may therefore happen that during the early stages of precipitation, the growth kinetics of the particles follows the linear law, while in the later stages of aging, as Z? approaches c, , eqn. (El) becomes valid. The following considerations, therefore, apply only to systems with sufficiently wide parabolic regions. If we rewrite eqn. (El) in terms of p, we find

f,g_

re

(P-l2 )

P

C=k2Vma

c,2 process.

032)

this equation being meaningful only for p 2= 1, i-e_ for the growth With this equation it folio-.vs from eqn. (B13) that

b--q2

p3 -3c

=o

(E4)

Fig.

c&)1

(schematically).

16

With the analogous reasoning as before, one then finds that the coefficients of this cubic equation must obey the relation li/ 2 4 c/9 It then follows for the maximum ~(t=t)=4C/gandp(t=t)=3 of the p* curve that

(E3)

reaches its maximum before the Again it can be shown that the p l curve aging rate $Jhas reached its maximum, and also that, as p * approaches its maximum, b + approaches a maximum with respect to p_

F. COMPARISON WITH THE LSW THEORY

during the early stages of the precipitation and then decreases again to approach zero as t - -. Before discussing the reasons for this apparent contradiction, we shall first discuss the approach of Greenwood [S] to describe the aging process. He considered the aging of particles with diffusion controlled growth in systems without convection (see Section D) and tried to evaluate an upper limit for the growth rate of the particles. For this purpose, he set _ the derivative of eqn. (D3) with respect to p equal to zero: _ = 0 which yields the well known solution (see eqn. D13) (Fl)

We summarize as follows: in the LSW theory it was suggested that the aging rate asymptotically approaches a constant value and remains constant for times long compared with experimental times, Our derivation shows, however, that this is not the case. Instead, the aging rate reaches a maximum

Pm = 2 i.e. rm = 2 rc

He then inserted this result into eqn. (D3) to find

(F2)

d(r:)/dt

= 3B

v-1

Greenwood realized that the particles as a whole would grow at a rate slower than that given by eqn. (F3) but expected eqn. (F3) to give the correct order of magnitude. I-Ie overlooked, however, that this result is valid only for that instant at which the p curve of the particle under consideration intersects with the pm curve (see Fig. 6), but by no means for the entire aging process. We shall now turn to the LSW theory. Since the procedure taken in the two papers is quite different, we have to treat both papers separately.

The procedure in the paper of Lifshitz and Slezov [5] may be summarized as follows: The authors introduce the quantity x(t) which is proportional to r,(t). They then conclude that n --t - for t --f -. This conclusion, however, is

17

correct only for open systems, while in closed systems, rC tends towards a finite value determined by eqn. (A5). The authors then consider the quantity r(t) being proportional to l/G, of which they conclude that there are three possibilities for its asymptotic behavior, namely y -+ 00, 0 or constant. The first possibility they exclude by showing that in that case, the amount of matter in the precipitate would tend to infinity, which, of course. is quite true for an open system. Since in the case of y + 0, the amount of matter would tend towards zero, they then conclude that y must tend towards some constant 70_ This constant they evaluate by concluding that the quantity u, being a measure for dp3/dt, must have a second order zero at some value of p3. To determine this point, they write (bottom of right hand side of page 38 El) u=Oanddu/dp3=0 (F4)

The first of these two equations (being equivalent to eqn. B12) determines the maximum of the p3 cuxxres, while the second one (being equivalent to eqn. D13) distinguishes the growth path of the largest particle from all other curves by selecting the one with the highest possible slope. Thus, the latter part of the calculation of Lifshitz and Slezov is equivalent to ours, in that they evaluated the aging rate at the first intersection between the p l and the Pm curve without, however, recognizing this fact. Wagner [6], on the other hand, set right from the beginning dF/dt = 0. The mass balance then reads

00

(F5)

iv= fVU(P)

f(W:

It

(BW

the mass balance becomes = const. (F6)

0

g(p)

v3& that

thus follows

f(f)

= k rp

(F7) ones

The total number of particles per unit volume including the subcritical is given by

WV WlW

one finds for p & I that

Because of eqn. (B7). g is also given by i =b~J=lj~(-N) I P From eqn. (D3), +-EL 6 P Equation

r ;F

U-1)

(FlO) then becomes

-B

CP2

f ~~~d?~P~ I

(FW

Since g must be finite, it follows that at p & 0 the size distribution g(p) must increase proportional to pz. For that reason, Wagner set

B(P) = PWP) ;

V13)

where all constants except B have been incorporated into yn. Because of the assumption eqn. (Bll), yD and consequently $J donot depend on time (which is approximately correct only at the maximum of J/). To evaluate yn as well as the size distribution h (p ). Wagner then inserted eqns. (Bll), (D3), and (F?! into eqn. (B8). 8ne then obtains as the differential equation for h (p)

dInh_

dp

Qp2 y;p~-3p

3 + 3

W16)

To solve this equation by partial integration, the denominator on the right hand side must be factorized_ This denominator, however, is identical with the cubic equation, eqn, (D5). Of the different positive roots, Wagner then heuristicahy chose the two identical roots, i-e, To = 9/4, which according to eqn. (D9) corresponds to the maximum of the growth path of the largest particle.

We have thus found that in both papers, the authors did not evaiuate the asymptotic behavior of the aging rate, but instead its value at t = t*. 0. THE SIZE DISTRIBUTION

AGING RATE OF THE PRECIPITATE AT THE MAXIMUM OF THE

For the evaluation of the size distribution N (r,t), we introduce the new variable p into eqn, (BS) which then reads

P

l

i,/r,

(G2)

By comparison ahiN

at +p

it then follows

.

.alnN+La;=O

ap

ap

(G3)

a2

,,+d%Y)

25 + u(x.y) = 0 aY

(-1

there exists no general solution. We, therefore, have to insert the corresponding expressions for b and (a; /ap) into eqn. (G3) to find the particular solution

for the problem.

As the first example we shall consider the case of the linear growth law, eqn. (Cl). With the corresponding eqn. (CZ) and

e-c__

reap

la+

bl

9p2

(G5)

alnN F+F=* 1

(G6)

In the LSW theory, this equation was solved by setting i = const. = b/2 (G-0

assuming that this was the aging rate for C * - and the solution of eqn. (G6) was thus the stationary size distribution during the later stages of precipitation. Inview of eqn. (C8) we realize, however, that eqn. (G7) gives the aging

20

rate at t = t*. The solution thus gives an approximate size distribution for a limited interval around the maximum of the aging rate. With t?;~ c.timption (G7), the coefficient of the second term, as well as that of the third term, depends only on p, while the coefficient of the first term depends only on f, For this reason, one can set

N(P

l o

f (0 - B(P

(BW

It then follows

that

;

4dInf --3-mt b dt

P<2

(G8)

The value of m can be evaluated from the mass balance which now reads

Q

V) 4

g(p)ps

3 VJn dp = 4n WY-C(~))

(G9)

At this point one has to make the further assumption that dc/dt = 0. With this assumption, the right hand side of eqn. (G9) becomes time independent. Since this also holds for the integral 4 on the left hand side, it follows that

fW

= const. - rF4

(F7)

With this result and eqn. (C8), one then obtains from the left hand side of eqn. (G8) : m = 1. The right hand side of eqn. (G8) then reads

@--PP~ 4P dlng+p2-110

dlnp

p2

(GlO)

l

(2 -p))-5

{-

4/(2 -p)}

312

PC2 GW Pa2

In view of eqn. (G7), this solution can only be accepted as an approximation for the size distribution around the maximum of the aging rate (see Fig. 5). Numerical values for this curve are given in Table 1. The shape of the curve is shown in Fig. 9. For the number of growing particles per unit volume, one obtains from eqn. (B1) under the same assumptions z(t) *

f (0

r, J

1

g(p)

dp

that

(G12)

l

(G13)

TABLE

1

Size Distribution at the Maximum of the Aging Rate (t a t*)

PiPmu

0.10

(Cl11

0.07

(G27)

0.02 0.04 0.07 0.14 0.24 0.40 0.61 0.84 1.00 0.65 0.04 l-32:0

(G31)

1.00

1.00

l-10 1.20 l-30 1.40 1.50 1.60 1.80 2.00 2.20 2-40 2.60

Maxlmum . P nlax

0.01 0.03 0.07 0.13 0.24 0.42 0.66 0.90 1.00 0.88 0.67 0.50 0.40 0.33 0.27 0.18 0.11 0.05

0.02 0.005

at g(p = Pm= 1 3.6:O

1.00

1.135

0.833

Fig. 9. Shape of size dhtribution g(p)/gmu values at the corresponding maxima. (----)

At this point we may use eqn, ((310) to check the assumption made with the inequality of eqn. (B7). This inequality may be written as

(Gl4)

(G15) Equation 1;;:,11

+q (GW

To find an expression for 0, we have to evaluate the number of monomers which get incorporated into the surface of a particle in unit time. This nun;ber is given by hN, = 4 If PkZN~ per particle is given by

(Cl71

where n is the number of moles and N* the Avogadro number, Further, the

number f of monomers

f p

4a p !!!k 3 Kn

it then follows that

(GlW

(GlQ)

where in the case of diffusion controlled

l

for D/S If we insert eqn. (A4) for r,, and eqn. (Cl) for i, eqn. (G16), we find

P+l <anNAuaVam vBR8 T3 CZ

as

into

(GW E (F c, )*

P2G+PP) The

left hand side of this inequality is shown in Fig, 10. As an example, for the right hand side we shall consider the aging of ionic crystals in a stirred aqueous solution, Bettig Y * 2, Q = 30 erg cmm2, V, = 60 cm3 mol-1 and T - 300 K. It then follows that

P+l

P2C+PP2

IG21)

23

of eqn. (G20).

where I- = F/c_ - II II. Since in Fig. 10 only the regicn around p = 1 is relcvant, we find that even at such considerable supersaturations as Z/cc, - 2, the inequality eqn. (G20) is fulfilled. We shall now proceed to determine the size distribution in the case of diffusion controlled growth in systems without convection. With eqn. (D4) and ldr: --Ir, dp B2--p 9 pa that

((322)

.

3rag&L!y+ P-1-L B at [ P2

3~~1

a_!EE+ i!zL??

ap pi

(G231

To obtain an approximation for the size dietribution around the maximum of the aging rate, we set a8 in the LSW theory according to eqn. (DB) i = conk = 4 B/9 (G24)

Proceeding in the same way as above, one then obtains from the ma= balance m = 16/27. The differential equation for the (time independent) shape of the size distribution then reads P -1

P3

GW

[ 5.61 --11/a

-(3+p)-7fam ( q-P

l

g(~)=const.*p~

expE_pl~

-P)]

(G26)

Numerical values for this curve are given in Table 1; the shape of the curve is shown in Fig. 9. For the number of growing particles one again Obtains eqn. (Gl3). The inequality (87) reads in this case 16 pB +27(~-2)

27 (p -l)-4ps

( II

ri 8

I

(~27)

while 8 is given by

WW

If we again insert eqn. (A4) into eqn. (G27), we find xs

I

*I

VaRa

16ps+27(p-2) 27(p--1)--4p=

p=(p

1

-1)

03vk

T3

r (r - 1 L

1)

-1

K=Q)

The left hand side of this inequality is shown in Fig. 11. In the case of a second order reaction (see eqn. El), one finda for the shape of the quasistationary size distribution [ 7 ] xdx xs+T(x-1)2 37

pa + 7

(p -

1

for 0 6 p 6 1

1)s (G30)

The values of g(p) for p < 1 in ref. 7 were obtained by numerical integration. The two parts of the curve may then be fitted by choosing an appropriate value for the constant.

const.

forl<

p < 3

25

a 0 0,s 1.0 w

Fig.

WITH

eqn. (G29).

H. COMPARISON

EXPERIMENT

Since the publication of the LSW theory, the number of experimental investigations of the aging process has increased considerably. In these papers, the theory has been applied to ripening processes in solid systems and the coarsening of droplets as well as that of crystals in liquid parent phases. It would exceed the frame of this article to give a review on the numerous results. One may, however, make the following statements: (a) Many authors restrict themselves to the plot of the cube of the mean radius 7 of the precipitate versus t. Since according to the LSW theory, T - r,,, this plot should dve a straight line, the slope of which is the inverse time constant of the asymptotic aging rate (see eqn. BlO). In such a plot, the limits of error are in general quite wide. The time constants found from the slopes were in many cases much larger than those predicted by the theory, Le. the aging rates were much lower. This result was found in particular in the case of the aging of crystals in aqueous solutions. (b) In many oi those papers in which the shape of the size distribution was determined and then compared with the predictions of the LSW theory, the experimental shape differed quite considerably from the predicted one, especially so in the case of aging processes in solid systems. Since most of these experiments will have to be reinterpreted in view of the theory presented in this article, we shall restrict ourselves to the discussion of a preliminary experiment which was carried out to verify Fig. 5 191. As mentioned before, t* cannot be predicted from our calculations, but has to be determjned experimentally. For this purpose, one has to measure

26

The shape of this curve is determined by two counteracting influences: the increase of r, and the decrease of i, with time. During the early stages of precipitation, r, increases by many orders of magnitude, causing a similar steep increase of &a2. As c(t) flattens off (see Fig. l), r, increases more and

more slowly, while the decrease of r, now causes a slow decrease of $/cl. One should thus expect an experimental curve as shown in Fig. 5. The time at which

this curve reaches its maximum then represents an upper limit for t*, while its value at this maximum represents an upper limit for 4 ( t=t*)/a2. In practice, the errors in the experimental determination of 4 on the right hand side of its maximum will increase as the experiment proceeds, since the change of C with time becomes smaller and smaller, as does the denominator in eqn. (Hl). We note that the denominator remains finite, although extremely small, since it wili approach c,fr*( t = -)] - c,(r = -). As an example, we consider the system HzO-KC104. The parabolic region (see Fig, 8) of these crystals is rather narrow, so that, at least during the early stages of precipitation, one may apply eqn. (A2), i.e. the equations derived in Section C. The following experiment was carried out at 16C: The supersaturation was produced by mixing equivalent volumes of HC104 and KOH, varying to 3*10-*mol cm-, the initial concentration difference (C - c,) from l-10-* the saturation concentration being c, = 1.0.10-4 mol cms3. To determine 5 as well as dZ/dt, the electrical conductivity of the solution was followed up to 30 h. The stirring rate was 3000 rpm. The result is shown in Fig. 12, where we have plotted $a* versus time.

The experiment yields

t*6

2602

20secand&(L=t*)/u2<

7+- 2sec-l.

With respect to the question raised in the paragraph following eqn. (Bll), we find that in this system the aging rate reaches the value claimed by the LSW theory as an asymptotic value during the early stages of the precipitation process. We further find that the aging rate passes through a distinct maximum and drops by one order of magnitude within about 600 set after the maximum has been passed. We thus find that in this system, the range of validity of eqns, (BlO)and (Bll)isshort compared with the duration of an experiment. However, in other systems with slower reaction rates, these times may increase by orders of magnitude. The rather rapid change of the aging rate around the maximum makes it questionable whether the shape of the size distribution as evaluated in Section G for constant aging rate at the maximum will be attained by the system. The

lo1

--

o0

- _oE

-3

t

m

10 0

I

0

o- *

o-0

0 0

o00

0

0

o-

-0

-0

0

10

200

LOO -

Fig. 12. Aging rate & divided by a2 vs. time t for the system Hz0 - KC104 initial concentration difference Ae = (cc, ) = l-10-* mol cmV3 _

trz

800

at 16OC and

same, of course, holds true for the shapes discussed in Section K. We may now compare the experimental value of G(t = t *) with the predicted one. Inserting a from eqn. (Al) and 6(t = t*) from eqn. (C9), we find G 7 see-, 406 In this equation, the thickness of the diffusion layer 6 is unknown. Setting = 2.9-lOK, D = 1-10m5 cm2 set-I, c, = 1-10B4 mo! cme3, u = 30 erg v=2,T cmV2, we find from the above equation that 6 = 5-10s2 cm, Since the thickness of the diffusion layer is determined by the relative velocity between the solution and the moving crystals, which will be much lower than between the solution and a fixed electrode, the above value for 6 is of the correct order of magnitude. It should be emphasized, however, that the course of 6 in Fig. 12 is representative only for this particular experiment and may change considerably if the experimental conditions, e.g. temperature, initial supersaturation or stirring rate are changed. Furthermore, $Jas well as t* may change by orders of magnitude if the system is changed, e.g. from a liquid to a solid solution. vRTDc_

I. RIPENING

WITH

PERIODIC

TEMPERATURE

CHANGES

The result of the preceding section, namely Fig. 12, gives an explanation for the welI known fact that after the early stages of precipitation, the aging rate of ionic crystals in aqueous solution is much lower than predicted by the LSW theory. Considering possible applications of Ostwald ripening in preparative chemistry and in chemical engineering, it may, therefore, be of interest to search for methods to increase the aging rate. This exploration has been done by Gordeeva and Shubnikov [lo] and independently by Hohmann and Kahlweit [II]. These authors found that appropriate periodic temperature changes during the aging process may increase the aging rate considerably. Figure 13 shows the result for the system H20-NaNOs where we have

Fig. 13. Mean radiu F of precipitate vs. time t for the system Hz0 - NaNO, at 25eC. (above) At periodically changing temperature AT = 0.9 C. f = 1.7 h- _ (below) At constant temperature_

changing

temperature

on

29

plotted the mean radius F of the precipitate versus time. The lower part shows the increase of F during an isothermal aging process at 298 K while the upper part shows the increase of F at periodically changing temperatures, the mean temperature again being 298 K, the amplitude 4T = 0.9 K and the frequency 1.7 h-I. In the case of periodically changing temperature the mean radius seems to increase linearly with time, This result holds for all our experiments. In the above experiment, one has dF/dt = 1.8.lo- cm see-, while at constant temperature one finds (at the beginning of the experiment, then slowing down) dF/dt = O.17-1O-8 cm set-. The slope thus increases by about one order of magnitude. In Fig. 14 we have plotted the dependency of (df-/dt) on frequency f and the amplitude AT. It turns out that within the range covered by this experiment, the slope increases more strongly than linearly with increasing f and 4T_ One can, however, predict that the slope will show a maximum at some higher frequency since for very high frequencies, the kinetics will not be able to follow the temperature changes any more. This upper limit may be estimated from the consideration that in the case of diffusion controlled transfer of matter, the mean displacement of the ions during one half of a period should be of the order of one half of the mean distance between two neighbouring particles, z. If 2 denotes the number of particles per unit volume, one has a = z-113 The mean square o;cdisplacement x=6Dt Setting t = (2fl- , one finds as upper limit (13) is given by (11)

(I21

f G 12DZ213

If the growth kinetics is determined by a reaction at the interface, this limit is lower. One aspect of this result is that the upper limit of f, and consequently also the frequency at the maximum, will decrease with increasing coarsening. The relation between (dF/dt) and 4T will depend mainly on the temperature dependence of the solubility. The bigger the relative chmge AC-/C_ with AT, the more substance may be transported from the smaller to the bigger particles. Since one has

AC,

c,=-

dlnc, d l/T

J-LIT

T2

(14)

the slope (dT/dt) should be proportional to d In c_/(d l/T), provided all other parameters are kept constant. This relationship was confirmed by experiments

1111.

30

We have not yet succeeded in the theoretical treatment of this effect, There seem, however, to be two factors which contribute to it: (1) The effect seems to be connected to the asymmetry of growth and dissolution, as shown in Fig. 8, This factor has been demonstrated by Hohmann 191, who compared the influence of periodic temperature changes on the aging of crystals with that of droplets, both in aqueous solution. It was found that the temperature changes increased only the aging rate of the cryst$ls but not that of the droplets, the latter having a symmetric characteristic with respect to growth and dissolution. (2) The second factor seems to be the fact that periodic temperature changes tend to roughen the surface of the crystals, while in an isothermal aging process, the surface smooths out with time. This effect leads to a marked increase of the growth rate of the rough crystals at a given supersaturation [9] and thereby to an increase of the aging rate.

K. FURTHER CONSIDERATIONS

We may summarize the results of the preceding sections as follows: After the end of the nucleation process (f in Fig. l), the aging rate increases rapidly, passes through a rraximum and then decreases slowly to approach zero after very long times (Fig. 5). The observed aging rates during the intermediate stages of the process should thus be considerably lower than those around the maximum (i.e. at t = f*). The time necessary to reach the final stage of the aging process, i.e. that stage at which r, approaches its final value given by eqn. (A5) should thus be much longer than that predicted by the LSW theory. We may, however, use the figures.for the aging rate at t = t* to find a lower limit for the time of the transition from the intermediate stages to the final stage. For this purpose, we assume that the aging rate does not decrease with time, but remains constant during the entire intermediate stages. Considering the aging of particles with diffusion controlled growth in systems without convection, we thus set

6 = c0nst.G

rZ (0

$(t = t*)

It then follows

by integration that

t*)

G1+

OW

For t Z+ t* we obtain

e(t) <

F t

(K3)

The final value of rc is given by eqn. (A5). To find a lower limit for the time of the transition to the final stage, we now write 4B gt> 3Kt -&V(Y--L)

(K4)

The time at which the aging process comes to its end thus depends on the total volume of the system, as was to be expected_ As an example, we shall consider the aging of ionic crystals in an unstirred aqueous solution, setting v = 2, 2 = 300 K, D = 2-10m5 cm9- set-, u = 30 erg cmM2, V, = 50 cm3 mol-l and r/c_ = 2, We then obtain from eqn. (K5) t > (4,5-1O11-V) set (f(6)

where V is in cm3. I.e., even in rather small systems it will take many years until the aging process has come to its end. Since we have assumed that the aging rate remains at its highest value during the entire process instead of decreasing with time, as it will, the time will in fact be much longer and of interest only in geological processes. One may further try to extend the procedure taken in section G to evaluate the shape of the size distribution of the precipitate. As an example we shah now consider the aging of particles with diffusion controlled growth in a stirred solution. The starting equation then is (G6). This equation was solved by making the second term time-independent by setting 6 = i(r = t*). One then obtains an approximation for the shape around the maximum of the aging rate. One may now attempt to set instead of eqn. (G7) tj = const, = j3, where fl is a parameter. One then obtains from eqn. (G6) W7)

ding

dlnp-2

1 +2Lo

b

This equation was solved by Dr. S.-K. Ghan*. The solution reads: (a) for 2 P/b 2 1, i.e. for that interval starting at t = t*, during which the aging rate exceeds b/2 and passes through its maximum (see Fig. 5). g (p ) = const. where

l p*A-

exp (-

3 i?/a)

(Kg)

,2

=2p4

b

fiir biophysikalbche Chemie. D-34 G&ttingen, West Germany.

* Max-Plan&-Institut

32

p

/Al;

sin a9 =b. P

,/A1/2

(b) for 2 P/b < 1, i.e. for the intermediate stages of the aging process after 4 has passed its maximum and dropped below b/2

g(p) = const. -p- (P-Q)-52 (Q/P)3i2E U-0)

where

P=p Q=P

+1+

c)

+1--E)

and

merge into eqn. (Gil). In Fig. 15 we have plotted g (p)/g,,, versus p for five values of 2 P/b > 1 is the value of g (p) at its maximum. As one can see, (eqn. Kg), whereg,,, the location of the maximum moves towards lower values of p as 2 P/b increases, the shape becoming reminiscent of that in the case of a parabolic growth law (see Fig. 9).

For 2 fl/b

+ 1 both solutions

Diffusion controlled growth

VS. p for aging rates higher than &t in systemrr with convection (see eqn. KS).

= P).

33

After 6 has passed its maximum, the location of the maximum of the size distribution will again shift to the right, until 6 has dropped to fl = b/2 again on the right hand side of the maximum in Fig. 5. From then on, eqn. (KlO) becomes valid. The behavior of this solution reflects the singularities contamed in the differential eqn. (KS !: The slope of the distribution curve dg/dp has either a pole or a zero at the point p =$(l --r) (Kll)

As long as 3/2 E > 7/2, this point is a zero. At 3/2 e = 7/2, i.e. at 2 p/b a 0.817, this becomes a pole so that d,g/dp = - -_ Furthermore, dg/dp has a zero at p = (b/2 p)i . When this value of p hits a pole of dg/dp , then dg/dp = + OQ because the singularity from the pole is stronger, This result occurs at = a ( I.- E) i.e. at 2 P/b = 0.64. For these reasons we have plotted the shape in two different figures. Figure for fox values of 2 P/b between 0.64 < 2 p/b < 1, while 16 shows g(p N&,x Fig. 17 shows g(p) versus p for three values of 2 p/b < 0.64. As one can see, the maximum moves further to the right as 2 P/b decreases, while the shape steepens at its right hand shoulder. These changes are in accord with the physical picture, since, as the aging process proceeds, r, catches up with the larger particles. At 2 P/b = 0.64, the maximum reaches its farthest

vs. p for aging rates lower than &t = t*). Fig. 16. Shape of size distribution g(p)/g,, Diffusion controlled growth in systems with convection (see eqn. KlO); parameter 2 B/b > 0.64.

34

0 0

qs

1.0

-s

Fig. 17. Shape of size distribution g(p) vs. p for aging rates lower than i(t = f*). Diffusion controlled growth in systems with convection (see eqn. K10); parameter 2 P/b < 0.64.

value to the right, namely p = 5/4. From then on, the maximum moves to the left again to return to p = 1, as 2 p/b decreases further. In this respect, the shapes shown in Fig_ 17 are physically meaningful only up to the singularity. We note that for 2 /3/b Q 1, the solution eqn. (KfO) simplifies to g(p)=const.-p~lp-lfl-(p-~2)4)-1, (K12)

which again is meaningful only for 0 G p < 1. We repeat, however, that the above discussion is relevant only if 4 may indeed be set approximately constant for certain periods of the aging process. If 6 changes too quickly with time. then the above shapes become increasingly poor approximations. I am indebted to Dr, S, -K. Chan and Dr_ EL Voss for heipful discussions

REFERENCES 1. 2, J.W. Gibbs, The Scientific Papers, Vol. 1, Dover, N.Y. HI, Ostwald, Analytische Chemie, 3rd ed., Engelmann, 1961, Leipzig

1901,

p_ 23 ff.

35 3. 4, 5. 6. 7. 8. 9.

10.

11.

R.E. Liesegang, 2. Phys. Chem., 75 (1911) 374. M. Kahlweit. in H_ Eyring. D. Henderson. and W. Jost (Eds.), Physical Chemistry, Vol. 10, Academic Press, N.Y. 1910. I.M. Lifshitz and V.V. Slezov, J. Phys. Chem. Solids, 19 (1961) 35. C. Wagner, Ber. Bunsenges, Phys. Chem., 65 (1961) 581. E. Hanitzsch and M. Kahlweit, in Industtiai CrystaUization. The Institution of Chemical Engineers, London 1969. p. 130. G.W. Greenwood, Acta Met., 4 (1956) 243. W.H. Hohmann, Thesis, Giittingen 1974 (WI). N.V. Gordeeva and A.V. Shubnikov, Sov, Phys. Cry.&., 12 (1967) 154. H.H. Hohmann and M. Kahlweit, Ber. Bunsenges. Phys. Chem_, 76 (1972) 933.

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