Ind. Eng. Chem. Res.

1996, 35, 1985-1994 1985

Formation and Aggregation of Polymorphs in Continuous

Precipitation. 1. Mathematical Modeling
Debasish Chakraborty and Suresh K. Bhatia*
Department of Chemical Engineering, Indian Institute of Technology, Powai, Bombay 400 076, India

In many cases of precipitation the product comprises of two or more polymorphs, either due to
their simultaneous nucleation or due to transformation of a metastable polymorph. These
polymorphs may have different growth rates as well as aggregation tendencies. In the present
work the population balance equation is applied to predict the size distribution of the precipitate
particles allowing for these features. The Hounslow method for discretization of the population
balance equation is modified for improved stability and accuracy, and used to solve the model
for polymorph precipitation in a continuous system. The effect of the aggregation tendencies of
the polymorphs, as well as of the ratios of their nucleation rates and of their grow rates, on the
particle size distribution and product composition is studied.

Introduction cipitation. It has long been known (Brooks, 1950; Wray

The estimation of particle size distribution and pre-
cipitation rates from supersaturated solutions is a
problem of great importance for researchers engaged in
studies of crystallization and precipitation. While this
is a straightforward matter when only the processes of
nucleation and growth are involved (Randolph and
Larson, 1985), numerous cases are rendered more
complex due to an attendant problem of aggregation.
Among the early studies reporting the latter phenom-
enon, Maruscak et al. (1971) observed agglomeration of
calcium carbonate crystals, while Halfon and Kaliaguine
(1976) found the effect to be significant in alumina
trihydrate crystallization. More recently the importance
of agglomeration for calcium carbonate precipitation has
also been confirmed by other workers (Hostomsky and
Jones, 1991; Chakraborty et al., 1994; Tai and Chen,
1995). Various other studies have shown agglomeration
to be important in the precipitation of other compounds
such as nickel ammonium sulfate (Tavare et al., 1985),
titania (Lamey and Ring, 1986), and copper sulfate
pentahydrate (Zumstein and Rousseau, 1989) as well.
The effect appears to be important in the precipitation
of organic salts also. Thus, Franck et al. (1988) found
agglomeration in salicylic acid precipitation, while Har-
tel et al. (1986) and Hounslow et al. (1988) report this
for calcium oxalate. In fact, in the latter case the
studies indicate agglomeration of calcium oxalate, rather
than particle growth, to be the dominant factor respon-
sible for formation of urinary stones.
The mathematical representation of the precipitation
process is generally approached via the population
balance equation (Hulburt and Katz, 1964), whose
solution in the presence of crystal agglomeration is a
difficult numerical problem (Marchal et al., 1988; Houn-
slow, 1990; Bhatia and Chakraborty, 1992). Even more
complex situations arise when the precipitate is present
as a mixture of polymorphs, each with a different
nucleation and growth rate as well as aggregation
tendency. In such a case the conventional population
balance formulation must be extended to allow for these
complications, but this has hitherto not been attempted.
An important example where such a more elaborate
analysis is essential is that of calcium carbonate pre-
* Author to whom correspondence should be addressed.
Now with Department of Chemical Engineering, The Univer-
sity of Queensland, St. Lucia, Brisbane, QLD 4072, Australia.
S0888-5885(95)00401-5 CCC: $12.00
and Daniels, 1957) that calcium carbonate precipitates
as a mixture of calcite, vaterite, and aragonite with the
relative proportions depending on process conditions.
Nevertheless even recent studies (Hostomsky and Jones,
1991; Tai and Chen, 1995), while confirming the poly-
morphism, have used the conventional single-species
formulation. The need for a more elaborate multispecies
analysis is most clearly evident from the recent study
of the authors and co-workers (Chakraborty et al., 1994)
which demonstrated the simultaneous nucleation of
calcite and vaterite from the solution under conditions
of heterogeneous nucleation and only vaterite under
conditions of homogeneous nucleation. The results,
obtained using cryo-electron microscopy, are not readily
possible with conventional scanning electron microscopy
or X-ray diffraction because of instability of the vaterite.
Indeed, it was demonstrated that the homogeneously
nucleated vaterite, being morphologically imperfect,
began to transform to calcite within the precipitator
itself which was operated in the continuous mode. The
gradual transformation of vaterite into calcite in the
supersaturated solution has also previously been re-
ported (Sohnel and Mullin, 1982). Further complica-
tions arise from the different aggregation tendencies of
calcite and vaterite, for it was noted (Chakraborty et
al., 1994) that calcite agglomerated much more strongly
than vaterite.
It may be noted that the transformation of different
phases is a well known phenomenon. The formation of
calcite following the nucleation of vaterite particles in
the presence of cholesterol is speculated as due to the
transformation of vaterite (Dalas and Koutsoukos,
1988). The effect of citrate ions in hydrolysis of ferric
chloride is well reported in the literature (Kandori et
al., 1992). A faster transformation of β-FeOOH into
cubic and rhomboidal hematite particles is achieved in
the presence of 0.05 mol % of citrate ions which reduces
the transformation period by 50%. As reported by
Kandori et al. transformation into the most stable state
takes a litter longer time without any other agent.
It is evident from the above discussion that situations
involving polymorphic precipitation, such as that of
calcium carbonate, will require extension of the con-
ventional population balance model and of its solution
methods. Among the numerical methods reported the
most accurate is that of Bhatia and Chakraborty (1992)
which avoids the finite domain error inherent to the
© 1996 American Chemical Society
1986 Ind. Eng. Chem. Res., Vol. 35, No. 6, 1996

Table 1. Aggregation Model The population balance equation (PBE) for species 1
constant in a well mixed continuous precipitator at steady state
type of type of aggregation is given by
particle particle product kernel
dn1 n1
species 1
species 2
+
+
species 1
species 2
f
f
aggregate
aggregate
β1
β2 G1
dl
) -n1(l)β1 ∫0∞n dl - τ
(1)
species 1 + species 2 f aggregate β1
species 1 + aggregate f aggregate β1 where n1(l) is the population density of species 1 and l
species 2 + aggregate f aggregate β1 is particle size. The PBE of species 2 can be expressed
aggregate aggregate f aggregate β1
as
+

other techniques (Gelbard and Seinfeld, 1978; Chang

and Wang, 1984a,b; Marchal et al., 1988; Hounslow, dn2
G2
1990). However, the method is computationally inten- dl
)
sive and unlikely to be practical for the more complex n2
situation of polymorphic precipitation. For such cases -n2(l)β1 ∫0∞n dl - n2(l)(β2 - β1)∫0∞n2 dl - τ
(2)
the method of Hounslow may be more attractive and
can readily be modified for enhanced accuracy and where n2(l) represents the population density of species
applied. In the present work we solve this problem for 2. The PBE of aggregates can be obtained from the
two possible situations. In the first case we consider formation by aggregation of smaller particles and the
the simultaneous nucleation, growth, and agglomeration loss of aggregates of a given size due to agglomeration.
of two different polymorphs. A constant aggregation Thus, PBE of aggregates can be written as
kennel is used, while assuming each polymorph to have
a different agglomeration tendency. In the second case dna β1 2 1n(λ)n((l
3
- λ3)1/3)
nucleation of a single polymorph is considered, but Ga
dl
) l
2
∫0 (l3 - λ3)2/3
dλ +
which subsequently transforms to a second one. The
latter continues to grow and aggregate along with the
(β2 - β1) 2 n2(λ)n2((l3 - λ3)1/3)
first. As seen above these situations are representative
of CaCO3 precipitation. While we present the models 2
l ∫01 (l3 - λ3)2/3
dλ -
and their solution here, in the sequel article we apply
na
these to our experimental data on this system. na(l)β1 ∫0∞n dl - τ
(3)
Theory
where na(l) is the population density of aggregates. Now
Simultaneous Nucleation of Two Polymorphs. the total number density is given by
Population Balance Formulation. As indicated
above the situation of simultaneous nucleation of two n(l) ) n1(l) + n2(l) + na(l) (4)
polymorphs is found in the case of calcium carbonate
where, in the presence of heterogeneous nucleation and while boundary conditions are
high supersaturation, both calcite and vaterite are
formed (Chakraborty et al., 1994). While not easily n1(0) ) B1/G1 (5)
evident by conventional methods this feature could be
confirmed by on-line video scans and by cryo-electron n2(0) ) B2/G2 (6)
microscopy. Further support is available from the
curvature of the particle size distribution (Bhatia and
Chakraborty, 1992; Chakraborty and Bhatia, 1995). In na(0) ) 0 (7)
light of these findings we consider here the case of
simultaneous nucleation with different growth rates and Dimensionless Formulation. Equations 1 and 2
aggregation tendencies. The two polymorphs are as- may be readily integrated to yield in dimensionless form
signed nucleation rates B1 and B2 and growth rates G1
and G2, respectively. The growth rate of aggregates is q1(y) ) exp[-R(1 + φ1m0)y] (8)
taken to be Ga, and a constant aggregation kernel is
and
assumed for each species. The constant aggregation
kernel is taken as β1 and β2 for the primary particles.
q2(y) ) exp[-(1 + φ1m0 + b(φ2 - φ1)µ02)y] (9)
Further, we consider species 1 to be much more ag-
gregating in nature than species 2. Thus, species 1 and Here
species 2 aggregate with a constant kernel β1, and
aggregates form mainly due to the aggregating nature
of species 1. Once the aggregate is formed, it attains a m0 ) ∫0∞(Rq1 + bq2 + bδqa) dy (10)
different growth rate, Ga. Aggregates are considered
to further aggregate with constant kernel β1, which is and
the same as that of the more aggregating primary
particles. The various aggregation processes are de- µ02 ) ∫0∞q2(y) dy (11)
picted in simplified form in Table 1. The assignment
of kernel β1 to events concerning all aggregates is clearly Equations 9 and 11 readily combine to yield a relation
approximate, as some of these would comprise only of between m0 and µ02
species 2. However, since this species is much less
agglomerating such aggregates would be relatively few 2
b(φ2 - φ1)µ02 + (1 + φ1m0)µ02 - 1 ) 0 (12)
and are neglected, thus avoiding further complications
of subdividing aggregates. Further, we define the dimensionless total population
 Ind. Eng. Chem. Res., Vol. 35, No. 6, 1996 1987
density the constant aggregation kernel β1 is assigned to the
aggregates formed from the primary particles. These
G2n(l) 1 features of the aggregation are considered the same as
q(y) ) ) (Rq1 + bq2 + bδqa) (13) those in the simultaneous nucleation model (Table 1).
B2 b Population balance of species 1 in a well-mixed continu-
ous precipitator at steady state then yields
which combines with the dimensionless form of eq 3 to
yield
dn1 n1
φ1 yq(λ)q((y
3 3 1/3
-λ ) )
G1
dl
) kn2 - n1(l)β1 ∫0∞n dl - τ
(18)
-
dq
dy
- δq + bδ y2
2
∫0 (y3 - λ3)2/3
dλ +
where n1(l) is the population density of species 1 and l
3 3 1/3 is particle size. The PBE of species 2 can be expressed
(φ2 - φ1) 2 q2(λ)q2((y - λ ) )
bδ
2
y ∫0y (y3 - λ3)2/3
dλ - as

dn2
bδφ1q ∫0∞q(λ) dλ + q1(1 + φ1m0)Rb(δ - R) + G1
dl
)
n2
(1 + φ1m0)(δ - 1)q2 - µ02b(φ2 - φ1)q2 ) 0 (14) -n2(l)β1 ∫0∞n dl - n2(l)(β2 - β1)∫0∞n2 dl - τ
- kn2
(19)
q(0) ) q1(0) + q2(0) ) + 1 (15)
R R
b b
where n2(l) is the population density of species 2. PBE
Equation 14 represents the general PBE of a simulta- for aggregates can be obtained from the formation by
neous nucleation system which includes the different aggregation of primary particles and the destruction of
growth rates and aggregation frequencies of two differ- the aggregates due to the aggregation. Thus, PBE of
ent species, following the model of Table 1. The aggregates can be written as
dimensionless total number of particles (µ0) can be
obtained analytically from integration of eq 13 as dna β1 2 n(λ)n((l3 - λ3)1/3)
Ga
dl
) l
2
∫01 (l3 - τ3)2/3
dλ +
µ0 ) ∫0 q(y) dy ) m0/b
∞
(16)
3
(β2 - β1) 2 ln2(λ)n2((l - λ3)1/3)
Integration of eq 14 over the domain [0, ∞] leads to a 2
l ∫0 (l3 - λ3)2/3
dλ -
second nonlinear algebraic equation relating m0 and µ02
na
φ1 2 1 na(l)β1 ∫0∞n dl - τ
(20)
m + (m - 1) - (1 + φ1m0)µ02 -
2b 0 b 0
b 2
where na(l) represents the population density of ag-
(φ - φ1)µ02 ) 0 (17) gregates. The total number density is as before given
2 2
by eq 4, while boundary conditions follow
Equations 12 and 17 can be solved simultaneously to
obtain m0 and µ02. Substitution of m0 in eq 16 gives n1(0) ) 0 (21)
the dimensionless total number of particles in the
system. This directly obtained zeroth moment can be and eqs 6 and 7.
compared with the moment obtained from numerical
Dimensionless Formulation. Equations 18 and 19
solution of the PBE of the present system represented readily integrate to the dimensionless forms
by eq 14 to check the adequacy of the latter.
Nucleation Followed by Transformation. Popu-
lation Balance Formulation. Here we consider the q1(y) )
nucleation of a single species and subsequent transfor- K
mation into another polymorph. It is assumed that ×
{R(1 + φ1µ0) - [1 + K + φ1µ0 + µ02(φ2 - φ1)]}
nucleation of species 2 occurs at rate B2, and this is
subsequently transformed into species 1. This trans- (q2 - exp[-R(1 + φ1µ0)y]) (22)
formation is assumed irreversible and governed by a
first-order rate constant k, i.e. and
k
species 2 98 species 1 q2(y) ) exp(-[1 + K + φ1µ0 + µ02(φ2 - φ1)]y) (23)
Transformed particles grow with a different growth rate
Here µ0 ) ∫∞0 q dy, as before, and the dimensionless
G1 while the mother particles are considered to have a
density q1 is now defined with respect to the nucleation
growth rate of G2. These two species are considered
rate of species 2 (B2). The dimensionless total popula-
prone to aggregation with constant aggregation kernel
tion density is now given, following eq 4, as
β1 and β2, respectively. Once the aggregates are formed,
they are assumed to have a different growth rate Ga.
As in the earlier section, species 1 is considered to be q(y) ) Rq1 + q2 + δqa (24)
more aggregating in nature. Thus, species 1 and species
2 aggregate with a constant of aggregation β1. Further, which combines with the dimensionless form of eq 20
1988 Ind. Eng. Chem. Res., Vol. 35, No. 6, 1996

to yield ties. A departure from the original presentation of

3 3 1/3 Hounslow is that we use the discretized form only for i
φ1 q(λ)q((y - λ ) )
-
dq
dy
- δq + δ y2
2
∫0y (y3 - λ3)2/3
dλ + g 2, while approximating Q1 analytically after neglect-
ing aggregation at the small sizes in the first interval
3
(i.e. for i ) 1). Additionally, we also consider the
(φ2 - φ1) 2 yq2(λ)q2((y - λ3)1/3)
δ
2
y ∫0 (y3 - λ3)2/3
dλ -
particles in the region O e y e y1, having dimensionless
number Q0, in formulating the discretized equation,
with Q0 being evaluated in the same way as Q1. With
δφ1q ∫0∞q(λ) dλ + q1R(1 + φ1µ0)(δ - R) + these modifications the method was found to have
improved stability as well as accuracy for a given value
q2[(1 + φ1µ0)(δ - 1) + K(R - 1) - µ02(φ2 - φ1)] ) 0 of N, in tests for the single-species case (Chakraborty,
1994). In the subsequent subsections we present the
(25) discretized forms for the PBE for the two cases of
with q(0) ) 1. Here the aggregation kernels are now polymorphic precipitation dealt with here.
made dimensionless by means of the nucleation rate B2. Simultaneous Nucleation. For this case discreti-
Integration of eq 23 now yields a second-order equation zation of the PBE in eq 14, following the procedure of
for µ02 as Hounslow (1990), and considering also the particles in
2 [0,y1], leads to
(φ2 - φ1)µ02 + (1 + Kφ1µ0)µ02 - 1 ) 0 (26)

[
i-1
while integration of eq 25 over the domain [0,∞] leads 1
to a second nonlinear algebraic equation relating µ0 and δbφ1 Qi-1 ∑
j)1 2
2
2j-i+1Qj + Qi-1 -

]
µ02
i-1 N
1 1
1 - δµ0 -
δφ1 2 δ(φ2 - φ1) 2
µ +
2 0 2
µ02 + Qi ∑
j)1
2j-iQj - Qi∑Qj + 22-iQi-1Q0 - 21-iQiQ0
j)i 3 3
+

K(δ - R)
[
i-2
1
{R(1 + φ1µ0) - [1 + K + φ1µ0 + µ02(φ2 - φ1)]}
× (2)
δb(φ2 - φ1) Qi-1 ∑
j)1
2j-i+1Q(2) (2) 2
j + (Qi-1) -
2
[R(1 + φ1µ0)µ02 - 1] + i-1 N

[(1 + φ1µ0)(δ - 1) + K(R - 1) - µ02(φ2 - φ1)]µ02 ) 0 Q(2)

i ∑
j)1
j - Qi ∑Qj +
2j-iQ(2) (2)

j)i
(2)

Equations 26 and 27 can be solved simultaneously to

yield µ0 and µ02. The directly obtained zeroth moment
(27) 1 2-i (2) (2) 1 1-i (2) (2)
3
2 Qi-1Q0 - 2 Qi Q0 +
3 ]
µ0 can be subsequently compared with the numerically
(δ - R)(1 + φ1m0)Q(1) (2)
R
obtained value from solution of the PBE in eq 25. i + (1 + φ1m0)(δ - 1)Qi +
b
Numerical Solution µ02b(φ2 - φ1)(δ - 1)Q(2)
i +

The above models of polymorphic precipitation require

a numerical solution due to the nonlinear nature of the
overall PBE. In an earlier work (Bhatia and Chakra-
borty, 1992) we have presented an approach based on
2
[
(1 + r)yi r2 - 1
r
Qi-1 + Qi -
r
r2 - 1
]
Qi+1 -

δQi ) 0, i ) 2, 3, ..., N (32)

an adaptation of the method of weighted residuals which
is more accurate than other procedures since it avoids where superscripts (1) and (2) represent species 1 and
the finite domain error. However, the method is com- 2, respectively. Now N - 1 nonlinear algebraic equa-
putationally intensive and was not considered practical tions are solved simultaneously to obtain Qi, i g 2, while
for the present case of more than one species, particu- Q0 and Q1 are obtained analytically by neglecting the
larly in view of the need to fit experimental data, as aggregate part in eq 13. With qa neglected, eqs 8 and 9
dealt with in the sequel article (Chakraborty and combine to yield, upon integration,
Bhatia, 1996). Consequently the Hounslow method
(Hounslow, 1990) is used here with some modification [1 - exp(-Rv1y1)] [1 - exp(-v2y1)]
to improve stability and accuracy. In this method we Q0 ) (33)
bv1 v2
+
consider N subintervals in the domain (y1, yN+1) with
boundary points satisfying
[exp(-Rv1y1) - exp(-Rv1y2)]
yi+1 ) ryi (28) Q1 )
bv1
+
where the ratio r is taken as 21/3. In each interval we
define dimensionless numbers of particles by [exp(-v2y1) - exp(-v2y2)]
(34)
Qi ) ∫yy
i
i+1
q(y) dy (29)
v2
where v1 and v2 are defined as
Q(1)
i ) ∫yyi+1
i
q1(y) dy (30) v1 ) 1 + φ1m0 (35)

Q(2)
i ) ∫yy
i
i+1
q2(y) dy (31) v2 ) 1 + φ1m0 + b(φ2 - φ1)µ02 (36)
and discretize the overall PBE in terms of these quanti- The jth moment may be obtained accurately by modify-
 Ind. Eng. Chem. Res., Vol. 35, No. 6, 1996 1989
ing Hounslow’s method and considering also the par- Consequently, upon integrating eqs 22 and 23
ticles below the first interval and is given by
[1 - exp(-Ru1y1)]

( )
Q0 ) -C1 +
N (1 + r) j Ru1
µj ) ∑
i)1 2
yi Qi +
(C1 + 1)
[1 - exp(-u2y1)]
(41)

[ ]
u2
j! j exp(-Rv1y1)
∑ (Rv1y1)k
R
1- + [exp(-Ru1y1) - exp(-Ru1y2)]
b (Rv )j+1 k)0 k! Q1 ) -C1
1

[ ]
+
Ru1
j! j exp(-v2y1) [exp(-u2y1) - exp(-u2y2)]
1- ∑ (v2y1)k k!
(C1 + 1)
u2
(42)
(v2)j+1 k)0
where u1 and u2 are defined as
j ) 0, 1, 2, 3 (37)
u1 ) 1 + φ1µ0 (43)
in which the last two terms represent the contribution
from the particles in [0,y1]. The present method also u2 ) 1 + K + φ1µ0 + µ02(φ2 - φ1) (44)
gives the individual zeroth moment of the different
species. The zeroth moment of species 1 is obtained and
analytically from integration of eq 8 and is expressed
as C1 )
RK
{R(1 + φ1µ0) -[1 + K + φ1µ0 + µ02(φ2 - φ1)]}
1 (45)
µ01 ) (38)
R(1 + φ1m0) Now the jth dimensionless moment may be obtained
accurately by modifying Hounslow’s method where all
while the zeroth moment for species 2, µ02 follows eq the particles below the first interval are considered, and
12. µ0a is obtained from substitution of µ01 and µ02 into is given by

( )
the integrated form of eq 13. N (1 + r) j
1
µj ) ∑
i)j 2
yi Qi -
µ0 ) (Rµ01 + bµ02 + b δµ0a) (39)

( [ ])
b
j! j exp(-Ru1y1)
where µ0 is the overall zeroth moment defined in eq 16. C1 1- ∑ (Ru1y1)k
k!
+
Nucleation Followed by Transformation. For (Ru1)j+1 k)0

[ ]
this case discretization of the PBE in eq 25, considering j exp(-u2y1)
j!
also the particles in [0,y1], leads to
(C1 + 1) 1- (u2y1)k ∑

[
(u2)j+1 k)0 k!
i-2 i-1
1 2
∑
δφ1 Qi-1 2j-i+1Qj + Qi-1
2
- Qi 2j-iQj - ∑ j ) 0, 1, 2, 3 (46)
j)1 j)1 in which the last two terms represent the contribution

]
N
1 1 from the particles in [0,y1]. The zeroth moment esti-
Qi ∑
j)i
Qj + 22-iQi-1Q0 - 21-iQiQ0
3 3
+ mated by the numerical method may be compared with
the value of µ0 obtained from the solution of eqs 26 and

[
i-2 27. We also obtain the analytical zeroth moment of
1
(2)
δ(φ2 - φ1) Qi-1 ∑
j)1
2j-i+1Q(2) (2) 2
j + (Qi-1) -
2
species 1 (i.e. µ01) by integration of eq 22 as
µ01 )
i-1 N
1
Q(2)
i ∑
j)1
j - Qi ∑Qj + 2
2j-iQ(2) (2)

j)i
(2)

3
2-i (2)
Qi-1Q(2)
0 -
K
{R(1 + φ1µ0) - [1 + K + φ1µ0 + µ02(φ2 - φ1)]}
×

1 1-i (2) (2)

3 ]
2 Qi Q0 + R(δ - R)(1 + φ1µ0)Q(1)
i + [µ02 -

while the zeroth moment of the aggregates µ0a is

1
R(1 + φ1µ0) ]
(47)

(1 + φ1µ0)(δ - 1)Q(2) (2)

i + µ02(φ2 - φ1)(δ - 1)Qi + obtained analytically from substitution of µ01 and µ02

[ ]
into the integrated form of eq 24
2 r r
K(R - 1) + Qi-1 + Qi - Qi+1 - µ0 ) Rµ0I + µ02 + δµ0a (48)
(1 + r)yi r2 - 1 r2 - 1
Results and Discussion
δQi ) 0 i ) 2, 3, ..., N (40) The set of N - 1 nonlinear algebraic equations
provided by eqs 32 or 40 was solved by a Marquardt
with Qi, Q(1) (2)
i , and Qi following eqs 29-31. As before N Levenberg method implemented in subroutine NEQNF
- 1 nonlinear algebraic equations are solved simulta- of the IMSL library. The mainframe CYBER 180 series
neously to obtain Qi, i g 2, while Q0 and Q1 are obtained computer was used for the computations, and conver-
analytically by neglecting the aggregates in eq 24. gence of the solution was obtained in 10-20 cpu
1990 Ind. Eng. Chem. Res., Vol. 35, No. 6, 1996
Figure 1. Effect of ratio of nucleation rates, b, on (a) fractional oversize distribution and (b) dimensionless moments, for R ) δ ) 1 and
φ1 ) φ2 ) 10.
seconds. With the modified method the solution was
obtained with N ) 30 and y1 ) 0.02, achieving faster
convergence than the original work of Hounslow (1988,
1990) where N ) 50 and y1 ) 0.002 were recommended.
The solution obtained in the form of the population
density is transformed into fractional oversize, since the
latter form is often that in which experimental data are
available. The fractional oversize of the individual
species as well as that of the total population is
estimated as
∫y∞q1 dy
θ1(y) ) ∞
∫0 q dy
∫y∞q2 dy
θ2(y) ) ∞
∫0 q dy
∫y∞qa dy
θa(y) ) ∞
∫0 q dy
∫y∞q dy
θ(y) ) ∞
∫0 q dy
Simultaneous Nucleation. Initially computations
were done for this case through the solution of eq 32,
with φ1 ) φ2 ) 10. For these values β1 ) β2, and the
assumption that all aggregates have aggregation kernel
β1 remains valid. Figure 1a depicts the results for the
fractional oversize distribution, with R ) δ ) 1, for
various values of b. The curvature is consistent with
that reported for aggregating systems (Bhatia and
Chakraborty, 1992). With increase in b the aggregation
terms become more important, as is readily seen from
eq 14, and the particle size distribution becomes finer.
Figure 1b shows the variation of the various moments
with b. At low values of b the rate of nucleation of
species 1 is relatively higher, leading to a larger value
of Rµ01/b as compared to that of µ02. Also the number
of aggregates is determined by species 1 so that µ0a is
closer to Rµ01/b, as is the total number represented by
Rµ0 (curve 4). At high values of b, however, species 1
has a relatively low nucleation rate so that Rµ02 exceeds
Rµ0/b. Similarly, the number of aggregates and the total
number of particles are now determined by species 2 so
that µ0a as well as µ0 is closer to µ02. Curve 5 shows
that the dimensionless total precipitation rate, repre-
sented by µ3, decreases with a increase in b, consistent
with the increased importance of aggregation mentioned
above.
Figure 2a illustrates the effect of R on the fractional
oversize distribution, with δ ) R, b ) 1, and φ1 ) φ2 )
10. For this situation an increase in R implies a
relatively lower growth rate of species 1 and the
aggregates, leading to a finer distribution. This also
(49) leads to a drop in dimensionless precipitation rate, given
by the third moment µ3, as shown in Figure 2b.
Figure 3a depicts the effect of aggregation parameter
φ1 on the oversize distribution, with φ2 ) 0 and R ) δ )
b ) 1. For these parameter values the contributions of
(50) all the species may be expected to be significant. As
expected, with an increase in φ1 the increasing signifi-
cance of aggregation leads to a finer particle size
distribution. Figure 3b depicts the variation of the
various moments with φ1. At low values of φ1 the
(51)
number of aggregates is smaller than that of species 1
or 2; however, with an increase in φ1 the proportion of
aggregates subsequently becomes higher than that of
these species. Further, since species 2 is nonaggregat-
ing (i.e. φ2 ) 0) its amount is always greater than that
(52)
of species 1. For the case of φ1 ) 0 with R ) δ ) b ) 1,
it may be anticipated that the oversize distribution
results match those for the single-species case, with µ0
) 2 and µ3 ) 12 (since each species has a dimensionless
zeroth moment of unity and third moment of six). This
was indeed borne out by a test computation which
yielded µ0 ) 2.024 and µ3 ) 12.357 following eqs 32 and
37.
Nucleation Followed by Transformation. In this
case it has been considered that only species 2 is
nucleated, which subsequently grows and aggregates
while also gradually undergoing transformation to spe-
cies 1. Nucleation of vaterite followed by transformation
to calcite is an example of such a system, besides others,
as discussed earlier. The overall population density
distribution follows eq 25 which has been discretized
in eq 40. Figure 4 depicts the fractional oversize
distribution obtained from the solution of the latter
equation, for parameter values φ1 ) 5, φ2 ) 0.1, R ) 1,
δ ) 0.8, and K ) 0.1. For this low value of the
dimensionless transformation rate constant K, species

Figure 2. Effect of ratio of growth rates, R, on (a) fractional oversize distribution and (b) dimensionless third moment, µ3, with δ ) R,
b ) 1, and φ1 ) φ2 ) 10.
Figure 3. Effect of aggregation parameter φ1 on (a) fractional oversize distribution and (b) dimensionless moments, for R ) δ ) b ) 1
and φ2 ) 0.
Figure 4. Fractional oversize distributions for various constitu-
ents and the overall product, for φ1 ) 5, φ2 ) 0.1, R ) 1, δ ) 0.8,
and K ) 0.1.
2 is much more numerous than 1, as seen from curves
2 and 1, and at small sizes the former dominates. At
large size, however, aggregates dominate, following the
relatively large value of φ1, as seen from curves 3 and
4. Figure 5a,b depicts the effect of K on the oversize
distributions for species 1 and 2, respectively, with the
Ind. Eng. Chem. Res., Vol. 35, No. 6, 1996 1991
other parameters having values φ1 ) 10, φ2 ) 0, R ) 1,
and δ ) 0.8. With an increase in the value of K the
transformation of species 2 to 1 is more rapid, so that
the proportion of the latter increases at small size.
However, because of the large aggregating tendency of
species 1, reflected in the value of φ1 ) 10, this leads to
a decrease in its proportion at large size as is evident
in Figure 5a. For the nonaggregating species 2 (φ2 )
0), however, the effect of an increase in K consistently
leads to a drop in its proportion at all sizes due to the
transformation. Figure 6 shows the effect of K on the
overall fractional oversize distribution, indicating a
significant shift toward finer sizes with an increase in
K. This is due to the higher aggregation tendency of
species 1 resulting from the transformation. Such
behavior is qualitatively consistent with that observed
by us in CaCO3 precipitation, where calcite aggregates
much more strongly than vaterite, as discussed earlier
by Chakraborty et al. (1994) and in the sequel article
(Chakraborty and Bhatia, 1996).
Figure 7 depicts the effect of growth rate ratio R on
the fractional oversize distribution, with δ ) R and other
parameters having values φ1 ) 10, φ2 ) 0, and K ) 1.
With an increase in R the relative growth rate of species
1 and of the aggregates (since δ ) R) is reduced, and
the distribution is finer. As a result the overall dimen-
sionless precipitation rate, represented by the third
1992 Ind. Eng. Chem. Res., Vol. 35, No. 6, 1996
Figure 5. Effect of dimensionless transformation rate constant, K, on fractional oversize distribution of (a) species 1 and (b) species 2,
for φ1 ) 10, φ2 ) 0, R ) 1, and δ ) 0.8.
Figure 6. Effect of dimensionless transformation rate constant,
K, on overall fractional oversize distribution for φ1 ) 10, φ2 ) 0, R
) 1, and δ ) 0.8.
Figure 7. Effect of ratio of growth rates, R, on fractional oversize
distribution with δ ) R, φ1 ) 10, φ2 ) 0, and K ) 1.
moment µ3, also reduces with increase in R as seen in
Figure 8. The effect of the dimensionless transforma-
tion rate constant and the aggregation parameter φ1 on
the various moments is depicted in parts a and b of
Figure 9, respectively. With an increase in K the total
number density of species 1 increases while that of
Figure 8. Dependence of dimensionless third moment, µ3, on ratio
of growth rates, R, with δ ) R, φ1 ) 10, φ2 ) 0, K ) 1.
species 2 reduces, as expected, as shown by curves 2
and 3, respectively, in Figure 9a. Simultaneously,
because of the greater aggregation tendency of species
1 the number density of the aggregates also increases
while the overall population density reduces (cf. curves
4 and 1, respectively). The higher aggregation tendency
of species 1 also leads to a reduction in the dimension-
less precipitation rate, µ3, with an increase in K was
shown by curve 5. This behavior is also consistent with
that depicted in Figure 9b for the effect of φ1 for K ) 1.
At constant K, an increase in φ1 causes a reduction in
the total number density as well as that of species 1
and 2, as seen from curves 1, 2, and 3. However, the
number concentration of aggregates initially increases
due to formation from agglomeration events involving
species 1, but then reduces due to loss from events
involving agglomerates themselves. This also leads to
a dominance of species 2 at large values of φ1, while at
low values both species 1 and 2 are comparable in
number.
Summary
The case of polymorphic precipitation is often encoun-
tered in industrial practice, with more than one poly-
morph simultaneously nucleating. In some cases this
is due to the transformation of one polymorph to another
within the precipitator itself. The formation of vaterite

Figure 9. Variation of dimensionless moments with (a) dimensionless transformation rate constant, K, for φ1 ) 10 and (b) dimensionless
aggregation parameter, φ1, for K ) 1 and R ) δ ) 1 and φ2 ) 0.
and calcite in CaCO3 precipitation is among the most
well-known examples of this situation, and depending
upon the operating conditions either of the above
mechanisms is followed. In the present work a popula-
tion balance model for the simultaneous nucleation as
well as transformation mechanism in a continuous
precipitation is developed and solved using an extension
of Hounslow’s method. The results show the product
composition and particle size distributions to be a strong
function of the ratio of growth rates and the ratio of
nucleation rates, as well as the aggregation tendencies
of the polymorphs.
Acknowledgment
This work was supported by a grant (No. DST/III-
4(17)/86-ET) from the Department of Science and Tech-
nology of the Ministry of Science and Technology,
Government of India.
Notation
b ) ratio of nucleation rates, B2/B1
B1 ) nucleation rate of species 1
B2 ) nucleation rate of species 2
G1 ) growth rate of species 1
G2 ) growth rate of species 2
Ga ) growth rate of aggregates
k ) transformation rate constant
K ) dimensionless transformation rate constant, kτ
l ) particle size
m0 ) eq 10
n(l) ) population density at size l
n1(l) ) population density of species 1
n2(l) ) population density of species 2
na(l) ) population density of aggregates
q(y) ) dimensionless population density, n(l)G2/B2
q1(y) ) dimensionless population density of species 1, n1(l)-
G1/B1 in case of simultaneous nucleation and n1(l)G1/B2
in case of nucleation of species 2 followed by transforma-
tion to species 1
q2(y) ) dimensionless population density of species 2, n2(l)-
G2/B2
qa(y) ) dimensionless population density of aggregates,
na(l)Ga/B2
Qi ) eq 29
Q(1)
i ) eq 30
Q(2)
i ) eq 31
r ) yi+1/yi ) (2)1/3
y ) dimensionless particle size, l/G2τ
Ind. Eng. Chem. Res., Vol. 35, No. 6, 1996 1993
y1 ) lower size of first interval, dimensionless
Greek Symbols
R ) ratio of growth rates, G2/G1
β1,β2 ) constant aggregation kernels
δ ) ratio of growth rates, G2/Ga
φ1 ) agglomeration parameter of species 1, β1B1τ2 in case
of simultaneous nucleation and β1B2τ2 in case of nucle-
ation of species 2 followed by transformation to species
1
φ2 ) agglomeration parameter of species 2, β2B1τ2 in case
of simultaneous nucleation and β2B2τ2 in case of nucle-
ation of species 2 followed by transformation to species
2
µ0 ) dimensionless zeroth moment, ∫∞0 q(y) dy
µ01 ) dimensionless zeroth moment of species 1,
∫∞0 q1(y) dy
µ02 ) dimensionless zeroth moment of species 2,
∫∞0 q2(y) dy
µ0a ) dimensionless zeroth moment of aggregates,
∫∞0 qa (y) dy
µj ) jth moment of q(y)
θ(y) ) fractional oversize, eq 52
θ1(y) ) eq 49
θ2(y) ) eq 50
θa(y) ) eq 51
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Received for review July 3, 1995
Accepted March 19, 1996X
IE9504011
X Abstract published in Advance ACS Abstracts, May 1,
1996.