Pc'at. Res. Vol. 26. No. 6. pp. 745-751. 1992 0043-1354,92 $5.00 + 0.

00
Printed in Great Britain. All rights resetwed Copyright ~ 1992 Pergamon Press Ltd

KINETICS OF CADMIUM HYDROXIDE PRECIPITATION

BI~ Luo t, JA,,m~sW. PATTERSONz(~ and PAUL R. ANDERSONl
'Department of Environmental Engineering, Illinois Institute of Technology, Chicago, IL 60616 and
:Patterson and Associates Inc., Chicago, IL 60603, U.S.A.

(First receired July 1991: accepted in rerisedform Not'ember 1991)

Abstract--The kinetics of cadmium hydroxide precipitation in the presence and in the absence of citrate
was investigated. Precipitation experiments were conducted in a continuous stirred tank reactor.
Experiments were performed with initial cadmium concentrations ranging from 2.0 to 4.0 x 10-4 M; a
range commonly occurring in electroplating rinsewater.
A population balance model was used to compute the nucleation and particle growth rates and relate
these to the supersaturation ratio. Particle growth rates found in the presence of citrate were much lower
than that in the absence of citrate. The examination of growth inhibition suggested that the mechanism
was surface reaction controlled.

Key words--cadmium hydroxide, precipitation, kinetics, nucleation, particle growth, growth rate,
population balance, growth inhibition, citrate

INTRODUCTION (1987). They showed that, while equilibrium solubili-

Precipitation is a widely employed treatment technol-
ogy for metal-bearing wastewaters. The technology is
generally capable of meeting conventional discharge
limitations and is favored for its low cost and ease of
implementation, as well as its ability to remove a
broad spectrum of metals concurrently. However,
there are deviations between practical performance
and theoretical predictions that suggest that the
kinetics of the hydrolysis and precipitation reactions
needs to be further explored.
The formation of precipitate begins with nucle-
ation and proceeds through particle growth and
ageing. The number, size, structure and morphology
of precipitated particles are primarily controlled by
nucleation. However, the nucleation process is not
well understood. The extremely small size of nuclei
complicates physical observations (Walton, 1967)
and this makes interpretation of particle growth.
dissolution and agglomeration in the overall precipi-
tation scheme more difficult.
One factor that affects the solubility of metals is the
presence of other constituents, particularly complex-
ing or adsorbing ligands, in the wastewater. A trace
of adsorbate is sometimes sufficient to completely
inhibit the growth of seed crystals in their super-
saturated solutions (Walton, 1967). The presence of
small amounts of soluble impurities alters both the
growth rate and habit of crystals formed in solution
(Walton, 1967).
One such impurity is citric acid and its salts, which
are often used in the plating industry. The effect of
citric acid on the precipitation of metal sulfides and
hydroxides has been investigated by Peters and Ku
ties were not significantly affected by the presence of
citrate, particle sizes were decreased. The cause for
this decrease was not reported, and in general, infor-
mation on the mechanisms of growth inhibition is
incomplete in the literature (Sears, 1958).
The goal of this study was to evaluate the kinetics
of Cd(OH): precipitation. Cadmium was selected
because of its high toxicity and the strict limitations
on the disposal ofcadmium-containing wastewater to
aquatic systems. The specific objectives were to: (!)
determine the effect of hydraulic residence time on
reaction kinetics and precipitate stability; (2) deter-
mine the nucleation and particle growth rates as a
function of supersaturation ratio; (3) examine the
mechanism of the particle growth process; and (4)
assess the influence of citrate on cadmium hydroxide
precipitation.
BACKGROUND
The basic precipitation reaction of cadmium hy-
droxide in aqueous solution can be written as:
Cd(OH),,~ = Cd :* + 2OH-. (I)
The conventional solubility product for equation (1)
is given by:
K,o = {Cd :~ } {OH-}:.
Although precipitate formation is predicted as
thermodynamically favorable at or above saturation
values (i.e. when the ionic activity product is greater
than or equal to the K,. for the solid phase), precipi-
tation will generally not occur until a significant
degree of supersaturation is reached (Nancoilas and

745
746 BIy L u o et al.
Purdie. 1964). The supersaturation ratio may be
defined as:
{Cd:" } { O H - } "
supersaturation ratio ( S ) =
X,o
Nucleation has traditionally been classified into
two types (Walton, 1967). The precipitation of a solid
from a homogeneous solution (in the absence of
pre-existing solid substrate) is called homogeneous
nucleation, while heterogeneous nucleation occurs on
a pre-existing surface. Because virtually all aqueous
solutions contain free particles of various types, most
nucleation is heterogeneous. This primary nucleation
stage is complete within a very short time and can
often be ignored in the evaluation of precipitation
kinetics (Walton, 1967).
Once nucleation has occurred, spontaneous par-
ticle growth may take place. Particle growth may be
divided into two distinct phases (Snoeyink and
Jenkins. 1980): (!) the movement of solute from bulk
solution to the crystal-liquid interface by means of
diffusion or convection and (2) adsorption of solute
onto the solid surface and incorporation into the
crystal lattice. As these are sequential reactions, the
slower reaction determines the overall reaction rate.
If mass transfer is faster than the reaction at the
surface, then the rate of growth is given by the rate
of the surface reaction, and vice versa.
The surface reaction phase of particle growth
can be influenced by secondary ions or complexing
ligands in tile wastewater matrix. For example, de
Hek et al. (1978) reported that the presence of sulfate
intluences the composition, texture and structure of
aluminum hydroxide precipitate, apparently due to
adsorption of sulfate ion onto the actively forming
solid phase. Similarly, Nancollas (1970) concluded
that the number of available growth sites of all the
divalent metal sulfates was reduced by the adsorption
of phosphate salts, which in turn reduced the overall
rate of crystallization.
Models o f mwh, ation anti growth
Nucleation and particle growth rates can be deter-
mined from an analysis of the population size distri-
bution. Randolph and Larson (1971) developed the
population balance model in a CSTR system as:
n = n" exp( - L/GO) (3a)
in which
L =
n =
size of the particle (L)
particle density (No./L~/L)
n"= nuclei population density (No./L]/L)
G= particle growth rate (L/T)
0= residence time (T).
This model assumes that the precipitation reactor is
a continuous stirred tank reactor (CSTR) operating
at steady-state conditions, that the growth rate is
independent of particle size, and that the suspension
is stable.
This model indicates that the logarithm of the
population density is a linear function of size:
log n = log n ° - L /G O. (3b)
(2)
The nuclei population density, n °, can be computed
from the intercept of a plot of log n ° vs L. The
particle growth rate, G, can be determined from the
slope of this plot.
The nucleation rate (Randolph and Larson, 1971)
is:
Bo = n °G. (4)
Heterogeneous nucleation rates depend on the size
distribution of initial molecular clusters (clusters are
groups of molecules that exist in solution prior to
the formation of nuclei), the rate of change of
this distribution and the level of supersaturation. In
laboratory experiments nucleation rates are com-
puted from equation (4). In industrial crystallization
practice, nucleation rates can also be empirically
correlated to the supersaturation at a given tempera-
ture (Nielsen, 1964). A proposed equation of this
form is (Randolph and Larson, 1971):
no = kS' (5)
where
S = supersaturation
Bo = nucleation rate (No./L3/T)
k = a kinetic constant (No./L}/T)
i -- a constant.
At low to moderate supersaturation, mass transfer
from solution to the particle surface is fast enough
that the particle surface growth process is rate-limit-
ing. The mechanisms of particle growth include screw
dislocation and two-dimensional surface nucleation.
At low supersaturation ratios, the screw dislocation
process dominates, and at higher supersaturation
ratios two-dimensional surface nucleation may
control growth (Nielsen, 1964). When the super-
saturation is very high, the transfer of material
lO
qr)- 5.0
A - 2 . 0 /zm/min
E
E
£
/I su°elc i°n-
ool Screw chslocotion domino e$
OOOl I 1
lo 'to0
Supersaturation ratio
Fig. I. Growth rate as a function of S according to the
surface nucleation and screw dislocation growth models.
 Kinetics of cadmium hydroxide precipitation
by diffusion from solution to surface becomes rate-
limiting.
The particle growth rate expression depends on
the corresponding growth mechanisms. For rate-
limitation by a screw dislocation growth or by diffu-
sion rate-limiting, the particle growth rate can be
approximated as a simple power function o f the
supersaturation (Walton, 1967: Nielsen, 1964):
G = k~S j (6)
where
K~ = rate constant (L/T)
j = constant.
For a surface nucleation growth mechanism, the
particle growth rate equation is (Walton, 1967):
[ -na:r
G = A exP~hkf-T-~.~iSi ) (7a)
where
A = growth rate factor (L/T)
a = two-dimensional cluster-solution edge en-
ergy (the interfacial energy between nuclei
forming cluster and solution (J/L)
t, = molecular volume (L ~)
h --cluster height (L)
T ffi absolute temperature (K)
k = Boltzmann's constant (J/K)
S = supersaturation.
This equation can be rewritten as
G = A exp[-~/In(S)] (7b)
where 4> is defined in this study as ~ = (ha z v / h k ' T ' ) .
At constant temperature k, T and a are constant,
while cluster height (h) and molecular volume (v)
depend on the degree of supersaturation. For differ-
ent ~ values, equation (7b) generates different curves.
Figure ! shows the theoretical dependence of the
growth rate on the supersaturation ratio for the two
different mechanisms.
In summary, the Randolph and Larson model can
be used to estimate nucleation and growth rates from
changes in particle size distribution during precipi-
tation in CSTRs. For a stable suspension the model
predicts a linear relationship between the logarithm
of particle population density and particle size. By
applying this model to experimental results, the
nucleation and particle growth rates can be obtained
from equation (3). These can then be related to the
supersaturation ratio to examine the rate limiting step
and the mechanisms of particle growth.
EXPERIMENTAL METHODS
Completely stirred tank reactor (CSTR) tests
Precipitation was carried out in a CSTR with an effective
volume of 325 ml. Influent NaOH and Cd(NOj) z solutions
were fed to the reactor with peristaltic pumps at the same
constant flow. Flow rates ranged from 108 to 650 ml/min to
give residence time. 0, of 0.5-3 rain. Before entering the
747
reactor the solutions passed through 0.2 ~m filters to re-
move foreign particles in the influent solutions. The reactor
was stirred with an impeller at 250 rpm and kept under a N:
atmosphere. The energy input from the stirrer to the sol-
ution in the reactor was about 0.08 W. The ionic strength
was 1.0 x 10-3M. Free cadmium concentration, pH and
conductivity were monitored continuously. When these
variables reached stable values, the system was considered
to be at steady state. Samples of the reactor contents were
collected at frequent intervals and analyzed for particle
concentration. When stable readings were obtained, particle
size distribution data were collected.
Analytical measurements
The stock solutions were analyzed for NaOH and
cadmium concentration by alkalimetric titrations and
atomic absorption spectroscopy (AAS). respectively. Total
and soluble (filterable) residual metal concentrations ([Cd]r
and [Cd],o~, respectively) were determined via atomic ab-
sorption spectroscopy (AAS). 10ml samples for the total
metal concentration analysis were withdrawn from the
reactor using a syringe. After acidification, the sample was
transferred into a sampling vial for the subsequent AAS
analysis. The same general procedure was used to take
samples for soluble metal concentration measurements. In
this case a disposable 0.45 l~m membrane filter was inserted
between the sampling tube and the syringe to remove the
precipitated solids.
During the course of experiments, the free cadmium
activity ({Cd :~ }) was measured with a cadmium electrode
(Luo, 1990). Particle concentration and size distribution
were measured on-line using a Hiac-Royco Model 4300
particle counter equipped with the Model 246 laser probe
(lower detection limit of 0.5/am). The instrument employs
a flow-through cell so that the particles may be measured in
real time. Due to the upper limitation of measureable
particle concentrations (Luo, 1990) a dilution system was
used. The diluting solution approximated the background
solution in the reactor so that the dilution process would not
alter the characteristics of the solid phase. This solution,
after having been sequentially filtered through a 0.45#m
filter and a 0.2 jura capsule filter, was mixed with the sample
stream immediately before entering the laser probe. In this
way, the contact time between sample and diluting solutions
was very short, and any influence on the suspension by the
dilution solution was minimized. Before each test, the
diluting solution was evaluated with the particle counter to
ensure a background of less than 100 particles per 100 ml
solution.
Calibrations of the cadmium eh,'ctrode, atomic absorption
spectrometer, electrokinetic analyzer {PenKem $3000), and
particle counter were performed before each test (Luo,
1990).
RESULTS AND DISCUSSION
Prior to the C S T R experiments, batch tests were
performed at preset values of total metal concen-
tration and base/metal molar ratios. The results (Luo,
1990) showed that the precipitation o f cadmium
hydroxide was too fast to study in batch processes. In
these experiments no differencc in filtrate cadmium
was noted between 0.45 and 0.2 p m membrane filters.
C S T R tests
A series of C S T R tests was performed to identify
experimental conditions (in terms of total metal
concentration and base/metal molar ratio) that were
suitable for kinetic studies. A O H / C d ratio near
748 BIN Lt:o et al.

33 & pH 9.4 I z10~ " 0 Citrate--free ~/

o Cd,=~ g C i t r a t e - 0resen~ o//
30 A 0 Cdt,ee ¢
TO 92

2.7 o -., 1110 8

o
" z~ 9.0 ~. z
~ 2.4 o
~ o *
o
U O ~ 1,1ff"
~ 0 [] [1
18 g
86 Z

1.5 I I
1 2
Residence time ( min ]
Fig. 2. Cadmium (total and free) concentration as a function
of CSTR residence time.
1.0 was studied; at higher ratio the precipitation rate
was too fast to study. The isoelcctric point of cad-
mium hydroxide is reportedly near pH 12 (Parks,
1965), and the positive surface charge expected for
the pH range in this study was confirmed by measure-
ments of the electrophorctic mobility (Luo, 1990).
Therefore, the suspension was stable. The acceptable
range of cadmium concentration for the kinetic study
was from 2.0 to 8.0 x l0 -4 M. The ionic strength was
about 1.0x 10 ~M. T h c 2 . 0 x l0 4 M limit is about
three times the thermodynamic solubility limit. Below
this limit the total precipitate yield was minimal, and
particle concentrations were too small to generate
reliable particle counts.
The upper limit was apparently the result of par-
ticle agglomeration. At cadmium concentrations
above 8.0 x 10"4M the suspension segregated into
a relatively clear supernatant layer over a denser
precipitate layer under regular mixing conditions.
As noted previously, a stable suspension is a pre-
requisite for using the particle population balance
model to study precipitation kinetics.
Figure 2 shows the results of one set of CSTR tests
performed with the same influent solutions (hence at
I
3 4
Ix10 6 I
10 100
Superso'turo'~ion ratio
Fig. 4. Calculated nucleation rate as a function of supersat-
uration ratio,
the same total cadmium concentration and OH/Cd
molar ratio) but varying CSTR residence times. With
increasing residence time, both residual soluble cad-
mium concentration and pH decreased until they
reached a constant value at a residence time of about
2.0 rain.
The results in Fig. 2 are consistent with the con-
sumption of hydroxide and free cadmium ions during
cadmium hydroxide precipitation. The results also
reflect a change in cadmium speciation with decreas-
ing pll. The decrease in total soluble cadmium con-
centration must be due to the precipitation reaction,
which consumes total cadmium and hydroxide ion
because the free cadmium concentration remains
nearly constant.
The kinetics o f precipitation
During the CSTR precipitation experiments par-
ticle size distribution data were collected and particle
population balances were performed to derive the
nucleation rate and particle growth rate based on
equation (3). A typical population balance for a

1 x l O e -- 0 Cltrote --free
"- Citrate -- present"
1 =10 7 0
A
c
0 0
0
1~106 0
E:L o 0
0 0
~::IL 1=10 5 OC] o.lo
o

o 1 ~ 104
5
¢: o
O
1 = 103 0

Ix102 [ '~ I O,01 I I I I I

0.3 0.4 0.5 0.6 0.7 0.8
0.5 10 1.5 2 0
l/InS
L(p.m)
Fig. 5. Calculated particle growth rate as a function of
Fig. 3. Particle size distribution for Cd(OH), precipitation. supersaturation ratio.
 Kinetics of cadmium hydroxide precipitation 749

Table I. Range of nucleation and particle growth rates

Precipitate Bo (No./ml mia) G~m/min) Reference
ZnS 1.4-4.6 x 10. 0.i55-0.33 Peters and Ku (1987)
Ba(NO3)~ 1.3 x 10J-9.3 x l0 s 1.68-23.3 Garside and Shah (1980)
CaCO~ 3.3 x 10~-2.5x 10. 0.24-0.66 Schierholzand Stevens(1975)
Cuz(OH)3NO3 1.5-8.6 x 10~ 0.014-0.065 Petropoulou(1991)
Cd(OH)~ 2.1 x 10'-8.0x 10" 0.12-0.26 This study
Cd(OH~z (citrate present) 2.2 x 10"-2.4 x 10' 0.014-0.079 This study

CSTR test is shown in Fig. 3. The logarithm of
particle population density, log n, decreases linearly
with increasing particle size, L over most of the range.
Two outliers in Fig. 3 correspond to very small
particle counts, so they were excluded from the
analysis. The population balance obtained is consist-
ent with Randolph and Larson's theory.
As noted earlier, the nucleation rate and particle
growth rate can be obtained from the slope and
intercept, respectively, of the regression line in Fig. 3.
Data from a precipitation experiment in the presence
of citrate which are also included in Fig. 3 will be
discussed below.
The supersaturation ratio was varied over a range
of 3-20 by changing the residence time, 0, cadmium
concentration and cadmium to hydroxide ratio,
Cd/OH. At each supersaturation, the nucleation rate
and growth rate were computed. In agreement with
nucleation theory (Walton, 1967), the nucleation rate
was dramatically affected by the supersaturation. The
logarithm of nucleation rate was then plotted as a
function of the logarithm of supersaturation ratio
(Fig. 4). The data fit the following equation:
Iog(Bo) = 4.15 + 3.48 log(S), r" = 0.9
where Bo has units of No./ml/min.
This linear model is statistically significant and can
explain over 90% of the total variability of the
logarithm of nucleation rate data.
The population balance analysis was also used to
obtain the growth rates at different supersaturation
ratios. The logarithm of growth rate was then plotted
vs logarithm of supersaturation ratio to find the
appropriate model to describe the growth mechan-
ism. In the range of supersaturation ratios investi-
gated, particle growth rate did not follow the power
law function described by equation (6). As mentioned
earlier, the power law function should fit the data if
the rate-limiting step is either screw dislocation
growth or diffusion of ions to the surface.
The model for the surface nucleation growth con-
trol mechanism [equation (7b)] was then tested
against the experimental data. Figure 5 is a plot of
growth rate vs supersaturation ratio. The experimen-
tal data are better described by this model. The
scattering of the experimental data may reflect
changes in the cluster height [h in equation (7a)] with
changes in the supersaturation ratio. Such a change
will cause the parameter ~ in equation (7b) to
fluctuate. Due to the limitation of the experiments.
the average magnitude of cluster height (h) and its
dependence on supersaturation could not be deter-
mined.
Table I presents a comparison of nucleation and
growth rates from this study with those from other
studies in the literature.
(8)
CSTR precipitation in the presence of citrate
When citrate anion was present in these solutions
and all other factors were the same, the cadmium
hydroxide precipitation rate was significantly lower
and the particle size distribution was shifted to a
range very close to the lower detection limit of the
particle counter (Fig. 3). The inhibition was signifi-
cant at citrate to cadmium ratios as low as 0.25.

0 Citrate -free
A C i t r a t e - - present o C i t r a C e -free
o C i t r a t e - present

0 0 0 0
(: 0
E 0 0
>
0 E 0 0
0 =L 0 . 1 0
E m

0 3

0 !
A
tAJ
2
O0
0 0

I I i I l 0.01
8 9 10 11 12 10

pH Supersaturation ratio
Fig. 6. Electrophoretic mobility (EM) of Cd(OH)2 as a Fig. 7. Calculated particle growth rate as a function of
function of pH. supersaturation ratio. The solid line is the regression line.
750
0100
c become adsorbed may be due primarily to adsorbed
E
E 00~0
n
0001 I I
0.0032 0.0034 0.0036 0.0038
1/7"
Fig. 8. Arrhenius type plot for Cd(OH): precipitation in the
presence of citrate.
Citrate also affected the surface charge of the
precipitate. Electrophoretic mobility measurements
in the presence and absence of citrate (Fig. 6) show
that the surface charge of the precipitate was lower in
the presence of citrate. Apparently, citrate adsorbed
onto the surface of the cadmium hydroxide precipi-
tate. reducing the surface charge, the particle growth
rate and the particle size.
The kineth's of precipitation
Due to the lower supersaturation ratio in the
presence of citrate, the nucleation rates were lower
th:,n in the absence of citrate. The nucleation rates in
the systems with citrate lit the equation:
log(B,,) -- 6.39 + 1.04 log(S)
with r " = 0.92. When citrate was absent [equation
(8)], the nucleation rate was much more strongly
affected by the supersaturation ratio (larger slope)
than it was in the presence of citric acid (Fig. 4).
When the supersaturation ratio was lower than 8.28,
the nucleation rate in the presence of citrate was
greater than that in the absence of citrate.
In the presence of citrate, the growth rate was
controlled by screw dislocation. A linear regression
analysis relating the log of the growth rate to the log
of the supersaturation ratio results in the following
equation:
log G = - 1.79 + 0.78 log S
or
G = 0.016 S °Ts
with r--0.90. Statistical analysis indicates that the
linear relationship is significant. Figure 7 shows the
experimental data and the linear regression line of
growth rate vs supersaturation ratio. At similar
values of the supersaturation ratio, the growth
rates in the presence of citrate are much lower than
those in the absence of citrate. The lower growth rates
in the presence of citrate are apparently caused by
adsorption of citrate on the surface of the solid.
BL~ Luo et al.
This result is consistent with others (Doraiswamy
and Sharma, 1984) who have noted that small
amounts of soluble foreign constituents may
markedly alter the growth rate of crystals and their
morphology. The retarding effect of substances that
molecules obstructing the deposition of latticed ions.
In some cases (Doraiswamy and Sharma, 1984) it has
been shown that the rate constant for particle growth
is reduced by an amount reflecting the extent of
adsorption.
Mechanism of particle growth inhibition
J The preceding results demonstrate that citrate in-
hibits cadmium hydroxide precipitation, especially
the particle growth process. What is not clear, how-
ever, is how citrate interferes with the precipitation
process, and whether the interference is primarily
associated with the transport, adsorption or reaction
step. One method of distinguishing between these
processes involves evaluating the activation energy of
the reaction. The activation energy of a physical
process such as diffusion is typically less than
5kcal/mol (Stumm and Morgan, 1981; Levenspiel,
1972). in contrast, the activation energy of a chemical
process such as surface adsorption is typically greater
than 10 kcal/mol.
To evaluate the activation energy, a series of
cadmium hydroxide precipitation experiments was
performed in the presence of citrate at five different
temperatures. The experimental temperatures ranged
from 6 to 35'C. At each temperature, a set of tests
with the same influent cadmium concentration,
(9) OH/Cd ratio, and Cit/Cd ratio was conducted at
different residence times. The particle population
balance was performed, and kinetic data (such as
nucleation rate and particle growth rate) were deter-
mined. In addition, the supersaturation ratio was
calculated at each temperature and from free cad-
mium ion activities and pH according to equation (2)
at different residence times. Then the growth rates
were correlated to supersaturation ratio through lin-
ear regression analysis (Luo, 1990). According to the
Arrhenius empirical rate law, the growth rate con-
stant, KG, can be related to the activation energy.
Thus log KG is plotted vs I/T for these experiments in
Fig. 8. From the slope the activation energy can be
(10a) obtained, which is equal to 15.6kcal/mol
(65.3 kJ/mol). This value suggests that the particle
growth process in the presence of citrate is controlled
(10b)
by a surface reaction process.
In these experiments, adsorption of citrate
anion on active Cd(OH), growth sites apparently
inhibits the spread of monomolecular steps on
the particle surface. In future research, citrate
adsorption at the surface of cadmium hydroxide
precipitate will be quantified. The information will
help to indicate the surface loading, !", at which
citrate starts to have an effect on the precipitation
reaction.
 Kinetics of cadmium hydroxide precipitation
CONCLUSION
Over the range of conditions studied the soluble
cadmium concentrations were dependent on the reac-
tor residence time in a continuous stirred tank reac-
tor. The precipitate formed had a positive surface
charge. Based on measurements of electrophoretic
mobility the particles were stable colloids.
A population balance model was used to determine
the nucleation and particle growth rates of cadmium
hydroxide. The nucleation rates were dramatically
affected by the supersaturation ratio, S. The kinetic
order for S in the nucleation reaction was 3.4. The
linear relationship between logarithm of nucleation
rates and logarithm of supersaturation ratio was
statistically significant. The results were in agreement
with classical nucleation theory.
The particle growth rates of cadmium hydroxide
did not follow a power law function with respect to
the supersaturation ratio. The growth rates were
consistent with rate limitation by surface nucleation.
Cadmium hydroxide precipitation was inhibited in
the presence of citrate. The particle growth rates
found in the presence of citrate were much lower than
those in the absence of citrate. This suggested that the
mechanism of inhibition was related to the growth
phase. The kinetic orders of the supersaturation ratio
for the nucleation reaction and particle growth pro-
cess in the presence of citrate were 1.0 and 0.8,
respectively.
Cadmium hydroxide precipitation experiments
at different temperatures were performed to deter-
mine the activation energy for the growth process
in the presence of citrate. The results indicate
that the mechanism of inihibition is most likely
surface reaction controlled rather than diffusion
controlled.
Acknowledgements--The authors would like to acknow-
ledge the US Environmental Protection Agency. whose
funding through the Industrial Waste Elimination Research
WR 26i6--D
751
Center made this study possible. The authors would also like
to thank Mark Benjamin for his careful review and valuable
comments on this paper.
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