3128 Ind. Eng. Chem. Res.

2007, 46, 3128-3136

Modeling of Formation of Gold Nanoparticles by Citrate Method†

Sanjeev Kumar,* K. S. Gandhi,* and R. Kumar
Department of Chemical Engineering, Indian Institute of Science, Bangalore 560012, India

Properties of nanoparticles are size dependent, and a model to predict particle size is of importance. Gold
nanoparticles are commonly synthesized by reducing tetrachloroauric acid with trisodium citrate, a method
pioneered by Turkevich et al (Discuss. Faraday Soc. 1951, 11, 55). Data from several investigators that used
this method show that when the ratio of initial concentrations of citrate to gold is varied from 0.4 to ∼2, the
final mean size of the particles formed varies by a factor of 7, while subsequent increases in the ratio hardly
have any effect on the size. In this paper, a model is developed to explain this widely varying dependence.
The steps that lead to the formation of particles are as follows: reduction of Au3+ in solution, disproportionation
of Au+ to gold atoms and their nucleation, growth by disproportionation on particle surface, and coagulation.
Oxidation of citrate results in the formation of dicarboxy acetone, which aids nucleation but also decomposes
into side products. A detailed kinetic model is developed on the basis of these steps and is combined with
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population balance to predict particle-size distribution. The model shows that, unlike the usual balance between
nucleation and growth that determines the particle size, it is the balance between rate of nucleation and
degradation of dicarboxy acetone that determines the particle size in the citrate process. It is this feature that
is able to explain the unusual dependence of the mean particle size on the ratio of citrate to gold salt
concentration. It is also found that coagulation plays an important role in determining the particle size at high
concentrations of citrate.

1. Introduction exchange of material between micelles. Both these features can

Nanoparticles have potential for many applications, and their
synthesis has assumed importance. Size obviously is their most
important property, and many applications depend on it. Poly-
dispersity in size is often an undesirable feature in these appli-
cations. Thus, prediction of both size and dispersity for a given
system is of concern in systematizing the manufacture of nano-
particles. A variety of methods to synthesize nanoparticles are
reported in the literature. A detailed account of these methods
is provided by Cushing et al.2 and Schmid.3 Broadly, these
methods can be classified into gas-phase and liquid-phase-based
methods. In gas-phase-based methods, bulk material is evapo-
rated using high-energy sources such as resistive heating and
lasers to obtain a supersaturated gas phase, which, under con-
trolled conditions, produces nuclei that grow to become nano-
particles. In liquid-phase methods, also known as wet methods,
precursors react to form a supersaturated solution, which nuc-
leates and gives rise to particles ranging from 1 to 100 nm in
size with stability ranging from a couple of hours to years. Wet-
synthesis methods are attractive at least for two reasons: they
are more energy efficient and they can be used to produce nano-
particles using the standard apparatus available in a laboratory.
So far, two strategies have been followed for wet synthesis.
In the first strategy, two reactants, usually both of them in
(reverse) micellized form, are mixed and nanoparticles form
inside them by precipitation. The size of particles is controlled
by the rates of nucleation and growth, and stabilization is
provided by adsorption of surfactant. Nucleation is correlated
to the size of micelles, and growth is determined by the rate of
* To whom correspondence should be addressed. E-mail: sanjeev@
chemeng.iisc.ernet.in (Tel., +91-080-22933110), gandhi@
chemeng.iisc.ernet.in (Tel., +91-080-22932320). Fax: +91-080-2360
8121.
† reducing agent. In all these methods, it is expected that the
The authors are happy to contribute this investigation to the special
issue honoring Prof. M. M. Sharma. A part of this work formed the
basis for a paper presented at CHEMCON04 held in Mumbai in
December 2004.
10.1021/ie060672j CCC: $37.00 © 2007 American Chemical Society
Published on Web 10/07/2006
be altered through chemical nature and concentration of
surfactant. This strategy offers scope for good control over
particle size and has been modeled by several investigators.
Results have been obtained by kinetic Monte Carlo simulations
using the method of interval of quiescence in several articles.4-6
Equivalently, mean-field population balance models have been
developed for nanoparticle synthesis7-9 and to study the effect
of mixing on the synthesis process.10 A large amount of
surfactant is, however, used in this method, which makes it
expensive. Recovery of surfactant, e.g., by using nanofiltration,
has been proposed as a remedy, but it needs to be evaluated
rigorously for determining the economics.
In the second strategy, precipitation is carried out in bulk in
the presence of stabilizers that adsorb on nanoparticles and
prevent coagulation of particles. Most of these methods were
first demonstrated for their ability to make gold nanoparticles
and then extended to the synthesis of other types of particles,
including those of semiconductors. Three widely used bulk-
precipitation-based techniques for the synthesis of gold nano-
particles are as follows: (i) citrate method of Turkevich et al.,1
(ii) citrate-tannic acid method of Muhlpfordt,11 and (iii) Brust-
Schiffrin method of Brust et al.12 The first two methods yield
particles which are stable against coagulation, whereas the last
one produces particles which are also capped and cannot be
grown bigger. Additionally, only the product of the Brust-
Schiffrin method can be dried and redispersed.
In the simplest procedure for preparation of gold particles
(Turkevich method), tetrachloroauric acid is reduced with
trisodium citrate. Here, citrate is both the reducing agent and
the stabilizer. Similarly, in the Brust-Schiffrin method, alkane
thiols that provide long-term stability also take part in reduction
of gold along with sodium borohydride, which is the main
relative amounts of gold salt to reducing agent influence the
particle size. The rate of adsorption of stabilizer also plays a
role in controlling particle size. Thus, a single reagent can play

Figure 1. Variation of particle size with ratio of initial concentrations of
citrate to gold salt.
multiple roles, which creates more complexity. This feature
combined with the fact that reactions that usually occur in these
systems are fast makes the particle size more sensitively
dependent on the concentrations of precursors, rate of addition
of precursors, state of mixing in the reactor, and other variables.
While this sensitivity requires strict adherence to protocols that
work, it also permits particle size and polydispersity to be
changed substantially merely by changing the concentrations
of the precursors. All the three synthesis protocols listed above
have been subsequently modified by changing the ratio of
common precursor tetrachloroauric acid to other reagents to
synthesize nanoparticles of significantly different sizes.13,14
Although direct precipitation using the citrate method is in
wide use because it produces uncapped but stable particles, a
quantitative model to predict particle size and the associated
distribution is not available. The objective of this paper is to
develop a quantitative model for the citrate method of Turkevich
et al.1 Because the chemistry involved and the processes of
nucleation and growth of particles are different from one another
in the three methods, the model developed here is for the
experimental method of Turkevich et al.1 only.
2. Features of the Citrate Process
We consider the formation of gold nanoparticles by reduction
of tetrachloroauric acid by trisodium citrate. The method has
been pioneered by Turkevich et al.,1 and variants of it are still
widely used15 to produce gold nanoparticles. Because of its
simplicity, various facets of the process have been investigated
by Frens,13 Freund and Spiro,16 Chow and Zukoski,17 Abid,18
and others. In this process, an aqueous solution of tetrachloro-
auric acid is brought up to boiling and a small volume of
trisodium citrate is then added to it. In ∼10 s, bluish color
appears, indicating formation of gold nuclei. In a few minutes
or less, the solution turns brilliant red because of the formation
of nanoparticles. The completion of reaction may take tens of
minutes depending upon the amount of citrate taken.
A plot of mean particle size against the ratio of initial
concentrations of citrate to gold species is presented in Figure
1. It summarizes data from Turkevich et al.,1 Ferns,13 Freund
and Spiro,16 Chow and Zukoski,17 and Abid.18 All the data
shown in this figure, except those of Chow and Zukoski,17 are
obtained for approximately the same concentration of auric
chloride and by varying concentration of sodium citrate. It is
interesting to note that the data spanning a 50-year period show
a good correlated trend.
Figure 1 reveals several interesting features. First is the widely
varying dependence of particle size on the ratio of citrate to
gold. When this ratio increases by a factor of 5, from ∼0.4 to
∼2, the particle size decreases by a factor of 7, which
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 3129
Figure 2. Illustration of complex of aurous species and dicarboxy acetone.
corresponds to a change of nearly 3 orders of magnitude in
volume. Yet, when the ratio increases from about 2 to 7, there
is very little change in the particle size. On the other hand, when
the concentration of sodium citrate is kept fixed and that of
auric chloride is varied, Chow and Zukoski17 found that the
particle size varies sensitively over a wide range of auric chloride
concentrations investigated. With a decrease in initial concentra-
tion of auric chloride, particle size first decreases, passes through
a minimum, and then increases (the experimental data are shown
in Figure 5).
Another interesting feature is that complete conversion of
auric chloride has been reported at all the ratios of citrate to
gold. Data with small ratios of citrate to gold were reported by
Frens,13 and the least of them corresponds to a ratio of ∼0.43.
A model is presented below that attempts to explain these
unusual features quantitatively.
3. Model
3.1. Chemical Reactions. Gold nanoparticles have been
synthesized using the citrate method for a long time now, and
although most reactions occurring in the method and the
intermediates formed in the process are known, some of the
steps are still not fully understood. In the following discussion,
we point out these and state how they are modeled in this work.
The initial step of this multiple-step process, with reactions
occurring in series and parallel, is the oxidation of citrate, which
yields dicarboxy acetone:
The second step is the reduction of auric salt to aurous salt:
AuCl3 + 2e- f AuCl + 2Cl- (2)
The next step is the disproportionation of aurous species to gold
atoms:
3AuCl f 2Auo + AuCl3 (3)
The disproportionation step requires three aurous chloride
molecules to combine. This is facilitated by dicarboxy acetone,
which, according to Turkevich et al.1 and Abid,18 plays the role
of organizer through the formation of a complex. An illustration
of the complex as visualized in this work is presented in Figure
2. In the chain-like structure pictured here, three Au+ can be
tethered by a minimum of two dicarboxy acetone molecules.
3130 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007
Once gold particles are formed, disproportionation can occur19
on the particle surface, too.
The overall stoichiometry of the reduction reaction can then
be represented as
If these were the only reactions that led to the formation of
gold atoms, the overall stoichiometry would require three citrate
molecules to reduce two auric chloride molecules. Since at high
temperatures dicarboxy acetone is lost in side reactions1 to form
acetone,
the stoichiometric ratio of citrate to gold required for complete
conversion of auric chloride should be even larger than 1.5. In
contrast, Frens13 reports complete conversion of auric chloride
at a stoichiometric ratio as low as 0.43. He, however, does not
discuss the chemistry involved. It appears reasonable to conclude
that some products of degradation of dicarboxy acetone reduce
trivalent gold, though the chemistry leading to the formation
of gold is not clear. Turkevich et al.1 and Davies20 have shown
that acetone can reduce auric chloride to produce gold particles,
though the conditions in the two experiments are different. In
view of the foregoing, we assume that it is acetone formed by
degradation of dicarboxy acetone that additionally reduces auric
chloride for its complete conversion. To explain the observations
of Frens,13 we assign a stoichiometric ratio of 4 for this reaction.
(CH3)2CdO + 4AuCl3 f 4AuCl + products (6)
This allows for complete reduction of ∼3 mol of auric chloride
by 1 mol of citrate. This assumption influences the model results
only for ratios of citrate to gold <1.5. Because the particle size
obtained at these ratios is large, the practical significance of
this regime may be less.
3.2. Overall Mechanism of Particle Formation. On the basis
of the above set of chemical reactions, the following mechanism
of particle formation and growth is proposed. Au3+ is reduced
in solution by citrate to Au+, which forms a multimolecular
complex with dicarboxy acetone. The complex disproportion-
ates, and gold atoms are formed. These atoms adsorb Au+ and,
by complexation with dicarboxy acetone, form large aggregates.
Further disproportionation leads to formation of still larger
aggregates of gold atoms. When the size of the aggregate reaches
a critical value, a nucleus of gold atoms is formed. The gold
atoms produced by disproportionation are absorbed by the
particle, resulting in its growth.
3.3. Nucleation. Turkevich et al.1 have investigated the
nucleation process in the citrate method in detail. They
considered nucleation to be possibly due to the presence of an
impurity, statistical fluctuations, or some other mechanism. On
the basis of their experimental findings, they ruled out the role
of impurities and statistical fluctuations in nucleation and
concluded that dicarboxy acetone plays a critical role in
nucleation through an organizer mechanism by forming a
complex with gold ions. Because no other mechanism for
nucleation of gold particles in the citrate process has been
proposed, in this work, we have attempted quantification of the
rate of nucleation by modeling the organizer mechanism through
a chemical reaction step.
The number of gold atoms needed to form a nucleus is an
open question. The so-called magic numbers determine the size
of stable clusters, but in the absence of stabilizing agents. A
number of Aun clusters with n values of 10, 15, 18, etc.
protected21 by glutathione are also reported, but they are not
relevant here. A fundamental model is needed to predict the
number of atoms that lead to the formation of a stable nucleus
in the actual system. In the present work, we have taken the
size of the nucleus to be 2 nm, as reported by Turkevich et al.1
and Turkevich.22 Because the mass contained in a nanoparticle
of typical size of tens of nanometers is much greater than that
contributed by a nucleus (of 2 nm diameter), we keep the model
simple by using an overall rate expression for the nucleation
process to capture the formation of nuclei. (Sensitivity of model
predictions to this parameter is discussed later.)
3.4. Coagulation of Particles. Yet another issue to be
addressed in the model is coagulation. There is some controversy
regarding the stability of particles at small ratios of citrate to
gold. For example, Turkevich et al.1 reported that particles are
unstable for a citrate-to-gold ratio <0.5. Frens,13 however,
reported formation of stable particles at a ratio of ∼0.4 as well.
Since neither citrate nor gold salt is left unreacted at these ratios,
identification of the stabilizing agent is an issue. Li et al.23 have
recently reported that acetone can stabilize gold nanoparticles.
Because acetone is produced in the present system, it can be
expected to play this role.
Turkevich and co-workers1 observed coagulation or ripening
of nanoparticles of gold at high citrate concentrations and
investigated the effect of addition of salts on coagulation in a
series of subsequent papers.24 They identified that coagulation
is promoted because of the compression of double layers by
the high sodium ion concentration. Chow and Zukoski17
investigated this aspect systematically. Their experimental data
(presented in Figures 1 and 5) shows an increase in particle
size at high counterion concentration, which suggests that
coagulation of particles has to be considered in the model.
A feature special to gold nanoparticles needs to be mentioned.
Electron micrographs indicate that most particles are not single
crystals, but are “twinned”. This structure is formed when two
very small particles, perhaps of the order of a nanometer,
coalesce and form a single particle for all practical purposes
and grow in all directions into a larger particle. Turkevich22
speculated that, in the initial stages, the particles are amorphous
and can coalesce. The agglomerate becomes structured as it
grows. Coalescence may be expected, since the melting point
of clusters of atoms decreases with their size25 and surface atoms
are quite mobile at temperatures well below the melting points.26
It is perhaps also related to the lack of a sufficient number of
adsorption sites on small particles, and hence, it is possible to
stabilize only large particles. In this connection, it is interesting
to note that particles of size smaller than ∼2.5 nm have not
been synthesized by citrate and citrate-tannic acid methods.
This size corresponds to a particle formed by coalescence of
two particles with a magic number of 55 (∼2 nm, the size of
the nuclei chosen in this work). Because the fine structure of
the particles is not of direct interest here, we do not assign any
enhanced rate of coagulation to nuclei in the current investiga-
tion. It may be mentioned in passing that Ostwald ripening does
not occur at the temperatures of synthesis and need not be
accounted for in the model.
 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 3131

3.5. Model Equations. For the purposes of prediction of d[N]

particle size, a model should quantitatively account for (i) ) 2kn[M]3[S]2 (12)
dt
reduction of Au3+ to Au+ in the bulk, (ii) growth of particles
by absorption of gold atoms formed by disproportionation on 3.5.5. Mass Balance of Species. The mass balance of auric
the particle surface, (iii) rate of nucleation, and (iv) growth due species in a batch system is, therefore, given by
to coagulation. We consider these in detail below.
3.5.1. Scheme of Reactions. Let T and C represent the auric d[T]
and citrate species, respectively. Let M and S represent the ) -kc[C][T] - kd[D][T] +
dt
∫V∞V2/3P(V) dV + knFVo[M]3[S]2
aurous and dicarboxy acetone species, respectively. Let D
represent acetone. The model can then be represented by the kh[M] (13)
o
following equations.
where Vo is the size of the nucleus. The last term on the right-
kc
Homogeneous reduction: T + C 98 M + S (7) hand side of the above equation accounts for the production of
auric chloride due to disproportionation leading to nucleation
events.
Heterogeneous disproportionation: Aurous chloride is formed through the reaction of auric
kh
3M 9 8 T + particle mass (8) chloride with citrate and acetone and is consumed when nuclei
particle are born. Thus, the mass balance of aurous species is identical
kn , S
to the above with changed stoichiometric coefficients:
Nucleation: 3M 98 nucleus + T (9)
d[M]
ks
) kc[C][T] + kd[D][T] -
dt
Degradation of dicarboxy acetone: S 98 D (10)
kd
3kh[M] ∫V∞V2/3P(V) dV - 3knFVo[M]3[S]2
o
(14)
Reduction by acetone: D + 4T 98 4M + products (11)
The mass balances for citrate and dicarboxy acetone can be
Because the nucleation and growth of particles can occur written along the same lines:
simultaneously, gold particles will not be monodispersed. Let
P(V) dV represent the number concentration of gold particles in d[C]
the system in the size range V to V + dV. All the particles ) -kc[C][T] (15)
dt
including those formed by coagulation are considered to be
spherical in shape. d[S]
3.5.2. Kinetics of Reductions in Bulk. Let us first consider ) kc[C][T] - ks[S] (16)
dt
the reactions involving trivalent auric species. It is consumed
by the homogeneous reduction reaction and produced in the d[D] 1
disproportionation reaction. The reduction is assumed to be first ) ks[S] - kd[D][T] (17)
dt 4
order with respect to citric and auric species. It is also consumed
in the reaction with acetone. We assume the rate of this reaction The initial conditions for the above equations are given by
also to be first order with respect to citrate and acetone.
3.5.3. Kinetics of Disproportionation. Disproportionation [T] ) [T]o, [C] ) [C]o, [M] ) [S] ) [D] ) 0 (18)
of monochloride at various temperatures has been reported by
Gammons et al.19 At 100 °C, equilibrium is heavily in favor of 3.5.6. Population Balance. The above set of equations can
trichloride. This reaction can occur in the bulk but is catalyzed19 be solved once we find the number concentration of particles.
by the gold surface since Au+ adsorbs on it. The surface of A population balance equation for the number density of
gold particles thus acts as a catalyst, and it is this mechanism particles is used to determine it. The number of particles in a
that is dominant in the citrate process. Because the stabilizer size range changes when smaller particles grow into it and when
also competes for the surface of gold particles, and the particles in it grow out of it through the convective process of
concentration of aurous chloride is expected to be small in view surface reaction. The Brownian coagulation of particles also
of the unfavorable equilibrium, it is likely that the rate of the results in birth and death of particles in the size range considered
disproportionation reaction is controlled by the rate of adsorption above. All these processes are accounted by the following
of aurous chloride. This might also be expected since diffusional number or population balance equation:
resistances are negligible at these length scales. Thus, the rate
of this reaction on each particle is assumed to be proportional ∞ q(V, V′)
to the surface area of the particle and the concentration of aurous
∂P
∂t
2
F
∂
) - kh[M] (V2/3P) - P(V) V
∂V o W
∫ P(V′) dV′ +
chloride [M]. Simultaneous with the disproportionation of 3 mol
1 V q(V - V′, V′)
of aurous species, 1 mol of auric species is formed.
3.5.4. Rate of Nucleation. As per the discussion in earlier 2 Vo
∫ W
P(V - V′)P(V′) dV′ +

sections on the nucleation process, three molecules of aurous δ(V - Vo)2kn[M]3[S]2 (19)
species are required for disproportionation to occur and at least
two molecules of dicarboxy acetone are required for complexing The first term on the right-hand side accounts for the convective
aurous species in solution. In view of this, it was assumed that growth processes due to surface reaction. The Brownian collision
the order of the nucleation reaction is 3 with respect to aurous frequency, q(V, V′), is given by
and 2 with respect to dicarboxy acetone. Nucleation occurs when
a sufficient number of gold atoms agglomerate in the solution 2ku -1/3
q(V, V′) ) [V + V′-1/3][V1/3 + V′1/3]
to reach critical size. 3µ
3132 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007
Further, W is the ratio of the number of collisions to those that
result in coagulation. The second and third terms on the right-
hand side thus account for loss and gain due to Brownian
coagulation, respectively. The last term accounts for the rate of
creation of particles at size Vo by nucleation. Here, δ(V - Vo) is
the Dirac delta function. Initially, the particle concentration is
zero. One boundary condition needed to solve the equation for
P(V) is provided as P(Vo, t) ) 0.
3.5.7. Coagulation Efficiency. Coagulation occurs when two
particles colliding with each other because of their Brownian
motion overcome the repulsive force between them and reach
primary minimum irreversibly. Repulsive force that resists
approach of particles before they reach primary minimum is
caused by double-layer interaction between the particles and
steric repulsion due to the adsorption of acetone on the particle
surface. Only a fraction of the collisions leads to coagulation.
Thus, the stability of particles against coagulation is represented
by the stability factor W defined as28
number of collisions between particles
W)
number of collisions that result in coagulation
In this paper, we incorporate all the interactions between the
particles through repulsive forces of ionic origin and consider
only irreversible coagulation of particles. Chow and Zukoski17
have shown that particles also reversibly aggregate in an open
cluster, which breaks apart in later stages of synthesis. Since
the particles are found to grow in these clusters unhindered
(evidenced by monolith product), we ignore this aspect in the
present model.
Reerink and Overbeek29 have developed a simplified expres-
sion for W, applicable when interaction potential possesses a
relatively sharp maximum. The expression is given by
log W ) -k1 log Ce + k2 (20)
Here, Ce is the concentration of the counterions. Constant k1
varies with surface potential, and k2 depends on the physical
system only. The surface potential depends on coverage of the
surface by the potential determining ions. Auric and aurous
chlorides, dicarboxy acetone, acetone, and citrate ion are all
possible candidates for adsorption on gold particles. Further-
more, as the concentrations of these species change in the course
of particle formation, W also changes. To ascertain the basic
features, several simplifications need to be made. As a first step,
we assume that adsorption of potential-determining ions is at
equilibrium with the bulk. Since equilibrium data are not
available, surface concentrations of ions can still not be
estimated. The following approximate but simpler approach is
pursued in the present model.
Chow and Zukoski17 examined simultaneous adsorption onto
gold particles from solutions of citrate and tetrachloroauric acid
(HAuCl4). They proposed that the auric chloride adsorbs
strongly on gold particles in comparison with citrate. Thus, the
fraction of area occupied (f) is biased toward gold species, which
we incorporate in the present work using the following
expression:
1
f)
[C]
1 + 0.1
[M]+[T]
Surface potential, which depends on the adsorbed ions, is dif-
ficult to measure or estimate from theory.17 The data of Chow
and Zukoski17 indicate that the surface potential is about
-90 mV under some conditions. The charge on aurous is equal
to that of auric but is three times smaller than that on citrate.
To allow for variation in surface potential with the changing
ionic environment in the bulk, the following empirical expres-
sion is used:
φ ) -90[f + 1.5(1 - f)]
The somewhat higher value of surface potential used here
compensates for the steric stabilization that is not incorporated
in the model. Coagulation efficiencies, theoretically calculated
and reported by Chow and Zukoski,17 were fitted approximately
to the expression of Reerink and Overbeek29 to obtain
560
log W ) log (3[C]o + [T]o) × 10-4 + 27.5
φ
The initial counterion concentration is given by the sum of 3×
the citrate concentration and the concentration of HAuCl4.
4. Results and Discussion
The model equations were converted to nondimensional form
before solving them. All the concentrations were nondimen-
sionalized using [T]o. Particle populations were scaled using
Nmax, the maximum number of particles per unit volume that
can be generated in the systems, i.e.,
[T]o
Nmax )
FVo
Time is scaled using (kc[T]o)-1, the time scale for reaction
between citrate and auric ions. The final set of nondimensional
equations has the following nondimensional groups in it.
kh
Kh ) (21)
kcFVo1/3
kn
Kn ) FV [T] 3 (22)
kc o o
ks
Ks ) (23)
kc[T]o
kd
Kd ) (24)
kc
1 × 10-3 2kBT
Kq ) · (25)
kcFVo 3µ
The initial conditions for the nondimensionalized [T] and [C]
are 1 and R ()[C]o/[T]o), respectively. All the other variables
have zero value at the initial time. Model predictions require
values for rate constants kc, kd, kh, kn, and ks. The nondimensional
groups identified above indicate that, if the particles are stable
against aggregation, only the ratios of the five rate constants
need to be fixed to predict particle size distribution. Kd should
be smaller than unity because the time taken for process
completion with a limited amount of citrate is significantly larger
than when citrate is in excess. The best-fit values of Kh, Kn,
and Ks required to predict the experimental data shown in Figure
1 for a [T]o value of 3 × 10-4 M, the concentration used by
Frens,13 were obtained. The value of F is taken to be 0.1 M/cm3
and Vo is 4.18 × 10-21 cm3, corresponding to a nucleus of 2
nm in size. The value of rate constant kc was fixed so as to

Table 1. Ratios of Rate Constants Used in the Model
kn (1.67 × 109)NAvg M-5 L-1 s-1
kh 2.5 × 10-5 L cm-2 s-1
ks 1 s-1
kd 4 × 102 M-1 s-1
kc 1.25 × 103 M-1 s-1
make the process time of the same order as the experimentally
reported values at 100 °C. Once kc is fixed, all the other rate
constants are also determined from the values assigned to groups
Kh, Kn, Ks, and Kd. These values are provided in Table 1. Later
we will report about the sensitivity of the results to the values
of the rate constants to gain insight into the importance of the
corresponding steps to the outcome of the process.
Predictions using the model were made as follows. Following
the discretization techniques of Kumar and Ramkrishna30,31 for
aggregation and convective growth processes, the integro-partial
differential equation for number density (eq 9) was converted
into a set of ordinary differential equations. In brief, the
continuous population density is discretized into bins, and the
resulting discrete populations are assigned to the respective
representative particle volumes called pivots, one for each bin.
The growth of particles, following the method of characteristics,
is incorporated through the movement of pivots. New pivots
are added at short intervals to account for nucleation, which
also grow with time. The number of pivots is kept to ∼100 by
collapsing densely populated pivots to their neighboring pivots.
Nondimensional versions of eqs 13, 14, and 17, and equations
for discrete populations and movement of pivots were integrated
using the initial condition given in eq 18. The particle-size
distribution and moments were computed from the results.
Coagulation was allowed at all times with the efficiency
predicted using the expressions provided above. Since the first-
and higher-order processes take infinite time to complete, the
process was considered complete when 99% of gold was
converted to particles.
4.1. Predictions of Mean Particle Size. Mean particle size
was predicted using the model for the experimental conditions
employed by Turkevich et al.,1 Frens,13 Freund and Spiro,16 and
Abid.18 All these investigations were carried out by using [T]o
≈ 3.0 × 10-4 M and varying [C]o. In Figure 3, predictions are
compared with observations of these investigators. Chow and
Zukoski17 made observations by varying [T]o from 0.4 × 10-4
to 1.2 × 10-5 while keeping [C]o constant at 1.6 × 10-3, and
hence, comparison of model predictions with these observations
will be considered separately.
From Figure 3, it can be seen that the model is able to predict
the observations with good accuracy. It is able to capture the
steep drop in particle size as the ratio [C]o/[T]o increases from
about 0.4 to 2.0. It is also able to predict the marginal decrease
in particle size as [C]o/[T]o increases from 2 to 7.
It is customary to anticipate that the particle size is mainly
the result of the balance achieved between nucleation and
growth. The citrate process is more complicated since nucleation
is aided by dicarboxy acetone, which, however, degrades during
the course of the process. In fact, it turns out that the kinetics
of this degradation reaction determines the particle size. In the
following discussion, it helps to remember that data were
acquired by keeping [T]o constant and varying [C]o. First, let
us consider the situation when the initial concentration of citrate
is low. As citrate decomposes, dicarboxy acetone is formed and
its concentration increases. However, the increase in the
concentration of dicarboxy acetone is prevented by its degrada-
tion as well as by the reduced rate of its formation since citrate
is being consumed. As a result, the concentration of dicarboxy
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 3133
Figure 3. Predictions of dependence of particle size on the ratio of citric
acid to gold for fixed value of [T]o ) 3 × 10-4 M.
acetone passes through a maximum. The maximum reached is
proportional to the initial concentration of citric acid. The rate
of nucleation is determined by the rate of formation of a
multimolecular complex with the aid of dicarboxy acetone.
Hence, rate of nucleation also passes through a maximum.
Further, rate of nucleation is steeply dependent upon the
concentration of dicarboxy acetone. Thus, an increase in the
initial concentration of citrate strongly favors nucleation.
Because [T]o is kept constant in the experiments, the mass of
gold particles that can form is also constant. Thus, a sharp
increase in the number of nuclei formed as the initial concentra-
tion of citrate is increased in turn causes the observed steep
decrease in particle size.
Now let us consider the situation at higher initial concentra-
tions of citrate. As the initial concentration of citrate is increased,
auric chloride becomes the limiting reactant for formation of
dicarboxy acetone. According to stoichiometry, this point is
reached when [C]o/[T]o ) 1.5. From then on, the maximum
concentration of dicarboxy acetone attained is limited to that
corresponding to complete consumption of auric chloride and,
in fact, is less than that because of its own degradation. In any
case, the maximum reached is a constant and is unrelated to
the initial concentration of citric acid. Thus, the rate of
nucleation becomes independent of [C]o and is only related to
the value of [T]o. The mass of gold that can form is also
proportional to [T]o. However, [T]o is kept constant in the
experiments. Hence, particle size becomes relatively independent
of the ratio [C]o/[T]o after ∼1.5. The rate of nucleation in this
range is also affected by the degradation of dicarboxy acetone.
The weak dependence of the particle size on the ratio [C]o/[T]o
is due to this. Thus, it is seen that it is not the balance between
nucleation and growth that determines the particle size in the
citrate method, but it is the balance between the rates of
degradation of dicarboxy acetone and nucleation that determines
the particle size. If dicarboxy acetone did not degrade or
degraded slowly, more nuclei would have formed, and the
particle size would have decreased sensitively at increased values
of [C]o/[T]o. The degradation of dicarboxy acetone, therefore,
is the key step in determining the particle size. While dicarboxy
acetone was identified as the key agent in the process of
nucleation, its role in effectively determining the particle size
is brought out by the present model.
4.2. Growth Processes. The above conclusions are also
supported by the nature of the growth process. Growth occurs
through a disproportionation reaction on the surface. The rate
of this reaction is proportional to the concentration of aurous
chloride and surface area. The concentration of aurous chloride
increases as auric chloride decomposes by reaction with citrate.
3134 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007
Figure 4. Predictions of particle size when dicarboxy acetone is not
permitted to degrade. Parameter set 1 is the same as that in Table 1, except
for ks being reduced to 0.001 s-1. Parameter set 2 additionally differs from
that in Table 1 in the value of kn, which is reduced from (1.67 × 109)NAvg
to (7 × 105)NAvg M-5 L-1 s-1.
At low initial concentrations of citrate, it is completely consumed
at an early stage of the process and aurous chloride can form at
later times only when auric chloride is consumed by reaction
with acetone. The latter is a slow reaction. Thus, the concentra-
tion of aurous chloride reaches a low pseudosteady value. As a
result, the growth process is a very slow one and does not
compete with nucleation. At high initial concentrations of citrate,
auric chloride is the limiting reactant and rapidly decomposes
to aurous chloride. As a result, the growth process is also
controlled by [T]o, which is kept unchanged. Thus, once again
the mean particle size is not affected much by the ratio [C]o/
[T]o. Even in this range of [C]o, it is found that nucleation is
complete because of the fast degradation of dicarboxy acetone
well before growth stops.
4.3. Effect of Degradation. We further support the above
analysis by investigating the effect of slowing down the
degradation reaction. This was done by reducing the rate
constant ks to 0.001 s-1. It may be noted that complete
conversion of auric chloride takes much longer since formation
of acetone is also slowed. The results of this investigation are
shown in Figure 4.
The curve corresponding to parameter set 1 uses the values
for rate constants listed in Table 1 except that ks is set equal to
0.001 s-1. As can be seen from Figure 4, more nucleation occurs
over the entire range of the ratio [C]o/[T]o and the particle size
is smaller. At values of this ratio greater than ∼1.5, the particle
size becomes constant as explained above. Its value now,
however, is ∼8 nm, as compared to ∼20 nm (see Figure 3)
when degradation is allowed. The better fit obtained here points
to a need for better tuning of the model for degradation. At
small values of [C]o/[T]o, the effect is more dramatic. When
this ratio is 0.43, the particle size reaches only 20 nm, as
compared to the observed value of 150 nm.
A different approach was used to further confirm the effect
of degradation of dicarboxy acetone. While letting ks be equal
to 0.001 s-1, the values of the other kinetic constants were
allowed to vary to get the best fit for the experimental data.
The results are shown in Figure 4 and correspond to parameter
set 2. Even to get only a reasonable fit at low values of [C]o/
[T]o, the rate of nucleation had to be reduced considerably, from
1.67 × 109NAvg to 7 × 105NAvg M-5 L-1 s-1. While the reduced
rate of nucleation in the absence of degradation of dicarboxy
acetone results in particle size in good agreement with the
experimental data at a value of ratio [C]o/[T]o near 0.5, the
particle size predicted at higher values of [C]o/[T]o increases to
Figure 5. Predictions of effect of coagulation: comparison with data of
Chow and Zukoski.17
∼55 nm, as compared to the observed value of 15 nm. Thus,
the fit is very unsatisfactory, lending support to the key role
played by the degradation of dicarboxy acetone.
4.4. Effect of Reduction by Acetone. Apart from other
factors, mean particle size depends on the extent of conversion
of auric chloride. Auric chloride can be completely consumed
when citrate is in stoichiometric ratio or in excess, and under
such conditions, the role of acetone is unimportant. When citrate
is the limiting reactant, auric chloride can be fully consumed
only by reaction with acetone, and the role of acetone is very
crucial. Thus, the stoichiometry and the rate expression for the
reaction between acetone and auric chloride plays a role only
when [C]o/[T]o is small. However, at such small ratios, as
discussed earlier, reduction by acetone is slow; hence, the
process takes longer to complete, in agreement with experi-
mental findings, but it has little effect on the dynamics of
nucleation. Thus, the particular stoichiometry and rate expres-
sions assigned to the reaction with acetone are not crucial to
the model.
4.5. Effect of Aggregation. Chow and Zukoski17 measured
mean particle size by keeping the concentration of citrate at
1.6 × 10-3 M and varying the gold salt concentration from 1.2
× 10-5 to 1.25 × 10-3 M. The emphasis of their experimenta-
tion has been to elucidate the role of coagulation. A comparison
of their observations with the predictions of the model is shown
in Figure 5. The parameters used are the same as used before.
The dicarboxy acetone formed is limited by auric chloride at
low initial concentrations of auric chloride. Therefore, it can
be inferred that the maximum reached in the concentration of
dicarboxy acetone is proportional to the initial concentration
of auric chloride. Thus, the extent of nucleation increases rapidly
with an increase in [T]o. Although the total mass of gold particles
is proportional to [T]o, the effect of increased nucleation rate
dominates and the particle size decreases rapidly as the
concentration of gold salt is increased from low values. The
observed minimum is due to coagulation. The double layer is
compressed because of high counterion concentration brought
in by gold salt. Thus, as gold concentration is increased,
coagulation is promoted and the particle size increases. The
model is able to predict the location of the minimum in the
particle size, and the sharp increase in particle size as the gold
concentration is lowered well. But it does not do so well in
predicting the particle sizes at low gold concentrations. Con-
sidering that the parameters were fitted to an entirely different
data set, the model’s predictions can be considered satisfactory.
The effect of coagulation on the particle size for the results
discussed in the previous section is shown in Figure 6. The

Figure 6. Predictions of particle size with and without aggregation and
degradation of dicarboxy acetone.
Figure 7. Predictions of particle size distribution.
figure shows model predictions in the absence of coagulation.
For comparison, the earlier predictions that included coagulation
are also shown. These results were obtained for [T]o )
3 × 10-4 M and [C]o in the range of 1.2 × 10-4 M to
1.2 × 10-2 M. At low citrate concentrations, it makes very little
contribution to the counterions and the double-layer compression
is small. As a result, colloids are stable, and one observes very
little effect of coagulation. At high citrate concentrations,
counterion concentration is high, and coagulation takes place,
leading to an increase in particle size. The model that neglects
it predicts smaller particle sizes, as can be seen from Figure 6.
As discussed earlier, if degradation of dicarboxy acetone is also
not permitted, the predicted particle sizes are quite small and
qualitatively different.
4.6. Particle-Size Distribution. The particle-size distributions
predicted by the model are shown in Figure 7. If coagulation is
not permitted, the nuclei formed at the earliest time will grow
to the largest size, and no particle can be larger than that. The
particle-size distribution at large sizes ends in a sharp edge.
This is what is observed in Figure 7. Coagulation leads to
formation of larger particles, and hence, the size distribution
becomes broader. This is also reflected in the figure.
4.7. Effect of Nucleus Size. Given the uncertainities in the
literature on the size of the nucleus, whether it should correspond
to a closed shell structure or intermediate sturctures stabilized
by stabilizer molecules through physical or chemical association,
several of the simulations reported above were repeated with a
nucleus size ranging from 2 nm (corresponding to critical
nucleation number of 55) to 0.25 nm (corresponding to a critical
nucleation number of <1). The model predictions remained
unchanged. Thus, for the citrate method, which produces
Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007 3135
particles in the size range of 20 nm, the size of the nucleus
plays no role. It is expected to play an important role in gold
nanoparticle synthesis using the Brust-Schiffrin method,12,14
which follows completely different chemistry because of the
capping of the growing particle and produces particles in the
size range of 1-5 nm. A detailed model for this method has
been developed by us and is being communicated separately.
5. Conclusions
A model for the citrate process of synthesis of nanoparticles
of gold has been developed. It proposes that Au3+ is reduced
to Au+ by the oxidation of trisodium citrate to dicarboxy
acetone. Dicarboxy acetone decomposes at the temperatures used
in the experiments. Gold atoms are formed when Au+ undergoes
disproportionation, which is also catalyzed by the gold surface,
and it is this reaction that leads to formation of nuclei as well
as growth. Nucleation requires formation of a multimolecular
complex between dicarboxy acetone and AuCl, and hence, the
rate of nucleation is affected strongly because of the degradation
of dicarboxy acetone. It is shown that the particle size is
determined by the balance between the degradation reaction and
nucleation, and it is different from the usual particle-formation
processes governed by the balance between nucleation and
growth. The model also includes coagulation and its efficiency
as controlled by ionic repulsive forces. The model is able to
predict observations made by many investigators. In particular,
it is able to predict the observed large sensitivity of particle
size to increases in the citrate concentrations when it is in
stoichiometric deficiency, as well as the insensitivity of particle
size to increases in the citrate concentrations when it is in
stoichiometric excess.
Acknowledgment
The authors thank Prof. Uday Maitra of Organic Chemistry,
IISc, for spending a lot of time with us in clarifying the
chemistry. The authors thank their colleague Dr. S. Venugopal
for many illuminating discussions on the synthesis and fine
structure of gold nanoparticles.
Nomenclature
C ) trisodium citrate; concentration if square brackets are
around it, and subscript zero refers to the initial concentration
Ce ) concentration of counterions
D ) product of degradation of stabilizershere it is presumed
to be acetone; concentration if square brackets are around it
k ) Boltzmann constant
kc ) rate constant for the reaction between trichloride and citrate
kd ) rate constant for degradation of stabilizer
kh ) rate of heterogeneous disproportionation reaction
kn ) nucleation rate constant
ks ) rate constant for degradation of stabilizer
k1, k2 ) constants in equation for W
M ) aurous chloride; concentration if square brackets are around
it
N ) number of nuclei; concentration if square brackets are
around it
NAvg ) Avogadro number
Nmax ) maximum number of particles (size Vo) that can be
formed
P(V) ) number density of particles of size V
3136 Ind. Eng. Chem. Res., Vol. 46, No. 10, 2007
q ) Brownian collision frequency
S ) dicarboxy acetone; concentration if square brackets are
around it
T ) auric chloride; concentration if square brackets are around
it, and subscript zero refers to the initial concentration
u ) temperature, K
t ) batch time
Vo ) volume of a nucleus
V ) volume of a particle
W ) coalescence efficiency
Greek Letters
F ) density of gold, moles per volume
µ ) viscosity
φ ) surface potential
Literature Cited
(1) Turkevich, J.; Stevenson, P.; Hillier, J. A Study of the Nucleation
and Growth Process in the Synthesis of Colloidal Gold. Discuss. Faraday
Soc. 1951, 11, 55.
(2) Cushing, B. L.; Kolesnichenko, V. L.; Connor, C. J. O. Recent
Advances in the Liquid-Phase Syntheses of Inorganic Nanoparticles. Chem.
ReV. 2004, 104, 3893.
(3) Schmid, G. Nanoparticles: From Theory to Applications; Wiley-
VCH Verlag GmbH & Co.: New York, 2004.
(4) Li, Y.; Park, C. W. Particle Size Distribution in the Synthesis of
Nanoparticles Using Microemulsions. Langmuir 1999, 15, 952.
(5) Bandyopadhyaya, R.; Kumar, R.; Gandhi, K. Simulation of Precipi-
tation Reactions in Reverse Micelles. Langmuir 2000, 16, 7139.
(6) Singh, R.; Durairaj, M.; Kumar, S. An Imporved Monte Carlo
Scheme for Synthesis of Nanoparticles in Reverse Micells. Langmuir 2003,
19, 6317.
(7) Bandyopadhyaya, R.; Kumar, R.; Gandhi, K. S.; Ramkrishna, D.
Modelling of Precipitation in Reverse Micellar Systems. Langmuir 1997,
13, 3610.
(8) Bandyopadhyaya, R.; Kumar, R.; Gandhi, K. Modeling of CaCO3
Nanoparticle Formation During Overbasing of Lubricating Oil Additives.
Langmuir 2001, 17, 1015.
(9) Kumar, A.; Hota, G.; Mehra, A.; Khilar, K. C. Modeling of
Nanoparticle Formation by Mixing of Two Reactive Microemulsions. AIChE
J. 2004, 50, 1556.
(10) Singh, R.; Kumar, S. Effect of Mixing on Nanoparticle Formation
in Micellar Route. Chem. Eng. Sci. 2006, 61, 192.
(11) Muhlpfordt, H. The Preparation of Colloidal Gold Particles Using
Tannic Acid as an Additional Reducing Agent. Expirentia 1982, 38, 1127.
(12) Brust, M.; Walker, M.; Bethell, D.; Schiffrin, D. J.; Whyman, R.
Synthesis of Thiol-Derivatised Gold Nanoparticles in a Two-Phase Liquid-
Liquid System. Chem. Commun. 1994, 801.
(13) Frens, G. Controlled Nucleation for the Regulation of the Particle
Size in Monodisperse Gold Suspensions. Nature 1973, 241, 20.
(14) Murray, R. W.; Hostler, H. J.; Wingate, J. E.; Zhong, C. J.; Harris,
J. E.; Vachet, R. W.; Clark, M. R.; Londono, J. D.; Green, S. J.; Stokes, J.
J.; Wignall, G. D.; Glish, G. L.; Porter, M. D.; Evans, N. D. Alkanethiolate
Gold Cluster Molecules with Core Diameters from 1.5 to 5.2 nm: Core
and Monolayer Properties as a Function of Core Size. Langmuir 1998, 14,
17.
(15) Slot, J.; Gueze, H. A New Method of Preparing Gold Probes for
Multiple-Labeling Microscopy. Eur. J. Cell Biol. 1985, 38, 87.
(16) Freund, P.; Spiro, M. Colloidal Catalysis: The Effect of Sol Size
and concentration. J. Phys. Chem. 1985, 89, 1074.
(17) Chow, M.; Zukoski, C. Gold Sol Formation Mechanisms: Role of
Colloidal Stability. J. Colloid Interface Sci. 1994, 165, 97.
(18) Abid, J.-P. Laser Induced Synthesis and Nonlinear Optical Proper-
ties of Metal Nanoparticles. Ph.D. Thesis, Ecole Polytechnique Federale
de Lausanne, Lausanne, Switzerland, 2003.
(19) Gammons, C.; Yu, Y.; Williams-Jones, A. The Disproportionation
of Gold(I) Chloride Complexes at 25 to 200 C. Geochim. Cosmochim. Acta
1997, 61, 1971.
(20) Davies, A. The Kinetics of the Coagulation of Gold Sols. J. Phys.
Chem. 1929, 33, 274.
(21) Negishi, Y.; Nobusada, K.; Tsukuda, T. Glutathione-Protected Gold
Clusters Revisted: Bridging the Gap Between Gold(I)-Thiolate Complexes
and Thiolate-Protected Gold Nanocrystals. J. Am. Chem. Soc. 2005, 127,
5261.
(22) Turkevich, J. Colloidal Gold, Part I. Gold Bull. 1985, 18, 86.
(23) Li, G.; Lauer, M.; Shulz, A.; Boettcher, C.; Li, F.; Fuhrhop, J.-H.
Spherical and Planar Gold(0) Nanoparticles with a Rigid Gold(I)-Anion or
a Fluid Gold(0)-Acetone Surface. Langmuir 2003, 19, 6483.
(24) Enustun, B. V.; Turkevich, J. Coagulation of Colloidal Gold. J.
Am. Chem. Soc. 1963, 85, 3317.
(25) Castro, T.; Reifenberger, R.; Choi, E.; Andres, R. P. Size Dependent
Melting of Temperature of Individual Nanometer-Sized Metallic Clusters.
Phys. ReV. B 1990, 42, 8548.
(26) Ding, F.; Bolton, K.; Rosen, A. Molecular Dynamics Study of the
Surface Melting of Iron Clusters. Eur. Phys. J. D 2005, 34, 275.
(27) Ramkrishna, D. Population Balances; Academic Press: New York,
2000; Chapter 3, p 99.
(28) Hunter, R. Foundations of colloid science, Vol. 1; Clarendon
Press: Oxford, U.K., 1995; Chapter 7, pp 441-447.
(29) Reerink, H.; Overbeek, J. T. G. The Rate of Coagulation as a
Measure of Stability of Silver Iodide Salts. Discuss. Faraday Soc. 1954,
18, 74.
(30) Kumar, S.; Ramkrishna, D. On the solution of population balance
equations by discretizationsI. A fixed pivot technique. Chem. Eng. Sci.
1996, 51, 1311.
(31) Kumar, S.; Ramkrishna, D. On the Solution of Population Balance
Equations by DiscretizationsIII. Simultaneous Nucleation, Growth and
Aggregation. Chem. Eng. Sci. 1997, 52, 4659.
ReceiVed for reView May 27, 2006
ReVised manuscript receiVed September 8, 2006
Accepted September 8, 2006
IE060672J