Hydrometallurgy 79 (2005) 62 – 68

www.elsevier.com/locate/hydromet

Shrinking core models in hydrometallurgy: What students are not

being told about the pseudo-steady approximation
KNona C. Liddell
Chemical Engineering Department, Washington State University, Pullman, WA 99164-2710, USA
Received 19 August 2002; received in revised form 22 April 2003; accepted 7 July 2003
Available online 16 August 2005

Abstract

There is a significant amount of early work that has been largely forgotten that deals with the validity of the pseudo-steady
approximation for liquid–solid reactions. Much of this was originally published in the chemical engineering literature but is
highly relevant to hydrometallurgical processes. The purpose of this paper is to summarize some criteria that have been
developed by various authors for determining the error associated with use of shrinking core models for liquid–solid systems
and to provide an illustrative example using data for a mineral leaching reaction.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Shrinking core models; Pseudo-steady state approximation

1. Introduction easily assimilated by beginning students and has

Studies of the fundamental aspects of shrinking
core models have undergone a renaissance in the last
10–15 years, with Crundwell and Godorr (1997),
Lapidus (1992), and Pritzker (1996) among those
making important recent contributions. Their work
adapts and extends earlier model equations to situa-
tions more complex than those that were first consid-
ered. Although these authors emphasized mineral
leaching reactions, the simple models in Levenspiel’s
(1972) classic text remain much more widely used by
hydrometallurgists. Levenspiel’s approach is also
E-mail address: liddell@che.wsu.edu.
0304-386X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2003.07.011
been emulated in newer texts (e.g., Fogler, 1992).
Two curious facts about the early development of
shrinking core models have generally been over-
looked. First, Levenspiel specifically restricts his dis-
cussion to gas–solid systems. He briefly comments on
some limitations on the validity of the familiar shrink-
ing core equations (Levenspiel, 1972, p. 373) but does
not mention liquid–solid cases at all. The assumptions
Levenspiel points out are that there must be a sharp
interface between the product layer and fresh reactant
and that the system must be isothermal. The latter
condition would virtually always be met for a leaching
process, but it is less clear that the former would be.
Microscopic examination of sections of partially
reacted particles is necessary to determine whether
 K.C. Liddell / Hydrometallurgy 79 (2005) 62–68
there is a definite product–reactant interface or a
diffuse reaction zone. Second, from the early 1960s
through the early 1980s, a number of research papers
and review articles examined the validity of shrinking
core models for liquid–solid systems, using both ana-
lytical and numerical methods. The pseudo-steady
state (PSS) approximation was the focus of this
work. Results from several research groups appeared
in leading chemical engineering journals but are
almost unknown today in the hydrometallurgical com-
munity. One consequence is that the shrinking core
models have been presented to several generations of
extractive metallurgy students with relatively little
attention to the range of applicability of the key PSS
assumption. From an instructional viewpoint, this is
clearly a lost opportunity to develop students’ ability
to make engineering approximations.
The purpose of this paper is to summarize the
relevant early papers on the PSS approximation and
its use in liquid–solid shrinking core models. It is
hoped that information from these publications will
become an integral part of the course materials taught
to future hydrometallurgists and metallurgical engi-
neers. The scope here is limited to shrinking core
models of monosized particles in a large volume of
solution, i.e., effects of particle size distribution, mix-
ing, and reactor type are not covered. The relevant
literature citations are from 1963 to 1983.
2. The pseudo-steady state assumption
We first review the pseudo-steady assumption for
systems controlled by product layer diffusion, then
consider the literature about it. For a spherical particle
surrounded by a large volume of fluid with which it
reacts, the differential mass balance on the particle is
as follows:


BCA DA B 2 BCA
e ¼ 2 r Rc brbRp ð1Þ
Bt r Br Br
R c and R p are the unreacted core and particle radius,
respectively; e is the porosity of the product layer; and
C A and D A are the concentration and effective diffu-
sivity of the fluid phase reacting species A. The
porosity and effective diffusivity are assumed con-
stant. This is a well-known diffusion problem and
63
has an analytical solution that involves the error func-
tion. In making the PSS assumption, the time deriva-
tive is neglected, so that the partial differential
equation is converted into an ordinary one.
In Levenspiel’s development of the equation relat-
ing particle conversion (fraction reacted) and reaction
time, the movement of the interface between the
unreacted and product solids is initially assumed to
be very slow relative to the rate species A diffuses
through the porous shell. This allows the concentra-
tion profile across the shell to be determined from a
steady-state diffusion equation. This is the physical
meaning of the pseudo-steady state assumption. Then
the motion of the interface is dealt with separately by
equating the mass flux to the rate of disappearance of
the reacting solid. Elementary calculus is all that is
required to obtain the familiar result:

2
3
t Rc Rc
¼13 þ2 ð2Þ
s Rp Rp
Here the time required for the particle to react com-
pletely is s; R c is time-dependent.
In 1968, Wen (1968) presented a tutorial review of
shrinking core and shrinking particle models for non-
catalytic reactions. Based on a series expansion of the
analytical solution for unsteady diffusion through a
porous solid slab and comparison with predictions
from the corresponding shrinking core equation,
Wen concluded that the shrinking core model for
liquid–solid reactions was likely to give erroneous
results unless the fluid reactant’s concentration is
very low. For accurate results, the ratio
eCA; 0
aCs; 0
would need to be small (b 0.1), but a detailed ana-
lysis of the error for particular circumstances was not
given. In this expression, a is the stoichiometric
coefficient for the liquid phase reactant, C A,0 is the
bulk concentration of the solution phase reactant, and
C s,0 is the initial concentration of the solid reactant.
This method of analysis can be applied to other
geometries but the details become somewhat more
complicated.
Also in 1968, Luss (1968) found upper and lower
bounds on the exact solution for Eq. (1) and compared
64 K.C. Liddell / Hydrometallurgy 79 (2005) 62–68
those with the PSS, shrinking core result. Although
the final conclusions are based on physical property
values typical of gas–solid reactions, the limits given
in Luss’ Eq. (19) are more general. The criterion in
that equation is
"
#
1  s ð1  sÞ2 1 Ca ðsÞ
0bdb þ 1 Max : x
Nu 2 Nu qs
ð3Þ
The error d is 0 when the shrinking core model is
accurate and in other cases is a function of the
dimensionless radius of the unreacted core s ¼ RRc ðpsÞ ,
the Nusselt number for mass transfer (also known as
k R
the Sherwood number, Sh) Nu ¼ gD p , the ambient
concentration C a (which need not be constant), and
the reactant solid density q s. Other quantities are the
core and particle radii R c and R p, the mass transfer
coefficient k g, the (effective) diffusivity D, and the
dimensionless time s ¼ RDt2 . A noteworthy feature of
p
this treatment is that the boundary conditions chosen
do not require any assumption about the kinetics of
the reaction. This criterion is in a form readily applic-
able to liquid–solid reactions but is not widely
known. It is also worth noting that Luss’ criterion
can be simplified slightly if the ambient concentration
is kept constant. Also, the ratio s approaches zero as
the reaction nears completion, leading to the further
simplification


1 1 Ca
0bdb þ1 : ð4Þ
2 Nu qs
Consistent with the common observation that shrink-
ing core models tend to fail as the conversion exceeds
0.3 or 0.4, the error d increases as leaching progresses
at constant C a.
An approximate solution to unsteady transport pro-
blems in confined spatial domains was developed by
Theofanous and Lim (1971). Their treatment is quite
general in that it applies to a rather wide class of heat
transfer and mass transfer problems, including shrink-
ing core models. The method involves a transforma-
tion of variables and leads to integrodifferential
equations from which successive approximations are
obtained. With the fluid reactant’s concentration C
and the new dependent variable defined by
/ ¼ Cr ð5Þ
and the dimensionless radial position (r) and dimen-
sionless core radius (R c) expressed as
r ¼1x Rc ¼ 1  d ð6Þ
the first-order approximation (PSS approximation) to
/ was shown to be
/1 ¼ 1  : ð7Þ
d
The second-order approximation is
C0 n3
 An þ
6aCs
/2 ¼ 1 þ : ð8Þ
B
Here C 0 and C s are fluid concentration at the surface
of the particle and the solid concentration, respec-
tively; a is the stoichiometric coefficient; and
x C0 C0
n¼ A¼1dþ B¼1dþ :
d 2aCs 3aCs
ð9Þ
The third-order approximation is also given in full.
Comparison with previous work, including that of
Bischoff (1965) (see below) indicated that the var-
ious methods were in good agreement, that there
would rarely be a need to use the third-order approx-
imation for a gas–solid system, and that numerical
results might be subject to significant round off
error. However, liquid–solid cases were not explicitly
considered.
Some 10 years later, Lindman and Simonsson
(1979) noted that Luss’ criterion indicates a large
upper bound on the error if the reaction involves a
liquid reactant at high concentration. They used
numerical methods to solve a generalized form of
Eq. (1) in which a term was added to account for
convection associated with the creation of additional
porosity during a first-order liquid–solid reaction.
Results of the computations were used to prepare a
series of graphs of the expected error in various
situations. The general conclusion from this work
was that the shrinking core model gives acceptable
accuracy even when there is a concentrated solution
phase reactant and high conversions are reached; the
error is smaller at lower concentrations. The convec-
tive term was reported to have a significant effect at
high concentrations.
 K.C. Liddell / Hydrometallurgy 79 (2005) 62–68 65

Bischoff revisited the question of the validity of the Unfortunately neither the original nor the transformed
PSS assumption several times over a period of some 20 problem lends itself to an analytical solution except in
years (Bischoff, 1963, 1965; Del Borghi et al., 1976; special cases. Numerical integration would usually be
Stakgold et al., 1983). The second paper in the series needed even if the PSS approximation was invoked,
(Bischoff, 1965) is a response to criticisms of the first and the governing differential balances must first be
(Bischoff, 1963) and refines the general approach, set up in a form consistent with those of Stakgold et al.
introducing an expansion in the perturbation parameter (1983).
d ¼ CqA . For small values of the parameter, the reaction In another paper from 1983, Taylor et al. (1983)
s
interface would be expected to move slowly and the explicitly considered liquid–solid reactions. This
PSS shrinking core solution is generated. The first- work is subject to a number of assumptions: the
order correction for the position of the moving bound- reaction itself is first order and irreversible; the
ary (radius of the unreacted core) is given by solution phase reactant concentration is constant;

 and the effective diffusivity in the product layer is
d 1  Rc;0
Rc ¼ Rc;0 1 þ þN ð10Þ constant. The governing equations were put in
3 Rc;0 dimensionless form, allowing dimensionless groups
where R c,0 is the 0th order shrinking core approxima- to be identified, and then solved numerically under
tion. The error associated with the PSS approximation conditions of porous medium diffusion control. The
is small for d bb 1. dimensionless group
The most mathematically rigorous examination of
the validity of the PSS approximation was given by aCB;0
c1 ¼ ð14Þ
Stakgold et al. (1983). Their derivation considers a bqs
generalized form of Eq. (1), which includes a term for
the rate of reaction of the fluid-phase reactant; trans- was shown to determine the validity of the PSS
formation of the coupled differential mass balances approximation. Here C B,0 is the bulk concentration
for the fluid and solid leads to a single reaction- of the fluid reactant, q s is the molar density of the
diffusion equation. It was shown that application of reacting solid, and a and b are the stoichiometric
the PSS assumption leads to an error Z, which is coefficients for the solid and fluid reactants, respec-
bounded by
e  2 
0bZb Rp þ 2aRp : ð11Þ Table 1
2n Data requirements for selected criteria for the validity of the pseudo-
steady state approximation
Here e is the porosity of the product layer, n is the
Reference Data Needed
dimension (typically 3), R p is the radius of the parti-
cle, and a is a non-negative constant in the boundary Luss (1968) Density of B
Bulk concentration of A
condition of the untransformed problem that indicates
Radius of unreacted core
whether there is a film diffusion contribution. With a Particle radiusa
flux (Neumann) boundary condition, it can be shown Mass transfer coefficienta
that Effective diffusivitya
Bischoff (1965) Density of B
Deff Bulk concentration of A
a¼ ð12Þ
km Rp Stakgold et al. (1983) Porosity
Particle radius
in the expression for the upper bound on Z. Sometimes Diffusivityb
a Dirichlet condition may be encountered instead, i.e., Mass transfer coefficientb
Taylor et al. (1983) Stoichiometric coefficient
the surface concentration is a known constant. In this
Density of B
case Bulk concentration of A
a
Sherwood number is Sh = (k mr p/D eff).
a ¼ 0: ð13Þ b
Needed with flux boundary condition at particle surface.
66 K.C. Liddell / Hydrometallurgy 79 (2005) 62–68

tively. Several graphs were constructed to permit Ti Leached from FeTiO3

quick evaluation of the approximation’s validity, 0.6
and it was concluded that pseudo-steady state Expt'l Data
could be safely assumed if 0.5

Conversion (X)
0.4
c1 V0:1: ð15Þ
0.3

This criterion is easily applied and fairly general, but

0.2
despite these advantages it appears to be rarely used
by hydrometallurgists. 0.1
Table 1 summarizes the data requirements of sev-
eral of the above criteria. Following Levenspiel 0.0
0 10 20 30 40
(1972), the reaction is represented Time (h)

Fig. 1. Fraction Ti leached from +35 to 45 Am FeTiO3 (trace impu-

AðfluidÞ þ bBðsolidÞYproducts: ð16Þ rities) in 3 M HCl, at 87 8C in a batch reactor stirred at 700 rpm.

Spherical particles are assumed.

The criteria of Bischoff (1965) and Taylor et al.
(1983) are very simple and easily applied. That of
Stakgold et al. (1983) will not be useful unless the
porosity of the particles has been determined or can
be estimated; the surface concentration of the fluid
reactant may also be needed, depending on the
boundary condition assumed. Similarly, Luss’s
(1968) error criterion requires knowledge of the
effective diffusivity (or Nu), a quantity that may be
unknown for a particle in a concentrated electrolyte
solution.
3. Examples
btighterQ of the two, with d b 1, while the other is
c 1 b 0.1. One might therefore expect that a shrinking
core model for spherical particles would fit the data,
but the R 2 value might be rather low.
Four shrinking core models were fit to this set of
data:
Model I, spherical particles under reaction control:
t~1  ð1  X Þ1=3 : ð18Þ
Model II, spherical particles under product layer
diffusion control:
t~1  3ð1  X Þ2=3 þ 2ð1  X Þ: ð19Þ

For illustrative purposes, we now consider the Model III, cylindrical particles under reaction
leaching of ilmenite (FeTiO3) by HCl (Orth, 1985): control:

t~1  ð1  X Þ1=2 : ð20Þ

2+ 2+ 
FeTiO3+4HClYFe +TiO +2H2O+4Cl (17)
Ti solution concentration data from a typical
experiment (3 M HCl, 87 8C, 700 rpm, +35 to 45
Am FeTiO3 with trace Fe3O4 and Fe2O3) in a stirred
batch reactor are shown in Fig. 1, presented as con-
version (X) versus time. Taking an ilmenite specific
gravity of 4.7, Bischoff’s criterion is d = 0.0965, sug-
gesting that the conditions for the PSS approximation
are not satisfied; Taylor’s criterion is c 1 = 0.024, con-
sistent with validity. The Bischoff criterion is the
Model IV, cylindrical particles under product
layer diffusion control:
t~X þ ð1  X Þlnð1  X Þ: ð21Þ
Here X is conversion and t is time. The results are
shown in Figs. 2–5. All four models fit the data very
well, and standard statistical methods would not
cause any of them to be ruled out. Indeed, not a
single data point lies outside the 95% prediction
interval on any of the graphs, even for models that
assume cylindrical particles. (Models III and IV
 K.C. Liddell / Hydrometallurgy 79 (2005) 62–68 67

Shrinking Core or Particle, Sphere, Reaction Control Shrinking Core, Cylinder, Reaction Control
0.30 0.5
Expt'l Data
0.25 R 2 = 0.9921 Expt'l Data
95% Prediction Interval 0.4 R2 = 0.9905
95% Prediction Interval
0.20
1 - (1-X)1/3

1 - (1-X)1/2
0.3
0.15

0.10 0.2

0.05
0.1

0.00
0 10 20
Time (h)
Fig. 2. Ti leach data fitted to Model I, shrinking core in spherical
particles under reaction control.
neglect the ends of the cylinder, so that it is effec-
tively infinitely long; diffusion and reaction occur in
the radial direction only.) For the ilmenite–HCl reac-
tion, these commonly used shrinking core equations
are insensitive to both leaching mechanism and par-
ticle shape! The ability of so many different models
to give excellent fits to these data results from the
fact that values of X cover a limited range (0 V X V 1)
to begin with, and appear in functions (variously
ln(1  X), (1  X)1/2, (1  X)1/3, and (1  X)2/3) that
flatten the range of values even further.
It is also important to note that besides explicitly
neglecting the time derivative, shrinking core models
implicitly assume that a single lumped parameter, the
effective diffusivity, adequately describes the mass
30 40 0.0
0 10 20 30 40
Time (h)
Fig. 4. Ti leach data fitted to Model III, shrinking core in cylindrical
particles under reaction control.
transport within a reacting particle. As a result, in some
instances topochemical models fail to fit experimental
data even when criteria for PSS validity are satisfied.
One such case is chrysocolla leached by NH4Cl/NH3
(Raghavan and Gajam, 1986); the fibrous structure and
high microporosity of the mineral were believed to be
responsible, and a structurally based, three-parameter
model was more successful in representing the leaching
behavior.
Examples of these kinds have a variety of uses in an
instructional setting. Perhaps most importantly, stu-
dents can see for themselves that there is no uniquely
right answer in fitting leaching data, and no uniquely
correct mechanism. Additional complications that
might be covered with an appropriate reaction include

Shrinking Core, Sphere, "Ash" Diffusion Control Shrinking Core, Cylinder, "Ash" Diffusion Control
0.16 0.25
0.14 Expt'l Data Expt'l Data
R2 = 0.9626 0.20 R 2 = 0.9656
1 - 3(1-X)2/3 + 2(1-X)

0.12 95% Prediction Interval

X + (1-X) ln(1-X)

95% Prediction Interval

0.10
0.15
0.08

0.06 0.10

0.04
0.05
0.02

0.00 0.00
0 10 20 30 40 0 10 20 30 40
Time (h) Time (h)

Fig. 3. Ti leach data fitted to Model II, shrinking core in spherical Fig. 5. Ti leach data fitted to Model IV, shrinking core in cylindrical
particles under product layer (bashQ layer) diffusion control. particles under product layer (bashQ layer) diffusion control.
68 K.C. Liddell / Hydrometallurgy 79 (2005) 62–68
extended leaching (X Y 1), and wide or bimodal parti-
cle size distributions. The use (and misuse) of statistical
methods can be illustrated with a varying amount of
detail, depending on the objectives and level of the
course. The derivation of the shrinking particle-
shrinking core family of models can be covered at
the undergraduate level using a treatment similar to
Levenspiel’s (1972), and then revisited more rigor-
ously in graduate transport and reactor design
courses. In both cases, the consequences of the
pseudo-steady state assumption can be explored
using experimental data on mineral leaching, some-
times with surprising results.
In summary, there is a fairly extensive body of
literature, largely unknown to hydrometallurgists, on
the validity of shrinking core models for liquid–solid
reactions. These papers provide some simple criteria
that could be taught to beginning students, and the
more mathematically sophisticated approaches should
be of interest to those teaching advanced courses.
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