Hydrometallurgy 96 (2009) 199–214

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Aqueous precipitation and crystallization for the production of particulate solids with
desired properties
G.P. Demopoulos
Department of Mining and Materials Engineering, McGill University, Montreal, Quebec, Canada H3A 2B2

a r t i c l e i n f o a b s t r a c t

Article history: It is the scope of this paper to review and apply the theory of crystallization kinetics to the analysis and
Received 9 October 2008 design of aqueous inorganic hydrometallurgical precipitation systems. In particular the critical role of
Accepted 9 October 2008 supersaturation in controlling the properties (crystallinity–stability, particle size and cleanliness) of the
Available online 28 October 2008
precipitated compounds is emphasized. The approach taken is of generic nature and not system-specific;
however, reference is made to particular precipitation systems such as production of very fine
Keywords:
Aqueous
monodispersed particles, hydrolysis/neutralization of acidic ferric sulphate liquors, iron precipitation from
Processing zinc process solutions, immobilization of arsenic in the form of crystalline scorodite, and gypsum
Precipitation crystallization in waste water treatment. Reference to these systems is not made with the purpose of
Crystallization describing the respective processes but rather to reinforce the validity of the supersaturation-controlled
Hydrometallurgy approach to industrial inorganic precipitation processes.
Supersaturation © 2008 Elsevier B.V. All rights reserved.
Powders
Non-ferrous metals
Inorganic materials

1. Introduction
Aqueous precipitation is one of the most important and often most
neglected unit operations in various processes involving aqueous
media for the purpose of inorganic materials production (e.g.
hydrometallurgy) or immobilization of toxic inorganic wastes (e.g.
industrial effluent and waste water treatment). Traditionally pre-
cipitation has been viewed (i) from a chemical equilibrium (solubility
product) standpoint and (ii) from an inorganic cation or anion removal
standpoint, i.e. the emphasis was on the solubility (=aqueous species
concentration) rather than on the characteristics and quality of the
precipitated compound. The latter, however, becomes now increas-
ingly more critical as process chemists and engineers are seeking to
prepare/synthesize materials with specific properties (“value adding
processing”) and to design effluent treatment processes that can
immobilize contaminants in compact and stable solids the disposal of
which can avoid or minimize adverse environmental effects (“clean
technology”). This shift of focus from the solubility to the quality of the
precipitated compound calls for the study and application of the
theory of crystallization to aqueous precipitation systems. This is
indeed the scope and content of this paper.
The material covered here is of generic nature and can be applied
to practically any aqueous precipitation system spanning from the
removal and rejection of iron from hydrometallurgical solutions
E-mail address: george.demopoulos@mcgill.ca.
(Dutrizac and Monhemius, 1986; Dutrizac and Harris, 1996; Dutrizac
and Riveros, 2006), to the production of alumina, and from the
production of ultra fine monodispersed powders of metals (Sugimoto,
1987) like Cu, Ag, Pd etc. used in the electronics industry and the
synthesis of precursor compounds for production of high temperature
superconductors (copper, barium and yttrium oxalates) (Dirksen and
Ring, 1991) to the treatment of effluents for the immobilization of
contaminants like As and P (Krause and Ettel, 1989; Ramalho, 1983). In
this paper reference to a number of specific precipitation systems is
made because on one hand this helps to reinforce crystallization
theory with specific examples and on the other because this reflects
current research interests of this author.
2. Crystallization theory of precipitation
According to crystallization theory, precipitation is defined as
reactive crystallization. This definition is preferred as it emphasizes
the formation of the solid product via a chemical reaction instead of
the classical definition which focuses on the metal ion removal aspects
of the process. In the analysis that follows the emphasis is given to the
factors which control the properties of the solid product, namely
composition, crystallinity, particle size, morphology, and cleanliness.
The correlation of the precipitation processing conditions to product
properties is determined via the study and control of the following
aspects of the process: (a) solid–liquid equilibria; (b) crystallization
kinetics, i.e. supersaturation, nucleation and growth; (c) colloid-
surface chemistry, i.e. the aggregation of particles and the adsorption

0304-386X/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2008.10.004
200 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214
Fig. 1. A new paradigm for aqueous precipitation research.
of impurities; and last but not least (d) reactor selection and design.
Full attention to all these issues is of critical importance in ensuring
excellent results. This integrated approach to aqueous precipitation
research is illustrated in Fig. 1.
2.1. Precipitation phase equilibria
When we consider the precipitation of a compound we have to
examine first the phase equilibria of the system, i.e. to define the
conditions, temperature, pressure and activities — concentrations
which favour the formation of one or the other phase from a
thermodynamic point of view. Precipitation or solubility diagrams
have to be consulted as part of this examination. As an example the
solubility diagram of goethite (α-FeOOH) at 25 °C is given in Fig. 2
(Baes and Mesmer, 1986). This diagram by no means, however, can be
interpreted as an indication of the feasibility of producing goethite (i.e.
the crystalline compound α-FeOOH) at 25 °C. This is so because
precipitation–dissolution reactions are not necessarily reversible,
especially when it comes to the degree of crystallinity of the
compound and also because in this type of thermodynamic repre-
sentation there are inevitably a number of assumptions and restric-
tions associated with it.
Let us consider the general case of precipitation of a compound
AB(s):
AðaqÞ + BðaqÞ + X−ðaqÞ + IðaqÞ + H2 OYABðsÞ + ð?ÞfABX and=or IB; ABOH etcg
ð1Þ
− as providing general trends.
where X is the matrix anion and I represents other ionic species.
Despite the fact that a simple thermodynamic analysis might
indicate that the formation of the solid product AB is feasible, side
reactions may be occurring simultaneously leading to production of
additional phases. A good example in this respect is the Fe(III)–SO4(II)–
H2O system where a range of iron (III) — containing phases can form
upon hydrolysis, depending on temperature and solution composition;
Fig. 2. The solubility diagram of α-FeOOH (25 °C). The numbered lines refer to the Fe–
OH aqueous complexes (reproduced from Baes and Mesmer (1986)).
such as hematite, α-goethite, basic ferric sulphate, jarosite, ferrihydrite
or totally amorphous hydrous ferric oxide (Posnjak and Merwin, 1922;
Voigt and Göbler, 1986; Jambor and Dutrizac,1998; Dzombak and Morel,
1990).
However, it is not only the possible formation of more than one
crystalline phase that complicates matters; there is also the possible
formation of metastable phases (i.e. phases enjoying a kinetic stability
despite their thermodynamic instability). In other words, in the
domain of thermodynamic stability of a compound, a less stable phase
may form due to favourable kinetics. Usually this metastable phase is a
precursor phase, which eventually, given the time, should convert to
the stable one. For example, hydroxycarbonate salts (i.e. M2(OH)2CO3)
tend to form ahead of their carbonate counterparts (i.e. MCO3) within
the domain of stability of the latter, or jarosite tends to form within the
domain of Fe2O3, (see shaded area in Fig. 3) (Zerella et al., 1983) during
pressure leaching of sulphide feedstocks.
At this point it is worthy to remind ourselves that in general all
equilibrium diagrams like the ones mentioned here have to be treated
with caution not only because they neglect the kinetics (after all they
are equilibrium diagrams) but because many of them are based on data
not collected with reliable experimental procedures or simply because
they were built on the basis of a number of simplifying assumptions.
One such case was the early solubility data and diagrams that were
published for FeAsO4·2H2O that were based on Fe as opposed to As
solution concentration measurements (Krause and Ettel, 1989). In a
review paper (Cheng and Demopoulos, 1997) dealing with the analysis
of the hematite precipitation system it has been shown that significant
discrepancies occur with a number of precipitation diagrams referring
to the system Fe(III)–SO4(II)–H2O. In connection with the latter it might
be added here that it is commonly accepted that hematite can be
produced only at temperatures above 130 °C (see also Fig. 3). However
the temperature at which hematite precipitation is favoured is highly
dependent on the concentration of the iron solutions, on the method of
precipitation, e.g. direct hydrolysis vs oxydrolysis or on the matrix of
the solution, i.e. sulphate vs. chloride vs. nitrate media. Refer for
example to Voigt and Göbler (1986), Cheng and Demopoulos (1997)
and Dutrizac and Riveros (1999). To explain these differences it is
important to resort to the analysis of the crystallization kinetics of iron
precipitation and in particular the effect of supersaturation on the type
and quality of the precipitated compound. Hence, published equili-
brium data and diagrams have to be interpreted with caution and only
Fig. 3. Goethite–jarosite–hematite equilibria as a function of temperature (adapted
from Zerella et al. (1983)).
 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214
2.2. Supersaturation
2.2.1. Saturation ratio
According to crystallization thermodynamics, a solid phase forms
out of a solution when
ΔG = −RTlnðα=α o Þb0
where ΔG: molar Gibbs free energy; R: the universal gas constnat; T:
the absolute temerature; α: activity of the solute in the initial
solution; and αo: activity of the solute in the final solution (i.e. in
equilibrium with the solid phase).
We define the ratio α/αo as the saturation ratio, S. If we take (a
rather gross simplification) activities equal to concentrations we have:
S = α=α o ≈C=Ceq
where Ceq: equilibrium concentration; when S N 1 we have ΔG b 0. This
is the condition of supersaturation. We define the supersaturation
ratio equal to


C−Ceq =Ceq = S−1
Therefore, supersaturation is the driving force for crystallization.
For the case of reactive crystallization, i.e. A(aq) + B(aq) → AB(s), the
saturation ratio is defined as;
S = ½A½B=Ksp
where Ksp = [A]eq[B]eq = exp(−ΔG°/RT).
It must be added here that the solubility of a compound (“Ksp”
value) is not only a function of its crystallinity (i.e. amorphous vs
crystalline precipitates) but as well a function of the crystallite size in
the case of nanocrystalline precipitates. This is described by the
Gibbs–Thomson equation (Sugimoto, 1987):
 
2γVm
Ceq = C∞ exp
rRT
where
Ceq solubility of crystalline particles
C∞ solubility of an infinite size crystal
γ specific surface energy (J m− 2)
Vm molar volume of the crystal (m3 mol− 1)
r radius of the particle (m)
Application of this equation to scorodite precipitates revealed that
the solubility increases at least 2 times when the crystallite size
decreases from 200 to 10 nm (Demopoulos et al, 1994).
2.2.2. Supersaturation state
The state of the supersaturated solution is not necessarily the same
as that in a dilute ionic solution. In dilute solutions we have ionic
species (free or complexed) solvated with H2O. As the concentration of
the solute increases extensive ion-association occurs (usually due to a
decrease in the activity of water) which leads to the formation of
electrically neutral ion-pairs (always solvated with water). When the
solution becomes supersaturated we have aggregation–polymeriza-
tion of the solute species, which leads to the formation of clusters of
ion-pairs/molecules (10–1000 monomers per cluster). This cluster is
the precursor of the particle (Flynn, 1984).
2.3. Kinetics of crystallization
2.3.1. Nucleation
The formation of a solid phase out of a solution involves the
phenomena of nucleation, growth and aggregation of particles. Depend-
201
ing on the site on which nucleation occurs we have different nucleation
mechanisms (Garside,1985), three of which are the most important ones:
(i) homogeneous, i.e. primary production of nuclei in the absence
of a surface
(ii) heterogeneous, i.e. primary production of nuclei on a foreign
surface and
ð2Þ
(iii) surface, i.e. secondary production of nuclei on the surface of a
solid of the same kind with the one which precipitates.
Other secondary nucleation mechanisms involve fragmentation of
crystals (apparent nucleation) and deposition on reactor walls
(contact nucleation) — the latter is discussed in Section 2.10.
2.3.1.1. Homogeneous nucleation. The molecules or ion-pairs of the
ð3Þ supersaturated solution combine together to form clusters or embryos
consisting of 10–1000 molecules/cluster. These embryos constantly
form and disappear until they assume a critical size (rc) above which
they are stable, i.e. they do not go back into solution. According to
crystallization thermodynamics (Dirksen and Ring,1991) the free energy
change associated with the formation of the embryo is given by:
ð4Þ
ΔGðr Þ = ΔGvol −ΔGsurf ð7Þ
where the first term is the free energy change associated with the
generation of volume and the second term is associated with the
generation of surface. The first term, i.e. ΔGvol is negative but the second
one is positive. So, it is only after a certain size rc that |ΔGvol| N|ΔGsurf| and
ð5Þ ΔG(r) becomes negative. A graphical representation of the ΔG(r)
function is given in Fig. 4 (Mullin, 1993). The ΔGmax represents an
activation energy barrier.
The critical nuclei size, rc is a function of the saturation ratio
(decreases as the latter increases) and may vary between 40 to 200 Å.
In practical terms then a high degree of supersaturation is expected to
yield a large population of ultra-fine particles.
Another critical feature of the dependency of the nucleation rate
on saturation ratio is the fact that nucleation starts only when a critical
ð6Þ S value (Scr,homo) is exceeded (Fig. 5). Beyond this Scr,homo value the
nucleation rate increases sharply, reaching quickly its maximum rate.
A commonly used log–log plot of the dependency of the nucleation
rate on saturation ratio is shown in Fig. 5 (Sohnel and Garside, 1992).
The form of the nucleation rate equation resembles that of the
Arrhenius equation (Dirksen and Ring, 1991):


J = 2D=d5 expð−ΔGmax =kB T Þ ð8Þ
where
J is expressed in number of nuclei per unit volume (m3) per
unit time(s),
D is the diffusivity of the solute species (m2 s− 1)
d is the molecular diameter of the solute species (m),
and
kB is the Boltzman constant; 1.38 × 10− 23 J·K− 1.
The maximum rate is a very large number of the order of ∼ 1030
nuclei cm− 3 s− 1.
It appears, therefore, that as soon as homogeneous nucleation
starts, it propagates quickly and in a rather short time we have the
formation of an ultra-fine colloidal precipitate.
Scr,homo is an intrinsic kinetic property of each precipitated
compound that may vary from as low as S = ∼ 1.1 to as high as more
than 10,000. It has been found that Scr,homo is a function of the size of
the precursor polymeric species; more specifically Scr,homo decreases
with increasing nc, where nc = number of monomers that make up the
critical nucleus. Conversely Scr,homo decreases as the specific surface
energy of the precipitating solid increases (refer to Fig. 5).
202 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214

2.3.2.3. Modes of growth. Depending on the relative magnitude of the

surface nucleation rate vs. the growth rate, two different modes of
growth arise (Randolph and Larsen, 1971). The first one is the layered or
mono-nuclear growth mode which occurs when the rate-limiting step is
surface nucleation; the second is the continuous or polynuclear growth
mode which occurs when growth is the rate-limiting step. In industrial
precipitation systems it is the latter that is most commonly observed.

2.3.2.4. Growth by aggregation. Growth units, i.e. nuclei of 0.01–0.1 µm

aggregate provided that colloid stability is suppressed.
The stability of a colloid suspension due to double layer interaction
can be described with the aid of the colloid stability factor (Dirksen
and Ring, 1991):

W = ða + bÞa + b I4 exp½V ðrÞ=kB T dr=r 2 ð10Þ

where

V(r) is the interaction potential energy of the two double layers

(J m− 2)
Fig. 4. Crystallization free energy change as a function of nuclei size (reproduced from kB is the Boltzmann constant (=1.38 × 10− 23 J K− 1)
Mullin (1993)). r is the distance between centers of two spheres (m)
a,b are the particle radii (m)

Thus for compounds preceded by spontaneous polymerization, as is

Aggregation is favoured as W decreases, i.e. as V(r) decreases. This is
the case with ferric (oxy)hydroxides (nc N 100), Scr,homo is less than 10 and
equivalent to double layer compression. This is achieved via an increase
this explains the difficulty of obtaining crystalline and “well behaving”
of the ionic strength (I) of the solution. Specific ion adsorption can have
precipitates. On the other hand BaSO4 forms small polymers (nc~10) and
an equally positive effect on colloid aggregation. Aggregation is also
this results in a very high Scr,homo value well above 1000. In other words
favoured as the population density of colloid increases. The phenom-
homogeneous crystallization of BaSO4 occurs without a problem even at
enon of colloid aggregation due to electrical forces is also known as
ambient conditions and this explains the success of the gravimetric
coagulation. High shear forces (agitation) tend to promote the formation
method of sulphate determination that involves accurate precipitation
of compact aggregates. Batch reactors are associated with extensive
and separation of BaSO4 crystals.
aggregation. Large particles are less prone to aggregation than fine
products. Aggregation is the major mode of growth in precipitation
2.3.1.2. Heterogeneous and surface nucleation. Nucleation on an
systems dominated by homogeneous nucleation. Another type of
existing surface is favoured as the surface energy is lower than that of
aggregation is that induced by polymers, otherwise called flocculation.
a new nucleus and ΔGmax is lower too. The result is the critical
Natural and synthetic macromolecules have been used successfully as
saturation ratio to decrease as well. Thus we have the following order:
aggregation agents — surfactants in water and waste treatment
1bScr; surface bScr; hetero bScr; homo (Gregory, 1978). Non-ionic surfactants work best at pHIEP, i.e. pH 8–9
for Fe(OH)3 (IEP is the pH at which the zeta potential is zero). The dosage
The order of critical saturation ratios is indicative of the order of of surfactant is critical. For flocculation only fractional coverage is
the activation energy which controls the nucleation rate. Finally, the required. With complete coverage colloid stabilization occurs instead.
rate equation for surface or heterogeneous nucleation is of the same
form with that of homogeneous nucleation.

2.3.2. Growth

2.3.2.1. Mechanism of growth. The incorporation of a solute species

to a growing crystal goes through a series of stages (Dirksen and Ring,
1991):
(a) Interfacial transport of solute, (b) adsorption on the particle
surface, (c) surface diffusion, (d) integration into the crystal at a kink
site (surface reaction), and (e) desolvation and water diffusion away
from the surface.

2.3.2.2. Growth rate. The growth of a spherical particle of radius r is

characterized by a first order and more rarely second order (in terms
of S) equation (Sugimoto, 1987; Randolph and Larsen, 1971):

G = dr=dt = kg Ceq ðS−1Þ ð9Þ

−1
where G is the crystal growth rate (m s ); kg is the growth constant
(m4 mol− 1 s− 1) and Ceq the solubility of the precipitating solute species
(mol m− 3).
In contrast, the nucleation rate (J) is an exponential or high power
function in terms of S (J ∝ S6–12) (Mullin, 1993; Sohnel and Garside, Fig. 5. Variation of homogeneous nucleation rate with S (log–log plot) for different values
1992). of precipitating solid surface energy ((reproduced from Sohnel and Garside (1992)).
 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214
Fig. 6. Definition of two distinct precipitation regimes with the aid of the rate vs.
saturation ratio curves (adapted from Demopoulos (1993)).
In an uncontrolled precipitation system (very common in batch
precipitation systems) what usually happens is that upon build-up of the
solute concentration, Scr,homo is exceeded and homogeneous nucleation
occurs. After some modest molecular growth the nuclei aggregate. With
the progress of the precipitation reaction the concentration drops below
Scr,homo and surface nucleation followed by molecular growth starts
which leads to cementing of the aggregates.
2.3.2.5. Particle morphology. The polynuclear and the aggregation
modes of growth are those that are most common (due to lack of
supersaturation control) in industrial precipitation systems. As a
result of this type of growth the produced particles are polycrystalline
with rough surfaces.
2.3.3. Precipitation regimes
A plot of the linear (growth) and exponential (homogeneous
nucleation) rate equations against saturation ratio helps to define two
distinct regimes of precipitation (Fig. 6). Thus when S b Scr, homo
precipitation occurs only on seed (i.e. crystallites of the same kind) or
foreign solids — this is the regime of growth-dominated precipitation.
On the other hand when S N Scr, homo homogeneous nucleation
dominates, thus leading to production of ultra-fine colloidal pre-
cipitates (regime of nucleation-dominated precipitation). In hydro-
metallurgy, where in general production of well grown precipitates is
preferred, it is deduced from the diagram of Fig. 6 that the
precipitation process will have to be designed in such a way that it
will operate at a supersaturation level just below Scr,homo, together
with recycling of the precipitate to provide for the necessary seed. The
use of this diagram is demonstrated later in relation to ferrihydrite
and scorodite precipitation.
2.4. Attainment of crystallinity
The factors favouring the direct production of crystalline (as
opposed to amorphous) compounds are high temperature and low
supersaturation. The role of these two factors can be elucidated by
referring to the mechanism of crystal growth.
2.4.1. High temperature
Elevation of temperature has the following beneficial effects:
(i) dehydration is favoured; (ii) neutralization of the charge of the
precursor complex is favoured; (iii) surface diffusion-mobility of the
adsorbed solute is enhanced; and (iv) the crystallization rate (i.e. the
reactive incorporation of solute into crystal) is accelerated.
Different phases can be produced at different temperature ranges
due to easier desolvation, e.g. formation of boehmite (γ-AlOOH) at
203
temperatures around 100 to 120 °C as opposed to gibbsite (γ-Al(OH)3)
that forms at temperatures below 100 °C; or production of hemi-
hydrate of calcium sulphate near the boiling point of water instead of
gypsum (CaSO4·2H2O) which forms at lower temperatures (Li and
Demopoulos, 2006).
2.4.2. Low supersaturation
Lowering of supersaturation has the following beneficial effects:
(i) the formation of large and immobile polymeric species is avoided;
(ii) homogeneous nucleation, which is responsible for the production
of amorphous particles (see Stranski's rule in the next section) and
extensive aggregation leading to solution entrainment is avoided;
(iii) the external mass transport process is decelerated and the solid/
liquid interface becomes less crowded, thus allowing the surface
integration reaction to proceed relatively uninhibited.
Thus maintenance of low S in combination with seed effectively results
in lowering of the crystallization temperature. While the effect of
temperature is well known, that of low supersaturation is not. The author
and co-workers have convincingly demonstrated the powerful effect
supersaturation control has on the attainment of crystallinity in the case of
scorodite (FeAsO4·2H2O) precipitation first from chloride media (Demo-
poulos et al., 1995a) and later from sulphate solutions (Droppert et al.,
1996; Filippou and Demopoulos, 1997; Dabekaussen et al., 2001). Thus
with supersaturation control scorodite was produced at 95 °C as opposed
to at least 150 °C required without supersaturation control (Dutrizac and
Jambor, 1988; Swash and Monhemius, 1994).
2.5. Phase transformation of precipitates
Many precipitates formed are often amorphous (due to either low
temperature or lack of supersaturation control or both), and upon
ageing are converted to crystalline compounds.
2.5.1. Stranski's rule
According to Stranski's or Ostwald Step Rule “the least stable phase
nucleates first as long as homogeneous nucleation determines the
rate” (Blesa and Matijevic, 1989). This is so because the interfacial
energy requirements are less stringent and as such nucleation is
easier. There is no other statement more true in precipitation reactions
than Stranski's rule. A good proof of the validity of this rule is Fe(III)
hydrolysis reactions which first yield an amorphous hydroxide which
upon ageing is converted to progressively more stable crystalline
phases (Blesa and Matijevic, 1989):
FeðIIIÞaq YFeOOHiH2 OðamÞYα−FeOOH or β−FeOOHYα−Fe2 O3 ð11Þ
The intermediate phases are simply metastable modifications.
2.5.2. The dissolution–recrystallization mechanism
As research in colloid chemistry has shown (Blesa and Matijevic,
1989) the phase transformation reactions in aqueous media proceed
Fig. 7. Dissolution–recrystallization processes (adapted from Blesa and Matijevic (1989)).
204 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214
mainly via the dissolution–recrystallization mechanism. According to
this mechanism (Fig. 7) the least stable phase (A) forms first (as a
consequence of Stranski's Rule) at a rate RA. When the concentration
of Fe(III) (aq) drops below the solubility of A(s), dissolution of the
latter starts at a rate R− A. Under the new low S environment created,
solid phase B forms (at a rate RB) which once more when the
conditions become favourable dissolves back slowly at a rate R− B. And
finally phase C forms out of the new very dilute and seeded aqueous
environment. It must be emphasized here that the time scale of these
phase transformation reactions might be very short, say minutes to
hours, (for example in-situ transformation of metastable phases at
elevated temperatures) or very long, say years (which is the case of
most of the natural ageing processes).
2.5.3. Hydrothermal conversion of ferrihydrite
Consider as an example the hydrothermal conversion of ferrihydrite
(FeOOH·xH2O(am)) to crystalline goethite (α-FeOOH) or hematite (α-
Fe2O3)(Norlund Christensen et al.,1980). The amorphous phase, through
dissolution–recrystallization in an aqueous environment converts to α-
FeOOH or α-Fe2O3 depending on the temperature and pH (Fig. 8). The
reaction sequence for goethite formation is shown below:
FeOOHdxH2 OðamÞ + 3H + dissolution NFe3+ + ð2 + xÞH2 O
Fe3+ + 2H2 ORecrystallization Nα−FeOOH + 3H +
The S-shaped kinetic curves of Fig. 8 are typical for nucleation-
growth type reactions (Sarraf-Mamoory et al., 1996).
Other examples are (i) the conversion of freshly prepared
amorphous ferric arsenate upon equilibration in the acidic region
(pH b4) to the crystalline equivalent (scorodite) (Nishimura and
Robins, 1996; Le Berre et al., 2008), (ii) the transformation of
akageneite (β-FeOOH) to hematite in chloride media (Dutrizac and
Riveros, 1999), and (iii) the hydrothermal conversion (at 220 °C) of
jarosite to hematite (Dutrizac, 1990).
2.6. Particle size control
For the production of very-fine monodispersed particles, two
conditions have to be met: (1) separation of homogeneous nucleation
and growth stages via supersaturation control and (2) control of
aggregation via colloid stabilization. According to the well known
LaMer diagram (Fig. 9) (Sugimoto, 1987) condition (1) is met by
causing an initial short-lived homogeneous nucleation event via the
sudden (but controlled) increase of supersaturation above Scr,homo (or
Fig. 8. Hydrothermal conversion of amorphous ferrihydrite — curve I corresponds to
production of a mixture of α-FeOOH and α-Fe2O3 at 120 °C and pH 10 while curve II
corresponds to production of α-Fe2O3 at 150 °C and pH 4.5. (data taken from Norlund
Christensen et al. (1980)).
Fig. 9. The LaMer diagram (adapted from Sugimoto (1987)).
Ccr,homo according to the diagram of Fig. 9) followed by regulation of S
(in the region: 1 b S b Scr,homo (or equivalently Ceq b C b Ccr,hono where
Ceq is the equilibrium concentration). Condition (2) is met by carrying
out precipitation away from the IEP and at low ionic strength or by
using surfactant-based steric stabilization.
On the other hand production of well grown crystals, which is the case
ð12Þ of relevance to industrial hydrometallurgy, is achieved via the use of seed
and the maintenance of low supersaturation, i.e. SbScr,homo (see Fig. 6). It is
the latter condition, i.e. the maintenance of low S that has been often
ð13Þ
neglected in aqueous precipitation process research and development.
2.7. Methods for the control of supersaturation
From the discussion so far it has become clear that supersaturation
control is of paramount importance if the quality of the precipitated
compound is to be enhanced. The question is however, how super-
saturation can be controlled in practice and moreover how Scr,homo can
be detected and avoided if the production of well grown and
crystalline precipitates is sought. Some of the methods available to
exercise supersaturation control are described below.
2.7.1. Via pH Control
For pH-dependent precipitation reactions, as are those of hydro-
lysis, supersaturation can be controlled via proper adjustment-
regulation of the pH of the solution. One of the methods that has
been practiced by colloid chemists is the use of a slow-releasing base,
like urea. In general slow neutralization is bound to provide
improvement in precipitation due to the inherent slow supersatura-
tion associated with it. In this respect, therefore, CaCO3 and CaO
(ignoring at this point any positive or negative interferences from the
formation of gypsum) would be expected to be better neutralizing
agents than NaOH. This has indeed been confirmed in the author's
laboratory in the cases, for example, of scorodite (Droppert et al., 1996)
and Ni(OH)2 precipitation (Sist and Demopoulos, 2003).
For full control of supersaturation, though, precise pH control is
needed and this can be accomplished with a step-wise neutralization
procedure as the one developed by the author (Demopoulos, 1993). This
step-wise neutralization procedure (Fig. 10) consists of the following
steps: First the solubility curve of the compound to be precipitated is
established in the form of C versus pH by equilibrating solids of the same
compound with solution at the temperature of interest.
Following that, supersaturation curves are drawn in parallel to the
solubility curve. These supersaturation curves are used to determine
alternate step-wise neutralization paths as shown in Fig. 10. Step-wise
neutralization involves neutralization of an acidic solution of initial
metal concentration Co and pH= pHo up to pH1. At this (or slightly lower)
pH, seed is added and heterogeneous precipitation is initiated during
which the pH is maintained constant (or at least within the
heterogeneous precipitation zone) with base addition. When pH stops
changing — an indication that precipitation is more or less complete at
 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214
Fig. 10. Supersaturation-controlled precipitation strategy.
this pH — further base is added and the pH is raised to the second
destination: pH2 and the procedure is repeated. By testing various
supersaturation levels the optimum one is defined for the production of
well grown (and crystalline if possible) precipitates. This semi-batch
step-wise precipitation procedure can be implemented on a continuous
industrial circuit operation by using a series of tanks (refer to Section 3.1),
the number of which and their respective operating (steady-state) pH
being the same as the steps and pH values defined in Fig. 10.
A critical feature during this stage of investigation is the
determination of the critical or otherwise called induction pH
(Droppert et al., 1996; Dabekaussen et al., 2001). This pH is defined
as the pH at which the onset of homogeneous nucleation is observed,
i.e. this is the pH corresponding to Scr,homo. These concepts and
methods are further explained in connection to the description of two
iron (III) precipitation systems discussed in Section 3, i.e. precipitation
of ferrihydrite and precipitation of scorodite.
The approach outlined here may be adapted and used in non-
hydrolytic precipitation systems where instead of stepwise addition
of base other precipitating agents may be used. This is the case, for
example, of metal sulphide precipitation with controlled dosage of
S2− (e.g. in the form of H2S). The controlled addition of precipitant as
a means of controlling supersaturation has been successfully
demonstrated in the case of high grade nickel sulphate crystal-
lization from spent electrolytes with isopropanol (Moldoveanu and
Demopoulos, 2002).
2.7.2. Via metal complexation and dissociation
In this method, which is better suited for the production of high
value compounds, the metal to be precipitated is complexed with
strong complexing agents like EDTA, NH3 etc. and then it is dissociated
in a controlled manner in order to allow its controlled release (and
thereby controlled supersaturation environment) and precipitation. A
good example of this approach is Sherritt's method for the production
of fine copper powders (Sutherland et al., 1990). This method consists
of the following steps:
1: Preparation of cuprous ammoniacal solution at around 80 °C:
CuB + CuðNH3 Þ2+ +
2 Y2CuðNH3 Þ2
2: Controlled dissociation of the Cu(I)-ammine complex by acid
addition:
CuðNH3 Þ+2 + xH+Yð1−x=2ÞCuðNH3 Þ+2 + xNH+4 + x=2Cu+
3: Spontaneous disproportionation of cuprous ions (simulta-
neously occurring with step 2)


x=4 2Cu + YCuB + Cu2 +
205
2.7.3. Via dilution
By dilution the concentration of the precipitating metal is
effectively kept low or equivalently the supersaturation level is kept
low and in this way the complications of homogeneous nucleation are
largely overcome. This approach is built-in in the operation of the
“crystallactor” – a specially designed fluid bed pellet reactor –
developed and used in Europe for the treatment of effluents (Van
Weert and Van Dijk, 1993). This reactor, illustrated in Fig. 11, via
recirculation and mixing of the treated liquor with the incoming
influent, causes dilution of the metal concentration to a level below
Scr,homo thus favouring the deposition of the precipitated compound
on sand or seed particles (pellets).
In the hydrometallurgical industry the goethite process developed
by EZ in Australia (Monhemius, 1980) is an example where in a
practical way the supersaturation is controlled via dilution. This
approach to goethite production is illustrated in Fig. 12(a). If
precipitation of goethite is attempted from undiluted zinc process
solutions (typical composition 20 g/L Fe3+; T ∼ 95 °C) poorly settling
ferrihydrite (“paragoethite”) or hydronium jarosite is produced
instead. Unpublished work done at McGill shows that there is
considerable room for optimization of the goethite process involving
direct precipitation from a ferric sulphate solution via dilution. Thus
with a combination of dilution and neutralization, goethite was
produced from a 5.5 g/L Fe3+ sulphate solution at 95 °C in the presence
of seed. Iron concentration was reduced from 5.5 to 1 g/L in 60 min
and the produced goethite contained only 1.2% sulphur as sulphate.
2.7.4. Via a redox reaction
In this method, which is suitable for precipitation of a multi-valent
metal ion, i.e. Fe2+/Fe3+, Mn2+/Mn4+ etc, controlled oxidation (or
reduction) is used to regulate the supersaturation level. The best
example of this approach is the goethite process developed by Vieille
Montagne, now Umicore (Belgium) (Monhemius, 1980). Thus upon
reduction of Fe3+ by reaction with concentrate (ZnS) the ferrous
sulphate solution (∼20 g/L Fe(II)) is oxidized with air at pH 3. Once
more, similar to the Australian method of goethite production by
dilution, the Fe3+ concentration is effectively maintained at low level
(∼2 g/L) (see Fig. 12 (b)), thus the complications of homogeneous
nucleation are largely avoided.
2.7.5. Via a dissolution reaction
In this method the metal to be precipitated is released (in a
controlled manner) via the dissolution of a precursor compound. This
ð14Þ
ð15Þ
ð16Þ Fig. 11. The crystallactor (reproduced from Van Weert and Van Dijk (1993)).
206 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214

Fig. 12. Goethite precipitation by dilution (a) and by oxidation (b).

method imitates the mechanism of dissolution–recrystallization 2.8.1. Matrix anion effects

discussed in Section 2.5.2. This type of dissolution-controlled
precipitation process usually happens in hydrometallurgy in situ
during pressure leaching operations. A good example of this is
oxidative pressure leaching of sulphides or the acid pressure leaching
of laterites; in connection with the latter Papangelakis and his co-
workers at the University of Toronto have clearly demonstrated how
hydronium alunite (H3O)Al3(SO4)2(OH)6 forms via the dissolution of
gibbsite at 230 to 270 °C (Blakey and Papangelakis, 1994).
At McGill some years ago, while studying the pressure oxidation of
arsenopyrite, the production of well grown scorodite crystals was
observed (Papangelakis and Demopoulos, 1990). The reactions
involved were as follows:
Dissolution:
150BC
FeAsSðsÞ + 13=4O2 + 3=2H2 OY Fe2+ + H3 AsO4 ðaqÞ + SO2−
4 ð17Þ
Oxidation:
+
2Fe2+ + 1=2O2 + 2H Y2Fe3+ + H2 O
(i) The matrix anion determines the nature of the precursor
complex-cluster. As the size, mobility and shape of the latter are
important in the crystal growth process it is understandable
that different crystal phases of the same compound may form
in different complexing media. For example, hydrolytic pre-
cipitation of iron(III) oxyhydroxide under ambient pressure but
elevated (80–90 °C) temperatures yields α-FeOOH (goethite) in
sulphate/nitrate media but β-FeOOH (akaganeite) in chloride
media.
(ii) The matrix anion may be incorporated in the solid phase due to
incomplete exchange of the matrix anion ligand by the
precipitating ligand.
Example:
FeSO4+ + 2OH− ðprecipitating ligandÞYFeðOHÞ+2 ð20Þ
+ SO2− + 2−
4 ðmatrix anion ligandÞYFeOOHðsÞ + H + SO4
−
The above example shows complete exchange of SO2−
4 by OH .
ð18Þ In the case of incomplete exchange, phases like Fe3(SO4)2

Precipitation:

Fe3+ + H3 AsO4ðaqÞ + 2H2 OYFeAsO4 d2H2 OðsÞ + 3H + ð19Þ

The leaching of arsenopyrite took place in a H2SO4 medium.

Attempts to precipitate scorodite from a similar medium but using
ferric sulphate as the source of iron failed to give crystalline solids —
another manifestation of Stanski's Rule.
Another example is the work of Van Weert and Droppert (1994)
who studied the conversion of As2O3 baghouse dust to crystalline
scorodite using a HNO3 medium and an autoclave (130–160 °C). When
iron was introduced as Fe(NO3)3 salt an extremely fine, difficult to
filter, scorodite material was produced; however when scrap iron was
used instead, coarse and easily filterable scorodite was produced. This
was so because iron release was regulated by the dissolution of scrap,
i.e. the supersaturation level was effectively kept low, thus favouring
the growth of crystals.

2.8. Matrix anion and impurity effects

The matrix anion of the solution plus many other minor

constituents of the solution (impurities) may exert significant effects Fig. 13. Composition of ferrihydrite precipitates produced by fast neutralization of ferric
to the quality of the produced compound(s). sulphate solutions (3 g/L Fe(III) at 50 °C (reproduced from Zinck (1993)).
 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214
(OH)5·2H2O may form. The net effect is to obtain a mixture of
precipitates. Since the ligand exchange process is a function of
pH, it is not surprising to find the content of a precipitate (in
matrix anion) to depend on the precipitation pH. This is
exemplified with the results of Fig. 13, taken from the work of
Zinck (1993). At least in part, the observed correlation of
sulphate incorporation to pH may be attributed to the existence
of Fe(III)-sulphato complexes (FeSO+4 and Fe(SO4)−2) in the acidic
region (Filippou et al., 1995).
As, described later, similar to solution complexes, inner-sphere
surface complexes have been observed to form. In this respect,
therefore, the incorporation of SO2− 4 in the precipitated ferric
oxyhydroxide can be attributed in part to surface complexation.
The amount though of the matrix anion incorporated into the
precipitated compound will depend not only on the pH or the
anion concentration but on the properties of the compound (i.e.
amorphous vs. crystalline; particle size etc.) as well and in this
respect on the way precipitation is conducted. Thus, direct
(without neutralization control) precipitation of ferrihydrite at
pH 3 and 50 °C was found to yield precipitates with 18% SO4
content (Fig. 13) while controlled precipitation of crystalline a-
FeOOH in the presence of seed at pH 2 and 95 °C was found to
yield precipitates with only 3.5% SO4 content (unpublished
research). Once more this is the manifestation of the impor-
tance of supersaturation control in precipitation processes.
(iii) The matrix anion interferes with the dehydration process and
thereby with the crystallization process. Thus, production of
crystalline phases from chloride-based solutions is in general
easier than from sulphate-based solutions. This is so because
−
the SO2−4 anion is highly aquaphilic as opposed to the Cl which
is not hydrated (Bates et al., 1970). This effect was observed by
Demopoulos and co-workers (Demopoulos et al., 1995a;
Droppert et al., 1996) who found crystalline scorodite to be
produced more readily from chloride media than from the
corresponding sulphate media. Similarly hematite produc-
tion from chloride media can be achieved under atmospheric
pressure conditions (b100 °C)(Dutrizac and Riveros, 1999) as
opposed to the case of hematite production from sulphate
media that requires higher temperatures (N130 °C) (Zerella
et al., 1983; Cheng, 2002).
(iv) The matrix anion finally through surface adsorption might alter
the growth mode of the precipitate. For example, precipitation
of Al(OH)3 from acidic sulphate solutions yields spherical
particles but from chloride solutions yields rods/needles
(Sugimoto, 1987).
2.8.2. Impurity effects
Many minor solution constituents tend to specifically chemisorb and
alter the particle morphology and growth mode of the precipitate. It
should be emphasized that it takes trace amounts of impurities (~10− 3M)
to cause significant effects on the crystal formation process (Dirksen and
Ring, 1991).
But in addition to interfering with the crystal growth process,
impurities tend to become incorporated into the main precipitated
phase, thus effecting its composition and properties (e.g. solubility–
stability, morphology etc.). Let us now consider in more detail the
main mechanisms of impurity incorporation in precipitates:
(i) Coprecipitation as a district phase; for example the coprecipita-
tion of arsenic(V) in the form of scorodite, FeAsO4·2H2O during
the removal of iron(III) from hot (95 °C) acidic sulphate
solutions as jarosite, NaFe3(SO4)2(OH)6. This mechanism may
be suppressed as long as there is a reasonable difference in the
solubility of the two coprecipitated compounds. This was
demonstrated by Demopoulos et al. (1995a) in the case of
scorodite/akageneite coprecipitation from chloride solutions.
207
(ii) Substitution: In this case a foreign constituent is substituted in
the crystalline lattice of the precipitated compound. Substitu-
tion requires good “fitting” of the substituent group in the host
site and favourable bond energy. We may have cation
substitution, such as Ca1 − x Mgx CO3 (Stumm and Morgan,
1981), or anion substitution, such as NaFe3(SO4)2 − y (AsO4)y
(OH)6 − x (H2O)x (Dutrizac and Jambor, 1987). Vacancies or
distortions may be introduced in the crystal due to charge
imbalance or non-size compatibility between the host site and
substituent group, hence altering properties such as solubility.
Thus, for example, scorodite produced from sulphate media
tends to contain up to 4% SO4. This mode of impurity
incorporation is the most difficult to avoid. One possible way
of avoiding cation substitution is complexing of the trouble-
some cation and changing thus its size and charge. One such
example is the complexation of Cd2+ (a very toxic element) with
Cl− to form CdCl−3 and thus avoid its incorporation in gypsum,
CaSO42H2O (Martynovich, 1994).
(iii) The other major mechanism of impurity uptake is via adsorption/
surface complexation. Due to its wide occurrence this mode of
impurity uptake is discussed separately in the following section.
2.9. Impurity uptake by adsorption
2.9.1. Surface complexation reactions
Solid surfaces are never smooth and chemically homogeneous.
Surface heterogeneity is a fact of life and nothing is more true than for
solids precipitated out of solution. Let us examine in this respect the
surface of an oxide (Dzombak and Morel, 1990). Due to incomplete
coordination of the surface specific “anion” and “cation” sites develop
on it. The non-fully coordinated cations are hydrated and this is
followed by surface hydrolysis which gives rise to a hydroxylated
surface: /XOHE. This hydroxylated surface is further hydrated and
eventually is engaged in reactions with solute species which enter the
electrical double layer.
This group of reactions is called surface complexation reactions
(Dzombak and Morel, 1990; Davis and Hayes, 1986). These reactions
are considered analogous to the formation of solution complexes. The
following discussion will focus on surface reactions occurring on
oxides. Cation or anion surface complexation are the two most
important types of surface reactions involved in impurity uptake:
Cation complexation
=XOHB + M2+ Y=XOM + + H + ð21Þ
Anion complexation
=XOHB + A3− + H + Y=XA2− + H2 O ð22Þ
Surface complexation of cations by hydrous oxides invokes the
formation of covalent bonds with surface oxygen (or hydroxyl)
anions and the release of protons from the surface. Specific
sorption of anions on hydrous oxides occurs via ligand exchange
reactions in which hydroxyl surface groups are replaced by the
sorbing ions. In addition to these surface complexation reactions
simple surface ion-association reactions leading to the formation
of ion-pairs via electrostatic attraction forces may occur. However,
due to the weakness of the electrostatic forces involved in these
reactions the retention of impurities is weak, hence washing is
effective in removing the latter. This is not the case with the
inner-sphere-forming surface complexation reactions (reactions
(21) and (22)). The retention of impurities by the latter reactions
is governed by pH. This is clearly manifested in the general
adsorption equilibrium curves illustrated in Fig. 14.
208 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214

Let us explain why this happens by analyzing the relevant surface

complexation equation

h i  +  h 2+ i
K = M2+ H = M ð1−θÞ ð23Þ
ads aq

where concentrations are taken equal to activities, [M2+]ads is

equivalent to /XOM+, and θ is the fraction of surface that is covered.
Considering now the distribution coefficient D, where D = [M2+]ads/
[M2+]aq, Eq. (23) can be written in the following logarithmic form:

 
logD = logK + logð1−θÞ−log H + ð24Þ

For the iso-distribution point, i.e. 50% cation adsorbed, D = 1 (for

which log D = 0) and the last equation is reduced to

 
log H + 50 = logK + logð1−θÞ ð25Þ

where [H+]50 is the [H+] corresponding to D = 1.

For low metal ion concentration we have low coverage, i.e. (1 − θ)low
is higher than (1 − θ)high, where the latter corresponds to high metal
ion concentration.
By writing the log [H+]50 equation for “low” and “high” concentra-
tions and subtracting we obtain
Fig. 14. Typical equilibrium curves for cation and anion sorption on hydrous iron oxide.
Arrows indicate direction of increasing sorbate/sorbent ratio (reproduced from    
Dzombak and Morel (1990)).
log H + 50;high −log H + 50;low = logð1−θÞhigh =ð1−θÞlow ð26Þ

Since (1 − θ)high/(1 − θ)low b 1 we get, log [H+]50,high b log [H+]50,low or

2.9.2. Impurity uptake pH50,high N pH50,low.
An extensive compilation of cation (Pb2+, Zn2+, Cd2+, Hg2+, Cu2+, Ag+, It is clear, therefore, why with increased metal ion concentration
Ni , Co2+, Cr3+, Ca2+, Sr2+, and Ba2+) and anion (PO3−
2+ 3− 3−
4 , AsO4 , VO4 , the adsorption isotherms move to higher pH. By following exactly the
H2AsO−3, H2BO−3, SO2−
4 , SeO2−
3 , S O
2 3
2−
, and CrO 2−
4 ) adsorption isotherms on same type of analysis it can be shown why the adsorption isotherm
hydrous ferric oxides can be found in Surface Complexation Modelling moves to lower pH when the amount of sorbent, i.e. the amount of
(Chapters 6 and 7) (Dzombak and Morel, 1990). Here only some hydrous ferric oxide is increased.
selected adsorption data are presented. On the other hand, since for each surface reaction there exists a
characteristic adsorption equilibrium constant (reflecting the stability
2.9.2.1. Cation sorption. Some typical cation adsorption data on of the surface complex), it becomes obvious as to why we have the
hydrous ferric oxide are plotted in Fig. 15 (Benjamin and Leckie, 1981). different cation adsorption curves. In general high valence cations
As can be seen the adsorption isotherms move towards higher pH (for adsorb at lower pH than low valence cations. The chemical nature of
the same cation) as the concentration of the cation increases. the hydrous oxide substrate seems to have a rather modest effect on
the adsorption distribution curves. Thus, for example the order of
adsorption with increasing pH for the cations Pb2+, Cu2+, and Cd2+ on
amorphous silica (Stumm and Morgan, 1981) is the same with that on
hydrous ferric oxide (Benjamin and Leckie, 1981).

2.9.2.2. Anion sorption. Typical sorption data of As(V) on hydrous

ferric oxide are plotted in Fig.16. The position of the adsorption isotherm

Fig. 15. Cation adsorption equilibria on hydrous ferric oxide; conditions: 10− 3M FeT, .5 H Fig. 16. Adsorption of As(V) on hyrous ferric oxide; [Fe]/[As] = 15; conditions: 5 × 10− 5M
10− 7M MeT (reproduced from Benjamin and Leckie (1981)). FeT, 3.34 × 10− 6M As (reproduced from Dzombak and Morel (1990)).
 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214 209

Table 1
Solubilities of Cu(OH)2 in dilute sulphate solutions at 25 °C (initial concentrations 10− 3M
CuSO4; 10− 3M Fe2(SO4)3)

pH Solution copper concentration (mg/L)

CuSO4/alone CuSO4/Fe2(SO4)3
5.98 33.55 (30.18)⁎ 3.47
6.42 4.21 (4.43)⁎ 0.81
6.8
6.87 (0.56) 0.11
7.02 0.35 (0.28)⁎ 0.05
7.26 0.12 (0.09)⁎
7.59 0.10 0.02
8.28 0.05 0.006

* Numbers in () denote solubilities calculated according to Baes and Mesmer (1986).

depends on the molar ratio [sorbent]/[sorbate]. Thus with increasing

anion concentration the anion adsorption isotherm shifts to lower
pH — the opposite of what happens with the cation adsorption
isotherms. On the other hand with increasing concentration of sorbent,
i.e. hydrous iron oxide substrate, the adsorption isotherm shifts to higher
pH.
The removal of arsenic by adsorption on hydrous ferric oxide or
ferrihydrite has been studied by Robins et al. (1988). Their “removal”
curves are the mirror images of the adsorption curves. At the high pH
region the adsorption curves move to higher pH with increasing molar
Fe/As ratio because in reality the amount of sorbent (i.e. Fe(OH)3)
increases and this results in a pH shift. Let us consider the surface
complexation reaction,
=XOHB + HAsO2− + −
4 + H Y=XHAsO4 + H2 O
  
K = ½Asads = ½Asaq H + ð1−θÞ
D = ½Asads =½Asaq
By similar analysis as done for the cation sorption system we get
pH50 = logK + logð1−θÞ
Thus, as 1 − θ increases, i.e. as the amount of sorbent increases pH50
increases i.e. the adsorption curves shift to higher pH and hence the
enhanced stability of arsenic in an extended pH region.
The stabilizing effect of cations (like Cu2+) on arsenic removal by
high Fe/As precipitation reported by Harris and Monette (1988) and
Emett and Khoe (1994) is postulated to be due to surface charge
neutralization, i.e. /HAsO−4d CuOH+.
Fig. 17. Formation of local supersaturation pocket in a poorly mixed reactor.
from (i) pure adsorption (=surface complexation) to (ii) surface
precipitation to (iii) bulk precipitation (=coprecipitation). This is the
case for example of arsenate adsorption on ferrihydrite from relatively
concentrated solutions and the conversion of the surface complexed
arsenate to ferric arsenate surface precipitate over time (Jia et al.,
2006, 2007).The surface precipitation mechanism is prevalent in
hydrolytic precipitation systems involving multi-metal ion solutions.
A consequence of adsorption occurring in co-precipitation systems
is the removal of a cation or anion at a level below the solubility of the
compound in which it is a constituent. Thus it has been determined in
our laboratory (unpublished research) that the solubility of Cu2+,
ð27Þ when the latter is precipitated as hydroxide by neutralization, is
significantly lower when it is co-precipitated with Fe3+ (Fe(OH)3) than
if it is precipitated alone. The relevant data are shown in Table 1.
ð28Þ
2.9.4. Impurity uptake control
ð29Þ Adsorptive incorporation of impurities during precipitation can be
greatly suppressed via the following measures: a) by reducing the
specific surface area via the growth of large and smooth particles; b) by
enhancing the crystallinity of the precipitate — (a) and (b) are achieved
ð30Þ by keeping the saturation ratio, S, below Scr,homo; c) by suppressing
aggregation which is responsible for solution uptake; d) by modifying
the pH or pX of the solution and thereby changing the character of the
troublesome impurity species (e.g. Zn2+ vs ZnSOo4 (aq) and the
character of the surface charge; e) by complexing the troublesome
cation (e.g. Cd2+ vs. CdCl−3); f) by using ionic surfactants which compete
with impurities for preferential adsorption; g) by employing recycling

2.9.3. Surface precipitation

The surface complexation reactions that were discussed above may
lead to surface precipitation if the sorbing ions (anions or cations) are
present at high concentrations (Dzombak and Morel, 1990). What
distinguishes surface precipitation from surface complexation is the
fact that in the former case we have the formation of a new surface
phase different from the substrate phase (e.g. formation of Cu(OH)2
layer on a Fe(OH)3 precipitate). In other words with increasing
concentration of sorbing–precipitating ions, we have a continuum

Table 2
Impurity removal by ferric hydroxide precipitation–adsorption (pH 4.5, 75 °C) (data
taken from Dutrizac (1993))

Element (ppm) Impure weak acid leach Purified neutral leach

Ge 1 0.1
As 0.2 0.02
Sb 1 0.1
Se – 0.01
Fig. 18. The mixed suspension classified product removal crystallizer (MSCPR).
210 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214

Fig. 19. The three alternative neutralization paths followed to effect hydrolytic
precipitation of Fe(III) hydroxide.

Fig. 21. Particle size distribution of the iron hydroxide solids produced via neutralization
path II (see Fig. 19).

of the precipitate, (for example a reduction of the SO4 content of

amorphous FeOOH from 9% down to 4% was achieved upon recycling
2.10. Design of precipitation reactors
20 times the precipitates (Zinck, 1993) and finally h) by purifying the
solution. The above can prove very useful in industrial precipitation
Mixing of reagents and agitation regime are very important in
applications where a precipitate free of impurities is sought, as it is for
precipitation. It is imperative to ensure uniform mixing in order to
example the case of producing high grade nickel sulphate from de-
avoid local supersaturation pockets (Fig. 17). On the other hand
copperized electrolyte (Moldoveanu and Demopoulos, 2002) or clean
agitation speed has to be optimized as it seems to act in two opposing
gypsum from zinc plant waste waters (Verbaan et al., 1999).
ways. First, as it was mentioned in Section 2.3.2 shear forces help to
On the other hand, when impurity uptake via surface adsorption is
prepare compact aggregates; on the other hand excessive agitation
sought, then production of an amorphous precipitate, like ferric
might lead to scaling problems due to favouring of contact nucleation.
hydroxide (ferrihydrite), is the ideal impurity scavenger-carrier. This is
Contact nucleation involves the plastering of fresh homogeneously
the case of impurity removal during neutral leaching in zinc circuits —
nucleated colloidal particles on the reactor's walls.
refer to data in Table 2 (Dutrizac, 1993). It is worthy to note that all
The rate of contact nucleation (J) is a function of the following
impurities listed are suspected to be in the form of anions hence their
factors (Dirksen and Ring, 1991):
adsorption is favoured in acidic solutions (pH 4–4.5) as predicted by
the adsorption isotherms of Fig. 15. JαkMT ðrpmÞ2−4 S1−2 ð31Þ

where

MT is the mass concentration of solids (kg m− 3)

rpm is the agitation speed (rev min− 1)
S is the saturation ratio
k is the reactor size and geometry factor (dimensionless)

Fig. 20. The effect of recycling on ferric hydroxide densification for (A) simple
neutralization with NaOH; for (B) neutralization with NaOH and supersaturation
control; and for (C) neutralization with lime and supersaturation control (reproduced Fig. 22. SEM photo of the ferric hydroxide produced via staged-neutralization and
from Demopoulos et al. (1995b)). recycling (Neutralization path III in Fig. 19) (reproduced from Demopoulos et al. (1995b)).
 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214
Fig. 23. Particle size distribution of the iron hydroxide solids produced via staged
neutralization (neutralization path III (in Fig. 19)).
It is evident from this equation that high slurry density and excessive
agitation speed all contribute to contact nucleation or in other words to
scaling/wall plating. On the other hand, since the exponent of S is much
lower than the corresponding one for homogeneous nucleation
(typically ranging from 6 to 12) the latter is expected to dominate at
high levels of supersaturation.
Batch reactors are characterized by variable supersaturation envir-
onment. In this respect then batch reactors are not good from the
standpoint of supersaturation control. To avoid this inherent deficiency
of the batch reactor, the precipitant will have to be added in a controlled
manner to ensure constant S (semi-batch configuration). This (for
example) is the approach taken in developing the step-wise neutraliza-
tion procedure for supersaturation control discussed in Section 2.7.1.
Continuous stirred tank reactors (CSTR), on the other hand, offer a
stable supersaturation and seeded environment due to their steady-
state operation. We can distinguish two types of continuous precipita-
tion reactors, the Mixed Suspension Mixed Product Removal Crystallizer
(MSMPR) and the Mixed Suspension Classified Product Removal
Crystallizer (MSCPR) (Fig. 18). The first one is nothing else but the
familiar CSTR-type reactor. This reactor in general results in fine particles
of wide size distribution (due to its inherent residence time distribution
function) and as such, while it is easy to operate, it fails nevertheless to
produce dense and well grown precipitates. However the MSCPR-type
reactor effectively operates in such a way that the liquid and solid phases
Fig. 24. Continuous staged-neutralization process circuit (reproduced from Demopoulos et al. (1995b)).
211
Fig. 25. The solubility curves of scorodite and akageneite and the two domains of
precipitation (reproduced from Demopoulos et al. (1995a).
have different mean residence times. The solution flows continuously
and rather fast while the solids either are removed periodically at a much
slower rate or are recycled. In this way the solids spend much longer
time inside the reactor thus allowing for their growth and crystallization.
Operation finally of a series of CSTRs with solids recycling and
distributed addition of the precipitant as described later in Fig. 24
appears to be the best configuration for a hydrometallurgical precipita-
tion process seeking to produce clean and well grown precipitated solids.
3. Case studies
3.1. Precipitation of Fe(III) (oxy)hydroxides
Hydrolytic precipitation is one of the most important groups of
precipitation reactions. Prior to the formation of the hydroxide solid
the metal ions undergo partial hydrolysis and form soluble hydrolysed
species. These hydrolysed species under high supersaturation
undergo polymerisation and eventually condensation via partial loss
of their solvation water. Due to the ease with which high valent
cations hydrolyse and polymerize, the products of their hydrolytic
precipitation reactions are highly amorphous. Meticulous control of S
at very low values is necessary to overcome this tendency of metal ion
hydrolytic polymerization. These phenomena are to be illustrated by
212 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214

Fig. 26. SEM photos of scorodite deposited on gypsum (reproduced from Singhania et al. (2005)).

referring to the most common metal ion hydrolysis system: that of Fe Finally neutralization was effected in a step-wise fashion (neu-
(III). For an extensive review of the hydrolytic chemistry of cations the tralization path III. Fig. 19) as described in Section 2.7.1 (see Fig. 10).
reader is referred to Baes and Mesmer (1986). For the specific system Once more sludge recycling as in the HDS method was employed and
of Fe(III) hydrolysis extensive reviews have been published among the total duration of each test was again 4 h. This crystallization
others by Flynn (1984) and Dutrizac (1979). treatment proved indeed the best approach in yielding high density
Acid rock (mine) drainage solutions contain iron(III) sulphate and ferric hydroxide sludges. The sludge consisted of distinct particles
several other base metal sulphates. Neutralization of the effluents (Fig. 22) with uniform and coarse particle size distribution (Fig. 23)
with lime is the standard treatment method used around the world. (20 µm average particle size) and a 55% solids density after only 8
The problem with this method, as practised today, is that it produces a recycles (Fig. 20 — curve B). Moreover the sludge exhibited 3 to 6 times
large volume of amorphous sludge, which is characterized by poor faster settling rate (12 m/h).
settling properties and low solids content, (b5% without recycling and
10–20% with recycling).
To demonstrate the superiority of the supersaturation-controlled
approach to the treatment of such acidic effluents, an extensive series
of laboratory tests has been performed, details of which are described
elsewhere (Zinck, 1993; Demopoulos et al., 1995b). In this work
synthetic H2SO4/Fe2(SO4)3 containing effluents (pH 2.5; 1000 mg /L
Fe3+, 6000 mg /L SO2− 4 ) were neutralized with NaOH at 50 °C following
three different neutralization procedures. NaOH was used instead of
lime since it was our aim first to understand the crystallization of
“ferric hydroxide” (the actual product was 2-line ferrihydrite (Jambor
and Dutrizac, 1998)) and for that the formation of gypsum had to be
avoided.
The first procedure involved direct conventional neutralization in a
single step to final pH 9. This is depicted in Fig. 19 as neutralization
path I. Solution was agitated at that pH for 4 hours. The produced
sludge (ferrihydrite) was found to be totally amorphous with low
solids content (b5%) and poor settling rate (b2 m/h). This approach to
neutralization and the obtained results correspond to the most
common way neutralization is practised in industry.
The second neutralization approach tested corresponds to the High
Density Sludge Process (HDS), i.e. it involved sludge recycling and a
relatively slow neutralization rate (neutralization path II — Fig. 19) but
not strict supersaturation control. At the end of each test 90% of the
precipitate was recycled as seed for the next test. The duration of each
test (during which pH was gradually increased) was about 4 h.
Recycling was found to significantly improve the sludge quality,
yielding a solids content of 25 to 30% after 15 recycles (Fig. 20 — curve
A). In terms of settling, the product was slightly better than that
produced in the first experiment with typical settling rates varying
between 2 and 4 m/h. Size distribution analysis (Fig. 21) revealed that
precipitation occurred under both homogeneous nucleation-con-
trolled and growth-controlled regimes (see Fig. 6 — Section 2.3.3) Fig. 27. SEM photos of gypsum produced with (top) and without seed (bottom) by controlled
due to lack of precise supersaturation control. neutralization at low S level (reproduced from Omelon (1998) and Verbaan (2000)).
 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214
Having proved that supersaturation control results in the
production of super dense and compact sludges it was decided
next to repeat the step-wise neutralization/recycling experiment
(under the same conditions as before) but now using slaked lime
instead of NaOH. Not only did this series of tests confirm the
effectiveness of the supersaturation-controlled approach but it
provided even more dense sludges with solids content as high as
67% after 10 recycles (Fig. 20 — curve C). The sludge generated
consisted of distinct phases: gypsum (66.5%) and ferrihydrite
(33.5%). No unreacted lime was detected in the sludge which is an
indicator of the inherent high efficiency of lime utilization
associated with this supersaturation-controlled neutralization
procedure.
The implementation of the newly developed staged-neutralization
process on a continuously operating industrial circuit is described in
Fig. 24. The number of tanks and the operating pH in each tank has
been determined for a specific effluent according to the neutralization
procedure described in Fig. 10.
3.2. Crystallization of scorodite
The production of scorodite (crystalline ferric arsenate dihydrate)
is advocated as the preferred route of immobilizing arsenic from
arsenic-rich metallurgical effluents and dusts (Demopoulos et al.,
1994; Swash and Monhemius, 1998; Harris, 2000; Riveros et al.,
2001; Demopoulos, 2005). One method of production is autoclave
precipitation at temperatures above 150°C (Swash and Monhemius,
1994, 1998). This approach is in agreement with the statement made
earlier that elevated temperature favours the attainment of crystal-
linity. The other avenue for producing crystalline scorodite, i.e. the
maintenance of low S, was explored by the author and co-workers
first from chloride media (Demopoulos et al., 1995a) and subse-
quently from sulphate media (Droppert et al., 1996; Filippou and
Demopoulos, 1997; Dabekaussen et al., 2001; Wang et al., 2000;
Demopoulos et al., 2003; Singhania et al., 2005, 2006). To this end
the controlled-supersaturation procedure of Fig. 10 combined with
the use of seed, described in Section 2.7.1 was employed at
temperatures below 100°C. More specifically crystalline scorodite
was produced first at 80 °C to 95 °C from chloride media
(Demopoulos et al., 1995a). Failure to control S b Scr,homo = 8) resulted
in production of amorphous ferric arsenate. In other words the
maintenance of low S effectively reduced the crystallization
temperature from N150 °C to b100°C.
The crystallization of scorodite from sulphate media at 85–95 °C
proved successful as well when the controlled-supersaturation
procedure was applied, but there were some key differences
between the two systems. The critical supersaturation associated
with the onset of homogeneous nucleation (i.e. Scr,homo) was found
to be at least 70, i.e. 10 times higher than that for the chloride
system. Equally surprising was the difference in behaviour when
scorodite is crystallized from solutions (chloride vs sulphate) with
high Fe(III)/As(V) molar ratio. Thus in the case of the chloride
system (Li and Demopoulos, 2006) it was possible by applying
strict supersaturation control to precipitate sequentially scorodite
(at pH b1.5) followed by akageneite (β-FeOOH)(at pH N1.5) (refer to
Fig. 25) from Fe/As = 4 solutions. However, the sulphate system
does not behave in the same manner. In the latter case the presence
of excess iron, i.e. at Fe/As N 2, it was found to significantly retard
the crystallization of scorodite — this most likely being the
manifestation of the difference in iron complexation prior to
precipitation (Singhania et al., 2006).
Finally, of interest to underline here, is that under proper
supersaturation control it is possible to grow scorodite not only on
scorodite seed but as well on other types of solids like hematite and
gypsum. The deposition of scorodite on gypsum is illustrated with the
SEM photo of Fig. 26.
213
Fig. 28. Impurity uptake during gypsum crystallization at pH 4 as a function of seeding
(Conditions 1 g/L cation concentration, except Na was 10 g/L, 50 g/L seed, 50 g/L CaO,
10 g/L, H2SO4 (reproduced from Verbaan (2000)).
3.3. Crystallization of gypsum
Formation of gypsum and precipitation is omnipresent in a variety
of hydrometallurgical processes, being more prevalent in neutraliza-
tion with lime or limestone of sulphuric acid-based process solutions —
as done for example at the Iijima Zinc Refinery in Japan (Yamada et al.,
1998) or for acidic waste waters (Verbaan et al., 1999). In the context of
the latter case we have studied the crystallization of gypsum with the
purpose of producing high density and clean gypsum (Omelon, 1998;
Verbaan, 2000). This research has focused on elaborating a neutraliza-
tion technique that promotes the production of well grown and clean
gypsum material via controlled supersaturation (achieved via the step-
wise elevation of pH — refer to Section 2.7.1) and product recycling. An
important finding of this work was that, in addition to controlling
supersaturation and recycling, the choice of starting seed material is
critical. Thus, simple recycling of freshly prepared gypsum material
proved ineffective even when all other controls were applied. It was
only with the use of synthetic or naturally occurring gypsum as seed
material (Omelon, 1998) that gypsum with the desired properties
could be produced. The characteristic differences in gypsum morphol-
ogy obtained by using no seed or synthetic seed can be appreciated by
examining the SEM photos of Fig. 27. The unseeded system produced
gypsum exhibiting the so-called “rosette” morphology characterized
by high specific surface area and thus prone to high impurity uptake
and poor settling behaviour. The material produced by simple
recycling of the freshly (homogeneously) prepared seed was very
fine in size that again gave poor settling behaviour. However, the
material produced with good quality seed (synthetic gypsum) and
under controlled (low) supersaturation environment proved to be
superior to the other ones.
The influence of seeding under supersaturation control on impurity
uptake is exemplified with the data of Fig. 28 (Verbaan, 2000). It can be
clearly seen that up to one order of magnitude lower impurity uptake
occurs when neutralization is conducted in such a way favouring the
production of smooth and large gypsum crystals (Fig. 27a) (refer to
Section 2.9.4).
4. Concluding remarks
By far supersaturation is the most important parameter that controls
the properties (particle size, morphology, crystallinity and cleanliness)
of a compound produced via aqueous precipitation. It would not be an
exaggeration to state that as long as supersaturation is controlled, it is
almost certain that a product of superior quality will be obtained.
214 G.P. Demopoulos / Hydrometallurgy 96 (2009) 199–214
Development of supersaturation-controlled aqueous precipitation
methods is expected to grow in the near future both in the area of
production of advanced materials such as nanosized powders (Li and
Demopoulos, 2008) but also in the area of industrial hydrometallurgy
and treatment of effluents from chemical and metallurgical opera-
tions. A solid understanding of crystallization theory is a prerequisite
to successful development and implementation of advanced pre-
cipitation technology.
Acknowledgement
The author is indebted to all past and current students and
research associates of his, who through their hard work and ingenuity
contributed to the work reviewed in this article.
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