PROJECT METALLURGIST

Prediction method for

equilibrium values in
Copper solvent extraction
in sulfate system
Effect of ionic strength

Kafumbila Kasonta Joseph

2022
Prediction method for equilibrium values in copper solvent extraction in sulfate system:
Effect of ionic strength
© 2022 Joseph Kafumbila
jokafumbila@hotmail.com

Joseph Kafumbila Page 1

 Contents

1. INTRODUCTION 4

2. CHEMISTRY OF SOLVENT EXTRACTION 6

2.1. CLASSIFICATION OF METAL SOLVENT EXTRACTION 6

2.1.1. Extraction by salvation 6
2.1.2. Extraction by cation exchange 6
2.1.3. Extraction by anion exchange 6
2.1.4. Extraction by chelation 7
2.2. CHEMISTRY OF COPPER SOLVENT EXTRACTION 7

3. CONSTRUCTION OF DISTRIBUTION ISOTHERMS 9

3.1. LABORATORY-SCALE TEST 9

3.2. PREDICTED DISTRIBUTION ISOTHERMS 10
3.2.1. Classification of predicted distribution isotherms 10

4. NEW SEMI-EMPIRICAL MODEL 14

4.1. EQUILIBRIUM CONDITION 14

4.2. VALUE OF 𝛙𝐞𝟏 15
4.2.1. Definition 15
4.2.2. Copper molar concentration in organic phase 15
4.2.3. Free extractant molar concentration in organic phase 15
4.2.4. Cu-Sulfate system 16
4.2.5. Constraint during copper solvent extraction 20
4.3. VALUE OF 𝛙𝐞𝟐 21
4.3.1. Definition 21
4.4. EQUATION OF THERMODYNAMIC EQUILIBRIUM CONDITION 22
4.4.1. Modelling of equilibrium condition Equation 22
4.4.2. Effect of initial free acid concentration 23
4.4.3. Effect of extractant volume percent in organic phase 24
4.4.4. Equation of equilibrium condition 26

5. REFERENCES 27

Joseph Kafumbila Page 2

 Process simulation
Chemical engineering can be defined from many different aspects. However, all
the scientists and professionals agree that the process is the center of it. To make a
distinction from any other discipline, the role of chemical engineering could be defined
with its purpose to develop, design, construct, control, optimize and mange any process
involving physical and/or chemical changes and make this process profitable.

Process simulation as discipline uses mathematical models as basis for analysis

prediction, testing, detection of a process behavior unrelated to whether the process is
existing in reality or not. Process simulation is there to increase the level of knowledge
for a particular process and chemical engineering in general.

So, when those two concepts are put together, we can look into the chemical
engineering as a discipline defining how the process should be developed and
simulation as the tool helping us to explore the options. Chemical engineering needs to
know how the process should be designed while chemical engineers use the simulation
to explore all the process design options and define the optimal one.

Joseph Kafumbila Page 3

1. Introduction

Copper production technology changes drastically in the last 25 years with

introduction of solvent extraction-electrowinning circuit as a copper production
method. The technology of copper solvent extraction produces the most economical
copper from low-grade copper ore. Copper solvent extraction technology consists of two
circuits connected by a common organic phase. In the first step, called extraction step,
metal is extracted from aqueous phase by organic phase. In the second step, called
stripping step, metal is recovered from organic phase. The second aqueous phase is
more pure and concentrated.

At the beginning, copper solvent extraction configuration operating on dilute

aqueous phases were constituted with two stages respectively to extraction and
stripping steps. Design of this 2Ex2S configuration was simple and based on the value of
copper transfer per extractant volume percentage of 0.22 (g/l/1% v/v). This value gives
copper extraction efficiency greater than 98% and copper stripping efficiency of 60%.
Afterwards, understanding that copper extraction efficiency was not the most important
parameter than the cost of copper production plant, one stage of stripping step was
removed and the value of copper transfer was increased to 0.26 (g/l/1%V). Design of
this 2Ex1S configuration was based on the expected value of copper extraction efficiency
of 90%.

MacCabe Thiele method was introduced in design of copper solvent extraction

configuration when copper solvent extraction technology started to be used for high-
grade copper ore. A large number of laboratory tests were required before obtaining the
optimal configuration by using MacCabe Thiele method. It was at this level that a
simulation model of equilibrium line of extraction and stripping steps was introduced.

Several simulation models of copper solvent extraction using chelating reagents

were made. There are three types of simulation models: empirical model, semi-empirical
model and chemical model. Empirical model is an extrapolation equation of the
distribution isotherms. Semi-empirical model is the extrapolation equation of the
distribution ratio of copper between organic and aqueous phases. Chemical empirical is
based on mass-action equilibrium equations of intermediate chemical reactions.

In the previous paper (KAFUMBILA J., 2017), a semi-empirical model which is the
extrapolation of thermodynamic property of a global chemical reaction of copper
solvent extraction has been developed. This model does not take account the ionic

Joseph Kafumbila Page 4

strength of aqueous solution. This model gives two equilibrium conditions respectively
for extraction step and stripping step.

The goal of this paper is to develop, in the same way, a semi-empirical model
which remains the extrapolation of thermodynamic property of a global chemical
reaction of copper solvent extraction and takes account of ionic strength in sulfate
media. The semi-empirical model is developed using lix984N as copper extractant.

Joseph Kafumbila Page 5

2. Chemistry of solvent extraction

2.1. Classification of metal solvent extraction

Solvent extraction of metallic cation can be classified on process of extraction.

There are four types [AIDI AMEL, 2013]:

 Extraction by salvation
 Extraction by cation exchange
 Extraction by chelation
 Extraction by anion exchange

2.1.1. Extraction by salvation

Solute molecules are associated with the solvent molecules - this is known as
salvation. In extraction by salvation solvent molecules are directly involved in formation
of the ion association complex. In this case the extracted species is solvated with a
certain number of solvent molecules on condition that the extractant must be inert.

2.1.2. Extraction by cation exchange

The extractant is an organic acid (HR) and can exchange hydrogen with cation.
The extraction will proceed with formation of a neutral uncharged species.

2.1.3. Extraction by anion exchange

The cation forms first a complex in aqueous phase having negative charge. The
extractant have an anion which can be exchange with the aqueous cation complex. The
extraction will proceed with formation of a neutral uncharged species.

Joseph Kafumbila Page 6

2.1.4. Extraction by chelation

. The extractant exchanges cation with hydrogen ion as in extraction by cation

exchange. In additional the extractant have chelating ligand. The ligand with two or
more points of attachments to metal atoms are called chelating ligands. The substance
which brings about chelation is called chelating agent and the product is called chelate.

2.2. Chemistry of copper solvent extraction

In case of copper solvent extraction, the extraction is typically achieved by an

oxime-based chelating mechanism. Under low acidic conditions (pH <1), extractant
exchanges hydrogen with copper (extraction). Under high acidic conditions (180 g/L
H2SO4), extractant exchanges copper with hydrogen (strip). Both extraction and
stripping steps are typically designed to achieve equilibrium conditions. The similarities
with binary distillation lead to the use of the McCabe-Thiele method for modeling the
process. The chemical reactions (2.a) and (2.b) give the copper extraction and stripping
reaction with an oxime-based extractant.

CuSO4 + 2HR → CuR2 + H2SO4 (2.a)

CuR2 + H2SO4 → CuSO4 + 2HR (2.b)

Where HR is the extractant and CuR2 is copper-organic complex

The organic phase is a mixture of extractant and diluent. Extractant is an

organic compound which extracts copper from aqueous phase. In industrial practices,
Properties of extractant are: tailored extractive strength, excellent Cu/Fe selectivity, fast
kinetics, good stability, low crud formation and excellent versatility [RITCEY G.M. ET AL,
1984]. There are three kinds of extractant:

 Ketoximes: Ketoximes are moderately strong copper extractants which operate best when
PLS is relatively warm and pH is ~1.8 or above
 Aldoximes: Modified aldoximes have good metallurgical properties even at low
temperatures and low pH
 Mixture of ketoximes and aldoximes: Properties of aldoxime/ketoxime blends reflect ratio of
components

Diluent is an organic liquid in which extractant is dissolved. In general, diluent

must allow solubilisation of extractant. Diluent must have minimum surface tension to
promote dispersion in mixer, low volatility, and high ignition point. Diluent must be
Joseph Kafumbila Page 7
cheaper. Diluent is constituted with various hydrocarbons. Kerosene is often used as a
diluent [RITCEY G.M. ET AL, 1984].

In industrial practices, maximum value of extractant volume percent (v/v) is

between 30 – 33% [RITCEY G.M. ET AL, 1984]. Viscosity of organic phase increases with
increasing extractant volume percent. Above this value, some organic components must
be added to organic phase to improve viscosity.

Joseph Kafumbila Page 8

3. Construction of distribution isotherms

Extraction and strip isotherms are a graphical representation of the equilibrium

copper concentration in the aqueous and organic phases at different organic-to-aqueous
(O/A) ratios. There are two ways of determining the distribution isotherms for a
particular operation: either by performing laboratory-scale tests or by predicted
distribution isotherms based on the extraction and stripping specific conditions.

3.1. Laboratory-scale test

The following procedure for determining the distribution isotherms is followed:

 Select at least 7 organic-to-aqueous (O/A) ratios at which to perform the

test;
 Measure the initial concentration of copper and free acid (PLS for
extraction isotherm or spent electrolyte for stripping isotherm);
 Combine aqueous feed (PLS for extraction and spent electrolyte for
stripping) with previously stripped organic for extraction isotherm or
loaded organic for stripping isotherm at the specified O/A ratio;
 Agitate mixture for a minimum 5 minutes and allow to settle;
 Once settled, sample and measure the concentrations of copper and free
acid in aqueous phase;
 For each O/A point, perform a mass balance to determine the
equilibrium copper concentration in the organic phase or the organic can
also be analyzed to verify the mass balance points

Joseph Kafumbila Page 9

3.2. Predicted distribution isotherms

3.2.1. Classification of predicted distribution isotherms

The theoretical prediction gives copper concentration in organic phase as a

function of copper concentration in aqueous phase. This function is called the model of
distribution isotherm. There are three types of distribution isotherm model: empirical
model, semi-empirical model and chemical model [NOIROT P.A., 1985].

3.2.2. Empirical model

The empirical model gives the equation that best matches the curve of
equilibrium line. Due to the absence of links with the modeled phenomenon, its
extrapolation can be risky and its use is limited to the field covered by the
experimentation.

The empirical model has been developed for dynamic simulation of copper
solvent extraction plant [MORENO C.M. ET AL, 2009]. The equation (3.1) gives the empirical
model of extraction isotherm.

A∗X
Y = X+B (3.1)

Where “Y” is copper concentration in the organic phase, “X” is copper concentration in
the aqueous phase.

Values of “A” and “B” are given by the equations (3.2) and (3.3).

A = a *ML (3.2)

(10−pH )b
B= (d ∗ CuPLS + f* CuRaff ) (3.3)
MLc

Where “ML” is the maximum loading (g/L), “𝐶𝑢𝑃𝐿𝑆 ” is copper concentration in the PLS
(g/L), “𝐶𝑢𝑟𝑎𝑓𝑓 ” is copper concentration in the raffinate and pH of PLS and “a”, “b”, “c”,
“d” and “f” are the constants.

The equation (3.4) gives the empirical model of stripping isotherm.

Joseph Kafumbila Page 10

 Y = C*X +D (3.4)

Where “Y” is copper concentration in the organic phase and “X” is copper
concentration in the aqueous phase.

Values of “C” and “D” are given by the equations (3.5) and (3.6).

C = g* ML (3.5)

h∗V%i
D= +m (3.6)
Acj

Where “V%” is the volume percent of extractant in the organic phase and “Ac” is the
acid concentration of spent electrolyte (g/L). “g”, “h”, “i”, “j” and “m” are the constants.

3.2.3. Semi-empirical model

Just like the preceding one, it is based on an equation but which best fits the
curve of distribution ratio of copper. Semi-empirical model uses the overall solvent
extraction reaction. If an aqueous phase containing copper is contacted with an organic
phase, than copper distributes between the aqueous and organic phase according to
equation (3.7).

Cu
DCu = Cuor (3.7)
aq

Where “𝐷𝐶𝑢 ” is the distribution ratio of copper, “𝐶𝑢𝑜𝑟 ” is copper concentration

in organic phase and “𝐶𝑢𝑎𝑞 ” is copper concentration in aqueous phase.

It has been observed that the distribution ratio (D) is a function of free ligand
concentration in the organic phase [LLOYD PHILIP J.D., 2004]. Equation (3.8) gives the
mathematical expression this observation.

Cu
DCu = Cuor = Do ∗ (Lt − mCuor )n (3.8)
aq

Where “𝐷𝑜 ” is the distribution ratio of copper at trace concentrations, readily

determined in the laboratory, “𝐿𝑡 ” is the total ligand concentration in the extractant,
“m” approximates the ratio of ligand molecules to extracted molecules close to
saturation, “n” approximates the ratio of ligand molecules to extracted molecules close
to infinite dilution.

It should be noted that “m” and “n” in equation (3.8) are sometimes equal, but
often differ in value, which underlines that fact that this equation has no theoretical
Joseph Kafumbila Page 11
basis. It is merely a convenient way of representing much experimental data using three
parameters that can readily be determined experimentally.

3.2.4. Chemical model

Chemical model requires the knowledge of all intermediate chemical reactions

of extraction reaction. The first suggestion of intermediate chemical reactions for copper
solvent extraction with oximes based extractant involves the dissolution of extractant in
aqueous phase [DREISINGER D.B., 1988]. Chemical reactions (3.a), (3.b), (3.c), (3.d) and
(3.e) give the intermediate chemical reactions:

HR or ↔ HR aq (step 1) (3.a)

The step 1 involves the dissolution of extractant in the aqueous phase.

+
HR aq ↔ Haq + R−aq (step 2) (3.b)

The step 2 involves the dissociation of extractant in the aqueous phase.

Cu+2 − +
aq + R aq ↔ CuR aq (step 3) (3.c)

The step 3 the first ligand is added to copper in aqueous phase.

CuR+aq + R−aq ↔ CuR 2 aq (step 4) (3.d)

The step 4 the second ligand is added to copper in aqueous phase.

CuR 2 aq ↔ CuR 2 or (step 5) (3.e)

The step 5 the copper complex is absorbed by the organic phase.

The second suggestion of intermediate chemical reactions for copper solvent

extraction with oximes based extractant involves two forms of extractant molecule in
the organic phase [ALGUACIF F.J., 1998]. Chemical reactions (3.f), (3.g) and (3.h) give the
intermediate chemical reactions:

Cu+2 +
aq + 2∗ HR or ↔ CuR 2 or + 2∗ Haq (3.f)

Cu+2 +
aq + (HR)2 or ↔ CuR 2 or + 2∗ Haq (3.g)

(HR)2 or ↔ 2∗ HR or (3.h)

Joseph Kafumbila Page 12

 In the case of sulfate solution, the chemical reaction (3.i) must be taken into
account.

HSO− + 2−
4 ↔ H + SO4 (3.i)

The modeling requires the knowledge of the corresponding mass-action

equilibrium equations for the chemical reactions listed above and the mass-balance of
copper, ligand and hydrogen.

The mass-action equilibrium equations and the mass-balance of copper, ligand

and hydrogen for the second suggestion of intermediate chemical reactions are given by
the equations (3.9), (3.10), (3.11), (3.12), (3.13) and (3.14).

All models consider that the chemical activity coefficients of species in aqueous
and organic phases do not change .

[Cu+2 ]aq ∗[HR]2or

[CuR 2 ]or = K1 * (3.9)
[H+ ]2aq

[Cu+2 ]aq ∗[(HR)2 ]or

[CuR 2 ]or = K 2 * (3.10)
[H+ ]2aq

[(HR)2 ]ot = K 3 * [HR]2or (3.11)

[Cu+2 ]taq = [Cu+2 ]aq + A * CuR 2 or (3.12)

[HR]tor = [HR]or + 2* [(HR)2 ]or + 2* [CuR 2 ]or (3.13)

[H +2 ]aq = [H + ]iaq + 2* A* [CuR 2 ]or (3.14)

Where [𝐶𝑢𝑅2 ]𝑜𝑟 is the concentration of copper complex in the organic phase (mol/L),
[𝐻𝑅]𝑜𝑟 is the concentration of the first molecule form of extractant in organic phase
(mol/L), [(𝐻𝑅)2 ]𝑜𝑟 is the concentration of the second molecule form off extractant in
the organic phase (mol/L), [𝐻𝑅]𝑡𝑜𝑟 is the total concentration of ligand in the organic
phase (mol/L), [𝐶𝑢+2 ]𝑎𝑞 is the concentration of copper in aqueous phase, [𝐶𝑢+2 ]𝑡𝑎𝑞 is
the total concentration of copper in aqueous and organic phases, [𝐻 + ]𝑖𝑎𝑞 is the
concentration of hydrogen ion in the feed solution, [𝐻 +2 ]𝑎𝑞 is the concentration of
hydrogen ion in the aqueous phase, and “A” is the ratio of organic phase volume on
aqueous phase volume.

Joseph Kafumbila Page 13

4. New semi-empirical model

4.1. Equilibrium condition

Extraction step is guided by thermodynamic disequilibrium between aqueous

and organic phases. Copper mass transfer is stopped when thermodynamic property
reaches equilibrium condition in both phases. Global copper solvent extraction chemical
reaction with Lix984N extractant is followed chemical reaction (2.a) [HOSSEN AMINIAN,
1999]. LIX 984N reagent, a 1:1 volume blend of LIX 860N-I and LIX 84N-I, is a mixture of
5-nonylsalicylaldoxime and 2-hydroxy-5-nonylacetophenone oxime.

Cu2+ + 2HR ↔ CuR 2 + 2H + (2.a)

where 𝐶𝑢2+and 𝐻 + are copper and hydrogen ionic species in aqueous phase, HR is acid
form of Lix984N extractant, and 𝐶𝑢𝑅2 is copper complex form in organic phase

Thermodynamic equilibrium condition of global chemical reaction (2a) is given

by equation (4.1) [BAUER G.L ET AL, 1976].

μ(CuR2) + 2μ(H+ ) - μ(Cu+2 ) - 2μ(HR) = 0 (4.1)

where μ𝜌 is chemical potential of species ‘ρ’

Chemical potential of species ‘ρ’ is given by equation (4.2).

μρ = μ°ρ +RTln( γρ ∗ Cρ ) (4.2)

where 𝜇𝜌° is standard chemical potential of species ‘ρ’, 𝛾𝜌 is chemical activity coefficient
of specie ‘ρ’, 𝐶𝜌 is molar concentration of species ‘ρ’, R is the perfect gas constant, and T
is the temperature

The substitution of equation (4.2) for all species in equation (4.1) gives
equation (4.3) which is the thermodynamic equilibrium condition. Equation (4.4) gives
Gibbs standard free energy of the chemical reaction (2.a).

Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2 −Δ𝐺° (γ(HR) )2

= e( )
(H )
RT * = ψe (4.3)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2 γ(CuR2)

ΔG° =μ°(CuR2 ) -μ°(Cu+2 ) -2μ°(HR) (4.4)

Joseph Kafumbila Page 14

 Where 𝐶𝜌𝑒 is equilibrium molar concentration of species “ρ”.

4.2. Value of 𝛙𝐞𝟏

4.2.1. Definition

The value of thermodynamic equilibrium condition ψe from left component of

Equation (4.3) called ψe1 is given by equation (4.5).

Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
= ψe1 (4.5)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

4.2.2. Copper molar concentration in organic phase

The value of copper molar concentration at the steady-state in organic is given

by equation (4.6).

e Cue(or)
C(CuR 2)
= (4.6)
63.54

𝑒
where 𝐶𝑢𝑜𝑟 is copper concentration (g/L) in organic phase

4.2.3. Free extractant molar concentration in organic phase

The value of free extractant molar concentration in organic phase is given by

equation (4.7).

e v/V%∗ 0.91∗ 1000 e

C(HR) = 100∗ 270
– 2*C(CuR 2)
(4.7)

where v/v% is extractant volume percentage (v/v) in organic phase. 0.91 is the density
of Lix984N extractant. 270 is the mass molar of Lix984N extractant.

Joseph Kafumbila Page 15

4.2.4. Cu-Sulfate system

4.2.4.1. Activity of soluble species

 Ionic strength

The ionic strength (I) of the solution is the first to know because the
electrostatic interactions depend on the concentration of charge. The value of ionic
strength is calculated using Equation (4.8). “Zn ” is the charge of soluble compounds “n”
and “Cn ” is the concentration of soluble compounds “n”. The ionic strength has
concentration units.

1
I=2 x ∑n Zn2 ∗ Cn (4.8)

 Helgeson Equation

The calculations of individual ion activity coefficient have been approximated by

Equation (4.9) in concentrated as well as dilute electrolyte solutions involved in
geochemical processes at high temperatures and pressures (H.C. HELGESON ET AL, 1981)
and suitable for overall equilibrium diagram calculations. “γp ” is the activity coefficient
of soluble compound “p”, “Zp ” is the electrical charge of compound “p” and “I” is the ionic
strength (mol/kg of water). “A”, “B” and “b” are temperature-dependent parameters.
Table (4.1) gives values of parameters “A”, “B” and “b” at 25°C ( B. BEVERSKOG ET AL, 1998).
“ä” is a distance of closest approach, which may be taken to be equal to that of NaCl (3.72
10−10m).

Z2p A√I
Log(γp )= - (1+Bä√I) – log(1+0.018015*I)+b*I (4.9)

Table 4.1: values of A, B and b parameter at 25°C

A B x 10−10 b
0.509 0.328 0.064

For neutral aqueous species it is usually approximated that the activity

coefficients are unity at all values of ionic strength and temperature. The approximate
applicability is up to value of ionic strength around 5 (mol/kg of water) (H.C. HELGESON
ET AL, 1981).

In copper solvent extraction the concentrations of species are less the 2mol/L.
In this case, molarity is equal to molality.

Joseph Kafumbila Page 16

  Activity of water

The activity of water (solvent) (𝑎𝑤 ) is given by Equation (4.10). “ϕ” is the
osmotic coefficient, “W” is the molecular weight of water (18.016) and “𝑚𝑖 ” is the
concentration (mol/kg water) of soluble compounds (CHARLES E. HARVIE ET AL, 1984)

W
ln (aw ) = - 1000 *ϕ *∑i mi (4.10)

The calculations of osmotic coefficient have been approximated by Equation

(4.11) (H.C. HELGESON, 1969). The value of “u” is given by Equation (4.12). Table (4.2)
gives values of parameters “a”, “b”, “c” and “d” at 25°C. “A” comes from Debrye-Huckel
equation for activity coefficient and is function of temperature. The value of “A” is
0.5092 at 25°C. “I” is the ionic strength (mol/kg of water).

2.303∗A 1 b∗I 2c∗I2 3d∗I3

ϕ=1- [u -2ln(u) - u] + + + (4.11)
a3 ∗I 2 3 4

u=1+a*√I (4.12)

Table 4.2: values of a, b, c and d parameter at 25°C

a b c d
1.454 0.02236 9.38 x10−3 -5.362x10−4

4.2.4.2. Cu-Sulfate-Water System

 Water

The chemical reaction (4.a) gives the water ionization reaction. Logarithm of the
equilibrium constant of the chemical reaction (4.a) is given in Table (4.3) at 25°C
(MINTEQA2-V.4, 1999).

H2 O = H + + OH − (4.a)

Table 4.3: Log(K) of reaction (4.a) at 25°C

Chemical reactions logK Reference

4.a -13.998 MINTEQA2-V.4, 1999

Joseph Kafumbila Page 17

 At pH below 2, the concentration of OH − is negligible in aqueous solution. The
designation of concentration (mol/L) of H + is C(H+) . Equation (4.13) gives the value of
C(H+) from a known value of pH.

10(−pH)
C(H+ ) = (4.13)
γ(H+ )

 Free sulfate

The free soluble compounds are the following: H2 SO4 , HSO4 − and SO4 −2 . The
chemical reactions (4.b) and (4.c) give the equilibrium reaction between SO4 −2 and
other substances. Table (4.4) gives the equilibrium constant of the chemical reaction
(5.b).

SO−2 + −
4 + H =HSO4 (4.b)

SO−2 +
4 + 2H =H2 SO4 (4.c)

Table 4.4: Log(K) of reaction (4.b) and (4.c) at 25°C

Chemical reactions logK Reference

4.a 1.99 MINTEQA2-V.4, 1999
4.b -0.053 MINTEQA2-V.4, 1999

The designation of concentration (mol/L) of soluble substances of sulfate is the

following:

Concentration of SO−2
4 is C(SO−2
4 )
,
Concentration of HSO−4 is C(HSO−4 ) ,
Concentration of H2 SO4 is C(H2 SO4) .

The concentrations C(HSO−4 ) and C(H2 SO4) are calculated as function of

concentration of soluble compounds (H + and SO−2
4 ) using Equations (4.14) and (4.15)
coming from the mass actions of the chemical reaction (4.b) and (4.c). The
concentration C(SO−2
4 )
is is unknown value.

(−1)
C(HSO−4 ) =10(1.99) *C(H+) *γ(H+) *C(SO−2
4 )
*γ(SO−2
4 )
*γ(HSO−4 ) (4.14)

C(H2 SO4 ) =10(−0.053) *(C(H+ ) ∗ γ(H+ ) )(2) *C(SO−2

4 )
*γ(SO−2
4 )
(4.15)

The assumption is that the positive charge of H + is neutralized by the negative

charge of HSO−4 which is the major sulfate soluble compounds in the range of pH from

Joseph Kafumbila Page 18

0.0 to 2.0. In this condition Equation (4.16) gives the concentration of free acid (Ac)
(g/L) in aqueous solution.

Ac=C(H+ ) *98.08 (g/L) (4.16)

 Copper

The major copper soluble compounds in the range of pH from 0.0 to 2.0 are the
following: Cu+2 , and CuSO4 . The chemical reaction (4.d) gives the equilibrium reaction
between the major soluble compounds of copper. Table (4.5) gives the equilibrium
constant of the chemical reaction (4.d).

Cu+2 + SO−2
4 = CuSO4 (4.d)

Table 4.5: Log(K) of reaction (4.d) at 25°C

Chemical reactions logK Reference

4.d 2.36 MINTEQA2-V.4, 1999

The designation of concentration of soluble substances of copper soluble

compounds is the following:

Concentration of Cu+2 is C(Cu+2 ) ,

Concentration of CuSO4 is C(CuSO4) .

The concentration C(CuSO4) is calculated as function of concentration of Cu+2 ,

and SO4 −2 using Equation (4.17) coming from the mass action of the chemical reaction
(4.d). The concentration C(Cu+2 ) is unknown value.

C(CuSO4 ) =10(2.36) *C(Cu+2 ) *γ(Cu+2 ) *C(SO−2

4 )
*γ(SO−2
4 )
(4.17)

Equation (4.18) gives the concentration of Copper in aqueous solution (Cu(aq) )

in (g/L).

Cu(aq) =(C(Cu+2 ) +C(CuSO4 ) )*63.54 (4.18)

 Electrical neutrality of aqueous solution

The electrical neutrality of solution is given by Equation (4.19).

C(HSO−4 ) +2C(SO−2
4 )
=C(H+) +2C(Cu+2 ) (4.19)

Joseph Kafumbila Page 19

  Constraints in the aqueous solution

 The concentration C(H+) is given by Equation (4.13) when pH is the

known value or by Equation (4.16) when free acid concentration is the
known value.
 Equations (4.14), (4.15), (4.17), (4.18) and (4.19) give the values of
C(HSO−4 ) , C(SO−2
4 )
, C(H2 SO4 ), C(Cu+2 ) and C(CuSO4 ) .

4.2.5. Constraint during copper solvent extraction

i
In the initial aqueous solution, the value of C(H + ) is given by Equation (4.20) or

i i i
(4.21) and the values of C(H 2 SO4 )
, C(i HSO−4 ) , C(SO i
−2 ) , C(Cu+2 ) , and C(CuSO ) are given by
4
4
i
Equations (4.22), (4.23), (4.24), (4.25) and (4.26). Total sulfur concentration (C(s) ) is
given by Equation (4.27) in the initial solution.

i 10(−pH)
C(H +)= (4.20)
γ(H+ )

i Aci
C(H +)= (4.21)
98.08

i i i i
C(iHSO−4 ) =10(1.99) *C(H + ) *γ(H+ ) *C
i
(SO−2 ) *γ(SO−2 ) /γ(HSO4 )
− (4.22)
4 4

i i (2) i
i
C(H 2 SO4 )
=10(−0.053) *(C(H + ) ∗ γ(H+ ) ) *C(SO−2 ) *γi(SO−2 ) (4.23)
4 4

i i i i i
C(CuSO 4)
=10(2.36) *C(Cu+2 ) ∗ γ(Cu+2 ) *C(SO−2 ) *γ(SO−2 ) (4.24)
4 4

i
Cui(aq) =(C(Cu i
+2 ) +C(CuSO ) )*63.54
4
(4.25)

i i i
C(iHSO−4 ) +2C(SO −2 ) =C(H+ ) +2C(Cu+2 ) (4.26)
4

i i i
C(s) =C(H 2 SO4 )
+C(i HSO−4 ) +C(SO i
−2 ) +C(CuSO )
4
(4.27)
4

After Copper solvent extraction, when Cue(aq) is the known value, the values of
e e e e e e
C(H + ) , C(H SO ) , C(HSO− ) , C
2 4 4 (SO−2 ) , C(Cu+2 ) , and C(CuSO4 ) are given by Equations (4.28), (4.29),
4
(4.30), (4.31), (4.32) and (4.33).

Joseph Kafumbila Page 20

 e e e e
C(eHSO−4 ) =10(1.99) *C(H + ) *γ(H+ ) *C
e
(SO−2 ) *γ(SO−2 ) /γ(HSO4 )
− (4.28)
4 4

e e (2) e
e
C(H 2 SO4 )
=10(−0.053) *(C(H + ) ∗ γ(H+ ) ) *C(SO−2 ) *γe(SO−2 ) (4.29)
4 4

e e e e e
C(CuSO 4)
=10(2.36) *C(Cu+2 ) ∗ γ(Cu+2 ) *C
(SO−2 ) *γ(SO−2 ) (4.30)
4 4

e
Cue(aq) =(C(Cu e
+2 ) +C(CuSO ) )*63.54
4
(4.31)

e e e
C(eHSO−4 ) +2C(SO −2 ) =C(H+ ) +2C(Cu+2 ) (4.32)
4

e e e
C(s) =C(H 2 SO4 )
+C(eHSO−4 ) +C(SO e i
−2 ) +C(CuSO ) =C(s)
4
(4.33)
4

4.3. Value of 𝛙𝐞𝟐

4.3.1. Definition

The value of thermodynamic equilibrium condition ψe from right component of

Equation (4.3) called ψe2 is given by equation (4.34).

−Δ𝐺° (γ(HR) )2
e( RT
)
* =ψe2 (4.34)
γ(CuR2)

In organic phase, the study done on the extractant Kelex 100, which is chelating
copper solvent extraction reagent, shows that ratio of chemical activity coefficients of
species in organic phase is a function of copper concentration in organic phase [ BAUER
G.L ET AL, 1976]. The assumption is that this thermodynamic property is also true for
chelating copper extractant as Lix984N.

Conclusion from this assumption is that the thermodynamic equilibrium

condition is given by equation (4.35).

Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H ) e
=f(C(CuR 2)
) (4.35)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

Joseph Kafumbila Page 21

4.4. Equation of thermodynamic equilibrium condition

4.4.1. Modelling of equilibrium condition Equation

Test conditions of lab test 1 done with pure copper sulfate aqueous phase are
the following:

 Initial copper concentration in aqueous phase: 8 g/l.

 Initial free acid concentration in aqueous phase: 5 g/l.
 Extractant: Lix984N.
 Extractant volume percentage in organic (v/v%): 20%.

Table (4.6) gives equilibrium line data of lab test 1 from which the values of
thermodynamic equilibrium condition ψe1 of each steady-state position are calculated.

Table 1: Value of ψe1 from equilibrium line data of lab test 1

Cu(aq) (g/L) 0.04 0.09 0.35 1.19 3.38 5.92 6.93

Cu(or) (g/L) 0.80 1.58 3.83 6.76 9.26 10.45 10.70

Figure (4.1) gives the values of thermodynamic equilibrium condition ψe1

versus the values of copper concentration in organic phase.

Results show that the value of thermodynamic equilibrium condition ψe1 is a

linear function of the value of copper concentration in organic phase. Equation (4.36)
gives the modelling of thermodynamic equilibrium condition.

ψe1 =a*Cu(or) +b (4.36)

Joseph Kafumbila Page 22

 Figure 4.1: Values of ψe1 versus values of copper concentrations in organic
phase of lab test 1

4.4.2. Effect of initial free acid concentration

Table (4.7) gives equilibrium line data of lab test 1, 3, 4 and 5. The initial acid
concentration is increased from 5 to 20g/L. Figure (4.2) gives the value of
thermodynamic equilibrium condition ψe1 versus the values of copper concentration in
organic phase for Data in Table (4.7).

Table 4.7: Equilibrium line data of lab tests 1, 3, 4 and 5

Lab test 1 Lab test 3 Lab test 4 Lab test 5

Cuiaq 8 g/l i
Cuaq 8 g/l i
Cuaq 8 g/l i
Cuaq 8 g/l
i 5 g/l i 10 g/l i 15 g/l i 20 g/l
Acaq Acaq Acaq Acaq
V/V% 20 % V/V% 20 % V/V% 20 % V/V% 20 %
Cueaq Cueor Cueaq Cueor Cueaq Cueor Cueaq Cueor
0.04 0.80 0.10 0.80 0.15 0.79
0.09 1.58 0.23 1.56 0.33 1.54
0.35 3.83 0.57 3.74 0.76 3.63 0.98 3.52
1.19 6.76 1.70 6.31 2.00 6.01 2.42 5.59
3.38 9.26 3.80 8.40 4.20 7.80 4.41 7.20
5.92 10.45 6.10 9.55 6.30 9.00 6.35 8.30
6.93 10.70 7.00 10.01 7.10 9.30 7.17 8.74

Joseph Kafumbila Page 23

 Figure 4.2: Values of ψe1 versus values of copper concentration in
organic phase of lab tests 1, 3, 4 and 5

The results on Figure 4.2 show that when the initial acid concentration
increases the thermodynamic equilibrium condition remains a linear function of copper
concentration in the organic phase and the initial free acid concentration of feed solution
does not affect the values of constants “a” and “b”.

4.4.3. Effect of extractant volume percent in organic phase

Table (4.8) gives equilibrium line data of lab test 1, 6 and 7. Figure (4.3) gives
the value of thermodynamic equilibrium condition ψe1 versus the values of copper
concentration in organic phase.

The results of Figure (4.3) show that the slope of equilibrium condition line
decreases when the extractant volume percent increases.

Joseph Kafumbila Page 24

Table 4.8: Equilibrium line data of lab tests 1, 6, and 7 of extraction step

Lab test 6 Lab test 7 Lab test 1

Cuiaq 8.04 g/l Cuiaq 5.5 g/l Cuiaq 8.01 g/l
i 20 i
g/l Acaq 0.980 g/l Acaq i 5.0 g/l
Acaq
v/v% 15 % v/v% 18 % v/v% 20 %
Cueaq Cueor Cueaq Cueor Cueaq Cueor
0.27 0.78 0.08 2.89 0.04 0.80
0.48 1.50 0.13 3.82 0.09 1.58
1.56 3.24 0.31 5.57 0.35 3.83
3.30 4.68 1.63 8.20 1.19 6.76
5.16 5.62 2.70 8.77 3.38 9.26
6.80 6.20 3.71 9.07 5.92 10.45
7.40 6.39 5.51 9.23 6.92 10.80

Figure 4.3: Values of ψe1 versus values of copper concentration in

organic phase of lab tests 1, 6, and 7

Joseph Kafumbila Page 25

4.4.4. Equation of equilibrium condition

The values of constants “a” and “b” are only function of extractant volume
percentage. Equilibrium condition on extraction and stripping steps is given by equation
(4.37) in the range from 8 to 32% of extractant volume percent. This Equation has been
obtained from pure copper aqueous solution.

Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-220.53 * v/v%(−1.943) ) ∗ Cue(or)+ 99.468 * v/v%(−0.878) (4.37)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

Figure (4.4) gives the experimental data of equilibrium line of lab test (1) and
simulated equilibrium line obtained from Equation (4.37).

Figure 4.4: Comparison between experimental Data and simulation

Data on lab test 1

Joseph Kafumbila Page 26

5. References

Kafumbila J. Design and optimization of copper solvent extraction configurations,

Technical repport, 2017.

AIDI AMEL, Etude thermodynamique de l’extraction des métaux de transition par

Salicylidèneaniline, Thèse, Université Mohamed Khider, 2013.

Ritcey G.M., Ashbrook A.W., Solvent extraction: principles and application of process
metallurgy, Part I, Elsevier, 1984.

Pierre-Antoine Noirot, Logiciels d’étude et de prévision des extractions par solvants :

application à la valorisation des solutions de chlorure de Nickel, Thèse, Université des
sciences et techniques de Lille, 1985.

C.M. Moreno, J.R. Pérez-correa, A. Otero, Dynamic modelling of copper solvent

extraction mixer-settler units, Minerals Engineering, 2009.

Philip J.D. LLOYD, solvent extraction principles and practice-Second Edition, Taylor &
Francis Group, 2004.

D.B. Dreisinger, Solvent extraction kinetic of divalent metals with organophorus acids
using the rotating diffusion cell technique, ISEC’88 volume II, USSR, 1988.

F.J. Alguacif, Modelling copper solvent extraction from acidic sulphate solution using
MOC 45, Rev. Metal. Madrid, 1998.

Hossen Aminian, Modélisation et simulation des opérations d’extraction par solvant et

d’électrolyse du Cuivre, thèse, université de Laval, Canada, 1999.

Gerald L. Bauer and Thomas W. Chapman, Measurement and correlation of solvent

extraction equilibria. The extraction of Copper by kelex 100, Metallurgical transaction B,
1976.

H.C. Helgeson et al, Theoretical prediction of the thermodynamic behavior of aqueous

electrolytes at high pressures and temperatures: IV calculation of activity coefficients,
osmotic coefficients, and apparent molal and standard and relative partial molal properties to
600°C and 5 KB, American Journal of Science, Vol. 281, December, 1981, PP 1249-1516.

Joseph Kafumbila Page 27

Bjorn Beverskog et al, Pourbaix diagrams for the system copper – chlorine at 5 – 100°C,
SKI Rapport 98:19, April 1998.

Charles E. Harvi et al, The prediction of mineral solubilities in natural water: Na-K-Mg-Ca-
H-Cl-SO4-OH-HCO3-CO3-CO2-H2O system to high ionic strengths at 25°C,
Geochemical et Cosmochimica Acta (1984) Vol. 48 pp 723-751.

H.C. Helgeson, Thermodynamics of hydrothermal systems at elevated temperatures and

pressures, American Journal of Science 267, 1969, 729-804.

Joseph Kafumbila Page 28