HYDRO-ELECTROMETALLURGY

Course Outline
I.
II.

Introduction to Hydrometallurgy
Thermodynamic and Kinetic Aspects
in Hydrometallurgy
III. Leaching and Solid-Liquid Separation
IV. Solution Purification and Metals
Recovery Methods from Pregnant
Leach Solution

Course Outline
V.

Leaching and Recovery of Metals and

Oxides Ores (Au, Ag, Zn, Al, Cu, Ni)
VI. Leaching and Recovery of Sulphide Ores
(Zn, Ni, Cu)
VII. Introduction to Electrometallurgy
VIII. Metals Production by Electrolysis in
Aqueous Solution
IX. Fused Salt Electrolysis

Literatures
1.
2.
3.
4.

5.

Havlik,T., Hydrometallurgy: Principles and Applications,

CRC publisher, 2008.
Habashi, F. A Textbook of Hydrometallurgy, Metallurgie
Extractive, Quebec,1993
Norman L. Weiss, SME Mineral Processing Handbook,
Volume II, SME, 1985
Unit
Processes
in
Extractive
Metallurgy:
Hydrometallurgy, A Modular Tutorial Course of Montana
College of Mineral Science and Technology
Biswas, A.K. And Davenport, W.G., Extractive
Metallurgy of Copper, Pergamon, Oxford, fourth edition,
2002

Literatures
6. Unit
Processes
in
Extractive
Metallurgy:
Electrometallurgy, A modular tutorial course of
Montana College of Mineral Science and Technology
7. Yannopoulus, J.C,The Extractive Metallurgy of
Gold, Von Nostrand Reinhold, New York, 1991

INTRODUCTION TO HYDROMETALLURGY

Hydrometallurgy
Extraction, recovery and purification of metals,
through processes in aqueous solutions. Metals are
also recovered in the other forms such as oxides,
hydroxides.
Electrometallurgy
Recovery

and

purification

of

metals

through

electrolytic processes by using electrical energy.

Hydrometallurgy Scope
Traditionally, hydrometallurgy is emphasized for metals
extraction from ores.
Hydrometallurgical processing may be used for the
following purposes:
Production of pure solutions from which high purity metals can be
produced by electrolysis, e.g., copper, zinc, nickel, gold, and silver.
Production of pure compounds which can be subsequently used for
producing the pure metals by other methods. For example, pure
alumina to produce smelter grade aluminium.

However, hydrometallurgy principles can be applied to a

variety of areas such as metals recycling from scrap,
slag, sludge, anode slime, waste processing, etc.

Unit Processes in Hydrometallurgy

In general, hydrometallurgy involves 2
(two) main steps:
1. Leaching
Selective dissolution of valuable metals from
ore.

2. Recovery
Selective precipitation of the desired metals from
a pregnant-leach solution.

General outline of hydrometallurgical

processes
Ore/concentrate
Leaching agent

Oxidant

leaching

Solid residu to waste

Solid-liquid separation
Pregnant Solution

Precipitant or
electric current

Solution purification

Precipitation

Pure compound

Metals

 Commonly, solution purification is conducted prior to

metals recovery from the solution.
Solution purification is aimed at obtaining a concentrated
solution from which valuable metals can be precipitated
in the next processes effectively
Solution purification methods which are commonly used
are as follows:
Adsorption by activated carbon
Adsorption by ion exchange resins
Solvent extraction (using organic solvents)
Precipitation with metals (cementation)

Solution purification
Solution purifications by adsorption with activated
carbon, ion exchange resins (IX) and solvent
extraction (SX) have the same unit operations,
namely:
Loading, and
Elution
In the elution step, the adsorbers are usually
regenerated for another process cycle.

Hydrometallurgy development

Hydrometallurgy

is developed after pyrometallurgy.

Metals smelting has been practiced since thousands
years ago.

Hydrometallurgy

was developed after the people

discovered acid and base solutions. However, modern
hydrometallurgy development is commonly associated
with the invention of Bayer Process for bauxite leaching
and cyanidation for gold extraction at the end of 19th
century (1887).

One

of important highlights of hydrometallurgy

development is uranium extraction (Manhattan Project)
aimed at nuclear weapon production in second world
war (1940s).

Important milestones in the development of

hydro-electrometallurgy
Cementation & Aqua Regia Use - 8th Century
Cyanidation - 1887
Bayer Process - 1887
Hall-Heroult Process - 1886, 1888
Copper Electrowinning - 1912
Zinc Electrolytic Process - 1916
Manhattan Project (IX/SX) - 1940s
Biooxidation of Sulphide Concentrates - 1960s
Pressure Leaching
Sherrit Gordon Nickel Process - 1954
Pressure Acid Leaching of Ni Laterites - 1955
Large Scale Copper SX/EW - 1960s

Important milestones in the development of

hydro-electrometallurgy
Carbon in Pulp (CIP)/Carbon in Leach (CIL)
for Gold Recovery - 1980s
Pressure Oxidation of Zinc Sulphides - 1981
Two-Stage Zinc Pressure Leach - 1993
Atmospheric Leaching of Zinc Sulphides
Albion (1993), Outokumpu (1999)
Recent Developments:
Skorpion Project (Anglo American) 2003 (Zn from ZnS)
Hydrozinc (TeckCominco) - 2004
Incos Goro and Voisey Bay Projects - 2007
Leaching of Chalcopyrite (CuFeS2) Ores
Hydrocopper (Outokumpu) Cu from sulfidic ores
Atmospheric leaching of nickel laterite ore: 2008?

Hydrometallurgy vs. Pyrometallurgy

Hydrometalurgy

Pyrometallurgy

Treat high grade

ore?

Less economic

More economic

Treat low grade ore?

Possible with
selective leaching

Unsuitable

Treat sulphide ore

No SO2; otherwise So SO2 generated (can

or SO42- are
be converted to
H2SO4)
generated

Separate similar
metal, such as Ni
and Co

Possible with certain

method

Not possible

Pollutant

Waste water,
solid/slurry residues

Gases and dust

Reaction rates

Slower

Rapid

Hydrometallurgy vs. Pyrometallurgy

Hydrometalurgy

Pyrometallurgy

Scale of operation?

Possibly economic to Unconomic at smale

be done at small
scale operation
scale operation and
expansion is easier

Capital cost

Generally lower than

pyrometallurgy

Higher

Energy cost

Lower

Higher

Materials Handling

Slurry Easy to be
Pumped and
Transported

Handle Molten
Metal, Slag,
Matte

Residues

Residues Fine
and Less Stable

Slags Coarse
and Stable

Thermodynamic and Kinetic

Aspects in Hydrometallurgy

Spontaneous Reaction, Equilibrium State

As has been learned in basic engineering courses,
chemical reaction will spontaneously occur when the
Gibbs free (G) < 0.
G = Go + RT ln K
G = 0 process is in equilibrium state
Go = standard Gibbs free energy
R = ideal gas constant = 8,314 J/K.mol
T = absolute temperature of the system (K)
K = equilibrium constant

Standard Gibbs free energy is determined at:

Gaseous components partial pressure = 1 atm
Temperature = 25 oC (298 K)
Ions activity = 1

Equilibrium Constant
For reaction:
aA + bB cC + dD

C D
K
A B
a

c a

a a

d
a

A = activity of A = [ A ] [ A ] = A concentrat ion

= activity coefficient of
component A

For gaseous component of X a X = p X,

in which p X = parsial pressure of X

Nernst Equation
Hydro-electrometallurgical processes often involve
electrochemical reactions.
For electrochemical reaction
G = -nFE, Go = -nFEo, therefore
RT
E E
ln K
nF
o

Nernst Equation

In which,
E = potential for reduction-oxidation reaction
Eo =standard potential for reduction-oxidation reaction
n = number of electron involved in the electrochemical reaction,
F = Faraday constant = 96485 Coulomb/mole of electron

Spontaneous process E > 0 G < 0

Chemical reactions usually

perform in leaching processes
Dissolution by acid
Example: ZnO(s) + 2H+ Zn2+(aq) + H2O(l)
Dissolution by base
Example: Al2O3(s) + 2OH- 2AlO2-(aq) + H2O(l)
Dissolution by complex ion formation
Example: CuO(s) + 2NH4+(aq) + 2NH3(aq)
Cu(NH3)42+(aq) + H2O(l)

Chemical reactions usually

perform in leaching processes
Dissolution by oxidation
Ex: CuS(s)+ 2Fe3+ Cu2+(aq) + 2Fe2+ + So(s)
Other oxidators: O2, ClO-, ClO3-, MnO4-, HNO3,
H2O2, Cl2
Dissolution by reduction mechanism
Ex: MnO2(s) + SO2(aq) Mn2+(aq) + SO42-(aq)

Correlation of free energy (G)

and heat (enthalphy = H)
G = H - TS
Go = Ho - TSo
Ho = Standard enthalpy (kJ/mol)
Go = Standard entropy (kJ/mol)
Go (reaction) = Go (products) - Go (reactants)
Ho (reaction) = Ho (products) - Ho (reactants)
So (reaction) = So (products) - So (reactants)

HT = H298 +

298

Cp dT

Cp = heat capacity at constant pressure (J/molK)

Where possible, processes are designed to be autothermal
maintain constant temperature by the heat given by the reaction

Calc. example 1
Find K for each reaction using
a) Standard free energy data
b) Standard electrode potential data

Calc. Example 2
a) What is the electrode potential of the
Ni2+/Ni reaction in sulphate solution at 25C
at a Ni2+ concentration of 0.005 M (assumption:
activity of Ni2+ is equal to its molar concentration)
b) At what pH is H2 at 10 atm at equilibrium
with this solution and pure nickel?
Ni2+ + 2 e = Ni
E = -0.26 V
2H+ + 2 e = H2
E = 0.00 V

Pourbaix Diagram
Pourbaix Diagram = Potensial (Eh) pH
Diagram.
The diagram represents thermodynamic
equilibrium of metal, ions, hydroxides (or,
oxides) in aqueous solution at certain
temperature (isothermal).
The boundary of stability regions of metal,
ion, hydroxides (or oxides) are equilibrium
lines.
Does not reflect reaction kinetics.

Pourbaix Diagram
Three possible types of equilibrium lines:
Horizontal
Vertical
Slope

Variations in ion activities are plotted as

contours/dashed lines
Horizontal Line: for equilibrium reactions
that are independent of pH.

Horizontal Line
Example:
Fe3+ + e = Fe2+
0.77 V

Eo =

R = 8.314 J/Kmol, T = 298 K, F = 96500 C/mol e-,

= 1 mol eRT aFe 2 +
o
E=E ln
nF a Fe3 +

If all ion concentrations are assumed to be equal to

their molar concentrations 10-6 M.
3+
[
]
RT
Fe
o
E =E ln
nF [ Fe 2+ ]

8,314 x 298 [ Fe 2+ ]
E = 0,77 ln
[ Fe3+ ]
2x96500
[ Fe 2+ ]
E = 0,77 - 0,0592 log
[ Fe3+ ]
E = 0,77

Vertical Line
Reactions do not involve electron n = 0, no
potensial , the equilibrium depends only on pH.
Example:
Fe2O3 + 6H+ = 2Fe3+ + 3H2O
K = [Fe3+]2/[H-]6
pH = - loga H+

- log[ H+ ] = 14 - pOH

pOH = - loga (OH)-

- log[ OH]

For certain Fe3+ concentration we can determine the

equilibrium pH for the above reaction.

Slope Line
For reactions that depend both on potensial
(Eh) dan pH.
Example:
If all ion concentrations are assumed to be equal to
their molar concentrations 10-6 M.

Water stability region (dotted lines)

Upper boundary line

At pO2 = 1 atm

Lower boundary line

At pH2 = 1 atm

Eh-pH diagram of Fe-H2O system at 25C

Eh-pH Diagram of Zn-H2O System at 25 oC.

Eh-pH Diagram of Cu-H2O System at 25 oC.

Application of Eh pH diagram in
hydrometallurgy
Predicting potential leaching behaviour
for certain mineral system
Predicting the possibility of metals ion
precipitation at the purification of
pregnant-leach solution

Application of Eh pH diagram in hydrometallurgy

Fe(OH)3 or Fe2O3 can be precipitated from Fe3+ at lower

pH than the precipitation of Zn2+ to Zn(OH)2 or ZnO.
Fe2+ have to be oxidized to Fe3+ to gain lower pH value for
Fe(OH)3 precipitation.

Pourbaix Diagram can be constructed at various

temperature for more than two systems

Eh-pH diagram of Zn-S-H2O system at 25oC

Diagram Pourbaix in Presence of Complex Ion

Example: Au-H2O system with the presence of cyanide (CN-) ion
(case of gold cyanidation leaching)
Equilibrium of Au3+/Au

Au 3 3e Au
G 0 G 0 f (Au) G 0 f (Au 3 )
433 KJ / mol
Standard reduction potential for Reaction 1:
0
3

G
433

10
E0

nF
3 96500
1.5 V

(1)

 Equilibrium reaction of O2/H2O

O 2 + 4H + + 4e = 2H 2 O

(2)

Eo = 1.23 V.

Au3+ / Au = 1.5
O 2 / H2O = 1.23

Au3 + / Au

> EO2 / H2O

Therefore, Au3+ ions are not stable in water and readily reduced to
Au by oxidation of H2O to O2 (the opposite of Reaction 2). In the
other word, gold can not be oxidized (dissolved) in water only with
the presence O2.

Potensial pH diagram of AuH2O system without

the presence of complexing agent

With the presence of CN-, Au3+ forms STABLE

COMPLEX of aurocyanide (Au(CN)2-) and the
potential-pH diagram for Au changes significantly as
follow:

Eh-pH Diagram of Au-CNH2O system at 25 oC for [Au]

= 10-4 M and [CN-] = 10-3 M

 By the presence of cyanide ions,

Au+ + e = Au
E = 1.69 0.0591 log [Au+]
Au+ + 2CN- = Au(CN)2- (K = 2 x 1038)
Au(CN)2- + e = Au + 2CN-

...........................

(3)

E 1.69 0.0591 log K 0.0591 log CN / a Au CN 2

In comparison to the first reaction that has Eo of 1.69 V,
Reaction (3) has much lower Eo at -0.57 V.
a

Dissolution of Au is limited by the following equilibrium of

Reaction (3).
During cyanidation leaching, dissolved oxygen is required to
oxidize Au prior to the formation of stable complex of
Au(CN)2-.

 Interactions in Electrolyte Solution

Two types of interactions in electrolyte:
- Ion-ion interaction, and
- ion-solvent interaction
Knowledge of interaction in electrolyte solution is
important because the interactions affect solvation
effects, diffusion, conductivity, ionic strength and
activity coefficients of ions in solution.
Interactions in electrolyte solution influence the
transport properties of ions in solution.

 Ionic Strength and Activity Coefficient

- Ionic strength (I), expresses the ionic concentration
that includes the effects of ionic charge.
- Ionic strength (I) is defined as follow:
1
2
I ci z i
2 i
in which ci = concentration of ion i in molar (mol/L)
and zi = the charge of ion i.
- It is found that activity coefficient, electrical
conductivity and the rates of ionic reactions are all
the functions of ionic strength.

Ionic Strength for unit concentration in molal

- Remember, molality = moles of solute in 1 kg
solvent. Molality can be converted to molality by the
following correlation:

ci
mi =
0.001 - c iMi
in which Mi = the molar mass of each solute in
kg/mol (not in g/mol), ci = molarity of solute i, and
is the density of the solution in kg/m 3 (=g/L)
- In dilute solutions, ci 0.001mio (in which o =
density of pure solvent).

Ionic Strength for unit concentration in molal

- Therefore for dilute solution,
1
1
2

I=
c i z i = 0.001m i o z i 2
2 i
2

0.001o
m z 2
I=
i i
2

If the solvent is water at 25oC (density 1000 kg/m3),

then:
1
Similar form with ionic
2

I
mi z i
strength in molarity
2i

- Molar activity coefficient can be converted to molal

activity coefficient by the following correlation:)

1 M s m

for salt, or
i

fi

1 M s m

for single ion.

in which = total moles of ion formed during

complete dissociation, m = ionic molality and Ms =
molecular weight of solvent (kg/mol).

Activity and Activity Coefficient,

DEBYE-HUCKEL LAW
- Debye Huckel Law correlates the activity coefficient (fi , i)
with ionic strength (I).
- Forms of Debye-Huckel equations depend
on
concentration of solution and the unit concentration used.
- For dilute solution at 25 oC and I given in molar (M),

log f i 0.51159 z i

log f = 0.51159 z + z - I

for single ion, and

for salt.

- The above equations are known as LIMITING DEBYE

HUCKEL LAW.

The limitation of LIMITING Debye-Huckel Equation

The D-H Limiting Law is called a limiting law
because it becomes increasingly accurate as the limit
of infinite dilution is approached.
Up to concentrations of about 0.01m THE LIMITING
D-H LAW gives reasonable values, but at higher
concentrations

the

calculated

activity

coefficient

become inaccurate (high %error compared to the

values determined experimentally).

 Debye-Huckel Law for Concentrated

Solution
- For concentrated solution (> 0.01 molal), Limiting
Law D-H is modified by considering the ionic size
parameter:
log f

A z z

1 Ba I

- in which A and B are constants that depend on the

kind of solvent and temperature, a = ion size
parameter.
- For aqueous solution at 25 oC, A = 0.51159 and B =
3.2914 x 109 meter.

ACTIVITY AND MEAN ACTIVITY

- Molar activity and molar activity of a single ion i is
determined as follow:
a i i mi
a i f i Ci
and
- For 1 mole of M+A- salt that dissociates to + mol of
Mz+ and - mole of AzM+A- + Mz+ + - Az = + + -

ACTIVITY AND MEAN ACTIVITY

Mean molal activity coefficient can be determined by
the following correlation:

1 /

Mean molality,

m m m

1/

Note that m m
Thus, mean molal activity,

a m

1 /

Exercise: 1
1. Determine the molar activity coefficient of Ca 2+ at 25oC using
relevant Debye Huckel Equation in the following solution:
a. 0.0004 mole of HCl and 0.0002 mole of CaCl 2 in one liter solution
b. 0.004 mole of HCl and 0.002 mole of CaCl 2 in one liter solution
c. 0.4 mole of HCl and 0.2 mole of CaCl 2 in one liter solution
Ion size parameter for Ca2+ = 0.4 nm.

Exercise 2:
2. The stoichiometric mean activity coefficient at 25 oC
of the sulphuric acid in a mixture of 1.5 molal
sodium sulphate (Na2SO4) + 2 molal H2SO4 is
0.1041. If the second dissociation constant, K2, for
sulphuric acid is 0.0102 and the pH of the solution is
0.671, calculate:
a) the molal activity of H2SO4
b) the molal activity of SO42c) the molal activity of HSO4d) the mean activity of H2SO4

Exercise:3
1 gram FeCl2, 1 gram NiCl2 and 1 gram of HCl are added to 200 ml of
deaerated water. Platinum electrodes are used to deliver electrical current so
that the electrolysis performs. The anodic and cathodic current density are
1000 A/m2. The following are the reactions and E o (in the reduction direction)
that may occur:
Fe2+ + 2e = Fe
Eo = -0,277 V
Ni2+ + 2e = Ni
Eo = -0,250 V
2H+ + 2e = H2
Eo = 0 V
Cl2 + 2e = 2ClEo = 1,359 V
a) Calculate molar activity coefficients of the cations and anion
contained
in the solution (use the Finite Size of Debye Huckel Limiting Law)
b)
Calculate the activity of the cations and anion contained in
the
solution
c) Determine the half cell potential of the above reactions
d) Which pair of redox (reduction oxidation reaction) that
would occur
(based on the calculation of c)

Exercise: 3 (cont.)
e) What would be the cell voltage of the reaction d
Data: Atomic weight Fe = 55.8, Ni = 58.7, Cl = 35.5, H =1
Ion size parameter in nm : Fe2+ = Ni2+ = 0.6, H+ = 0.9, Cl- = 0.3
H2 overpotential = 0.28 V
Cl2 overpotential = 0.03 V
Ohmic overpotential = 0.25 V.

Kinetics in Hydrometallurgy
Kinetics in hydrometallurgy deals with the kinetics of
leaching, adsorption and precipitation
Studying of leaching kinetics is done for the establishment
of the rate expression that can be used in design,
optimization and control of metallurgical operations.
The parameters that need to be estabished:
Numerical value of the rate constant
Order of reaction
Rate determining step
Activation energy

Leaching Kinetics
Consider the dissolution of a metal oxide, MO, with
an acid by the following reaction:
MO(s) + 2H+(aq) M2+(aq) + H20(aq)
The reaction rates for this leaching system can be
given by
dCMO
1 dCH+
rR = = dt
2 dt
or
dC 2+ dCH O
M
2
rP =
=
dt
dt

Leaching Kinetics
For general example if a chemical reaction involves A
and B as reactants and C and D as products, the
stoichiometric reaction can be written as follows:
k1

aA + bB cC + dD

(1)

k2

where
a, b, c, and d = stoichiometric coefficients of species A,
B, C, and D, respectively
k1, k2 = reaction coefficients in the forward and
reverse directions, respectively

Leaching Kinetics
The rate expression of this stoichiometric reaction
can be written in a more general way:
1 dC A
1 dCB 1 dCC 1 dCD
= =
=
= k 1CnA CBm - k 2CpCCDq
a dt
b dt
c dt
d dt

(2)

where
CA, CB, Cc, and CD are concentrations of species A, B,
C, and D, respectively and m, n, p, q are orders of
reaction.

Leaching Kinetics
However, if the reaction given in Eq. 1 is irreversible, as in most
leaching systems, Eq. 2 is reduced to the following form:

1 dC A
= k 1CnA CBm
a dt
or

where kdC
1= k
A1 x a. '

dt

= k 1CnA CBm

 For this system, the rate constant, k1', and the orders of
reaction, n and m, should be determined with the aid of
leaching experimental data.
The rate expression given in the above equations can be
further reduced if the reaction is carried out in such a way
that the concentration of A is kept constant.
For such situations, the rate expression is reduced to:

dC A
= k 1CBm
dt
where k1= k1 x CAn. It should be noted that the rate constant
and
the
order
of
reaction
are
constant
as
long as the temperature of the system is maintained
constant.

 Consider the dissolution of zinc in acidic medium:

Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)
For the above reaction, the rate of disappearance of H+
ion is directly related to the rate of appearance of Zn2+ ion;
thus,

dC

Zn2 +

dt

1 dCH+
= k CmZnCHn = kCHn
2 dt

 If concentration of zinc metals is assumed to be constant and CH is further

abbreviated generally as CA, then the equation can be written as follow:

dC
- A = kCnA
dt of reaction, n, can be any real number (0, 1, 2, 1.3, etc.).
The order

When n = 0, the reaction is referred to as zero order with respect to the

concentration of A.

dC A
= kC A 0
dt
CA

Co
A

dC A = C A - C

o
A

= k

dt = -kt

k
where or
CAo X
represents
the concentration of A at t = 0, and XA represents
=
o t
A
CA
the fractional conversion,
i.e., XA = [ (CAo CA)/ CAo].

 If the plot of XA versus t gives a straight line, the zeroorder assumption is consistent with experimental
observations and the k value can be obtained from the
slope of the plot.
XA
k/CAo

time

When n = 1, the reaction is first order with respect to the

concentration of A:
dC A
= kC A
dt

t
dC A

= -k dt = -kt
o
0
C
CA
A
CA

CA
ln o = -kt
CA

ln( 1 - X A ) = - kt or X A = 1 - e -kt

ln (1 - XA)
k

time

For second order reaction,

t
dC A

2 = - k dt = -kt
o
0
C
CA
A
CA

1
1
= -kt
C A CoA
XA
= CoA kt
1 - XA

XA
(1 - XA)

CAok

time

If the second-order assumption is valid, we obtain a

straight line from a plot of XA/(1 - XA) versus t, and the
rate constant can be determined from the slope of the
plot.

Temperature Effect on the Reaction Rate

(Arrhenius Law)
Reaction rate increases markedly with increasing
temperature. It has been found empirically that
temperature affects the rate constant in the manner
shown in the following equation:
k = k o e -Ea / RT
ln k = ln k o -

Ea 1
R T

log k = log k o -

Ea
1
2.303R T

where Ea is the activation energy and k is a constant

known as the frequency factor, frequently assumed to
be independent of temperature.

Modeling of heterogenous reaction

kinetics
Heterogenous
reaction
between
solid
and
fluid
in
hydrometallurgical processes is frequently modelled with
shrinking core model.
If we select a model we must accept its rate equation, and vice
versa.
If a model corresponds closely to what really takes place, then its
rate expression will closely predict and describe the actual
kinetics;
If a model differ widely from reality, then its kinetic expressions
will be useless.
Detailed of modeling and relevant kinetics equations for various
rate determining steps can be found in previous course
(Metallurgical Kinetics).

 For determination of Ea, number of experiments, at least

at three or four different temperatures are needed, with
all other variables being kept constant. The next step is to
calculate the rate constant for each temperature as
discussed previously.
A plot of In k versus 1/T yields a straight line from which
the activation energy, Ea, can be determined
Activation energy value can be used to predict the rate
determining step of the reaction:
Ea = 40 80 kJ/mol: process is controlled by surface chemical
reaction
Ea = 8 20 kJ/mol: process is controlled by diffusion to and from
the surface

Mass Transfer in Solution

For hydrometallurgical system, mass transfer of
component i in solution frequently consists of a
molecular diffusion term, migration term, and convective
diffusion term, as indicated in the following expression:

Ni =

- Di Ci - ziiFCi + Ci V

where
Ni= flux of i, Ci = concentration of i, Di = diffusion coefficient of i
Ci = concentration gradient of i, zi = valence of the specified ion,
i = ionic mobility, F = the Faraday constant, = electrical
potential gradient, and V = net velocity of the fluid of the system

First and Second Ficks Law of Diffusion

If Ni consists of the molecular diffusion term only,
Ni = -Di Ci

(Fick's first law)

Ci
+ Di 2Ci = 0
t

(Fick' s second law )

Dimensionless Parameter for Convection Calculation

LV LV

D i D i

where = the viscosity of the

fluid, = the density of the
fluid

Dimensionless Parameter for

Convection Calculation
The parameter LV/Di is known as the Peclet number and can be
separated into two other parameters: Lv/ that known as the
Reynolds number, and /Di is the Schmidt number.
Peclet number is regarded as a measure of the role of
convection against diffusion,

LV
Ci V
convective diffusion
=
=
D i D i ( C i / L) molecular diffusion
For most hydrometallurgical systems, the Schmidt number is on
the order of 1,000 because the diffusivity of ions and kinematic
viscosity of water are, respectively, on the order of 10 -5 cm2/s
and 10-2 cm2/s.

 Therefore, if the Reynolds number is greater than 10-3,

the Peclet number is greater than 1, and consequently,
convective diffusion is more dominating than molecular
diffusion in such systems.
Mass Transfer Coefficients for Convective Diffusion
For systems with large Peclet numbers, it is frequently
assumed that there is a diffusion boundary layer at some
distance from the solid surface. For such systems, it is
quite common to write the mass flux from the bulk
solution to the solid surface as follows:
Ni = km (Cb - Cs)

where
Ni = mass flux of species i
km = mass transfer coefficient, in cm/s
Cb = concentration of species i in the bulk solution,
mol/cm3
Cs = concentration of species i at the solid surface,

in
in mol/cm3

Because the units of measure of km are the same as those of (D/), where
is the diffusion boundary layer thickness, km, is often substituted by this ratio.
Therefore,

The diffusion boundary layer thickness is often estimated by the

D
relationship
=bD/,
km is known.
)
N i = km( C
- Csprovided

Mass Transfer from or to a Flat Plate.

The mass transfer coefficient for a flat plate where fluid
is flowing over the plate at a velocity V0 has been well
documented.
The mass transfer coefficient for such a system can be
estimated from first principles and has the following form:
1/ 2
2 / 3 -1 / 6 -1 / 2
k
=
0
.
664
D

L
V
0
where m

For Re < 106

D = the diffusivity of the diffusing species

v = the kinematic viscosity of the fluid
L = the length of the plate

Rotating Disk.
Although it is not a practical geometry, because the
mathematical representation of the system is exact and
follows very closely to the experimental data, a rotating
disk is frequently used to determine the mass flux and
the mass transfer coefficient.
The mass transfer coefficient for this system is as follow

k m = 0.62D 2 / 3 -1/ 61/ 2

The equation is valid for the Reynolds number, r 2/ is
less than 105, where r and are, respectively, the radius
and the angular velocity of the disk.

Particulate System
It has been demonstrated that the mass transfer
coefficient for particulate systems can be given by the
following equation:

2D
km =
+ 0.6Vt1/ 2 d -1/ 2 -1/ 6 D 2 / 3
d
where d = the diameter of the particle, Vt = the slip
velocity, which is often assumed to be the terminal
velocity of the specified particle.

 The terminal velocity of a particle can be

calculated using the following equation
depending on the Reynolds number of the
system, which is defined by dVt/, where is
the density of the fluid:
2 r 2 ( s - ) g
Vt =
9

where s is the density of the particle. The

preceding equation is often referred to as the
Stokes' equation and is valid as long as the
Reynolds number is less than 1.

When the Reynolds number is between 1 and

700, the following equations are used:
A
Vt = 10
d
1/ 2
(
)
A = 5.0 0.66 + 0.4 log K - 5.55

4gd 3( s - )
K=
32
where g is the gravitational coefficient.

Example 1:
A cementation reaction, Zn + Cu2+ Cu + Zn2+,
is taking place at the surface of a zinc plate of
10 cm x 10 cm area.
Feed flowing parallel to the plate at a velocity of
1 m/s contains copper at 1 mo/dm 3.
Suppose we want to estimate the rate of
deposition assuming that the mass transfer of
Cu2+ to the zinc plate is rate determining step.
The diffusivity of Cu2+ is 7.2x10-6 cm2/s, and the
kinematic viscosity of water is 0.01 cm 2/s.

1 dN Cu 2+
= k m ( Cu 2b+ - Cu s2+ ) = k m Cu 2b+
S dt
where
S
Ncu2+
Cub2+
Cus2+

= the surface area of the plate

= the number of moles of Cu 2+ ion
= the concentration of Cu2+ in the bulk
= the concentration of CU2+ at the interface

km = 0.664 (7.2 x 10-6)2/3 (0.01)-1/6 (10)-1/2 (100)1/2

= 0.664 x 3.7 x 10-4 x 2.15 x 0.316 x 10
= 1.7 x 10-3 cm/s.

Therefore,

1 dN Cu 2

1.7 10 3 1,000 1.7 mol / cm 2 .s

S dt
and
100 10
Re
105
0.01
Example 2:
Consider the situation from the previous example,
except that instead of a zinc plate, zinc particles 100 m
in diameter are suspended in a 1 mol/dm 3 Cu2+ solution.
Suppose we want to estimate the rate of deposition of
Cu2+ (Note that the density of Zn is 7.14 g/cm 3.)

For particulate,

4 981 0.01 1 7.14 1

K
80.3
4
3 10
1/ 2
A 5 0.66 0.4 log 80.3 5.55 0.412
3

Therefore ,
Vt 100.412 2.58 cm / s

Re 10 2 2.58 / 10 2 2.58

As a result ,
2/3
2 7.2 10 6
km
0.6 2.581/ 2 0.011/ 2 0.011/ 6 7.2 10 6
0.01
1.44 10 3 7.75 10 3

9.19 10 3 cm / s
Finally ,
1 dN Cu 2
km
9.19 10 3 1,000 9.19 mol / cm 2 .s
S dt