KINETICS OF GOLD

DISSOLUTION IN CYANIDE

Fathi Habashi
Department of Mining, Metallurgical and Material Enginnering

Laval University, Quebec City, Canada

Fathi.Habashi@arul.ulaval.ca
• The word cyanide is derived from Greek
“cyanos” meaning blue, because
hydrocyanic acid (blue acid) was obtained
for the first time from Prussian blue
pigment when heated with sulfuric acid.
• The dissolving action of cyanide solution
on metallic gold was known as early as
1783 by the Swedish chemist Carl Wilhelm
Scheele (1742–1786).
• Franz Elsner (1802-1874) in Germany in
1846 studied this reaction and noted that
atmospheric oxygen played an important
role during dissolution.
 John Stewart MacArthur
(1856–1920)

• The application of this

knowledge to extract gold
from its ores was
patented in 1887 in
England by MacArthur.
• German chemist Guido
Bodländer (1855-1904) in
1896 found out that
hydrogen peroxide is
formed during the
reaction.
• Its impact on hydrometallurgy had been
tremendous
- Extremely large reactors known as Dorr
agitators in which the finely ground ore was
agitated with the cyanide leaching agent and
equipped with compressed air injection in the
pulp have been designed and built by the
metallurgical engineer John Dorr.
- Huge filtration plants designed to obtain clear
leach solutions for metals recovery were
similarly constructed.
• The ancient process of cementation which
was applied for precipitating copper from
solution by scrap iron was applied to gold
solutions, iron being replaced by zinc.
• In spite of all these advances in
engineering and the wide application of
the process, the theory still remained
lagging behind.
Stoichiometry of cyanidation:
A) Consumption of cyanide

Observed
Amount of gold
consumption of
Time dissolved Molar ratio
cyanide
[hours] [KCN/Au]
equivalent moles
mg mg
(x 10–3) (x 10–3)
0.5 0.96 4.86 0.62 9.52 1.96
1.0 2.01 10.2 1.26 19.4 1.90
3.0 7.49 38.0 4.94 76.0 2.00
7.0 15.91 80.9 10.50 162.0 2.01
10.0 18.77 95.1 12.46 192.0 2.01
Average 2.0
Stoichiometry of cyanidation:
B) Consumption of oxygen

Time Ag dissolved O2 consumed

[Ag]/[O2]
minutes equivalent (x 10–5) moles (x 10–5)
10 2.96 1.45 2.05
20 7.76 3.07 2.50
30 9.36 4.17 2.25
40 12.42 5.40 2.30
120 36.06 16.00 2.25
Average 2.2
Stoichiometry of cyanidation:
C) Formation of hydrogen peroxide

Metal dissolved H2O2 formed Metal

equiv./moles
equivalent moles
mg mg H2O2
(x 10–5) (x 10–5)
Gold 57.3 29.0 5.11 15.0 1.93
47.6 24.1 4.02 11.8 2.04
Silver 2.96 1.43 2.06
7.76 3.09 2.50
9.36 4.00 2.24
12.42 5.51 2.26
36.06 14.76 2.44
Average 2.3
• For every 1 equivalent of metal dissolved,
2 moles of cyanide are consumed.
• For nearly every 2 equivalents of metal
dissolved, 1 mole of oxygen is consumed.
• For nearly every 2 equivalents of metal
dissolved, 1 mole of H2O2 is produced.
• The dissolution of gold and silver in cyanide
solutions was one of the puzzles that faced
metallurgists for many years for two reasons:
- Gold, the most noble metal that dissolved only
in aqua regia, dissolved readily in a very dilute
solution of sodium cyanide.
- Although gold did not tarnish in air, air was
essential for its dissolution.

[
 Cyanidation is similar to corrosion
• The puzzle was solved when it was
recognized in 1947 that the dissolution of
gold is similar to a corrosion
phenomenon.
• It is an oxidation–reduction process in
which cyanide ion forms a strong complex
with Au+ ion and the reduction of oxygen
on the surface of metal may take place
partially to the hydrogen peroxide stage or
completely to hydroxyl ion
 Demonstration the electrochemical nature of
dissolution of a gold particle in cyanide solution,
1947
• Oxidation: Au → Au+ + e–
Complex formation: Au+ + 2CN– → [Au(CN)2]–
Reduction: O2 + 2H2O + 2e– → H2O2 + 2OH–
O2 + 2H2O + 4e– → 4OH–
• Overall reactions:
2Au + 4CN– + O2 + 2H2O
→ 2[Au(CN)2]– + H2O2 + 2OH–
4Au + 8CN– + O2 + 2H2O → 4[Au(CN)2]– + 4OH–
• The electrochemical nature of this process has
been demonstrated by embedding a small gold
sphere in a KCN gel to which air was introduced
from one direction.
• It was found that the gold corroded at the
surface far away from the air flow, i.e., an
oxygen concentration cell was formed around
the sphere: The surface less exposed to oxygen
acted as anode while the surface in direct
contact with oxygen acted as cathode.
• According to this stoichiometry, 1 gram mole of
oxygen and 4 gram moles of NaCN should be
present in solution.
• At room temperature and at atmospheric pressure,
8.2 mg O2 are dissolved in 1 liter of water. This
corresponds to 0.27 x 10–3 mol/L.
• Accordingly, gold dissolution should occur at a
concentration of NaCN equal to 4 x 0.27 x 10–3 x 49 =
0.05 g/L or 0.005%.
• Thus a very dilute sodium cyanide
solution would be enough for
dissolving gold.
• The fact that oxygen was necessary for
dissolution was not readily recognized
because as seen from the above
calculations, oxygen in solution as a
result of air solubility is enough to
bring about the reaction.
• The explanation of this phenomenon will
be dealt with later.
 Effect of hydrogen ion
concentration
• It is essential that the cyanide solution be kept
alkaline during leaching to prevent the formation
of HCN which is a poisonous gas. Hydrogen
cyanide may form as a result of absorption of
atmospheric CO2:
CO2 + H2O → H2CO3
H2CO3 + CN– → HCN + HCO3–
• High alkalinity, however, decreases the rate of
dissolution.
• The natural pH of a 0.1 % KCN solution is 10.5
due to hydrolysis:
CN– + H2O → HCN + OH–
• The alkalinity of cyanide solutions should,
therefore, be carefully controlled to
achieve high dissolution rates. In practice,
the pH usually ranges from 11 to 12.
• Solutions kept alkaline by Ca(OH)2, when
compared to others at the same pH kept
alkaline with KOH, show a remarkable
retarding effect in the case of lime.
• The retarding effect is supposed to be due to the
formation of calcium peroxide layer on the
surface of the metal which prevents the reaction
with cyanide. Calcium peroxide was considered
to be formed by the reaction of lime with H2O2
accumulating in solution, according to:
• Ca(OH)2 + 2H2O2 → CaO2 + 2H2O
• Lime is one of the reagents commonly used in
industry to adjust the pH of the pulp. Its use
must, therefore, be carefully considered.
 Effect of temperature

• Increasing the
temperature increases
the rate of dissolution.
• On the other hand, the
oxygen content of the
solution decreases with
increasing temperature.
• Therefore, there should
be an optimum
temperature for the
maximum rate.
• This was found to be at
about 85°C
 Effect of agitation

• The rate of dissolution increases with

increased agitation,
 Effect of foreign ions
• Most gold occurs as native metal, nearly all alloyed with
various amounts of silver.
• Certain minerals are characteristically associated with gold,
and the most important are pyrite, galena, zinc blend,
arsenopyrite, stibnite, pyrrhotite, and chalcopyrite.
• Various selenium minerals and magnetite may also be present.
• In Witwatersrand, South Africa, uraninite, and to a lesser
extent, thucholite are associated with the gold ore; uranium is
recovered as a by-product of gold milling.
• Carbonaceous matter is associated with some gold ores. The
most common gangue minerals are quartz, feldspar, micas,
garnet, and calcite.
• Although the gangue minerals are insoluble in cyanide
solution, some metallic minerals are soluble to some extent.
• Carbonaceous matter in gold ore is a source of trouble,
because it adsorbs gold cyanide complex.
• With the exception of a few ions such as Na+,
K+, Cl–, NO3- and SO42- which have no effect on
the rate of dissolution of gold and silver in
cyanide solution, ions may have an accelerating
or a retarding effect.
• Lead(II) ions may have either an accelerating or
a retarding effect, depending on their
concentration in solution.
• The study of the effect of these foreign ions on
cyanidation is complicated because the
dissolution process is composed of two
simultaneous reactions: The oxidation reaction
involving the formation of the auro- or the
argento-cyanide ion and the reduction of oxygen
as mentioned above.
• Which of these reactions is affected by the
foreign ion is usually difficult to say, and
many contradictory statements are found
in the literature.
• Data available were mainly obtained by
studying the effect of foreign ion in the
gold leaf test.
• An approach to this problem is to study the
effect of the foreign ion on the cathodic
and the anodic reactions separately. This
can be achieved by studying the change in
potential-current density characteristics of
the gold (or silver) electrode in two
separate experiments:
• Gold electrode + [Au(CN)2]– + CN– +
foreign ion, oxygen being excluded from
the system.
• Gold electrode + O2 + H2O + foreign ion, in
the absence of cyanide ion.
• In the first experiment, the effect of the foreign
ion on the reduction of oxygen on the gold
surface can be studied, and in the second
experiment, the effect of the same ion on the
anodic reaction of gold dissolution in cyanide.
• The results of such tests should be interpreted
with care, however, as the application of external
emf to cause dissolution does not correspond to
actual cyanidation practice.
• Thus, for example, under these conditions
oxygen is reduced to OH– and not to H2O2.
• Another approach involves the use of
radioactive indicators of the ions being studied
 Accelerating effect

• It has been reported that small amounts of lead, bismuth,

thallium, and mercuric salts accelerate the dissolution.
This was confirmed later by many researchers.
• From calculations of electrode potentials in cyanide
solutions, it was concluded that gold metal can actually
displace the ions of only these four metals.
• It was, therefore, suggested that the rapid dissolution of
gold in the presence of these ions might be due to
alteration in the surface character of gold by alloying with
the displaced metals.
• Early researchers detected the presence of lead on the
surface of gold when the cyanide solution contained Pb2+
ions, but did not identify its nature.
• It was recently
confirmed by
electron
microscopic
studies that lead
alloys with gold on
the surface.
• The alloy then
dissolves rapidly,
hence lead acts as
a catalyst.
• The presence of metallic cations such as Fe2+, Cu2+,
Zn2+, Ni2+, Mn2+, Ca2+, and Ba2+ (the latter two only at
high alkalinity) has a retarding effect.
• Lead(II) plays a unique role in cyanidation, and there
has been much confusion regarding its effect on the
rate of dissolution of gold.
• Besides the accelerating action already described,
some reports describe a retarding effect.
• It can be concluded from those studies that when
Pb2+ is present in very small amounts as compared
to the CN– ion, an accelerating effect is observed,
whereas when the [Pb2+]/[CN–] ratio exceeds a
certain value there is a retarding effect.
• It is also known that the sulfide ion and
certain flotation agents such as xanthate
ion, which is sometimes used to
concentrate the sulfides with which gold is
associated have a retarding effect on the
rate.
 Retarding effect may be due to one or
more of the following reasons:
• Consumption of oxygen from solution
• Consumption of free cyanide from
solution
• Film formation on the surface of the
metal
 Consumption of oxygen from
solution
• Because oxygen is necessary for gold
dissolution, any side reactions in which the
cyanide solution is deprived of its oxygen
content will lead to a decrease in the rate.
• Pyrrhotite accompanying gold in some
ores decomposes in alkaline medium
forming ferrous hydroxide and sulfide ion:
FeS + 2OH– → Fe(OH)2 + S2–
• In presence of oxygen, ferrous hydroxide
is easily oxidized to ferric hydroxide:
2Fe(OH)2 + 1/2O2 + H2O → 2Fe(OH)3
while sulfide ion is partly oxidized to
thiosulfate and polysulfide:
2S2– + 2O2 + H2O → S2O32– + 2OH–
S2– + H2O → HS– + OH–
2HS– + 1/2O2 → S22– + H2O
thus contributing to the depletion of
oxygen from solution.
 Consumption of free cyanide from
solution
• Formation of complex cyanides: Some copper, zinc,
and iron minerals that may be associated with gold
ore dissolve in cyanide solution and therefore
deplete the solution of its cyanide content, e.g.:
ZnS + 4CN– → [Zn(CN)4]2– + S2–
• Formation of thiocyanate: Sulfide ion liberated, when
the ore contains sulfide minerals, reacts with
cyanide and oxygen to form thiocyanate ion, which
has no action on gold:
S2– + CN– + 1/2O2 + H2O → CNS– + 2OH–
• Adsorption on gangue material: Auriferous ores and
concentrates may contain quartz, aluminosilicates,
or other silicates which, if finely divided in an
aqueous alkaline medium, form colloidal silica and
alumina; if iron sulfides are present in the ore, ferric
hydroxide is also formed. These gangue materials
have a strong adsorptive capacity for potassium
cyanide.
 Film formation on the surface of the metal
• Sulfides: The retarding effect of the sulfide ion in the cyanide solution
is well-known. As little as 0.5 ppm of the sulfide ion retards the
dissolution. This cannot be accounted for by the depletion of the
solution of its cyanide or oxygen contents, as the leaching solution
usually contains excess oxygen and excess cyanide. It is believed that
an insoluble aurous sulfide film is formed on the gold, which protects
it from dissolution.
• The effect of sulfide ion on the electrode potential of gold in KCN
solution in the absence of oxygen is negligible, while its effect on the
electrode potential of gold in the absence of KCN but in the presence
of oxygen is great. It appears that the trace sulfide poisons the gold
surface toward the cathodic reduction of oxygen but does not affect
the anodic reaction.
• Peroxides: Calcium ion has no effect on gold dissolution. At pH > 11.5,
however, the rate of dissolution is greatly reduced. At the same pH,
solutions kept alkaline by Ca(OH)2 show a remarkable decrease in the
rate of gold and silver dissolution when compared with others kept
alkaline with KOH. It was suggested that the decrease may be due to
the formation of calcium peroxide on the metal surface, which
prevents the reaction with cyanide. Calcium peroxide was thought to
be formed by the reaction of lime with H2O2 accumulating in solution
according to:
Ca(OH)2 + H2O2 → CaO2 + 2H2O
• It was possible by chemical analysis to identify the precipitate
formed as calcium peroxide. This was confirmed later by
means of X-ray diffraction analysis; Ba(OH)2 behaves similarly.
Lime is one of the reagents commonly used in cyanide mills to
adjust the pH of the pulp and to help settling. Its use must
therefore be carefully considered.
• Oxides: Ozone when added to cyanide solution decreased the
rate of dissolution of gold. Apparently a layer of gold oxide,
which caused a visual change of the gold to brick red,
produced the retarding effect. However, potassium cyanide is
also oxidized by ozone according to:
3KCN + O3 → 3KCNO
• The rate of dissolution decreases with the addition of as little
as 0.4 ppm of potassium ethyl xanthate. When flotation is used
to concentrate the sulfides with which gold is associated, prior
to cyanidation, difficulties are frequently faced. The gold
surface was reported to turn reddish. A gold xanthate film was
probably formed. This was confirmed by using potassium
xanthate marked with S35.
 Gold leaf test
• The accumulation of impurities in solution
retards dissolution. The effectiveness of the
cyanide solution is tested frequently by
measuring the time required for a gold leaf to
dissolve under prescribed conditions of shaking.
• The faster the gold leaf dissolves, the more
effective is the cyanide solution. One way of
minimizing such difficulties is by adding a lead
salt such as lead oxide, nitrate, or acetate.
• This precipitates the sulfide ion as soon as
it is formed in the form of insoluble lead
sulfide. The addition of small amounts of
potassium permanganate also eliminates
this difficulty by oxidizing the sulfide ion to
sulfate.
• Another way is to agitate the ore pulp in an
alkaline medium using Ca(OH)2 to
decompose sulfide minerals, and form
harmless precipitates:
 FeS + 2OH– → Fe(OH)2 + S2–
2Fe(OH)2 + 1/2O2 + H2O → 2Fe(OH)3
S2– + 2O2 → SO42–
SO42– + Ca2+ → CaSO4
• The sulfide-free pulp is then subjected to
cyanidation.
 MECHANISM OF CYANIDATION

• Cyanidation reaction is a heterogeneous

process involving a solid [the ore], a liquid [the
aqueous cyanide solution], and a gas [air or
oxygen].
• A homogeneous process takes place in one
phase only; it can be in a gas phase for
example, the reaction of hydrogen and chlorine
to form HCl, or a liquid phase for example, the
neutralization of an acid by a base.
• Heterogeneous reactions take place between
more than one phase; the surface separating the
phases is called interface at which the reacting
species have to be transferred.
Bonding in Minerals
 The interface
• The interface is the boundary between two
phases.
• For example, in a solid–gas reaction the
interface is the outside surface of the solid
in contact with the gas.
• For two immiscible liquids, the interface is
the surface of contact between the two
liquids.
• For a solid-liquid reaction the interface is
the surface of the solid.
• Lattice defects, non-stoichiometry, and
impurities at the interface influence the
rates of chemical reactions.
• When a product layer is formed on the
reacting solid the kinetics of these
reactions will evidentally be governed by
the character of this coating whether it is
porous or nonporous.
• Only two phases are actually taking part in any
heterogeneous process, although more may be
present in the reaction mixture.
• The reason is that the overall rate of reaction is
determined by the rate of a single step — the
rate-determining step, which is slower than all
others.
• For example, the dissolution of gold (solid) in
sodium cyanide solution (liquid) in presence of
oxygen (gas), the process is reduced to a solid–
liquid reaction since oxygen can be transferred
from the gas phase to the liquid phase at a
faster rate than the other reactions taking place.
 The boundary layer
• A solid in contact with a liquid is covered by a
stagnant film of liquid about 0.03 mm in
thickness called the Nernst boundary layer.
• The existence of this layer is manifested when a
liquid is flowing in a pipe in a streamline flow, the
velocity of the liquid will be maximum at the
center and gradually decreases to zero at the
inside walls.
• This concept was first applied to explain the
dissolution of solids and was later extended to
other heterogeneous reactions such as solid–
gas and liquid–liquid reactions.
Adolf Fick Walther Nernst
• When a solid C is agitated in water and
the solution is analyzed at intervals, it will
be found that the rate of increase of the
solute concentration follows the equation
d C
----------- = k  C  s –  C  
dt
where [C] is the concentration of the solute at time t, [C]s is its
solubility in water at the experimental temperature, i.e., its
concentration at saturation, and k is the velocity constant.
 C t
d C 
 ------------------------- = k dt
 C s –  C 
0 0
C t

 dln   Cs –  C   = k dt
0 0
 Cs
2.303log------------------------
- = kt
 C  s –  C
• The plot of log [C]s/([C]s – [C]) against t
gives a straight line.
• It was therefore suggested that a
saturated layer is rapidly formed at the
interface and that the observed velocity is
the rate at which the solvate molecules
diffuse through this layer into the bulk of
the solution.
 Diffusion

• Diffusion is the tendency of any substance

to spread uniformly throughout the space
available to it.
• It is a result of molecular movement; no
other outside force is influencing the
mixing action.
• It is exhibited by gases, liquids, and solids,
but it is most rapid in gases, and most
slow in solids. Diffusion in gases, liquids,
and solids in governed by Fick’s law.
 Fick’s law
C1
C2

dn dC
= –D A dx
A
dt dX

C2 > C1
• Where dn is the quantity of a dissolved
substance which diffuses in time dt through the
cross-sectional area A, from the direction of high
concentration to that of low concentration, and is
proportional to the concentration gradient in the
direction of diffusion –dC/dX and the cross
section A.
• D is the diffusion coefficient of the substance
and defines the quantity (grams or moles)
diffusing in unit time through a cross section of 1
cm2, when the concentration gradient is unity.
• The concentration must be expressed in the
same units. The diffusion coefficient is usually
expressed in cm2·sec–1.
 Effect of temperature on the diffusion
• The effect of
temperature on the
diffusion in aqueous
solution follows the
Stokes–Einstein RT
equation. D = -----------------
• Where R is the gas 6rN
constant, N is
Avogadro’s number, η
the viscosity of the
medium, and r is the
radius of the diffusing
molecule (supposedly
in the form of a sphere).
 Applying Fick’s law of diffusion to
cyanidation process
• Where n = the number
of species diffusing in
unit time, D = the
diffusion coefficient, A =
dn D A
surface area of the = ---------   C  s –  C 
solid, and  = the dt 
thickness of the
saturated layer adhering
to the surface of the
solid, i.e., the boundary
layer.
 n
• Since  C  = ---
V
where V is the volume of solution, the above equation becomes:

d C  D A
----------- = ----- ---   C  s –  C  
dt V
• Thus, the rate constant k can be identified by
DA/dV. This equation explained the following
observations:
- The rate of dissolution of a solid in water
increased with increased agitation because the
thickness of the boundary layer decreased.
- The rate of dissolution was not influenced by
increased temperature; an activation energy < 5
kcal/mole was usually observed. This is in
agreement with a physical process such as
diffusion.
Types of heterogeneous reactions

• It was first thought that all dissolution processes

were controlled by diffusion.
• But, when many processes were studied and it
was found that in some cases the rates were
independent of stirring and the activation energy
was higher than 5 kcal/mole, it was concluded
that, only physical processes are diffusion-
controlled, but chemical and electrochemical
reactions may be diffusion-controlled, chemically
controlled, or intermediate-controlled reactions.
 Physical processes

• The dissolution of an ionic solid such as

NaCl in water is a typical example.
• A crystal of the salt immersed in a certain
volume of water will be immediately
covered by a thin layer of a saturated
solution of NaCl.
• The ions will then diffuse spontaneously in
water following Fick’s law until the whole
volume of water becomes a saturated
solution.
 Chemical processes

• Consider an ionic or a
covalent solid in form
of a plate of surface
area A in contact with
an aqueous solution
containing a reagent R
that reacts with the
species C dissolving
from the solid.
• At the interface, the
concentration of the
solute will be that of a
saturated solution, [C]s,
and in the bulk of
solution will equal [C].
 Three cases may be considered:

• When the rate of reaction of the reagent with the

dissolving species in the bulk of the solution is very
fast, then the concentration of C will equal zero and
the process will be controlled by the rate of diffusion
of C through the boundary layer.
• When the rate of reaction of the reagent with the
dissolving species in the bulk of the solution is very
slow, then the diffusion does not play any role, and
there will be accumulation of C in solution, i.e., [C] 
[C]s. The rate of reaction will, therefore, depend on
the concentration of the reagent R since [C]s is
constant, i.e., the process is chemically controlled.
• When the rate of reaction of the reagent with the
dissolving species in the bulk of the solution equals
that of the rate of diffusion, then the process is
known as intermediate control.
• Cyanidation is neither a physical nor a
chemical process - - it is an
electrochemical process.
 Electrochemical processes

• This is the case of a metal or a

semiconducting solid which reacts through
an oxidation–reduction process, i.e.,
transfer of electrons.
• The reagent in solution of concentration
[D] diffuses through the boundary layer to
pick up electrons from the interface.
• The symbol D stands for depolarizer, i.e.,
an oxidant.
• The liberated metal ion would hydrolyze
forming insoluble compounds that would
block the anodic zone and the reaction
would stop unless a complexing agent is
present.
• If [D] = the concentration of the
depolarizer, [C] = the concentration of the
complexing agent, A1 = the surface area of
the cathodic zone, A2 = the surface area of
the anodic zone, k1 and k2 are the velocity
constants at the cathodic and the anodic
zones, respectively, then:
 V1 = k1A1[D] and V2 = k2A2[C]
where V1 and V2 are the velocity of the
cathodic and the anodic reactions,
respectively.
• At the steady state, the rate of the
cathodic reaction equals that of the anodic
reaction, i.e.:
k1A1[D] = k2A2[C]
A1 k2 C 
------ = ---------------
A2 k1 D 
 A1 k2 C 
------------------ = ------------------------------------
A1 + A2 k1 D  + k2 C 

A2 k1 D 
------------------ = ------------------------------------
A1 + A2 k1 D  + k2 C 
 Therefore:

k2 C 
A1 = ------------------------------------ A
k1 D  + k2 C 

k1 D 
A2 = ------------------------------------ A
k1 D  + k2 C 
 where A is the total surface area of the
solid in contact with the solution:
A = A1 + A2
• Substituting the value of A1 (or A2) in any
of the rate equations, gives the following:

k1k2A D   C 
Rate of dissolution= ------------------------------------
k1 D  + k2 C
This equation has the following characteristics:
• At low concentration of C, the second term in the
denominator may be neglected in comparison with the
first, and the rate equation simplifies to:
Rate = k2A[C]
• i.e., the rate of dissolution in this case is only a function of
the hydrogen ion or the complexing agent concentration.
• At high concentration of C, the first term in the
denominator may be neglected in comparison with the
second, and the velocity equation simplifies to
Rate = k1A[D]
• i.e., the rate of dissolution under these conditions depends
only on the concentration of the depolarizer.
• When the first and second terms in the
denominator are of equal magnitude, i.e.,
when
k1[D] = k2[C]
then the rate of dissolution reaches its
limiting value, i.e., when the rate curve
changes its direction. This change takes
place at a certain ratio of [C]/[D], as can be
deduced from the equation:
 C k 1
--------- = ----- = Constant
D  k2
• The process was found to be strongly
dependent on the speed of agitation, and
the activation energy to be < 5 kcal/mole
which are the characteristics of a diffusion-
controlled process.
 k1k2A D   C 
Rate of dissolution= ------------------------------------
k1 D  + k2 C
• When –
D –  CN  = 4D O2 O 2
CN
–
 CN  D O2
---------------- = 4-------------
 O2 D –
CN
the rate of dissolution reaches its limiting value.
 D O2 –5 2 –1
= 2.76 × 10 cm sec
and D KCN = 1.83 × 10–5 cm2sec–1

–
 CN 
---------------- = 6
 O2
• Experimental data showed that the rate of gold
dissolution was 3 mg·cm–2·hr–1 in a 0.25%
NaCN solution at atmospheric pressure with
air agitation.
• On using unified units: rate = 4.22 × 10–9
g·equivalent·cm–2·sec–1, [NaCN] = 51 × 10–6
M·mL–1, = 0.21 atm = 0.27 × 10–6 M·mL–1,
then:
4.22 × 10–9
–5 –5 –6 –6
2  1  1.8310  2.7610  5110   0.2710 
= ---------------------------------------------------------------------------------------------------------------------------------
–5 –6 –5 –6
-
  1.8310  5110  + 4  2.7610  0.2710  
–22
13910
= -------------------------------------------------------
–11 –11
-
  9310 + 310 
 = 3.4 × 10 cm
–3
 Other leaching reagents
None so far used on industrial scale

- Thiourea
- Au → Au+ + e–

Au+ + 2(NH2)2CS →
[(H2N)2CS·Au·SC(NH2)2]+

Fe3+ + e– → Fe2+
This takes place in acid medium, is
faster than cyanidation, and less
toxic. However, thiourea undergoes
appreciable decomposition during
leaching.
- Thiosulfate: Na2S2O3
Used in photographic industry to solubilize AgCl
Conducted in basic medium. Copper ion must be
present as catalyst
Au + 5 S2O32– + Cu(NH3)42+ →
Au(S2O3)23– + 4 NH3 + Cu(S2O3)35–
- Thiocyanate:
Acidic medium and
ferric ion as
oxidant.
SUMMARY
REFERENCES
THANKS