Hydrometallurgy, 21 (1989) 67-85 67

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

The Dissolution of Silver in Ferric S u l p h a t e -

Sulphuric Acid Media

R.M. MORRISON
Metallurgical Chemistry Section, CANMET, 555 Booth Street, Ottawa, Ont. K1A OG1 (Canada)

ABSTRACT

Morrison, R.M., 1989. The dissolution of silver in ferric sulphate-sulphuric acid media. Hydro-
metallurgy, 21: 67-85.

The dissolution of silver metal in ferric sulphate-sulphuric acid media was studied using the
rotating disk technique. The effects of ferric ion, ferrous ion, acid, trace chloride ion, and total
sulphate concentration as well as temperature, ionic strength and disk rotation speed on the silver
dissolution rate were determined. The reaction rate is fast although its analysis is complicated by
an apparent non-stoichiometric dissolution. Temperature studies at various ferric concentrations
gave an activation energy of 28 kJ mol- 1and this value is typical of a reaction whose kinetics are
fully or partially mass transport controlled. At ferric ion concentrations below 0.5 M, the rate
depended upon the 0.65 power of the ferric ion concentrations whereas at higher concentrations,
the rate was independent of ferric concentration but still was a function of the disk rotation speed.
The reaction rate was simulated well at the lower ferric ion concentrations by the simple Levich-
type laminar flow model and ferric ion diffusion rate control. Ferrous sulphate additions to the
ferric ion solutions gave rate behaviour consistent with thermodynamic arguments based on the
oxidative buffering effect of the ferric-ferrous couple. Sulphate added as sodium sulphate greatly
reduced the silver dissolution rate but the slow reaction is nearly stoichiometric. Added perchlo-
rate at equivalent ionic strength had no significant effect on the rate.

INTRODUCTION

I n 1980, it was e s t i m a t e d t h a t h a l f of the w e s t e r n w o r l d ' s p r o d u c t i o n of pri-

m a r y silver o r i g i n a t e d as a b y - p r o d u c t of copper, lead a n d zinc p r o d u c t i o n [ 1 ].
T h e m e t h o d s of t r e a t i n g residues for silver recovery a n d m a x i m i z i n g yields in
existing circuits are of c u r r e n t interest. A l t h o u g h silver recovery in t h e p y r o -
metallurgical processes is good, its r e c o v e r y in h y d r o m e t a l l u r g i c a l o p e r a t i o n s
has n o t been fully explored. T h e c h e m i s t r y of silver in r e l e v a n t solutions de-
serves some b a c k g r o u n d study. Studies of silver lixiviation b y ferric ion in acidic
s u l p h a t e a n d chloride solutions are, therefore, i m p o r t a n t . T h e s u l p h a t e s y s t e m
was selected for s t u d y here because t h e c h e m i s t r y is n o t c o m p l i c a t e d b y silver
chloride p r e c i p i t a t i o n a n d chloride c o m p l e x f o r m a t i o n . Silver s u l p h a t e is fairly
68

soluble in sulphuric acid solution [2] and thus deleterious equilibrium precip-
itation phenomena should not present a problem. Dutrizac in related work has
reported on the leaching of silver in chloride media [ 3 ].
Generally, the mineralogy of silver is not simple [4]. The native metal oc-
curs but does not predominate. Other common silver minerals include the chlo-
ride, the sulphide and various sulphosalts. Silver also is a constituent in solid
solution with other minerals such as sphalerite, tetrahedrite and galena. Silver
metal is studied here both because it is common and because it offers a rela-
tively simple system for initial study.
Few reports have dealt with the reaction of silver with ferric solutions. In
1950, Salzberg and King [5] studied the rate of corrosion of silver in ferric
sulphate. This work was done before the widespread use of the atomic absorp-
tion spectroscopy analytical technique which allows the measurement of the
trace concentrations of silver generated in model solutions. The dissolved sil-
ver in the Salzberg and King experiments was found by weighing the corroded
silver material as a function of time. The leaching was done under turbulent
conditions and the interpretation of the results and the breadth of the experi-
mental conditions suggest that the solution hydrodynamics were not well
understood. The reaction rate was shown to be dependent on the rotational
speed, and on the silver, ferric and ferrous ion concentrations.
More recent work by Chen et al. [6] reported on the dissolution of silver in
acidic thiourea solutions using iron (III) as an oxidant. They found that the
silver dissolved quickly and that passivation occurred after an hour of reaction.
The ferric ion reaction in the absence of formamidine disulphide (derived from
thiourea) and ligating thiourea was not studied. A study of the reaction of
ferric ion and silver in the sulphate medium may aid in the interpretation and
understanding of the results of Chen et al.
Dutrizac [3] studied the kinetics of ferric chloride leaching (FeC13-NaC1-
HC1) of silver, antimonian silver and silver chloride over the temperature range
45-95 ° C. Silver is found to be rapidly attacked by the ferric chloride with the
accumulation of AgC1 on the surface; similar behaviour is seen for antimonian
silver. The rate of reaction is controlled by the outward diffusion of the Ag (I)
reaction product and is a function of the disk rotation speed. The linear kinet-
ics of silver and antimonian silver leaching are dominated by the kinetics of
silver chloride dissolution.
The rotating disk technique has been used recently as a method of deter-
mining the kinetics of mineral dissolution; e.g., the dissolution of niccolite in
ferric chloride media [ 7 ]. Its use in the study of leaching reactions allows some
insight into the reaction mechanism. The hydrodynamics of the system are
well understood and thus the rate of appearance and disappearance of reac-
tants and products at the disk surface can be modelled under a variety of con-
ditions. Generally, this technique is most useful for reactions under partial or
full solution mass transport control. The easy adjustment of the disk rotational
 69

speed (w) allows the testing of the w 1/2 vs. rate relationship required for solely
mass transport rate controlled reactions. Any deviation of the reaction rate
from the model behaviour may be used to infer information on the nature of
the rate controlling step. Moreover, the rotating disk system gives reproducible
rate data which can be used for comparative purposes such as the assessment
of the rate dependence of reagent concentrations and the utility of additives.
Thus, along with the theoretical modelling that the rotating disk technique
allows, empirical correlations between the reaction variables and the reaction
rate also can be made. The kinetics of the dissolution of silver metal in various
ferric sulphate-sulphuric acid media as a function of rotation speed, temper-
ature, ferric ion, ferrous ion, and acid concentration are reported here.

EXPERIMENTAL

Fine silver (99.9%) disks of 13 mm diameter were used. The silver disks
were bound in a 38 mm diameter cylindrical block and attached to an acrylic
stirring shaft. The disk surface was polished to a mirror finish with 1.0 ~m
alumina prior to leaching.
The leaching apparatus and chemicals were the same as described previously
[ 7 ]. Silver and total iron were determined by atomic absorption spectroscopy
and ferrous ion was determined by dichromate titration.

RESULTS AND DISCUSSION

Reaction

The reaction between ferric ion and metallic silver can be formulated ideally
as:

Fe 3+ (aq) +Ag-mAg+ (aq) + F e 2+ (aq) (1)

Silver normally does not form higher valency compounds under the conditions
studied here [8]. The standard free energy for reaction 1 at 25°C with unit
activities of reactants and products in a sulphate system is approximately zero
[9].
Unit activities for reactants and products were not maintained as a predom-
inant part of this experimental study but some observations on the concentra-
tion of reagents used can be made. The ferric ion concentrations were not buff-
ered by ferrous ion additions to maintain constant oxidizing power; the
experimental results, a linear relationship between soluble silver concentra-
tion and time (Fig. 1 ), indicate that essentially the same conditions applied
throughout the leaching period. Soluble silver usually does not build up to high
levels in leach systems sand thus high activities of silver are not a concern. As
70

seen from the leaching curves (Fig. 1), silver levels up to 150 mg 1-1 do not
influence the shape of the leaching curve.
The Nernst equation (see Eq. 3 and 5) can be used to calculate the ther-
modynamic driving force of the respective half-cell reactions in the presence
of different concentrations or activities of reactants and products. The simpli-
fying assumption that the concentration is equal to activity is used in the cal-
culations. For the half-cell reaction 2, the standard potential [9] in 0.5 M
H2SO 4 is 0.679 volts (V):

Fe '~3+(aq) + e--mFe 2+ (aq) (2)

In the absence of added ferrous ion (nominally I mg 1-~) and 50 mg 1-1

ferrous ion, the calculated potentials from Eq. 3:

E=E°+ (RT/nF) In ( [ F e 3 + ] / [ F e 2 + ] ) (3)

(assuming 0.2 M Fe ~+ ) are 0.93 and 0.82 V ( - 90 and - 79 kJ m o l - 1), respec-
tively. The half-cell reaction of silver metal oxidizing in sulphate media is given
by reaction 4:

Ag + (aq) + e - -mAg(s) (4)

assuming a standard potential of 0.653 V [9], the reduction potentials in the

absence of soluble silver (nominally 1 mg 1-1) and in the presence of 100 mg
l - 1 Ag + are 0.35 and 0.47 V ( - 84 and - 46 kJ m o l - 1), respectively, using Eq.
5:

E=E°+RT/nFln ([Ag+ ] ) (5)

The driving force of the coupled reactions in 0.25 M Fe 3+ is 0.58 V ( - 5 6 kJ
m o l - 1) in the presence of 50 mg l - 1 of ferrous ion and 100 mg l - 1 of silver ion.
Since it is often found empirically that a driving force > 0.30 V indicates that
a reaction will be under diffusion control as compared to activation control
[ 10 ], diffusion controlled kinetics might be expected under the conditions stated
above if thermodynamic rather than kinetic factors are dominant.
Figure 1 shows the silver concentration as a function of time for various
rotation speeds for silver disks leached in 0.25 M Fe3+-0.15 M H2SO4. As il-
lustrated, the silver concentration increases linearly with time and the rate of
dissolution varies with the rotation speed. The straight line leaching charac-
teristics indicate that the small ferric ion depletion and silver ion accumulation
probably do not influence the reaction rate. The dependence of the rate on o~
indicates that solution mass transport is probably involved in the rate deter-
mining step. The magnitude of the rates of silver dissolution agrees well with
the ferric ion fluxes, and this suggests that the transport of ferric ion is rate
limiting. The interrelationships of the rotation speed with the reaction rate
 71

200
• 6 0 min -~
A 200 "
o 350 "
13 1000 "
E lO0-

o.z5 0.50 o.z5 L.oo ,25 ,.5o .z5 z.o

TIME ( h }

Fig. 1, Plot of soluble silver against time ( T = 4 0 ° C ; [Fe :~+ ] =0.25 M a n d [H2SO4] =0.15 3/I) for
various disk rotation speeds.

and other experimental conditions will be discussed later. The reaction stoi-
chiometry observed in the experiments, however, differed from the ideal case
typified by reaction 1.

Reaction stoichiometry

Although the appearance of soluble silver is proportional to time, the soluble

silver to ferrous ion ratio in the final solution is not as given in reaction 1. The
soluble silver is always less than the value predicted from the ferric ion reduced
to ferrous ion. Figure 2 shows the molar ratio of [Fe 2+ ] to rAg + ] for a variety
of leaching tests plotted against the final silver concentration. It should be
noted that the ferrous ion determinations at low concentrations are subject to
error and the resultant scatter at low silver concentrations in Fig. 2 probably
reflects this fact. The average value of the [Fe 2+ ] / r A g + ] is 1.3 ( + 0.2) and

2ot
i
* i
.s.
• t.'-''.% " •
• 0•0 • •
1.0

I l I
0.I00 0.200 0.300
SILVER IN SOLUTION ( g !. I)

Fig. 2. Plot of the ferrous/soluble silver ratio as a function of soluble silver concentration.
72

this demonstrates that only ~ 80% of the oxidized silver is solubilized. Sup-
posedly, the remaining oxidized silver is not released from the surface.
Other samples of non-ideal silver dissolution in sulphate media have been
observed. Warren et al. [ 11 ] in their study of the anodic dissolution of silver
sulphide electrodes noted that solid Ag2SO4 formed on the surface although
the experimental conditions were well removed from Ag2SO4 saturation. Other
workers have observed less than 100% current efficiency for the anodic disso-
lution of silver in sulphate media [12,13]. Clearly, the relationship of silver
sulphate solubility, silver precipitation and perhaps silver redissolution under
dynamic oxidizing conditions such as ferric ion leaching or anodic dissolution
in sulphate solutions is important.
Another possibility in this ferric leaching system is silver jarosite formation.
The basic salts of ferric sulphate (AgFe3 (OH) 6 ($O4) 2 in this case ) are insol-
uble in acidic sulphate solutions [ 14 ]. Although higher temperatures favor its
precipitation, silver jarosite probably can be obtained under less severe con-
ditions and in nearly invisible amounts which might hinder the dissolution
kinetics. The behavior of this phase might be indistinguishable from that of
the saturated silver sulphate solutions just described.
The presence of chloride in solution could result in the precipitation of AgC1
on the silver disk surface and could give the apparent non-stoichiometric dis-
solution. Some tests were performed where a small concentration of NaC1 was
added to the leach solutions to demonstrate the effect of the chloride ion on
the leaching curves and these curves are illustrated in Fig. 3. For the 600 mg
l - 1 chloride solutions, the silver concentration was constant at 2 mg l- 1. At 60
mg l-1 chloride, the concentration results were very erratic; there was a sus-

60 C I- Added /

40 .

20 • " 6 0 mq ~ '

./ °~ °

/" / ,k
6oom~,
h ,k
c'
h h A
0.25 0.50 O.75 1.00 1.25 1.50 1.75 2.00
TIME ( h )
Fig. 3. Effect of trace chloride concentrations on the leaching curves of silver in ferric sulphate
media.
 73

pension of AgC1 in the leaching vessel indicating that the dissolution was fol-
lowed by a precipitation phenomenon. At 6 mg l - 1 chloride, the leaching curve
was similar to that obtained in the absence of chloride except that there was
an apparent induction period of 0.5 h when little silver was dissolved. Gener-
ally, however, the effects of gross chloride contamination were not observed in
the ferric sulphate leaching of silver. In fact, some difficulties were encoun-
tered with one batch of ferric sulphate reagent which gave results similar to
the 6 mg l- ~chloride test; this reagent was considered impure and was rejected
for that reason.
After leaching in sulphate media, the surface of the silver disk was matted
white. No identification of the leached surface was attempted. It is not unusual
for a mineral surface to appear different from the original, but such surfaces
generally have no effect on the stoichiometry of the reaction as determined
from the solution analyses. In this leaching system, the solution analyses in-
dicate that the solid phase may contain appreciable amounts of oxidized but
insoluble silver. This conclusion may be important because the solid material
on the disk may eventually hinder the kinetics of the dissolution reaction. In
addition, the formation of a solid phase may be a consequence of the energetics
of the silver metal-oxidized silver surface that is an unknown factor in the
energy calculations previously described.

T H E E F F E C T OF T E M P E R A T U R E ON T H E R A T E OF D I S S O L U T I O N

Figure 4 shows the log r vs. 1/Tplot for silver dissolution in the 0.25 M F e 3+-
0.15 M H2S04 medium. The apparent activation energy is 28 kJ tool -1 (7 kcal

3.6

3.4

3.2

~ 3.0 \:
2.8

2.6 ,\
2.4
I I I I I I 1 i
2.7 2.8 2.9 3.0 3.1 :3.2 3.3 3.4
IO]l/T (in K "1 )

Fig. 4. Plot of log r against the inverse of temperature for [ Fe 3+ ] = 0.25 M, [ H 2 S 0 4 ] = 0.15 M and
200 m i n - 1.
74

TABLE 1

Apparent activation energies for the dissolution of silver disks in various ferric ion concentrations
(200 min-1; H2S04=0.15 M)

[Fe 3+ ] AH
(M) (kJ/mol)

0.1 26.6
0.25 28.0
0.5 31.9
1.0 20.6

m o l - 1 ), and this is indicative of a diffusion controlled mechanism or a mixed

activation-diffusion controlled reaction. The temperature dependence of the
reaction rate was studied at a variety of ferric ion concentrations at 200 m i n - 1
and the results are presented in Table 1. There is no variation of the apparent
activation energy over the entire range of ferric ion concentrations (the ferric
ion dependence of the rate is depicted in Fig. 7).

T H E E F F E C T OF ROTATION SPEED ON T H E RATE

The reaction rate, as measured by the appearance of soluble silver, varies

with the rotation speed of the disk (Fig. 1 ). If the rate is under solution mass
transport control, the rate of reaction should be related to the flux ( J ) of the
rate controlling species calculated from the Levich equation under conditions
of laminar flow [15]. Equation 6 shows the form of the relationship for the
flux of ferric ion:
JFe:~+ ----0.62D e/a v - 1/6(2) 1/2 ( CB _ Cs ) (6)

where: D is the diffusion coefficient (m 2 s -1 ), v is the kinematic viscosity (in

m 2 s - l ), (2) is the angular velocity of the disk (in radians s - 1) and Cu and Cs
are the bulk and surface concentrations (in g m -a) of the diffusing species. In
a diffusion controlled reaction, the value of Cs is equated to zero since the
reaction rate at the surface is much faster than the rate of diffusion; this as-
sumption simplifies the Levich equation 7:
Jre3 + = 0.62D 2/a v - 1/6(/)1/2 ( CB ) (7)

The value of D derived for 40 °C using the datum at 25 °C (4.55 × 10-lo [16],
and assuming an activation energy of 28 kJ tool- 1 ) was 7.3 × 10- lO m 2 s - 1. The
kinematic viscosity derived from the viscosity of water [9] and the calculated
density of the solution was 0.653 × 10 -6 m 2 s-1. The relationship:
r = (107 × 9/55 × 85)Jfe3+ (8)
was used to equate the ferric ion flux to the equivalent silver ion dissolution
 75

for the ideal reaction 1. The predicted rate for the 0.25 M Fe3+-0.15 M H2SO4
case is shown in Fig. 5 along with the experimental values. It is seen clearly
that the predicted rates are higher t h a n the experimental rates and the inclu-
sion of an 80% dissolution efficiency factor does not significantly improve the
match of predicted to observed behaviour. The comparison of the magnitude
of the rates predicted by the ferric ion diffusion and by the nature of the ferric
concentration-rate functional relationship indicates, however, that ferric ion
transport is at least partially rate determining.
If the rate of diffusion of ferric ion to the surface is greater t h a n the rate of
reaction of the ferric ion at the surface, then the assumption that Cs = 0 is not
valid. The predicted rate would have to be modified by a factor equal to
(CB-Cs)/CB(= C") to compensate for the slowness of the surface reaction
compared to the diffusion step (cf. Eq. 6 and 7). It is difficult to assign a value
to Cs; thus, it is necessary to derive a value from the experimental rate by
dividing it by the nominal ferric ion concentration. If the surface concentration
were zero, this parameter would be equal to 0.62 D 2/3 v - 1/~ ( = 9.0 at 200 m i n - ' );
i.e., C" = 1. Table 2 shows the factors calculated at 200 m i n - 1 from the least-
squares t r e a t m e n t of the rotational speed dependence data. The calculated
factors are all less than 9.0 as expected, and with the largest ones (lowest sur-
face concentration; i.e., C" closest to unity) at the lowest reactant levels. These
C" values correlate with the ratio of the observed rate to theoretical rate i.e.,
the observed rates vary from 80% (0.01 M Fe :3+ ) to 9% (1.0 M Fe 3+ ) of the
theoretical values. Thus, results at the lower reagent concentrations were bet-
ter simulated by the simple Levich model than the results at the higher reagent
concentrations. This may indicate the effect of the formation of a slowly dis-

2000-- Calculated from/ /Corrected for

Levich equation/" ~non- stoichiometry •

I000 --

• ~ / •ill

J, , i i I I i I l I
0 5.0 I0.0
~½ IS i )
Fig. 5. Plot of rate (r) vs. o) li2 for [Fe 3+ ] =0.25 M, T = 4 0 ° C and [H2SO4] =0.15 M.
76

TABLE 2

Results of surface concentration factor calculations at 200 min- 1

[Fe3+ ] Rate of silver Calculated equivalent Factorb (CB-Cs)/(C~)

(M) dissolution ferric fluxa
(gm-2h - ' ) (gm-2h -1)
0.01 80 40 7.2 0.80
0.1 400 210 3.8 0.42
0.25 640 330 2.4 0.27
0.5 860 450 1.6 0.18
1.0 910 470 0.8 0.09
[H2SO4] =0.15 M; T=40°C.
/55.85~

~'Calculated ferric flux/nominal ferric concentration = 0.62 o) '/21.,'- 1/~D 2/~ ( CB -- Cs ) / CB" If Cs = 0
then the ferric flux/nominal ferric concentration=0.62 w ' / e v - 1 / G D 2 / 3 = 9 . 0 g m -2 h -1 at 200
min -~, T=40°C.

solving layer t h a t increases with i n c r e a s i n g rate of ferric reaction. O n e conclu-

sion t h a t can be r e a c h e d is t h a t this layer is n o n - p a s s i v a t i n g since t h e overall
rate is similar in m a g n i t u d e to t h e p r e d i c t e d diffusion limited rate.

THE EFFECT OF FERRIC ION CONCENTRATION ON THE RATE

Figure 6 shows the effect of ferric ion c o n c e n t r a t i o n on t h e rate of silver

leaching at 4 0 ° C a n d 200 m i n -1. I n t h e c o n c e n t r a t i o n range greater t h a n 0.5
M Fe 3+, the rate is insensitive to i n c r e a s i n g ferric ion c o n c e n t r a t i o n s a l t h o u g h
still d e p e n d e n t u p o n o). T h e limiting rate of r e a c t i o n above 0.5 M Fe ~+ at 200

5.0 I

o
S 2.0

_1 I I
-2.0 -I.0 0 1.0
LOG [ Fe 3+ ]
Fig. 6. Plot of log r vs. log [Fe3+ ] at T=40°C and [H2SO4] =0.15 M.
 77

m i n - ' , 0°C and 0.15 M H 2 S O 4 w a s approximately 900 g m -2 h -1. The molar

ratio of ferrous ion to silver ion was greater than unity in all cases.
At lower ferric ion concentrations, the reaction rate is dependent upon the
0.65 power of the ferric concentration whereas in an ideal mass transport re-
action, the rate would be related to the first power of the concentration. Cou-
pling this observation with the reaction rate-ferric flux relationship and the
non-stoichiometric dissolution of the silver, the reaction does not conform to
the simple diffusion model completely. The only conclusion that can be reached
is that ferric ion diffusion is at least partially rate controlling at the lower ferric
ion concentrations.
The rotation speed dependence of the silver dissolution rate at 0.5 M Fe 3+
and 1.0 M Fe 3+ indicates that liquid phase diffusion control is still operative
under these conditions although the rate is insensitive to ferric ion concentra-
tion. The analysis of the rotation speed dependence shows there is less agree-
ment with the simple ferric ion diffusion model with increasing ferric concen-
tration using the least-squares data fitting at 200 m i n - 1. This implies that the
same factors apply over the whole range of concentrations but that the inhib-
iting aspect is more important at higher concentrations. There are four factors
which could give no rate increase with increasing ferric ion concentration: (i)
the rate of layer formation increases with ferric sulphate concentration and
reaction rate; (ii) the rate of silver ion diffusion becomes comparable to the
inward flux of ferric ion; (iii) the outward diffusion of ferrous ion produced by
the reaction becomes rate limiting; or (iv) there is a coupled activation-dif-
fusion process where the activation process is ferric ion dependent.
Surface layer effects Can be inferred from the diffusion of low concentrations
of silver ions (200 times lower in concentration than the ferric ions), and would
have a great inhibiting effect although the solid state diffusion of the silver ion
in the solid phase formed also may be involved. The effect of ferrous ion is,
explored later. One possibility for a clear definition of the kinetics is to consider
the presence of coupled diffusion-activation reaction rate control.

MODEL OF ACTIVATION-DIFFUSIONRATECONTROL

MacDonald and Owen [ 17 ] have studied the dissolution of magnesium sul-

phate in dilute sulphuric acid where a diffusion-activation coupled reaction
rate dependence was observed. These authors derived an expression for the
rate constant (k):

k--kTkca/ ( kT + kca ) (9)

where k T and kc are the rate constants for the transport (diffusion) and chem-
ical activation reaction, respectively, and a is a roughness factor. Analysis of
the kinetic data can be made by the use of the expression:
78

k-l= ( akc) - l + l.613D - 2/3v-1/%) -1/2 (10)

The plot of the reciprocal of the observed rate constant, k - 1, vs. the reciprocal
of the square root of the rotational speed should give a slope of 1.613 D-2/3
v - 1/~ and an intercept of ( a k c ) - 1. The activation rate constant can be obtained
from the intercept. It should be noted that similar arguments for current mea-
surements for electrochemical reactions under activation-diffusion control have
been advanced by Gileadi et al. [18].
The model for the reaction of ferric ion with silver metal can be formulated
as consisting of a number of steps: (1) the transport of oxidant to the surface;
(2) the reaction of the oxidant with the substrate; (3) the separation of the
oxidized substrate from the surface; (4) the transport of the reduced oxidant
from the surface; and (5) the transport of the oxidized substrate from the
surface. If steps 1, 4 and 5 are rate controlling, the reaction rate is dependent
upon ~o. The fact that the mass transport model does not fit the experimental
results suggests that steps 2 or 3 have some effect on the kinetics. The derived
activation rate constant may give some information on this surface reaction.
The r - 1 vs. (o - 1/2 data for the 0.01, 0.1, 0.2, 0.5, and 1.0 M Fe 3+ solutions at
various rotation speeds were analyzed to give the intercepts at ~o - i/2 = 0 (des-
ignated r~ 1 ) which are tabulated in Table 3. The values obtained are negative
numbers and their absolute values are plotted against the logarithm of the
ferric ion concentration in Fig. 7. There appears to be no good correlation of
the intercept with the ferric concentration. It should be noted that the inter-
cept values are very small and the resultant calculated rint values are large and
consequently large relative errors are incurred in their derivation. The nega-
tive values for the intercepts also are difficult to rationalize physically. The
activation-diffusion model does not describe the kinetics of the system; and
this is perhaps not surprising given the complicated chemistry and the ther-
modynamic prediction of a diffusion-controlled reaction.
The simulation of the silver dissolution reaction kinetics by the rotating disk
models has not been entirely successful, particularly the coupled activation-

TABLE3

D a t a from d i f f u s i o n - a c t i v a t i o n control calculations

I n t e r c e p t of [Fe :~+ ] rin t

r-lvs, o)-l/2: ( r - l ) i n t added (g m - 2 h - l )
( g - ~m2 h) (M)

- 0.008 1.0 - 125.0

-0.013 0.5 -77
-0.018 0.25 -56
-0.012 0.1 --83
-0.5 0.01 -2
 79

2O
I I
..C

o I0

c_
t.

0
-2.0 - 1.0 0.0
LOG [ Fe~* 1
Fig. 7. Plot of [rintl against log [Fe 3+ ] (T=40°C and [H2S04] =0.15 M).

diffusion model. It is apparent, however, that ferric ion diffusion is at least

partially involved in the rate determining step. Some further reaction condi-
tions (acid concentration, ferrous ion additions, total sulphate and ionic
strength) were tested under two ferric ion regimes (less and greater than 0.5
M) to attempt to differentiate the mechanisms in the two regions.

THE EFFECT OF ACID CONCENTRATIONON THE RATE

The acid dependence of the rate of silver dissolution at 0.3 M Fe 3+ and 1.0
M Fe 3+ was examined. The two sulphuric acid concentrations of 0.15 M and
1.0 M H2SO4 did not give appreciable variance at either ferric concentration.

THE EFFECT OF FERROUS ION CONCENTRATION ON THE RATE OF SILVER

DISSOLUTION IN FERRIC SOLUTIONS

The effect of ferrous ion concentration also was studied at two ferric ion
levels under standard conditions (200 min-1, 0.15 M H2S04, 40 °C ). The effect
of ferrous ion concentration on the completeness of silver dissolution cannot
be measured because of the difficulty of determining small amounts of ferrous
ion reaction product against the large ferrous background. Figure 8 shows the
relationship between the rate and the calculated solution potential for the fer-
ric/ferrous couple (Eq. 3) where the standard potential [9] is 0.679 V. The
curves for the two ferric ion concentrations follow the same contour. At low
ferrous concentrations (higher calculated potentials), the rates are high and
do not change significantly with the apparent calculated potential. By con-
trast, at higher ferrous concentrations (low calculated potentials), the rates
are lower and change more significantly with apparent calculated solution po-
80

~e ~
100- • 0.3M
&
• 1.0 M ~-~
.~
80- &//"
A/
N /

~- 4 0 - -

20-

I / [ I I
0.650 0.700 0.750 0.800
CALCULATED SOLUTION POTENTIAL (Volts v$ NHE )
Fig. 8. Plot of the rate of reaction for Fe 3+ = 0.3 and 1.0 M vs. the calculated reversible potential
of the ferric-ferrous medium ( T = 4 0 ° C ; 200 r a i n - l ; [H2SO4] =0.15 M ) .

tential. It is interesting to note that both ferric concentrations exhibit the same
behaviour towards ferrous ion additions suggesting the overall dissolution
mechanism to be the same in both cases.
As mentioned previously, electrochemical reactions are likely to be mass
transport controlled when the overvoltage is greater than 0.3 V. The calculated
potential of reaction 4 at 100 mg 1-1 Ag + using Eq. 5 is 0.47 V; the maximum
and minimum calculated solution potentials of Fe3+/Fe 2+ studied here are
0.82 and 0.67 V, respectively. From the simplistic thermodynamic analysis, it
would be expected that there would be diffusion control at the lower ferrous
concentrations because the calculated potential difference is 0.3 V or greater.
Coupled activation-diffusion control might be expected at high ferrous con-
centrations. Although the variation of the rate with the calculated potential is
as expected, the non-stoichiometric dissolution, the non-integral rate depen-
dence on the ferric ion concentration and the failure of the model to predict
the absolute rate precisely suggest that simple diffusion control is not an exact
model for the reaction system.

E F F E C T OF S U L P H A T E C O N C E N T R A T I O N ON T H E SILVER D I S S O L U T I O N RATE

The effect of sulphate concentration (as Na2SO4) on the leaching charac-

teristics of silver in 0.3 M Fe 3+- 0.15 M H2SO4 solution at T = 4 0 ° C and 200
m i n - 1 was studied. Table 4 shows the depressing effect of added sulphate on
the rate of silver leaching. This effect is not due to ionic strength effects be-
cause similar additions on non-sulphate salt (0.1 M and 0.25 M Mg(C104)2)
to a similar solution had no effect on the rate (Table 5). Figure 9 shows the
plot of log (r) vs. the log (sulphate concentration added) (the datum at
[Na2SO4] =0.0 is not plotted). At the higher sulphate levels (0.25 M and
 81

TABLE 4

The effect of sodium sulphate concentration on the silver dissolution rate

Na2S04 Rate of silver

added dissolution r
(M) (g m-2 h -1 )
0.0 740
0.025 630
0.1 590
0.25 520
0.5 390
1.0 310

TABLE 5

Silver dissolution rates at various magnesium perchlorate concentrations

Mg (Cl04) 2 Rate of silver

added dissolution r
(M) ( g m - 2 h -1)

0.0 740
0.1 700
0.25 710
0.5 660

[Fe3+ ] =0.3 M; [H2S04] =0.15 M; 200 min-1; T=40°C.

3.0 I I I

2.0
-J

I I I
- 2.0 - 1.0 0 i.o
• oG { [ ~ , s o . ] Aooco ]
Fig. 9. Plot of log r against the log (Na2S04 added).
82

above ), the rate is related to sulphate by: (where r is in g m - 2 h - 1and [ Na2S04 ]

is molar)
log r = A + B log [Na2SO4] (11)
where A -- 2.49 and B -- - 0.38.
The ferric-ferrous sulphate-sulphuric acid system has m a n y complex equi-
libria [ 19 ] which can change the dominant solution species with the increasing
sulphate concentration. The nature of the ferric-ferrous species, the soluble
silver compounds and the precipitation phenomena can be altered. It is diffi-
cult, however, to speculate on the exact cause of the lowered rate with increas-
ing sulphate.
The addition of sulphate might be expected to have some effect on the com-
pleteness of the reaction. In fact, the high sulphate tests gave almost stoichi-
ometric ferrous-silver ratios. It can be speculated that the slower reaction rates
give more ideal dissolution behaviour because the conditions are more nearly
reversible (i.e., slower and thus under near equilibrium conditions). And the
non-solubilized silver formation may be prevented because the silver dissolves
at the same rate as it is oxidized, and the metastable surface phase is not formed.

DISCUSSION

Under the conditions used in this investigation, silver displays some unusual
characteristics. The variation of the rate with disk rotational speed and ferric
ion concentration suggests that the reaction is facile. The ferrous ion concen-
trations exert the influence that might be expected from equilibrium argu-
ments. The residue of silver left on the disk is totally unexpected from the
solubility data but similar phenomena have been reported in the literature.
Whether this residue is due to a disequilibrium phenomenon or the slow dis-
solution of a presently uncharacterized intermediate phase is unknown.
The earlier work of Salzberg and King [5] did not measure soluble silver
and they could not have drawn the same conclusions obtained here. There is
fundamental agreement with the thiourea-free ferric ion leaching work of Chen
et al. [6] with respect to reaction rates. There is more work to be done on this
system. The means of attaining complete dissolution, the origin or mechanism
of the layer formed on the silver disk and extensions of this work to other anion
systems such as chloride (see Dutrizac [3] ) are relevant research topics.
The interpretation of the results must include the completeness of the re-
action and the rate of reaction. It is likely that reaction of silver at the surface
does not release all the oxidized silver and is not adequately described by re-
action 1. An alternate expression is reaction 14:
Fe 3+ (aq) ÷ 2Ag(s) ~ F e 2+ (aq) ÷ 0.8Ag + (aq) ÷ (0.2Ag + )Ag(s) (14)
 83

where (0.2Ag + ) Ag represents the oxidized silver remaining on the disk. The
reaction rate is fast and is partially controlled by ferric ion diffusion to the
surface. The rate of reaction is not greatly slowed by the presence of the oxi-
dized silver material on the disk. Table 2 indicates that the experimental rates
are 9-80% of the theoretical based on diffusion control of various ferric ion
concentrations. This indicates that the layer may be porous.
Although complex, the silver-ferric reaction in sulphate media can be ra-
tionalized in terms of thermodynamics, mass transport and some form of poorly
soluble silver phase formation. As was discussed briefly, the presence of trace
chloride ion had an effect on the leaching kinetics due to AgC1 formation and
passivation.
Dutrizac [3] has shown that the AgCl dissolution rate dominates the kinet-
ics of silver oxidation in FeCI~-NaC1-HC1 media. At 200 min-1, 80 ° C, 0.3 M
FeC13, 0.3 M NaC1, and 3.0 M HC1, the silver dissolution rate is approximately
150 g m -2 h -1 (Ref. [3], Fig. 8). In similar sulphate solutions at 200 min -1,
80°C, 0.25 M Fe 3+, 0.25 M H2SO4, the rate is 2300 g m -2 h -1. The apparent
activation energies determined in the chloride and sulphate media above are
37.1 and 28.0 kJ mol- 1, respectively. Although both media show diffusion con-
trolled activation energies, the silver dissolves faster in sulphate than in chlo-
ride media (15 times, in this example). The advantage of chloride is that it
gives more reproducible silver deportment in commercial solutions. Silver is
less noble in chloride than in sulphate media, and this means that the soluble
silver is more stable in a chloride than in a sulphate medium. This soluble
oxidized silver is less likely to be reactive and to precipitate from chloride
solution.
There are ramifications of these results concerning other hydrometallurgical
systems. A dynamic model of silver deportment in sulphate systems can be
envisioned: an initial lixiviation reaction releases silver as a soluble species.
Reaction with a reactive sulphide produces a liberated base metal ion and ce-
mented silver sulphide, with the silver sulphide reacting with an oxidizing agent
such as ferric ion to form soluble silver again. If the silver metal dissolves at
only 80-90% efficiency leaving behind insoluble compounds, there will be a net
loss of recoverable silver. If this scenario is correct for commercial systems,
silver chloride precipitation is not the only aspect of silver chemistry impor-
tant to enhanced silver recovery. The identification of the silver phase or
chemistry which causes this phenomenon should be established. MacKinnon
and Brannen [20] have shown silver precipitation on some sulphides in ferric
solution and there also is some cyclic behaviour between precipitation and
redissolution. Beutier et al. [21] have shown that metallic silver can cement
onto some mineral surfaces.
It is interesting to note that in the high sulphate media, the ferrous-soluble
silver ratio is nearer to unity than in lower ferrous sulphate media. If the re-
action proceeds quickly, the kinetics of dissolution are such that there is a local
84

supersaturation or precipitation of the metastable phase. If the leaching reac-

tion is slow, however, the equilibrium conditions are maintained (the reaction
is more reversible) and more ideal complete dissolution is attained. During
leaching under high ferrous sulphate conditions, the silver may leach more
slowly but more completely.

CONCLUSIONS

The study of the kinetics of silver metal dissolution in ferric sulphate-sul-

phuric acid media has shown that the kinetics are fast and largely controlled
by solution mass transport. The observed rates are similar to those from a
simple ferric ion diffusion control model. The analysis of the data has shown,
however, that the reaction system is not completely predicted by thermody-
namics and simple electrochemical half-cell reactions. The non-stoichiometric
dissolution, the non-integral dependence of the rate on lower ferric ion con-
centrations and experimental rates lower than those predicted by simple lam-
inar flow rotating disk calculations show the complexity of the reaction.
The activation energies of 28 kJ mo1-1 over the studied range of ferric con-
centrations, and the fact that the energy calculations and the ferrous sulphate
addition results are consistent with thermodynamic arguments indicate that
the reaction system is a perturbation of the simple diffusion controlled reac-
tion. Although the results are well correlated within this context, there is an
indication that unknown dynamic factors distort the kinetics such that a sim-
ple analysis does not model the system well.
In sulphate based hydrometallurgical solutions, there is concern about silver
deportment since the perturbations of the system are based on the undesirable
non-stoichiometric dissolution and relatively slow kinetics under more prac-
tical conditions of high sulphate concentrations and highly reduced solutions.
On one hand, the highly oxidizing media give fast dissolution rates but a low
efficiency with respect to the generation of soluble silver whereas high sulphate
media give slower dissolution rates but with a high efficiency of dissolving
silver.
The rates for silver metal dissolution by acidic ferric ion solutions were shown
to be much faster in sulphate media than in chloride media.

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