Journal of Electroanalytical Chemistry, 361(1993) 39-41 39

JEC 02851

Thermodynamics of Ag-Cl-H,O, Ag-Br-H,O

and Ag-I-H,0 systems at 298 IS

N.J. Welham, G.H. Kelsall and M.A. Diaz

Department of Mineral Resources Engineering, Imperical College, London, SW7 2BP (UK)
(Received 23 March 1993)

Abstract

The thermodynamics of silver-halide-water systems are summarized in the form of potential-pH and activity-pH diagrams,
calculated from recently published standard Gibbs energies of formation of the various species and phases considered.
Stabilities and hence solubilities of Ag(I) halide species are predicted to increase in the order Cl < Br < I, which is reflected in
the corresponding potential-pH diagrams by a decreasing potential for the AgXk)/Ag and AgXy-“-/Ag couples, and a
transition from solid phase to solution complex predominance with increasing free halide activities.

1. Introduction This paper summarizes the behaviour of both silver-

water and silver-halide-water systems in the form of
Gold and silver ore processing has changed little in potential-pH and activity-pH diagrams. A description
the past hundred years, but, with increasing legislative of the thermodynamics of halide-water and gold-
commitment to low pollution processes, a re-evaluation halide-water has been published previously [26]. Silver
of alternative systems is needed to meet increasing is oxidized at less positive potentials than gold in the
environmental constraints on effluents. The leaching of aqueous halide solutions, although silver halides are
gold and silver with aerated alkaline cyanide is slow less soluble than those of gold.
and the cyanide is normally not recycled. Recently,
2. Thermodynamics of silver systems
work has been published on the recovery of gold and
silver using chloride [l-5], bromide [4,6-111, iodide Table 1 gives the Gibbs energies of formation data,
[4,12-141, thiosulphate [4,15-171, thiocyanate [l&19] from the most recent critically assessed review [27], for
and thiourea [4,20-241; and excellent review of the the various species and phases considered in the calcu-
current state of gold extraction has recently been pub- lation. The potential-pH diagrams were calculated us-
lished [25]. In general, these have shown improvements ing the COPLOT module of MTDATA [28]. Activity-
in the rate and recovery of both gold and silver, com- pH diagrams were calculated using a spreadsheet. In
pared with cyanidation, most significantly with ores not the potential-pH diagrams, halide ions were treated
considered amenable to direct cyanidation. merely as complexants, their predicted oxidation be-
Halide-based processing systems have been studied haviour having been considered previously [26]. The
closely because both gold and silver complex with eqns. for the lines representing the various equilibria in
halides; also, the halides are comparatively cheap pre- the diagrams, are given in the Appendix, parenthesis
cursors in electrochemical generation of halogen oxi- refer to activities of dissolved species.
dants, which could be the counter reaction to elec-
trowinning of gold and silver, dissolved in an external 2. I. Silver-water systems
leach reactor [51. A potential-pH diagram for a silver-water system is
Despite these experimental investigations [l-3,6- shown in Fig. 1, indicating an area of predominance for
17,19-24], very little work on the thermodynamic prop- the oxide AgO rather than Ag,O,, contrary to both
erties of the silver-halide systems has been published. the original diagram derived by Pourbaix [291 and a

0022-0728/93/$6.00 0 1993 - Elsevier Sequoia S.A. All rights reserved

40 NJ. Welham et al. / Thermodynamics of siber-halide-water systems

TABLE 1. Gibbs free energies of formation of species in silver- (1100, and should be written as Ag,O,. The existence
halide-water systems at 298 K [27]
of equilibria between Ag(OH& and Ag,O and AgO
Species AGF/kJ mol-’ Species AGF/kJ mol-’ has been established experimentally [44].
&+ 77.16 &Cl(c) - 109.86 Though Fig. 1 predicts that it is capable of oxidizing
Ag*+ 269.16 &C&q) - 54.16 water, AgO is relatively stable both when dry and in
AgO+ 225.63 A&I; - 215.88 alkaline solution. An in situ Raman spectroelectro-
AgO- - 22.98 A&I:- - 345.97
chemical study [45] of the anodic films formed on silver
Ag,O(c) - 11.22 AgCl:- - 478.46
Ag202k) 27.63 AgBrk) -95 at pH 13 showed that AgO was the silver oxide formed.
AdOH); - 260.37 AgBr(aq) - 26.87 Though oxidation peaks in the cyclic voltammogram
AgOH - 80.21 AgBr; - 172.46 were attributed to Ag,O formation [45,47-511, Raman
Ago(c) 14.65 AgBri- - 284.65 spectroscopy did not detect that phase, owing to
Ag,O,k) 121.39 AgBrd- - 387.67
photo-oxidation by the 488 nm laser light:
Ago,(c) - 10.99 AgIk) - 66.22
AgH(g) 2486.11 AgI(aq) 25.53 Ag,O + H,O + 2h+ 2 2AgO + 2H+ (I)
H2O - 237.178 AgI; - 87.07
OH- - 157.293 A& - 154.04 The AgO proved to be stable at an applied potential of
cl- - 131.0563 A& - 209.72 -70 mV, over 300 mV lower than that predicted for
Br- - 103.97 AgBrC$ - 465.6 the reduction of Ag,O:
I- - 51.67 AgBr,CI”- - 420.0
Ag,O + 2H++ 2e- F 2Ag + H,O (2)
Examination of the Ag/Ag,O couple at pH 13 [52]
more recent publication [30], though Fig. 1 is similar in showed the initial formation of a monolayer of AgOH,
form to other published diagrams for the silver-water followed by fast dissolution of Ag(OH); ions:
system [l&31,32].
AgOH + H,O = Ag(OH), + H+ (3)
Although AgO, is present in the data set used, no
discussion concerning its properties is presented; other preceding Ag,O phase formation on the electrode.
commonly used data sources [29,33] do not contain that Silver has been found to form two distinct oxidized
phase and other publications [l&29-32,34-36] do not monolayers in alkaline solution [53]; both are formed
consider its presence. The standard reference texts at an underpotential to the Ag/Ag,O couple and were
[37-391 for inorganic chemistry do not contain any attributed to AgOH and Ag,O. In acidic solution the
information on Ago,, though it is likely to be silver(I) passivating layer of Ag,O was not formed [541.
superoxide. In view of the dearth of information about The more recent diagram [30] does not consider
this phase, AgO, has not been considered in the AgO, Ag(OH); or AgOH within the calculation; how-
calculation of the halide diagrams presented below, but ever, AgO; ions are included. Despite these differ-
is included on the silver-water diagram. ences the diagrams are similar in appearance and the
It has been suggested [40-431, and confirmed by species AgO/Ag,O, and AgO-/Ag(OH& can be
neutron diffraction [38], that AgO exists as Ag(I).Ag considered equivalent.
Ag2+ ions are known to be very powerful oxidants,
oxidizing Mn2+ to MnO; [55], and are used for analyt-
2.4 , ical determinations of vanadium, chromium, man-
I
ganese and cerium in acid solution [561. The standard
potential of the Ag+/Ag2+ couple is well above the
oxidation potential for water; the mechanism of water
oxidation by Ag2+ has been determined in nitric(V)
acid media [57], the overall reaction being
4Ag2+ + 2H,O = 4Ag++ 0, + 4H+ (4)
Oxidation of 1 km01 Ag(1) in 4 km01 nitric(V) acid me3
at 2.1 V vs. SHE on platinum produced tetranitratoar-
gentate(I1) ions [58], which have been used to oxidize
waste organic materials in the “silver bullet” process
O-2 0 2 4 6 8 10 12 14 16 [591.
PH
Fig. 1. Potential-pH diagram for a silver-water system at 298.15 K:
2.2. Silver-halide-water systems
- aAg = 10m4, _ _ _ _ _ _ aAg = lo-*, . . . . . aAg= lo-‘, Ago, Silver is found to occur in nature as halides; these
present. are formed by secondary processes such as oxidative
 NJ. Welham et al. / Thermodynamics of silver-halide-water systems 41

TABLE 2. Naturally occurring silver halide minerals [61]

Name Composition
Chlorargyrite AgCl
Bromargyrite AgBr
Iodargyrite AgI
Embolite Ag(Cl,Br)
Iodembolite Ag(CI,Br,I)

alteration of elemental silver and silver sulphides, with

no evidence of formation by precipitation from brines
[60]. The halide ions may substitute for each other,
forming a series of natural silver halides, listed in -2 0 2 4 6 8 10 12 14 16

Table 2. PH
There is some evidence of dissolved silver(I) species, Fig. 2. Potential-pH diagram for a silver-chloride-water system at
298.15 K for aAg = 10m4: - ac,-=l,------ao-=2.Chloride
primarily tetrahaloargentate(I), which have mixed lig-
treated as electro-inactive.
ands; thermodynamic data have been presented for
tribromomonochloroargentate(1) and monobromotri-
chloroargentate(1) [27,33] from which the standard po- Increasing the chloride activity to 2, corresponding
tentials of formation can be calculated: to the dashed equilibrium lines in Fig. 2, is predicted to
AgBr,C13-+ e- e Ag + Cl-+ 3Br- (5) cause dissolution of solid silver chloride as tetra-
chloroargentate(1) ions, which could have significant
Es/V = 0.2380 + 0.1775 log(Br-) + 0.0592 log(Cl-)
implications for envisaged processes coupling leaching
- 0.0592 log(AgBr,C13-) to electrowinning in three-dimensional electrodes [51:

AgBrCii- + e - FAg+3Cl-+Br- AgCl(c) + 3Cl- = AgCli- (7)

(6)
E,/V = 0.3269 + 0.1775 log(Cl-) + 0.0592 log(Br-) The initial electro-oxidation of silver in chloride solu-
tions [64] has been found to form two different mono-
- 0.0592 Iog(AgBrCl:-) layers at potentials below that of the Ag/AgCl couple.
Although the potentials of formation are higher than The first monolayer was considered to be a mixture of
that of the haloargentate(1) ions, the potential depen- AgOH and AgCl; the coverage of the second was a
dence upon two halide activities can lead to a range of function of chloride concentration and considered to
conditions under which the mixed halide forms. Iodide be AgCl. Birss et al. [65] found similar results but
is thermodynamically likely to substitute bromide
which, in turn, would substitute chloride; thus, there is
the possibility of complete series of mixed ligand 0
haloargentate(1) complexes. However, the limited data
set does not allow calculation of potential-pH dia- &Cl (cl

ill ,_i . /j
grams containing mixed halide complexes.
The values of the stability constants for the mixed
complexes can be calculated using the technique of
Wang [62], giving new diagrams. However, the calcu-
2
lated Gibbs energy values for the two complexes were . A& /
not sufficiently close to experimentally determined G -6 AgCl;
thermochemical data [27] to warrant inclusion of these AgCl:-
species within the silver-halide-water diagrams. 2? -8.
AF’ &Cl (4 Ag3H
2.3. Silver-chloride-water systems
Comparison of the silver-chloride-water potential- -lo-2 0 2 4 6 8 10 12 14 16
pH diagram shown in Fig. 2, with a previously pub-
PI-I
lished diagram [32] shows a similarly large area of Fig. 3. Silver(I) activity-pH diagram for a silver-chloride-water
predominance for AgCl(c), which has also been pre- system in equilibrium with AgCl(c) at 298.15 K for a,,- = 1; chloride
dicted to form at 200°C [631. treated as electro-inactive.
42 N.J. Welham et al. / Thermodynamics of silver-halide-water systems

2- Similar results have been reported [68] for silver

AgCl; AgCl;’ AgCli- solubility in ammonium brines; also, increasing CaCl,
1
0 and HCl concentrations were found [2] to increase
i silver concentrations in leach solution from the dissolu-
‘E
- -2 1 tion of tailings from a complex pyrite sulphating roast.
In the dissolution of silver from electronic scrap,
AS1 tc>
redox potentials greater than +0.77 V were found [691
to result in a surface layer of both AgCl and silver
g -6. oxide, which inhibited dissolution; below +0.77 V, the
2 &+ silver dissolution kinetics were considerably faster since
no oxide layer was formed.
-8
The increased solubility of silver at high chloride
-%$l W ,,
concentrations has been exploited in the leaching of
-lo0 2 4 6 8 10 12 14 16 Peruvian silver ores in brine at pH < 2 [70], in leaching
PI-I silver from copper smelter flue dust [71] and in solubi-
Fig. 4. Chloride activity-pH diagram for a silver-chloride-water lizing silver in a pressure oxidation leach of refractory
system in equilibrium with AgCl(c) at 298.15 K for aAg = 10m4;
complex sulphide ore [3].
chloride treated as electro-inactive.

2.4. Siher-bromide-water systems

Comparison of Fig. 1 with Fig. 5, a potential-pH
diagram for a silver-bromide-water system with a dis-
suggested that one layer could have been adsorbed
solved silver activity of 10m4, indicates that the addi-
chloride ions. Two reduction peaks, attributed to AgCl
tion of 1 kmol Br- m -3 decreases the required poten-
formed by different mechanisms, were evident in cyclic
tial for silver oxidation by approximately 500 mV but,
voltammograms.
unlike chloride, gives a soluble product:
Figure 3 shows that unity activity chloride is pre-
dicted to constrain the maximum silver(I) activity AgBr:- + e- e Ag + 3Br- (9)
severely; the total dissolved silver(I) activity for pH < 14
However, decreasing the bromide activity to 10-i
is predicted as approximately 10e4.* (6.8 ppm), owing
(dashed line, Fig. 5) leads to the formation of solid
to AgCl(c) formation. Increasing the chloride activity
silver bromide:
increased the pH range of predominance of AgCl(c), as
shown in Fig. 4, but only up to the activity at which AgBr(c) + e- G==== Ag + Br- (10)
tetrachloroargentate(1) ions form. The silver speciation is dependent on bromide activity,
The raised chloride activity gives an increase in the as shown in Fig. 6, which predicts that, in the presence
solubility of silver chloride species in acidic solution. of 10e4 Ag(1) activity, solid silver bromide will form
This agrees with a report [66] that silver dissolution in over the range of bromide activities of approximately
6 km01 HCl rnp3 proceeded extremely rapidly accord- lO-‘.z to about 1, with Ag(OH); ions forming at
ing to pH > 12:

Ag + nCl- - AgCl(“-‘)-
n + e- (8) Ag(OH), + Br-+ 2H + ti AgBr(c) + 2H,O (11)

The solubility of silver chloride has been reported [67] The formation of AgBr on a silver anode [72] has been
to increase with chloride activity. Increasing the tem- found to occur by a fast electron transfer step, the film
perature from 10 to 100°C increased the solubility formed by lateral spreading from nucleation sites de-
from 3.7 to 13 mol rnp3 (400 to 1400 g me3) at pH 0.5 creasing the rate of further AgBr formation to that
in 3.2 km01 FeCl, rnp3; the thermodynamically pre- limited by diffusion of Br- ions through pores.
dicted solubility at 25°C is 2 mol me3 (220 g mp3) The silver(I) activity-pH diagram for silver in unity
which is half that found at 10°C. Low pH was found to bromide activity, shown in Fig. 7, predicts that dis-
enhance the solubility, as was the presence of NaCl solved silver(I) activities are constrained to 10e3.” by
and FeCl,. In 0.5 km01 FeCl, me3 at pH 0.5, the the formation of AgBr(c) in equilibrium with
solubility of AgCl was less than 1 mol rnp3 (less than AgBr’“-,) ‘)- ions.
100 g rnp3) until the NaCl concentration was increased
above approximately 1 km01 rnp3, at which tetra- 2.5, Silver-iodide-water systems
chloroargentate(1) ions are predicted to begin to pre- Comparison of Fig. 1 with the corresponding dia-
dominate. gram for the silver-iodide-water system at unity iodide
 N.J. Welham et al. / Thermodynamics of’siluer-halide-water systems 43

01
1

-2 I AgBr$
AgBr Cc>

‘;;j AgBr%
% 0.6 - i I
58 0.2
0.4 - Ag(OH); --i
r___________________-______~~
4 0
E -0.2 - AgBr,
8 -0.4 - Ag

’ -‘52 0 2 4 6 8 10 12 14 16
PH -lo-2 1 1 2 4 8 10 12 I 14 16
Fig. 5. Potential-pH diagram for a silver-bromide-water system at
p6H
298.15 K for aAg = 10m4: ~ aBr- = 1, - - - - - - aBr- = 0.1. Bro-
Fig. 7. Silver(l) activity-pH diagram for a silver-bromide-water
mide treated as electro-inactive.
system in equilibrium with AgBl(c) at 298.15 K for anr- = 1; bromide
treated as electro-inactive.

activity, shown in Fig. 8, indicates that the required

potential for silver oxidation is decreased by approxi-
ened. In 1 kmol NaI m-3, the solubility of silver is
mately 750 mV, and results in a soluble product:
high; thick granular films of AgI formed at a rate
AgIj- + e- =Ag+41- (12) limited by solid-state migration of ions in the bulk of
However, decreasing the iodide activity to 10-l (indi- the film.
cated by the dashed lines in Fig. 8) is predicted to ‘The reaction of iodide ions with AgO, as used for
result in the formation of solid silver iodide: the analytical determination of AgO [741, has been
studied using Raman spectroscopy [75]; the AgO forms
AgI(c) + e- =Ag+ I- (13) an ill characterized silver-iodine surface phase which
The formation of AgI on a silver anode [73] has been prevents further formation of AgO. AgO was also
found to occur by a fast electron transfer step; at an found to oxidize iodate(V) to iodate(VI1). Wet grinding
iodide concentration of 2.5 mol NaI rne3, a highly of AgO with KI led to the formation of a solid phase
porous film was formed at a rate limited by bulk similar to AgIO,. At pH 13, electro-oxidation of silver
diffusion of iodide to the surface. However, at 100 mol in iodide solution gave silver dihydrogeniodate(VII),
NaI rne3, the initial solution phase diffusion control Ag,H ZIO,; the presence of dehydrogeniodate(VI1)
switched to pore diffusion control, as the film thick- ions at pH 13 has been predicted from thermodynamic
considerations [51.

2
AgBr ;
AgBr ‘3. 1.8 I ., 1
/ > 1.61
AgBr 3/4 iii 1.4 -
8 1.2-
? 1-
0.8 -
;;i
% 0.6 - (-- -)AgI (c)
ti 0.4 -
5a 0.2 -

PH
Fig. 6. Bromide activity-pH diagram for a silver-bromide-water Fig. 8. Potential-pH diagram for a silver-iodide-water system at
system in equilibrium with AgBr(c) at 298.15 K for aAg = 10e4; 298.15 K for aAg = 10m4: ~ a,- = 1, - - - - - - a,-= 0.1; iodide
bromide treated as electro-inactive. treated as electro-inactive.
44 NJ. Welham et al. / Thermodynamics of silver-halide-water
systems

A@ (cl
-2
f? AgI:-

. I I

A&
Ag(OH);
:
~o~~~i 8 10 12 14 16
-lo-2 1 0 2 4 6 8 10 12 14 I 161 PH
Fig. 11. Total silver(I) activity-pH diagram for silver-halide-water
PH systems in equilibrium with AgX(c1 at 298.15 K for ax- = 0.1, 1 and
Fig. 9. Silver(I) activity-pH diagram for a silver-iodide-water system 5: - chloride, - - - - - - bromide, - - - iodide. Halide treated
in equilibrium with AgI(c) at 298.15 K for a,- = 1; iodide treated as as electro-inactive.
electro-inactive.

The silver(I) activity-pH diagram, shown in Fig. 9, 3. Conclusions

for unity activity iodide, predicts that if the silver
activity is greater than 10e2, then AgI(c) will form in For aqueous silver(I) solutions to which chloride,
equilibrium with triiodoargentate(1) ions as the pre- bromide or iodide ions are added, there is a critical
dominant solution species. The solubility of AgI in 1 activity above which dissolved silver will be precipi-
km01 NaI me3 has been reported [76] to be 10 mol tated as its corresponding halide. Figure 11 shows that
mp3, in good agreement with the thermodynamic pre- high free halide activities are required for high silver
diction, Fig. 9. solubility.
Figure 10 predicts that a solution with lop4 Ag(I) Stabilities and solubilities of Ag0) halide species are
activity will precipitate AgI(c) provided a,-< lo-‘.‘. predicted to increase in the order Cl < Br < I; this is
There has also been evidence 1771 for more complex reflected in the corresponding potential-pH diagrams
silver iodide ions such as Ag,I; and Ag,,It; but no by a decreasing potential for both the AgX(c)/Ag and
thermodynamic data are yet available for such species. AgX’“-“-/Ag couples, and a transition from solid
phasi to solution complex predominance at practical
free halide activities, as the halogen group is de-
scended.

A& Acknowledgement
AgI ;-
/
/ The authors thank Billiton Research BV, Arnhem,
F -2 AgI “4. The Netherlands for the provision of a studentship for
E N.J.W.
-g -4
. AgI (c) References
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46 NJ. Welham et al. / Thermodynamics of siluer-halide-water systems

Appendix A: thermodynamic equations Ag(OH), + 4Cl-+ 2H + = AgC13,- + 2H,O

(A14)
Silver-water systems
log{(AgCl,3-)/(Ag(OH),)} = 29.47 + 4 log(Cl-)
Chemical reactions
- 2pH
2Ag+ + H,O e Ag,O + 2H+ (Al)
log(Ag+) = 6.27 - pH Electrochemical reactions

Ag,O + 3H,O e 2Ag(OH), + 2H+ Ag,O, + 2Cl-+ 6H++ 4eP e 2AgCl-t 3H,O
(A2)
log(Ag(OH),) = -35.39 + 2pH (A15)
EAIJV = 2.0483 - 0.0296 log(Cl-) + 0.0887pH

Electrochemical reactions Ag,O, + SCl-+ 6H++ 4e- e 2AgC13,- + 3H,O

Ag,O, + 6H++ 2e- = 2Ag2++ 3H,O (A3) (A16)

EA3/V = 1.526 + 0.0592 log(Ag2+) + 0.1776pH E/,&V = 1.9210 - 0.1183 log(Cl-) + 0.0887pH

Ag2++ e- =Ag+ + 0.0296 log(AgCl;-)

(A4)
E/&V = 1.990 + 0.0592 log((Ag+)/(Ag2+)} AgO + Cl-+ 2Ht+ e- GAgCl+H,O (A17)
Ag,O, + 2H++ 2e- e 2AgO + H,O EA17/V = 2.3904 - 0.0592 log(Cl-) + 0.1183pH
(A5)
EM/V = 1.7063 - 0.0592pH AgO + 4ClP+ 2H++ e- e AgC13,- + H,O (A18)

AgO + 2H++ e- s===Ag++H20 (A6) E,&V = 2.1357 - 0.2366 log(Cl-) + 0.1183pH

E&V = 1.8103 - 0.1183pH - 0.0592 log(Ag+) + 0.0592 log(AgCl;-)

2Ag0 + 2H++ 2e- = Ag,O + H,O (A7) AgCl+e- =Ag+Cl- (A19)
EAT/V = 1.4391- 0.0592pH EA,,JV = -0.2197 + 0.0592 log(Cl-)

AgO+H,O+e-e Ag(OH), (AS) AgCli- + e- =Ag+4Cl- (A20)

EA8/V = 0.3923 + 0.0592 log(Ag(OH),) EAzO/V = -0.4743 - 0.0592 log(AgCl;-)

Ag,O + 2H++ 2e- e 2Ag + H,O (A9) + 0.2366 log(Cl-)

EJV = 1.1710 - 0.0592pH
Silver-bromide-water systems
Ag(OH)i + 2Hf+ e- = Ag + 2H,O (AlO)
E,&V = 2.2178 - 0.1183pH + 0.0592 log(Ag(OH),) Chemical reactions

Ag++ e- v=Ag (All) AgBr + 2Br- e AgBr:- (A21)

E/&V = 0.7997 + 0.0592 log(Ag+) log(AgBrf- ) = - 3.20 + 2 log( Br-)

Ag(OH), + Br-+ 2H + e AgBr + 2H,O (A22)

Silver-halide-water systems
log(Ag(OH), ) = - 35.92 - log(Br-) + 2pH
Silver-chloride-water systems
Electrochemical reactions
Chemical reactions
AgBr + e- eAg+Br- (A23)
AgCl + 3Cl- d AgC13,- (A12) EA2,/V = 0.0930 + 0.0592 log(Br-)
log(AgCli-) = -4.31 + 3 lo&Cl-)
AgBrf- + eP e Ag + 3Br- (A24)
Ag(OH), + Cl-+ 2H+ e AgCl+ 2H,O (A13)
E,,/V = 0.2855 - 0.0592 log(AgB$)
log(Ag(OH),) = -33.78 - log(Cl-) + 2pH + 0.1775 log(Br-)
 N.J. Welham et al. / Thermodynamics of silver-halide-water systems 47

AgO + Br-+ 2H++ e- e AgBr + H,O (A25) Electrochemical reactions

EAz5/V = 2.5171- 0.0592 log(Br-) + 0.1183pH
AgI+e- ===Ag+I- (A30)
AgO + 3Br-+ 2H++ e- e AgBrz- + H,O
EAxO/V = -0.1508 + 0.0592 log(I-)
(A26)
AgIi- + e- eAg+41- (A31)
EAz6/V = 2.3275 - 0.1775 log(Br-) + 0.1183pH

+ 0.0592 log(AgBri-) E&V = -0.0315 - 0.0592 log(AgI:-)

Ag,O, + 2Br-+ 6H++ 4e- e 2AgBr + 3H,O + 0.2366 log(I-)

(A27)
Ag,O, + 21--t 6Hf+ 4e- = 2AgI + 3H,O (A32)
EA2,/V = 2.1117 - 0.0296 log(Br-) + 0.0887pH
Em2/V = 2.2336 - 0.0296 log(I-) + 0.0887pH
Ag,O, + 6Br-+ 6Hf+ 4e- e 2AgB$ + 3H,O
(A28) Ag,O, + 81-+ 6H++ 4e- e 2AgI;- + 3H,O

E,&V = 2.0169 - 0.0887 log(Br-) + 0.0887pH (A33)

+ 0.0296 log(AgB$) EA:&V = 2.1739 - 0.1183 log(I-) + 0.0887pH

+ 0.0296 log(AgI;-)
Silver-iodide-water systems

Chemical reaction

AgI + 31- = A& (A29)

log(AgI;-) = - 2.02 + 3 log(I-)