CHAPTER 6 AQUEOUS STABILITY DIAGRAMS

6.1. Introduction........................................................................................................... 1

6.2 Thermodynamic and Mathematical Formulation of Relative Stability .......... 1

6.2.1 Relative Stability Lines and Predominance Areas................................... 1

6.2.2 Multi-species Systems and Constrained Relative Stability Lines ........... 6

6.3 Metal-Water and Metal-Ligand-Water Systems ............................................... 11

6.3.1 Metal-Water Systems............................................................................... 11

6.3.2 Ligand-Water Systems............................................................................. 18
6.3.3 Metal-Ligand-Water Systems .................................................................. 28
6.3.4 Metal-Multiligand-Water Systems .......................................................... 39

6.4 Metal-Metal-Water Systems ................................................................................ 42

6.4.1 Complex Oxide Systems.......................................................................... 42

6.4.2 Complex Chalcogenide and Related Systems.......................................... 45

6.1 Introduction
Diagrams which delineate the relative stabilities of the chemical species in a given
aqueous environment are of considerable aid in understanding and predicting equilibrium
reactions in aqueous systems. The most well-known of such stability or predominance area
diagrams is the Eh-pH diagram introduced by the work of Pourbaix. Eh-pH diagrams enable us
to see at a glance the range of stability of aqueous species and solid compounds under specified
conditions of Eh (or redox potential) and pH.
Aside from Eh-pH diagrams (and the related pε -pH diagrams), other predominance area
diagrams of interest include log {M}-pH and log {Ligand}-pH diagrams. In this chapter the
thermodynamic basis and the mathematical formalism underlying the construction of
predominance area diagrams are developed. These thermodynamic and mathematical concepts
are then applied to simple systems of the type Metal-H2O followed progressively by more
complex systems such as those of the type Metal-Ligand-H2O, and Metal-Metal-Ligand-H2O.

6.2 Thermodynamic and Mathematical Formulation of Relative Stability

6.2.1 Relative Stability Lines and Predominance Areas
Consider the reaction involving the two M(I) and M (II) species M2O and M2+:

M2O + 2H+ = 2M2+ + H2O + 2e- (6.1)

Osseo-Asare Aqueous Processing 1

The reaction quotient, Q, is given by

Q = {M2+}2{e-}2/{H+}2 (6.2)
or:
log Q = 2 log{M2+} + 2 log{e-} - 2 log{H+} (6.3)

If K is the equilibrium constant for Equation 6.1, then it follows that M2O will dissolve
to give M2+ so long as log K>log Q. That is, M2+ is more stable than M2O if

log K > 2 log{M2+} + 2 log{e-} - 2 log{H+} (6.4)

On the other hand, M2O is more stable than M2+ if logK < logQ, i.e., if

log K < 2 log{M2+} + 2 log{e-} - 2 log{H+} (6.5)

In contrast, under equilibrium conditions,

log K = 2 log{M2+} + 2 log{e-} - 2 log{H+} (6.6)

or
log K = 2 log{M2+} - 2 pε + 2 pH (6.7)

According to Equations 6.3-6.7, there are three variables which must be considered in
order to completely specify the M2+/M2O stability relation, i.e., {M2+}, {e-}, and {H+}. The
equilibrium condition can be represented by a straight line if any one of these variables is
maintained constant while the other two are varied. For example, if {M2+} is kept constant,
Equation 6.7 becomes

pε = [-(1/2) log K + log{M2+}] + pH = constant + pH (6.8)

A plot of pε versus pH should give a straight line of slope 1 and intercept [-(1/2) log K +
log {M2+}] at pH = 0, as shown in Figure 6.1a. In view of the inequalities given by Equations
6.4 and 6.5, M2+ should be the stable copper species above the equilibrium line, while M2O
should be the stable species below this line. The equilibrium line divides the plotting space into
two regions, termed predominance areas or stability fields. Thus the region above the line
represents the stability field of M2+ while the lower portion of the diagram depicts the stability
field of M2O.

Osseo-Asare Aqueous Processing 2

 M2+ M2 O
log{M2+} M2+
pε pε
M2 O M2+
M2 O
pH pH log{M2+}
(a) (b) (c)

M2 O
M2+ M2+
log P log P
Eh O2 H2
M2+
M2 O M2 O
pH pH pH
(d) (e) (f)

Figure 6.1 Relative stability lines and predominance areas for M2O/M2+ equilibria

The equilibrium equation which is obtained when pε is kept constant, is:

log{M2+} = [(1/2) log K + pε] - pH = constant - pH (6.9)

In log{M2+} versus pH coordinates, Equation 6.9 is a straight line with a negative slope of unity.
In this case, in order to satisfy Equations 6.4 and 6.5, M2O must be the stable species above the
equilibrium line and M2+ must be stable below the line, as shown in Figure 6.1b. Finally, if pH
is kept constant, the equilibrium condition becomes,

pε = [-1/2 log K + pH] + log{M2+} = constant + log {M2+} (6.10)

Thus a plot of pε versus log{M2+} should give a straight line of slope 1 as shown in Figure 6.1c.
We have so far demonstrated that the relative stability between M2+ and M2O can be
represented in terms of three types of diagrams:

pε versus pH
log{M2+} versus pH
and pε versus log{M2+}

Other plots are also possible, e.g., by replacing pε with Eh, log PO2, or log PH2.

Osseo-Asare Aqueous Processing 3

 To obtain an Eh-pH representation of the M2O/M2+ relative stability, we recall the
relationship

Eh = (2.303 RT/F) pε (6.43)

Combination of Equations 6.43 and 6.8 gives:

Eh = (2.303 RT/F) [-(1/2)logK + log{M2+}] + (2.303 RT/F)pH (6.11)

At 25°C, Equation 6.11 may be rewritten as:

Eh (volt) = 0.059 [-(1/2)logK + log{M2+}] + 0.059 pH (6.12)

Here too, it can be seen that for a constant M2+, a straight line will be obtained by plotting Eh vs
pH, as illustrated in Figure 6.1d.
If we wish to show the stability relation as a function of log PO2 and pH, the electron in
Equation 6.1 can be eliminated by writing a reaction between water and oxygen in terms of
hydrogen ions and electrons:

1/2 O2(g) + 2e- + 2H+ = H2O (6.13)

Combining Equation 6.13 with Equation 6.1 gives

1/2 O2(g) + M2O + 4H+ = 2M2+ + 2H2O (6.14)

That is,
log PO2 = [-2 log K' + 4 log{M2+}] + 8 pH (6.15)

where K' is the equilibrium constant for reaction 6.14. Thus, if we plot log PO2 against pH,
while maintaining log{M2+} constant, we obtain a straight line of slope 8, as shown in Figure
6.1e.
Similarly, in the case of a log PH2 vs pH plot, we need a relationship between H2 and e-:

2H+ + 2e- = H2(g) (6.16)

Combination of Equations 6.1 and 6.16 gives:

M2O + 4H+ = H2(g) + 2M2+ + H2O (6.17)

Osseo-Asare Aqueous Processing 4

The corresponding equilibrium relation is:

logPH2 = [logK" - 2log{M2+}] - 4pH (6.18)

where K" represents the equilibrium constant for reaction 6.17. Figure 6.1f illustrates a log PH2
vs pH plot with log{M2+} constant.

EXAMPLE 6.1 The Stability of Water

The decomposition of water can take two possible routes, yielding oxygen and hydrogen respectively:

1/2 H2O = 1/4O2(g) + H+ + e- log K = -20.75 (1)

H2O + e- = OH- + 1/2H2(g) log K = -14.0 (2)

(a) Consider the equilibrium between water and oxygen gas at 1 atmosphere pressure. What is the
limit of water stability as a function of pε and pH?

(b) Consider the equilibrium between water and hydrogen gas at 1 atmosphere pressure. What is the
limit of water stability as a function of pε and pH?

(c) Repeat (a) and (b) in terms of Eh.

Solution

(a) According to Equation 1, H2O → O2(g) if log Q < logK, i.e., if

1/4 log PO2 + log {H+} + log{e-} < -20.75

That is, if

1/4 log PO2 - pH -pε < -20.75

or
pε > 20.75 + 1/4 log PO2 - pH (3)

Thus at 1 atmos O2 pressure, H2O → O2(g), i.e., water decomposes to O2 if

pε > 20.75 -pH (4)

Equation 4 may be represented graphically in a pε-pH coordinate system as a straight-line pε = 20.75 -

pH, which divides the plotting area into two regions, as indicated in Figure E6.1a. It follows from Equation 4 that
above line 4, H2O → O2(g), i.e., O2 is more stable than H2O. Thus the stability field of H2O lies below line 4.

(b) In order to permit analysis in terms of pH, Equation 2 must be combined with the water ionization
reaction:

H2O + e- = OH- + 1/2 H2 (g) log K = -14.0

H+ + OH- = H2O log K = 14.0

H+ + e- = 1/2 H2 (g) log K = 0 (5)

Osseo-Asare Aqueous Processing 5

 20.75 1.22
O2 (g) O2 (g)
H2O (4) H2O
(7)
Eh(V)
pε
0 0
Η+ (aq) Η+ (aq)

H2(g) (6) H2(g) (8)

0 pH 0 pH
Figure E6.1 Stability of Water

o o
It should be noted that Equation 5 is consistent with the convention that ΔGf (H+) = 0, ΔGf (e-) = 0, and
o
ΔGf (H2(g)) = 0. It follows from Equation 5 that H+ → H2(g) if log Q < log K, i.e., if

1/2 log PH2 + pH + pε < 0

or, for PH2 = 1 atm, if

pε < - pH (6)

On the basis of Equation 6 the H+/H2 equilibrium can be represented graphically in terms of a straight
line (pε = -pH) as indicated by line 6 in Figure E6.1a. According to Equation 6, H2 is more stable than H+ for
conditions below line 6 (i.e., for pε < -pH).

(c) Referring to Equation 8.43, Eh(V) = 0.059 pε. Therefore Equation 4 can be re-stated as:
H2O → O2(g) if

Eh(V) > 1.22 - 0.059 pH (7)

Similarly, for Equation 6, H+ → H2(g) if

Eh(V) < = -0.059 pH (8)

Equations 7 and 8 are depicted graphically in Figure E6.1b.

6.2.2 Multi-Species Systems and Constrained Relative Stability Lines

Ιn the discussion in Section 6.2.1, we were concerned with the stability relation between
two species: M2+ and M2O. This is a rather restricted system. In practical solutions, several
other M-containing species may be present and these should also be considered, e.g., M(s), MO,
MOH+, etc. Systems with more than two species involve multiple equilibria. Thus a system
with m M-containing species will require consideration of m(m-1)/2 relative stability equations.
When all these relative stability lines are considered simultaneously it may be found that certain
lines have to be eliminated or shortened in order to satisfy the overall equilibrium of the system.

Osseo-Asare Aqueous Processing 6

In this section we develop the methodology which will permit us to undertake a systematic
graphical analysis of such multiple equilibria.
____
EXAMPLE 6.2 Relative Stabilities in the Multi-species Cu-H2O System.

Selected thermodynamic data for the Cu-H2O system are provided below:

Cu = Cu2+ + 2e- log K = -11.5 (1)

CuO + 2H+ = Cu2+ + H2O log K = 7.3 (2)
Cu2O + 2H+ = 2 Cu2+ + 2e- + H2O log K = -7.0 (3)

Using these data, determine the relative stabilities of the following species:

(a) CuO, Cu2O, and Cu, in terms of pε-pH coordinates.

(b) CuO, Cu2O, and Cu, in terms of log{Cu2+}- pH coordinates; assume pε = 5.0.
(c) Cu2+, CuO, and Cu2O , in terms of pε-pH coordinates; assume {Cu2+} = 1.0.
(d) Cu2+, CuO, and Cu2O, in terms of log {Cu2+} - pH coordinates; assume pε = 5.0.

(a) We need to consider the relative stabilities of the following pairs: (i) CuO → Cu2O, (ii) Cu → CuO, and
(iii) Cu → Cu2O

(i) CuO/Cu2O: Combination of Equations 2 and 3 gives:

2CuO + 2H+ + 2e- = Cu2O + H2O log K = 21.6

log Q = 2pε + 2pH

Thus CuO → Cu2O if log Q < logK, i.e., if pε < 10.8 - pH (4)

(ii) Cu/CuO: Combination of Equations 1 and 2 gives:

Cu + H2O = CuO + 2H+ + 2e- logK = -18.8

log Q = -2pH - 2pε
Thus Cu → CuO if log Q < logK, i.e., if pε > 9.4 – pH (5)

(iii) Cu/Cu2O: Combination of Equations 1 and 3 gives:

2 Cu + H2O = Cu2O + 2e- + 2H+ logK = -16.0

log Q = -2pε - 2pH
Thus Cu → Cu2O if log Q < logK, i.e., if pε > 8.0 -pH (6)

Osseo-Asare Aqueous Processing 7

 10.8 CuO 10.8 CuO
A
(4) (4)
Cu2O

9.4 CuO 9.4

Cu B Cu2O
pε (5) pε

8.0 8.0
Cu (6) C (6)
Cu
D
0 pH 0 pH

(a) (b)

Figure E6.2a and b

The relative stability equations are summarized in Table E6.2 and plotted in Figure E6.2a. It can be seen
from Figure E6.2a that the relative stability lines divide the pε-pH space into four regions, identified as A, B, C, and
D respectively. Region A indicates a single stable species, i.e., CuO. Similarly region D indicates a single stable
species, Cu. However in region B there are two competing species: Cu2O and CuO. Similarly region C shows two
competing species, i.e., Cu and Cu2O. We need to determine the predominant species in regions B and C. In order
to establish whether CuO or Cu2O is the predominant species in region B, we must invoke the relative stability
equation for the CuO/Cu2O pair, i.e., CuO → Cu2O if pε < 10.8 - pH (Equation 4). According to this constraint
CuO is unstable relative to Cu2O in region B. By following a similar procedure it can be shown that in region C,
Cu2O is more stable than Cu. Thus line 5 must be eliminated in Figure E6.2a. The resulting diagram is shown in
Figure E6.2b.

A B C D A B C D

Cu CuO Cu CuO
log[Cu2+] log[Cu2+]
(9) (8) (7) (9) (8) (7)

Cu2O Cu2O
CuO Cu2O Cu2O CuO
Cu Cu
3.0 4.5 5.8 pH 3.0 4.5 5.8 pH

Figure E6.2c, d.

(b) Again we must consider the relative stabilities of the pairs: (i) CuO→ Cu2O, (ii) Cu → CuO, and (iii)
Cu → Cu2O. Here too the constraints given by Equations 4, 5 and 6 must be followed, except that now
pε = 5.0 is specified. The resulting relative stability equations are summarized in Table E6.2 and plotted
in Figure E6.2c.

The relative stability lines labeled as 7, 8, and 9 divide Figure E6.2c into four regions identified as A, B,
C, and D. Among these, regions B and C indicate competing species. In region B the competing species
are Cu and Cu2O. The relative stability of these species is described by Equation 9 according to which
Cu2O is more stable than Cu above pH 3.0. Thus line 8 must be eliminated. The result is Figure E6.2d

Osseo-Asare Aqueous Processing 8

 Table E6.2

Species Type of Diagram Reaction Relative Stability Equation

(a) CuO, Cu2O, Cu pε-pH CuO → Cu2O pε < 10.8 - pH (4)

Cu → CuO pε > 9.4 -pH (5)
Cu → Cu2O pε > 8.0 -pH (6)

(b) CuO, Cu2O, Cu log{Cu2+}-pH CuO →Cu2O pH < 5.8 (7)

Cu → CuO pH > 4.5 (8)
Cu → Cu2O pH > 3.0 (9)

(c) Cu2+, CuO, Cu2O pε-pH Cu2+ → CuO pH > 3.65 (10)
Cu2+ → Cu2O pε < 3.5 + pH (11)
CuO → Cu2O pε < 10.8 -pH (4)

(d) Cu2+, CuO, Cu2O log{Cu2+} -pH Cu2+ → CuO log{Cu2+}>7.3-2pH (12)
Cu2+ → Cu2O log{Cu2+}>1.5-pH (13)
CuO → Cu2O pH < 5.8 (7)
_____

(c) The relative stability equations must be developed for the pairs (i) Cu2+ → CuO, (ii) Cu2+ → Cu2O,
and (iii) CuO → Cu2O.

(i) Cu2+/CuO . Equations 2 can be re-expressed as:

Cu2+ + H2O = CuO + 2H+ log K = -7.3

log Q = -2pH - log{Cu2+}

Thus Cu2+ → CuO if log Q < logK, i.e., if

pH > 7.3/2 - (1/2) log{Cu2+}

i.e.,
pH > 3.65, for {Cu2+} = 1.0 (10)

(ii) Cu2+/Cu2O. From Equation 3,

2 Cu2+ + 2e- + H2O = Cu2O + 2H+ log K = 7.0

log Q = -2pH - 2log{Cu2+} + 2 pε

Thus Cu2+ → Cu2O if log Q < logK, i.e., if

pε < 7.0/2 + log {Cu2+} + pH

i.e., if
pε < 3.5 + pH, for {Cu2+} = 1.0 (11)

(iii) CuO → Cu2O. The relevant relative stability equation was derived previously, i.e., CuO → Cu2O
if

Osseo-Asare Aqueous Processing 9

 pε < 10.8 -pH (4)

The relative stability equations are summarized in Table E6.2 and plotted in Figure E6.2e. It can be seen
that the relative stability lines divide the pε-pH space into six regions depicted as A, B, C, D, E, and F. In order to
determine the predominant species in region A, we must invoke the Cu2+/CuO relative stability relation, i.e.,
Equation 10. According to this equation, Cu2+ is stable relative to CuO when pH < 3.65. Thus we must eliminate
CuO and hence line 4 from region A. The result is a combined region A-B occupied by Cu2+ and bounded by lines
10 and 11 as illustrated in Figure E6.2f.

The competing species in region C are Cu2+ and Cu2O. Invoking the Cu2+/Cu2O relative stability
relation, i.e., Equation 11, it is found that Cu2+ is unstable below line 11. Accordingly Cu2+ and hence line 10
must be eliminated from region C. The result is a combined C-D region occupied by Cu2O and bounded by lines 4
and 11 as illustrated in Figure E10.2f.

In region E, CuO, and Cu2O are competing for occupation. The relevant relative stability relation is
provided by Equation 4, according to which Cu2O is unstable above line 4. Thus Cu2O and hence line 11 must be
eliminated from region E. The result is a combined E-F stability field occupied by CuO as shown in Figure E6.2f.

(d) The following relative stabilities must be considered: (i) Cu2+ → CuO, (ii) Cu2+ → Cu2O ,
(iii) CuO → Cu2O.

(i) Cu2+/CuO. From part (ci), Cu2+ → CuO if

log{Cu2+} > 7.3 - 2pH (12)

(ii) Cu2+/Cu2O . From part (cii), Cu2+ → Cu2O if

log{Cu2+} > -3.5 + pε -pH

That is, for pε = 5.0, if

log{Cu2+} > 1.5 + - pH (13)

(iii) CuO/Cu2O. The necessary relation was derived previously, i.e., Cu → Cu2O if

pH < 5.8 (7)

CuO Cu2+ CuO F

Cu2O A pε
pε (10)
(4) Cu2+ (10)
Cu2O Cu2+ CuO
(11)
7.15 B 7.15
E
CuO (4)
C Cu2O
(11)
Cu2+ (4)
(11)
(10)
Cu2O 2+ D
Cu CuO
3.65 pH 3.65 pH
(e) (f)
Figure 6.2e, f.

The relative stability equations are summarized in Table E6.2 and plotted in Figure E6.2g. It can be seen
from Figure E6.2g that the relative stability lines divide the plotting space into six regions, identified with the labels

Osseo-Asare Aqueous Processing 10

A, B, C, D, E, and F respectively. In region A, the competing species are CuO and Cu2O. Therefore, the pertinent
relative stability relation is provided by Equation 7. According to Equation 7, CuO is unstable relative to Cu2O
when pH < 5.8. Thus CuO, and hence line 12 must be eliminated. It can be seen that in the absence of line 12, a
Cu2O stability domain is obtained, bounded by lines 13 and 7.

In region C, the competing species are Cu2+ and Cu2O. The Cu2+/Cu2O relative stability is defined by
Equation 13. According to this relation, below line 13, Cu2O is unstable relative to Cu2+. Thus Cu2O is unstable
relative to Cu2+. Thus Cu2O and hence line 7 must be eliminated from region C. With the elimination of line 7, a
Cu2+ stability field is obtained, with its upper boundaries consisting of lines 12 and 13.

In the case of region E, the contending species are Cu2+ and CuO and the relevant relative stability
relation is Equation 12. According to Equation 12, CuO is the stable species above line 12. Therefore Cu2+ and
hence line 13 must be eliminated. The elimination of line 13 reveals a CuO predominance area bounded by lines 12
and 7. The final overall diagram is presented in Figure E6.2h.

6.3 Metal-Water and Metal-Ligand-Water Systems

6.3.1 Metal-Water Systems
We are concerned here with predominance area diagrams of systems of the type M-
H2O, e.g., Ag-H2O, Al-H2O, Fe-H2O, Pt-H2O, Y-H2O, and Zr-H2O. Both equilibrium and
pseudoequilibrium diagrams are of interest. In constructing equilibrium diagrams it is necessary
to consider the relative stabilities of pairs of all the M-containing species for which the relevant
thermodynamic data are available. On the other hand, in the case of pseudoequilibrium
diagrams, certain species may be deliberately eliminated from consideration in order to match
experimental observations where kinetic conditions do not favor the formation of the
thermodynamically stable species.
____
EXAMPLE 6.3 pε-pH and log{M}-pH diagrams for the Cu-H2O System

The Cu2+/Cu equilibrium is given by

Cu2+ + 2e- = Cu logK = 11.44

Based on this and the data presented in Example 6.2, prepare (a) pε-pH, and (b) log{Cu}-pH diagrams for the Cu-
H2O system. For the pε-pH diagram assume {Cu2+} = 1.0 and for the log{Cu}-pH diagram use pε = 5.0.

Solution

The pertinent Cu-containing species are CuO, Cu2O, Cu(s), and Cu2+. There are four species and
therefore 4(3)/2 = 6 relative stability equations are needed: (i) CuO → Cu2O, (ii) Cu → CuO, (iii) Cu → Cu2O,
(iv) Cu2+ → CuO, (v) Cu2+ → Cu2O, and (vi) Cu2+ → Cu. With the exception of the Cu2+/Cu pair, all the
relevant equilibria were considered above in Ex. 6.2. In the case of the Cu2+/Cu equilibrium, Cu2+ → Cu if

- log{Cu2+} + 2pε < 11.44

That is, for {Cu2+} = 1.0, if

Osseo-Asare Aqueous Processing 11

 pε < 5.72 (14)

or for pε = 5.0, if

log {Cu2+} > -1.44 (15)

The above equations are numbered in continuation of the numbering system used in Ex. 6.2. The predominance
area associated with Equations 14 and 15 are shown in Figures E6.3a and b in terms of pε-pH and log{Cu2+}-pH
diagrams respectively.

pε log {Cu}2+
Cu
Cu 2+
−1.44
(15)
(14) Cu 2+
5.72
Cu

pH pH
(a) (b)
Figure E6.3a,b.

Table E6.3a. Line Elimination for the pε-pH diagram

Region Competing Species Rel. Stab. Eq. Stable Species Action _____

A CuO, Cu2+ 10 CuO Eliminate line 14 to obtain combined

region A-G.

B Cu2O, Cu2+ 11 Cu2+ Eliminate line 14 to obtain combined

region B-C.

D Cu,Cu2+ 14 Cu Eliminate line 11 to obtain combined

region D-E.

F Cu,Cu2O 6 Cu2O Eliminate line 14 to obtain combined

region F-H.
______

(a) In Figure 6.3c, the relative stability lines depicted in Figures E6.2b, E6.2f, and E6.3a have been
superimposed. These lines establish eight regions identified as A, B, C, D, E, F, G, and H. Each
region indicates a pair of competing species. In each region we must establish which of the two
species represents the predominant species. In order to accomplish this, we need to invoke the
appropriate relative stability equation. This analysis is summarized in Table E6.3a, and the final
diagram is presented in Figure 6.3d.

(b) For the log{Cu2+} -pH diagram, we must consider the superposition of the relative stability lines
shown in Figures 6.2d, 6.2h, and 6.3b, as is indicated in Figure 6.3e. It can be seen in Figure 6.3e
that the interaction of the relative stability lines produces eight regions: A, B, C, D, E, F, G, H
each with a pair of competing species. Table E6.3b summarizes the line elimination process and
Figure 6.3f presents the overall log{Cu2+}-pH diagram.

Osseo-Asare Aqueous Processing 12

 Table E6.3b Line Elimination for the log{Cu2+} -pH diagram

Region Competing Species Rel Stabl. Eq. Stable Species Action _____

A Cu2+,CuO 12 CuO Eliminate line 15 to obtain

combined region A-B.

C Cu2O,Cu 9 Cu2O Eliminate line 15 to obtain

combined region C-H.

D Cu2O,Cu 9 Cu Eliminate line 13 to obtain

combined region D-E.

F Cu,Cu2+ 15 Cu2+ Eliminate line 9 to obtain

combined region F-G.
_____

Cu 2+ CuO

B (10)
8.0 Cu2O
Cu A
7.5 (6) (4)
pε H
Cu2+
C (11) Cu2O CuO
Cu2O
Cu 2+ (14) Cu 2+ (14) Cu2+
5.72 Cu Cu (14) Cu
(6) (4) G
F
D
(11) Cu2O CuO
Cu 2+
E Cu2O
Cu
Cu2O

2.22 3.65 5.08 pH

(c)

pε

Cu2+ CuO
7.5

5.72

Cu 2 O
Cu

2.22 3.65 5.08 pH

(d)
Figure E6.3c, d

Osseo-Asare Aqueous Processing 13

 Figure E6.3e, f

EXAMPLE 6.4 Eh-pH Diagram for the Ga-H2O System

In the Eh-pH diagram of the Ga-H2O system at 25°C and {Ga} = 10-3, predominance fields appear for
-
the following species: Ga3+, Ga2O3(s), Ga(OH)4 , and Ga(s). Given the data provided below, generate the
relevant Eh-pH diagram for -2.0 <Eh(V) < 2.0, 0 < pH < 14.

Ga(s) = Ga3+ + 3e- logK = 28.4 (1)

Ga2O3(s) + 6H+ = 2Ga3+ + 3H2O logK = 4.03 (2)
-
Ga(OH)4 + 4H+ = Ga3+ + 4H2O logK = 16.6 (3)

Solution
-
There are four Ga-containing species: Ga3+, Ga(s), Ga2O3(s), and Ga(OH)4 . Thus 4(3)/2 = 6 relative
-
stability equations are needed, i.e., (i) Ga(s) → Ga3+, (ii) Ga2O3(s) → Ga3+, (iii) Ga(OH)4 → Ga3+, (iv) Ga(s) ∅
- -
Ga2O3(s), (v) Ga(s) → Ga(OH)4 , and (vi) Ga2O3(s) → Ga(OH)4 .

(i) Ga(s)/Ga3+: From Equation 1,

Ga(s) = Ga3+ + 3e- logK = 28.40

L → R if log{Ga3+} -3pε < logK = 28.40

i.e., if pε > -28.40/3 + 1/3 log{Ga3+} = -9.47 + 1/3 log{Ga3+}

Thus, for {Ga} = 10-3, Ga → Ga3+ if

pε > -10.47, i.e., Eh > -0.62V (4)

(ii) Ga2O3(s)/Ga3+: From Equation 2,

Osseo-Asare Aqueous Processing 14

 Ga2O3(s) + 6H+ = 2Ga3+ + 3H2O logK = 4.03

L → R if 2 log{Ga3+} + 6pH < logK = 4.03

i.e., if pH < 4.03/6 - 1/3 log{Ga3+} = 0.672 - 1/3 log{Ga3+}

Thus, for {Ga} = 10-3, Ga2O3 → Ga3+ if

pH < 1.67 (5)

-
(iii) Ga(OH)4 /Ga3+: From Equation 3,
-
Ga(OH)4 + 4H+ = Ga3+ + 4H2O logK = 16.6
-
L → R if log{Ga3+} + 4pH - log{Ga(OH)4 } < logK = 16.6
i.e., if pH < 16.6/4
- -
where it is assumed that at the Ga(OH)4 /Ga3+ boundary, {Ga(OH)4 } = {Ga3+}.
-
Thus, Ga(OH)4 → Ga3+ if

pH < 4.15 (6)

(iv) Ga(s)/Ga2O3(s): From Equations 1 and 2,

2 Ga(s) = 2Ga3+ + 6e- logK = 2(28.4) = 56.8

2 Ga3+ + 3H2O = Ga2O3(s) + 6H+ logK = -4.03

2 Ga(s) + 3H2O = Ga2O3(s) + 6H+ + 6e- logK = 52.77

L → R if -6pH - 6pε < logK = 52.77

i.e., if pε > - 52.77/6 - pH

Thus, Ga → Ga2O3 if

pε > -8.80 - pH, i.e., Eh > -0.52 - 0.059 pH (7)

-
(v) Ga(s)/Ga(OH)4 : From Equations 1 and 3,

Ga(s) = Ga3+ + 3e- log K = 28.4

-
Ga3+ + 4H2O = Ga(OH)4 + 4H+ logK = -16.6

-
Ga(s) + 4H2O = Ga(OH)4 + 4H+ + 3e- logK = 11.8

-
L → R if -4pH - 3pε + log{Ga(OH)4 } < logK = 11.8
-
i.e., if pε > -11.8/3 + (1/3)log{Ga(OH)4 } - (4/3)pH

Osseo-Asare Aqueous Processing 15

 Table E6.4

Figure Region Competing Species Rel. Stabl. Eq. Stable Species Action____

10.4a, b A Ga3+ only - Ga3+ Keep Ga3+ in region

A.

B Ga3+, Ga2O3 5 Ga2O3 Eliminate line 6 to

obtain combined
region B-C.

- - -
D Ga(OH)4 only - Ga(OH)4 Keep Ga(OH)4 in
region D.

- -
10.4c, d A Ga(OH)4 , Ga2O3 9 Ga(OH)4 Eliminate line 8 to
obtain combined
region A-F.

-
B Ga(OH)4 ,Ga2O3 9 Ga2O3 Eliminate line 8 to
obtain combined
region B-C.

D Ga,Ga2O3 7 Ga Eliminate line 9 to

obtain combined
region D-E.

- -
10.4e, f A Ga3+,Ga(OH)4 6 Ga(OH)4 Eliminate line 4 to
obtain combined
region A-G.

B Ga3+,Ga2O3 5 Ga2O3 Eliminate line 4 to

obtain combined
region B-H.

C Ga3+,Ga2O3 5 Ga3+ Eliminate line 7 to

obtain combined
region C-D.

E Ga3+,Ga 4 Ga Eliminate line 5 to

obtain combined
region E-F.
_____

Osseo-Asare Aqueous Processing 16

 Figure E6.4 Eh-pH diagram for the Ga-H2O system

Osseo-Asare Aqueous Processing 17

 -
Thus, for {Ga} = 10-3, Ga → Ga(OH)4 if

pε > -4.93 - 1.333 pH, i.e., Eh > -0.291 - 0.0786pH (8)

-
(vi) Ga2O3(s)/Ga(OH)4 : From Equations 2 and 3,

Ga2O3(s) + 6H+ = 2Ga3+ + 3H2O logK = 4.03

-
2Ga3+ + 8H2O = 2Ga(OH)4 + 8H+ logK = -33.2

-
Ga2O3(s) + 5H2O = 2Ga(OH)4 + 2H+ logK = -29.17

-
L ∅ R if -2pH + 2 log{Ga(OH)4 } < logK = -29.17
- -
i.e., if pH > 29.17/2 + log {Ga(OH)4 } = 14.6 + log{Ga(OH)4 }

-
Thus, for {Ga} = 10-3, Ga2O3 → Ga(OH)4 if
pH > 11.6 (9)

The line eliminations are summarized in Table E6.4 and Figure E6.4.
____________________________________________________________________________________________

6.3.2 Ligand-Water Systems

The introduction into the aqueous phase of a complexing ligand or an anion which
forms an insoluble compound and/or complexes with the metal ion complicates the solid-
solution equilibria. In some cases the ligands may be protolyzable and/or may undergo redox
reactions. Therefore, before considering stability relations in metal-ligand-water systems, it is
useful to examine the corresponding ligand-water equilibria.

(a) Methanol-CO3-H2O (b) Formate-CO3-H2O

Figure 6.2a and b Eh-pH diagrams for the C-H2O System.

Osseo-Asare Aqueous Processing 18

 (c) Oxalate - CO3 -H2O

Figure 6.2c and d Eh-pH diagrams for the C-H2O system.

Figure 6.2 presents Eh-pH diagrams illustrating the relative stabilities of several soluble
derivatives of carbon. According to these diagrams it is theoretically possible to reduce
- 2-
H2CO3(aq), HCO3 and CO3 to compounds such as methanol (CH3OH; Figure 6.2a), formic
acid (HCOOH; Figure 6.2b), and oxalic acid (H2C2O4; Figure 6.2c). In practice however, these
reduction reactions are not observed at ordinary temperatures and pressures since they are not
kinetically favorable. Also these diagrams show that methanol, graphite (C), formic acid and
formates, as well as oxalic acid and oxalates are all oxidizable to carbonates. However these
reactions tend to be extremely slow, and in the absence of catalysts and/or extreme reaction
conditions these oxidations are not observed.

Figure 6.3a presents an Eh-pH diagram of the N-H2O system and it shows the stability
regions of dissolved nitrogen compounds. It can be seen that from a thermodynamic standpoint
nitric acid (HNO3) can be reduced readily to nitrous acid (HNO2). Nitrous acid in turn readily
+
decomposes to give NH4 . Corresponding reduction of the nitrate ion involves similar reaction

Osseo-Asare Aqueous Processing 19

 - - +
sequences, e.g. NO3 → NO2 → NH4 . The Eh-pH diagram for the CN-H2O system shown
in Figure 6.3b indicates that the water stability region is occupied mainly by the cyanate ion
(CNO-). In practice, however, the formation of cyanate from cyanide (CN-) and cyanogen
(HCN) is inhibited by the slow kinetics of cyanide oxidation in aerated solutions.

(a) N-H2O

(b) CN-H2O

Figure 6.3 Eh-pH diagrams for the systems: (a) N-H2O, (b) CN-H2O at 25˚C.

Osseo-Asare Aqueous Processing 20

 (c) P-H2O

(d) As-H2O

Figure 6.3 (cont’d). Eh-pH diagrams for the systems: (c) P-H2O,
(d) As-H2O at 25˚C.

Osseo-Asare Aqueous Processing 21

 An Eh-pH diagram for the P-H2O system is presented in Figure 6.3c. It can be seen
that elemental phosphorus is highly unstable in aqueous solution, its domain of stability lying
below the water stability region. This is indeed observed in nature; phosphorus is not found in
the elemental state but the oxidized state in minerals such as apatite. The location of the stability
domains of hypophosphorous acid (H3PO2) and the hypophosphite
-
H2PO2 (i.e., below the lower water stability line) suggests that these compounds are strong
reducing agents and that they should be extremely unstable in aqueous solution. That is, they
should reduce water with hydrogen evolution and be oxidized themselves to phosphorous acid
- 2-
(H3PO3) and phosphites (H2PO3 , HPO3 ). This reaction is extremely slow and therefore in
the absence of oxidizing agents, hypophosphorous acid and hypophosphite exhibit considerable
stability in aqueous solution. The reducing power of these phosphorous compounds is, however,
readily observed in the presence of catalysts (e.g. Cu, Ni, Pd, C (graphite powder)). The location
-
of the stability regions of orthophosphorous acid (H3PO3) and the orthophosphite ions (H2PO3 ,
2-
HPO3 ) also indicates considerable instability with respect to water. However, again, the
- 2-
kinetics are slow and thereforein the absence of catalysts, H3PO3 as well as H2PO3 and HPO3
remain in solution. Finally it can be seen that in the entire stability field of water, phosphoric
- 2- 3-
acid (H3PO4) and the phosphates (H2PO4 , HPO4 , PO4 ) represent the thermodynamically
stable phosphorus compounds.
The aqueous stability of arsenic compounds is presented in the Eh-pH diagram of Figure
6.3d. It can be seen that, under nonoxidizing conditions, elemental arsenic has some
thermodynamic stability within the water stability domain. Oxidation of arsenic gives
successfully As(III) compounds (the arsenyl cation AsO+, arsenious acid HAsO2, arsenious
-
anhydride As2O3, and the arsenite anion AsO2 ), and As(V) compounds (arsenic acid H3 AsO4,
- 2- 3-
and the arsenates H2AsO4 , HAsO4 , AsO4 ). In general, the oxidation of the As(III) to As(V)
compounds is slow and strong oxidizing agents are required. Similarly the reverse reaction, the
reduction of As(V) to As(III) compounds tends to be slow.
The equilibrium Eh-pH diagram for the S-H2O system is presented in Figure 6.4a. It
- 2-
can be seen that the stability domains of the sulfate species HSO4 and SO4 together cover
- 2-
most of the water stability region. It is thermodynamically possible to reduce HSO4 or SO4 to
elemental sulfur and sulfides (H2S, HS-, S2-). However the reduction reaction is too slow to
proceed under ordinary conditions. Figure 6.4b presents an Eh-pH diagram for the S-H2O
- 2-
system in which the thermodynamically stable compounds HSO4 and SO4 were not
considered. A comparison of Figures 6.4a and b emphasizes the fact that when found in aqueous
Osseo-Asare Aqueous Processing 22
 2- 2-
solution, the lower sulfur oxides (e.g. sulfite, SO3 ; thiosulfate, S2O3 ) represent metastable
species. The equilibrium stability relationships in the Cl-H2O system are presented in Figure
6.4c. It can be seen that the thermodynamically stable species are molecular chlorine (Cl2),
-
perchlorate ion (ClO4 ), and the chloride species HCl and Cl-. It follows therefore that the
- -
presence of chlorates (ClO3 ), chlorites (ClO2 ) and hypochlorites (ClO-), in aqueous solution
represents metastability. The domains of predominance of HCl and Cl- occupy practically the
entire waterstability domain. Thus the perchlorate ion is thermodynamically unstable in aqueous
-
solution. However the ClO4 to Cl- reaction is negligibly slow. The corresponding equilibrium
- -
diagram for the Br H2O system is shown in Figure 6.4d. The Br stability domain occupies
almost the entire water stability region. Here too, hypobromite (BrO-) solutions must be viewed
as existing under partial equilibrium.

Osseo-Asare Aqueous Processing 23

 (a)

(b)
-
Figure 6.4 Eh-pH diagrams at 25˚C for the systems: (a) S-H2O, (b) S-H2O, with HSO4
2-
and SO4 not considered.

Osseo-Asare Aqueous Processing 24

Figure 6.4 (contd.) Eh-pH diagrams at 25˚C for the systems: (c) Cl-H2O, (d) Br-H2O, (e) I-
H2O; {X} = 1.0.

Osseo-Asare Aqueous Processing 25

Figure 6.5 Eh-pH diagrams for the systems: (a) Au-H2O, (b) Ag-H2O, (c) Pt-H2O, (d) Pd-H2O.

Osseo-Asare Aqueous Processing 26

Figure 6.6 Eh-pH diagrams for the systems: (a) Au-Cl-H2O, (b) Ag-Cl-H2O, (c) Pt-Cl-H2O, (d) Pd-Cl-H2O.

Osseo-Asare Aqueous Processing 27

EXAMPLE 6.5 Selective Recovery of Gold from Chloride Solutions Containing Precious Metals

A strongly acidic solution contains chlorides of Au(III), Pt(IV), and Pd(IV). With the aid of Figure 6.6,
show that this solution can be treated with a reductant to selectively precipitate metallic gold.

Solution

Figure E6.5a shows a superposition of the acidic regions of the Au-Cl-H2O and Pt-Cl-H2O diagrams taken from
Figure 6.6. The corresponding superposition of the Au and Pd systems is shown in Figure E6.5b. It can be seen
-
that as the Eh is lowered, AuCl4 is reduced to give metallic gold under conditions where Pt and Pd remain in
2- 2-
solution. Platinum will remain unchanged as PtCl6 , whereas palladium will undergo reduction from PdCl6 to
2-
PdCl4 .

PdCl 2-
6
1.2 AuCl -4 1.2 AuCl -4
Au Au

PtCl 2-
Eh(V) 6 Eh(V)
PtCl 2-
4
PdCl 2-
0.4 Pt 0.4 4
Pd

pH pH
(a) (b)
Figure E6.5 (a) Superposition of the Au-Cl-H2O and Pt-Cl-H2O systems,
(b) Superposition of the Au-Cl-H2O and Pd-Cl-H2O systems.

6.3.3 Metal-Ligand-Water Systems

2- 2-
In the previous section it was found that, in principle, ligands such as CO3 , C2O4 ,
2-
NH3, PO4 , Cl-, and S2- can undergo both protonation and redox reactions. When constructing
predominance area diagrams for metal-ligand-water systems involving protolyzable and/or
oxidizable/reducible ligands, it is necessary to consider the protonation and redox equilibria of
the ligands. However as indicated in Section 6.3.2, under ordinary temperatures and pressures,
many of the ligand-based redox reactions are kinetically unfavorable. Thus under these
conditions it is usually reasonable to neglect the redox behavior of the ligand; the protonation
reactions must, however, be taken into consideration.
Consider a ligand L which protonates up to HnL (for simplicity the charges on the ligand
and the protonated species are not indicated), and forms complexes of the type MLj (complexes
of other types e.g., M(HL)i may form without changing the argument). Where pH is a plotting
variable (e.g., diagrams of the type pε-pH, Eh-pH, log{M}-pH, log{L}-pH), it becomes
necessary to view the plotting space in terms of (n + 1) subdiagrams. This is schematically
Osseo-Asare Aqueous Processing 28
illustrated in the Eh-pH diagram presented in Figure 6.7 for the case of a protolyzable ligand
where n=3.
In constructing an Eh-pH diagram for the M-L-H2O system, relative stability equations
in region A must be written with the dissolved "free ligand" shown as H3L, e.g.,

A B C D
Eh

2+
H3L 3+ H 2L HL+ L

pH

Figure 6.7 Subdiagram regions for the M-L-H2O system based on the predominance areas
of L-containing species in the L-H2O system.

z+
MLj + 3jH+ = Mz+ + jH3L3+ (6.19)
Similarly in regions B, C, and D, the pertinent dissociation reactions are Equations 6.20, 6.21
and 6.22 respectively:

MLjz+ + 2jH+ = Mz+ + jH2L2+ (Region B) (6.20)

MLjz+ + jH+ = Mz+ + jHL+ (Region C) (6.21)
MLjz+ = Mz+ + jL (Region D) (6.22)
____
EXAMPLE 6.6. pε-pH Diagram for the Au-CN-H2O System

Selected thermodynamic data for the Au-CN-H2O system are provided below. Using these data, generate
a pε-pH diagram in the range -15<pε<30, 6<pH<12. Assume {Au} = 1.0, and {HCN + CN} = 1.0.

Reaction logK
Au(OH)3(s) + 3H+ + 2e- = Au+ +3H2O 45.32
Au = Au+ + e- -28.62
-
Au(CN)2 = Au+ + 2CN- -38.10
H+ + CN- = HCN 9.21

Solution

We must first take note of the hydrogen cyanide equilibrium, Equation 1:

H+ + CN- = HCN logK = 9.21 (1)

According to this equation, CN → HCN if

Osseo-Asare Aqueous Processing 29

 logK = 9.21 > log{HCN} + pH - log{CN-} (2)

At the boundary between the HCN and CN stability regions, {HCN} = {CN-} and therefore, Equation 2 can be
interpreted to mean, CN → HCN if,

pH < 9.21 (3)

The stability diagram described by Equation (c) is depicted in Figure E6.6a.

pε
HCN(aq) CN -

9.2 pH

Figure E6.6a

Table E6.6. Summary of pε-pH Relative Stability Equations for the Au-CN-H2O System

Eq. for {Au} = 1.0

Reaction Eq. No. General Equation {HCN + CN-} = 1.0

Au(OH)3(s) → Au 4 pε<24.65 - pH pε<24.65 - pH

Au(OH)3(s) → Au+ 5 pε<22.66-3/2pH - 1/2log {Au+} pε<22.66 - 3/2 pH

-
Au(OH)3(s) → Au(CN)2 6a(HCN) pε<32.5 - 1/2pH - 1/2log pε<32.5 - 1/2 pH
-
{Au(CN)2 } + log {HCN}

6b(CN-) pε<41.71-3/2pH-1/2log pε<41.71-3/2 pH

-
{Au(CN)2 }+log{CN-}

Au → Au+ 7 pε>28.62 + log{Au+} pε>28.62

-
Au → Au(CN)2 8a(HCN) pε>8.94-2pH - 2log{CN-} pε>-9.48
-
+ log{Au(CN)2 }

8b(CN-) pε>-9.48 - 2log{CN-} pε>-9.48

-
+ log{Au(CN)2 }

-
Au+ → Au(CN)2 9a(HCN) pH> -9.84 - log{HCN} pH> -9.84

9b(CN-) 19.05 > - log{CN-} 19.05 > 0

Osseo-Asare Aqueous Processing 30

 When considering the Au-CN-H2O system, the fact that the cyanide species changes from HCN to CN-
above pH 9.21, means that the total plotting space must be considered in terms of two sub-diagrams; one involving
the HCN region (pH < 9.21) and the other the CN- region pH > 9.21.
-
There are four Au-containing species to be considered: Au(OH)3(s) , Au(s), Au+ and Au(CN)2 .

Therefore the following 4(4-1)/2 = 6 relative stability relations must be developed: Au(OH)3(s) /Au,
- - -
Au(OH)3(s)/Au, Au(OH)3(s)/Au(CN)2 Au/Au+, Au/Au(CN)2 and Au+/Au(CN)2 . Table E6.6 summarizes the

resulting relative stability equations.

Inspection of Equations 9a and 9b reveals that the aurous ion, Au+ is unstable with respect to the
- -
aurocyanide complex, Au(CN)2 . According to Equation 9a, Au+→ Au(CN)2 if pH > -9.84: our present analysis is
-
for pH > 6.0. Similarly, according to Equation 9b, Au → Au(CN)2 if 19.05 > 0, an inequality which is, of course,

satisfied. Thus all equations involving Au+ can be ignored (i.e., 5, 7, 9a and 9b). Figure E6.6b presents plots of
the remaining equations (i.e., 4, 6a, 6b, 8a and 8b). It should be noted that in view of the HCN/CN- stability
relation (see Figure E6.6a), Equations 6a and 8a are valid only for pH < 9.21, while Equations 6b and 8b are valid
only for p>9.21.

Osseo-Asare Aqueous Processing 31

 A B C
30 Au(OH)3 (3b)
K - L
Au(CN)2 (3a) (3a)
(3b) Au(OH)3
Au(CN)-2 D
20 Au(OH)3
J M
Au (9)
Au(OH)3
Au E
p ε 10

0
I
Au(CN) 2-
Au (5a) -
H (5b) Au(CN) 2
-10 (5b) Au F
(5a) G
(b) 6 8 10 12
pH

Au(OH)3
30 L
K (3a)
(3b)
D
20

p ε 10 Au(CN)2-

0
I
(5a)
H (5b)
-10 F
Au
6 8 10 12
(c) pH

Figure E6.6b,c

Osseo-Asare Aqueous Processing 32

 -
Region KLMJ in Figure E6.6b indicates the presence of two species: Au(CN)2 and Au(OH)3. The
relative stability of these species is given by Equation 9a, according to which Au(OH)3 is unstable below line 9a
(i.e., line KL). Therefore line JM must be eliminated. Similar reasoning eliminates line ME. The final diagram is
shown in Figure E6.6c.

(a)

Figure 6.8 Eh-pH diagrams for the systems (a) Cu-S-H2O

As indicated above, oxidizable/reducible ligands may be encountered in certain M-L-

H2O systems. Examples of such systems are those of the type L = S, Se, Te, As. Figure 6.8
presents Eh-pH diagrams for the systems Cu-S-H2O, Ag-Se-H2O, Ag-Te-H2O, and Ga-As-H2O.
Table 6.1 shows that these diagrams are the result of the combination of several subdiagrams. It
is interesting to note that the ligands indicated in Table 6.1 undergo both redox and protonation
reactions.

Osseo-Asare Aqueous Processing 33

 (b) (c)

(d)

Figure 6.8 (contd) Eh-pH diagrams for the systems: (b) Ag-Se-H2O, (c) Ag-
Te-H2O, (d) Ga-As-H2O.

Osseo-Asare Aqueous Processing 34

Table 6.1. Subdiagrams for M-L-H2O systems with protolyzable and oxidizable/reducible
ligands

M-L-H2O No. of L Species Corresponding

System subdiagrams to Individual Subdiagrams

- 2-
M-S-H2O 6 HSO4 , SO4 , S, H2S(aq), HS-, S2-

- 2- - 2-
M-Se-H2O 9 HSeO4 , SeO4 , H2SeO3(aq), HSeO3 , SeO3
2-
Se, Se2 , H2Se, HSe-

- 2-
M-Te-H2O 12 Te(OH)6(aq), TeO(OH)5 , TeO2(OH)4 ,
+ - 2-
Te(OH)3 , TeO2(s), TeO(OH)3 , TeO2(OH)2 ,
2-
Te, Te2 , H2Te, HTe-, Te2-

- 2-
M-As-H2O 9 H3AsO4(aq), H2AsO4 , HAsO4 ,
- 2- 3-
As2O3(s), H2AsO3 , HAsO3 , AsO3 ,
As, AsH3(g)

EXAMPLE 6.7. pε-pH Diagram for the Zn-S-H2O System

Selected thermodynamic data for the Zn-S-H2O system are presented below. On the basis of these data,
prepare a pε-pH diagram for the range -2 < pH < 2, - 20 < pε < 15. Assume {Zn} = 10-6, {S} = 1.0.

Reaction logK
-
ZnS + 4H2O = Zn2+ + HSO4 + 8e- + 7H+ -43.83
Zn = Zn2+ + 2e- 25.82
-
S + 4H2O = HSO4 + 7H+ + 6e- -34.24
-
H2S + 4H2O = HSO4 + 8e- + 9H+ -38.98

Solution

There are three Zn-containing species: ZnS, Zn, and Zn2+; therefore the required relative stability
equations involve the pairs ZnS/Zn, ZnS/Zn2+ and Zn/Zn2+. It must be noted that ZnS decomposition produces
-
different sulfur species (HSO4 , S, H2S) depending on the pε and pH. Thus, we need to consider the S-H2O

stability relations before tackling the Zn-S-H2O system. For the S-H2O system, the relevant species in the specified
-
Eh-pH space are HSO4 , S, and H2S. There are three species, and therefore three relative stability equations are

- -
necessary, i.e., (i) HSO4 → S, (ii) HSO4 → H2S, (iii) S → H2S. The relevant relative stability equations are

Osseo-Asare Aqueous Processing 35

presented in Table E6.7b and plotted in Figure E6.7a. The conflicting claims for predominance are reconciled by
eliminating line 2, as indicated in Figure E6.7b.

Reaction General Relative Stability Equation Equation for {S} = 1.0

- -
HSO4 → S(1) pε < 5.71 + 1/6 log {HSO4 }-7/6pH pε < 5.71 - 7/6 pH
-
HSO4 → H2S(2) pε < 4.87 - 9/8 pH pε < 4.87 - 9/8 pH
S → H2S(3) pε < 2.90 - 1/2 log{H2S}-pH pε < 2.40 - pH

5.71 5.71
- -
HSO4 HSO4
S
pε pε
-
HSO4
H2S S

2.4 S 2.4
H2S
H2S

pH pH

Figure E6.7a,b The S-H2O system

Table E6.7b Relative stability equations for the Zn-S-H2O system

Reaction Eqn.No. General Equation Eqn. for {Zn2+}=10-6 and {S} = 1.0

-
ZnS → Zn 1a pε>11.60-7/6pH + 1/6log{HSO4 } pε>11.60 - 7/6pH

1b 35.70 < 0 35.70 < 0

1c pε<-15.41 - pH - 1/2log{H2S} pε<-15.41 - pH

-
ZnS → Zn2+ 2a pε>5.48 - 7/8 pH + 1/8log{HSO4 } pε>4.73 - 7/8 pH
+ 1/8log{Zn2+}

2b pε>4.96 + 1/2log{Zn2+} pε> 1.96

2c pH< -2.52-1/2log{Zn2+} pH< 0.48

- 1/2log{H2S}

Zn → Zn2+ 3 pε>-12.90 + 1/2log{Zn2+} pε>-15.90

Osseo-Asare Aqueous Processing 36

 It can be seen from Figure E6.7a that for the Zn-S-H2O system, we need to consider three subdiagrams,
-
involving: Zn-HSO4 -H2O, Zn-S-H2O and Zn-H2S-H2O. The relevant relative stability equations are presented in
Table E6.7b.

Zn A HSO-4 STABILITY
10 ZnS 1a 10 2+
Zn 2+ B Zn
ZnS 2a 2a
0 0
-pε -pε ZnS
C
-10 -10
2+
3 Zn
Zn D
-20 -20
-2 -1 0 1 2 -2 -1 0 1 2
(c) pH (d) pH

Figure E6.7c,d

2+
Zn
10 A o 10 o
S STABILITY S STABILITY
Zn 2+
0 ZnS 2b 0 2b
pε pε
ZnS
B
-10 -10
2+
3 Zn
Zn C
-20 -20
-2 -1 0 1 2 -2 -1 0 1 2
(e) pH (f) pH

Figure E6.7e,f

10 A 2c 10 2c
F
So So
H 2S H 2S
0 0
pε Zn 2+ ZnS pε ZnS
Zn 2+
-10 ZnS -10
Zn 2+ E
3 B Zn 3
C Zn D 1c Zn 1c
-20 -20
-2 -1 0 1 2 -2 -1 0 1 2
(g) pH (h) pH
Figure E6.7g,h

Osseo-Asare Aqueous Processing 37

 HSO -4

S
(2b)
H2S

pε Zn 2+
(2c)
ZnS
(3)
(1c)

Zn
0.48
(i) -2.0 pH 2.0

Figure E6.7i. Composite diagram for the Zn-S-H2O system.

-
The Zn-HSO4 -H2O System. Equations 1a, 2a and 3 have been plotted in Figure E6.7c. The lines

corresponding to these equations divide the plotting space into the regions identified as A, B, C, D. Region B
shows two competing species, ZnS and Zn2+. The relative stability equation for this pair of species, Equation 2a,
indicates that ZnS is unstable above line 2a. Therefore line 1a separating regions A and B must be eliminated.
Region C shows two competing species, ZnS and Zn2+. Again, referring to the ZnS/Zn2+ relative stability
equation, Equation 2a, Zn2+ is unstable below line 2a, and therefore line 3 must be eliminated. The resulting
equation is shown in Figure E6.7d.

The Zn-S-H2O System. According to Equation 1b, ZnS → Zn if 35.70 < 0. Since this requirement is
impossible, it follows that within the stability range of elemental sulfur, ZnS cannot be transformed to Zn.
Therefore ZnS is the stable species relative to Zn. Equations 2b and 3 have been plotted in Figure E6.7e. In region
B, two competing species are indicated: ZnS and Zn2+. The relevant relative stability equation is Equation 2b.
According to this equation, Zn2+ is unstable below line 2b; therefore line 3 must be eliminated. The final diagram
is shown in Figure E6.7f.

The Zn-H2S-H2O System. Equations 1c, 2c and 3 have been plotted in Figure E6.7g. In region A, the

Zn2+/ZnS relative stability must be determined. According to Equation 2c, ZnS is unstable when pH<0.48;
therefore the portion of line 1c separating regions A and B must be eliminated. In region C, Zn/Zn2+ must be
considered. According to Equation 3, Zn2+ is unstable below line 3; therefore the portion of line 2a separating
regions C and D must be eliminated.
In region E, the pair Zn/ZnS must be compared with Equation 1c. According to this equation, Zn is
unstable above line 1c; therefore the portion of line 3 separating regions E and F must be eliminated. The final
diagram for the Zn-H2S-H2O system is shown in Figure E6.7h.

Osseo-Asare Aqueous Processing 38

 Figures E6.7d, f and h can be combined to give the composite stability diagram for the Zn-S-H2O system.
In combining these figures, the constraints imposed by the stability diagram of the S-H2O system (Figure E6.7b)
-
must be borne in mind, i.e., only the part of Figure E6.7d occupying the HSO4 stability region of Figure E6.7b is

to be used; similarly the S region for Figure E6.7f and the H2S region for Figure E6.7h apply. The resulting
composite diagram is shown in Figure E6.7i.

6.3.4 Metal-Multiligand-Water Systems

Aqueous solutions are inherently multi-ligand systems. Thus even the simple metal-
water system contains H2O and OH- as potential ligands. However in this section we are
particularly interested in systems which have more than two ligands besides the usual H2O -
derived ligands i.e., systems of the type M-L1-L2-H2O, M-L1-L2-L3-H2O, etc., where L1, L2,
L3, etc are different ligand species. The simplest examples of such systems are those containing
only two ligands, e.g., M-SO4-Cl-H2O, M-CN-Cl-H2O, and M-NH3-CO3-H2O.

pε HA pε
A- H3B H2B- HB2- B3-

(a) pH (b) pH

HA HA A- A- A-
pε
H3B H2B- H2B- HB2- B3-

(c) pH

Figure 6.9 Subdiagrams for the M-A-B-H2O system.

If the ligands are susceptible to redox and/or acid base reactions, then before tackling
the metal-multiligand-water system, it is first necessary to examine the separate ligand-water
systems as well as the multiligand-water system. Consider the case of the system M-A-B-H2O
where A gives a monoprotic acid and B a triprotic acid. Suppose we wish to generate a pε-pH
diagram for this system. Then we need to first obtain the corresponding diagrams for the A-H2O
and B-H2O systems as shown in Figures 6.9a and 6.9b. Superposition of Figures 6.9a and 6.9b
shows that when treating the M-A-B-H2O system, it would be necessary to consider five
subdiagrams where the predominant A-containing and B-containing species are respectively: (a)
HA, H3B, (b) HA, H2B-, (c) A-, H2B-, (d) A-, HB2-, and (e) A-, B3-, as illustrated in Figure 6.9c.
_____

Osseo-Asare Aqueous Processing 39

 EXAMPLE 6.8 log{Mn}-pH Diagrams for the Systems Mn-NH3-CO3-H2O, and Mn-NH3-SO4-H2O.

Figures E6.8a, b, c, and d present log{Mn}-pH diagrams for the systems Mn-H2O, Mn-NH3-H2O, Mn-
NH3-CO3-H2O, and Mn-NH3-SO4-H2O. When Figures (a) and (b) are compared, it is seen that the presence of
NH3 results in a decrease in the predominance field of Mn(OH)2(s), and a replacement of about 50% of the Mn2+
2+
field by ammine complexes (MnAj , 1≤ j ≤ 3, A = NH3): Also the MnOH+ and part of the Mn(OH)2(aq) fields
are replaced by ammines.

A comparison of Figures (b) and (c) indicates that the addition of carbonate severely limits the size of the
metal ammine stability region. In contrast, comparison of Figures (b), (c) and (d) shows that the presence of sulfate
does not interfere with the stability of the ammines, although much of the stability region Mn2+ is taken up by
MnSO4(aq).

It will be noticed that certain points in Figures (b), (c) and (d) are identified with the labels A, B, and C
+
respectively. The pH corresponding to A represents the NH4 /NH3 relative stability boundary, whereas B and C
- -
respectively depict the H2CO3(aq)/HCO3 and HCO3 /CO32- relative stability boundaries.

The Mn-NH3-H2O system involves two subdiagrams corresponding to the NH4+ and NH3 regions
respectively. In the case of the Mn-NH3-CO3-H2O system, four subdiagrams must be considered, as illustrated in
- - 2-
Figure E6.8e: Regions A (NH4+, H2CO3(aq)), B (NH4+, HCO3 ), C (NH3, HCO3 ), and D (NH3, CO3 ). For the
pH range of 0-14, the Mn-NH3-SO4-H2O involves three subdiagrams, as illustrated in Figure E6.8f, i.e., regions
-
A(NH4+, HSO4 ), B (NH4+, SO42-), and C (NH3, SO42-)

(b)
(a)

Figure E6.8a,b. log{Mn}-pH diagrams for the systems: (a) Mn-H2O; (b) Mn-NH3-H2O.

Osseo-Asare Aqueous Processing 40

 (c) (d)

Figure E6.8c,d log{Mn}-pH diagrams for the systems: (a) Mn-NH3-CO3-H2O; (b) Mn-NH3-SO4-H2O.

It is interesting to notice in Figure E6.8b, the inverse V shape of the Mn(OH)2(s)/Mn(NH3)32+ relative
stability boundary centered around pH 9.24. The discontinuity in this boundary line is due to the fact that, the
relative stability equations are written with free ammonia indicated as NH4+ for pH < 9.24 and as NH3 for pH >
2+
9.24. That is, for pH < 9.24 Mn(OH)2(s) → Mn(NH3)3 if

2+
Mn(OH2(s) + 3NH4+ → Mn(NH3)3 + H+ + 2H2O logK = -10.67 (1)
2+
log{Mn(NH3)3 } - pH - 3 log{NH4+} < -10.67
or

2+
log{Mn(NH3)3 } < [3log{NH4+} - 10.67] + pH (2)

o - - 2- -
H2 CO 3 HCO 3 HCO3 CO 3 HSO4 SO 2- SO 2-
4 4
log{Mn} log{Mn}
+
NH 4+ NH 4 NH 3 NH 3 NH +4 NH 4+ NH 3

(e) pH (f) pH

Figure E6.8 (e) and (f)

On the other hand, for pH > 9.24, Equation 1 must be rewritten with NH4+ replaced by NH3. That is,
Equation 1 must be combined with Equation 3:

NH3 + H+ = NH4+ logK = 9.24 (3)

Osseo-Asare Aqueous Processing 41

The result is:

2+
Mn(OH)2(s) + 3NH3 + 2H+ = Mn(NH3)3 + 2H2O logK = 17.05

2+
Thus in this case, Mn(OH)2(s) ∅ Mn(NH3)3 if

2+
log{Mn(NH3)3 } + 2pH - 3log{NH3} < 17.05
or
2+
log{Mn(NH3)3 } < [17.05 + 3 log{NH3}] - 2pH (4)

Comparison of Equations 2 and 4 shows that for pH < 9.24, the log{Mn}-pH plot has a positive slope of
unity whereas for pH > 9.24, the corresponding slope is -2.

6.4 Metal-Metal-Water Systems

6.4.1 Complex Oxide Systems
Ternary and more complex compounds containing at least two different metals (M and
N) are encountered in diverse natural and technological systems. Among the ternary
compounds, complex oxides of the type (MaNbOy) and complex sulfides of the type (MaNbSy)
are most common. Table 6.2 presents examples of complex oxides of the ternary type; complex
chalcogenides are discussed in Section 6.4.2.

Table 6.2 Complex Oxides

Complex Oxides M(II) Compound Complex Oxides M(II) Compound

Aluminate M(AlO2)2 Tantalate M(TaO3)2
Borate M(BO2)2 Titanate MTiO3
Chromate MCrO4 Tungstate MWO4
Chromite M(CrO2)2 Uranate MUO4
Molybdate MMoO4 Vanadate M(VO3)2
Molybdite MMoO3 Zirconate MZrO3
Niobate M(NbO3)2 Ferrite M(FeO2)2
Silicate (Meta) MSiO3 Germanate MGeO3
____

When constructing predominance area diagrams for systems in which complex M-N-O
oxides occur, the analysis may be viewed in terms of M-N-H2O or N-M-H2O systems. The
approach in both cases is similar to that utilized previously for M-L-H2O systems. In the case of
M-N-H2O systems, the heterogeneous equilibria of the N-H2O system defines the necessary

Osseo-Asare Aqueous Processing 42

subdiagrams. On the other hand in the case of the N-M-H2O system, the subdiagrams are based
on the M-H2O system.

EXAMPLE 6.9 Eh-pH Diagram for the Ca-W-H2O System

Construct an Eh-pH diagram for the Ca-W-H2O system, given the data provided in Table E6.9. Assume
{Ca} = {W} = 10-3 and use -2.0 < Eh(V) < 2.0 and 0 < pH < 16.

Table E6.9 Selected Thermodynamic Data for the Ca-W-H2O System

Reaction logK
Ca(s) = Ca2+ + 2e- 96.8
+ 2+
CaO(s) + 2H = Ca + H2O 32.55
+ 2+
Ca(OH)2(s) + 2H = Ca + 2H2O 22.8
CaWO4(s) = Ca2+ + WO42- -8.8
CaOH+ + H+ = Ca2+ + H2O 12.75
W(s) + 4H2O = WO42- + 8H+ + 6e- -3.0
WO2(s) + 2H2O = WO42- + 4H+ + 2e- -13.4
α-WO3(s) + H2O = WO42- + 2H+ -12.25
H2WO4(s) = WO42- + 2H+ -15.8
HWO4- = WO42- + H+ -3.5
H2WO4(aq) = WO42- + 2H+ -8.1

Solution

In order to construct a predominance area diagram for the Ca-W-H2O system, we must first examine the
W-H2O system so that we can identify the necessary subdiagrams. Figure E6.9a presents the Eh-pH diagram
obtained by considering all the seven relevant W-containing species listed in Table E6.9a. It can be seen from
Figure E6.9a that only four out of the seven species possess stability fields under the conditions utilized, i.e., W,
WO2, H2WO4(s), and WO42-. Thus the Ca-W-H2O system involves four subdiagrams. That is, for each Ca-W
species four different dissociation reactions must be written involving W, WO2, H2WO4(s) and WO42-
respectively. Figure E6.9b presents the resulting Eh-pH diagram for the Ca-W-H2O system.

Osseo-Asare Aqueous Processing 43

 2.0 2.0

1.5 1.5
CaWO4
1.0 1.0
H2WO4 (s) 0.5
0.5
Eh Eh
0.0 WO 4−2 0.0 Ca(OH)2

-0.5 -0.5 Ca2+

2
WO
-1.0 -1.0
W Ca(OH)+
-1.5 {W} = 10-3 -1.5 {Ca} = {W} = 10-3
-2.0 -2.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH pH
Figure E6.9 (a) Eh-pH for the W-H2O system; (b) Eh-pH diagram for the Ca-W-H2O system.

0.0

-1.0
CaWO4
-2.0

-3.0 Ca(OH)2
Log (Ca)

-4.0

-5.0 Ca2+

-6.0
Ca(OH)+
Eh = 0.0 V
-7.0
{W} = 10-3
-8.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
Figure E6.9c log{Ca}-pH diagram for the Ca-W-H2O system.

EXAMPLE 6.10 log{M}-pH Diagrams for the Ti-Ba-H2O System

Thermodynamic data for the Ti-Ba-H2O system are presented in Table 6.10a. On the basis of these data,
develop the following graphical representations of the heterogeneous equilibria: (a) log{Ti}-pH diagram for {Ba} =
10-3, and -12 < log{Ti} < 0; (b) log{Ba}-pH diagram for {Ti} = 10-3, and -12 <log {Ba} < 0. In both cases use the
pH range 8 < pH < 16.
Osseo-Asare Aqueous Processing 44
 Table E6.10 Selected Thermodynamic Data for the Ti-Ba-H2O System

Reaction logK
TiO2(s) + 2H2O = Ti(OH)4(aq) -9.63
Ti(OH)22+ + 2H2O = Ti(OH)4(aq) + 2H+ -4.8
Ti(OH)3+ + H2O = Ti(OH)4(aq) + H+ -2.5
BaTiO3(s) + 2H+ + H2O = Ti(OH)4(aq) + Ba2+ 11.30
Ba(OH)2 ⋅ 8H2O + 2H+ = Ba2+ + 10H2O 22.35
BaOH+ + H+ = Ba2+ + H2O 13.47

(a) In order to determine the log{Ti}-pH diagram for the Ti-Ba-H2O system, it is necessary to first examine
the Ba-H2O system. Figure E6.10a presents the log{Ba}-pH diagram for the Ba-H2O system. It can be
seen that {Ba} = 10-3 implies two subdiagrams for the Ti-Ba-H2O system, i.e., subdiagram 1 for the Ba2+
region (pH < 11.2), and subdiagram 2 for the Ba(OH)2 ⋅ 8H2O (s) region (pH > 11.2 ). Figure E6.10b
presents the corresponding log{Ti}-pH diagram for the Ti-Ba-H2O system.

(b) In the case of a log{Ba}-pH diagram for the Ba-Ti-H2O system, we must first consider the system Ti-H2O.
Figure E6.10c presents a log{Ti}-pH diagram for the Ti-H2O system. It can be seen that for the entire pH
range of interest, {Ti} = 10-3 corresponds to TiO2 formation. Thus the Ba-Ti-H2O system with {Ti} = 10-3
involves only one subdiagram, i.e., the TiO2 stability domain. Figure E6.10d presents the resulting log
{Ba}-pH diagram for the Ba-Ti-H2O system.

Figure E6.10 log{M}-pH diagrams for the Ti-Ba-H2O system: (a) log{Ti}-pH diagram; (b) log{Ba}-pH
diagram.
_____

6.4.2 Complex Chalcogenide and Related Systems

In this section we are concerned with compounds of the type MaNbXy where M, and N
are different metals and X is S, Se, Te, and As. Also included in the discussion here are
Osseo-Asare Aqueous Processing 45
compounds where both N and X are taken from among the group S, Se, Te, and As. Examples
of these compounds are collected in Table 6.3.
Suppose we wish to generate an Eh-pH diagram for the M-N-X-H2O system, under
conditions where the ternary compound MaNbXy exhibits a stability domain. The complete
analysis involves three steps: consideration of (a) the X-H2O system, (b) the N-X-H2O system,
and finally (c) the M-N-X-H2O system. As previously discussed in Section 6.4.1, predominance
area diagrams for the N-X-H2O system are prepared in terms of subdiagrams based on the X-
H2O system. Similarly consideration of the N-X-H2O system identifies the domains of the
subdiagrams which must be combined to provide the composite diagram for the M-N-X-H2O
system. Figures 6.10 and 6.11 present Eh-pH diagrams for the Fe-As-S and Cu-Fe-S systems
respectively.

Figure 6.11 Eh-pH diagram for the Cu-Fe-S system at 25°C.

Osseo-Asare Aqueous Processing 46
 Table 6.3 Selected Ternary Chalcogenides
M-N-X Type Mineral Name Chemical Formula
Cu-Fe-S Bornite Cu5FeS4
Chalcopyrite CuFeS2
Cubanite CuFe2S3
Idaite Cu3FeS4

M-As-S Arsenopyrite FeAsS

Cobaltite CoAsS
Gersdorffite NiAsS
Lautite CuAsS

Ag-Au-X Fishesserite Ag3AuSe2

Petzite Ag3AuTe2
Sylvanite AgAuTe4

Ag-S-Se Aguilarite Ag4SSe

Ag-Cu-Se Eucairite AgCuSe

Au-Cu-Te Kostovite AuCuTe4

Bi-S-X Laitakarite Bi4SSe2

Joséite Bi4STe2

Bi-Te-X Kawazulite BiTe2Se

Tetradymite Bi14Te13S8

Ni-Te-Se Kitkaite NiTeSe

Pd-Hg-Te Temagamite Pd3HgTe3

Pd-Sb-Te Borovskite Pd3SbTe4

Figure 6.10 Eh-pH diagram for the Fe-As-S system at 25°C.

Osseo-Asare Aqueous Processing 47

FURTHER READING

1. M. Pourbaix, Thermodynamics of Dilute Solutions, Arnold, London, 1949.

2. M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions, Pergamon,

London, 1966.

3. R. M. Garrels and C. L. Christ, Solutions, Minerals and Equilibria, Harper and Row,
New York, 1965.

4. J. N. Butler, Ionic Equilibria: A Mathematical Approach, Addison-Wesley, Reading,

MA, 1964.

5. M. Pourbaix and A. Pourbaix, eds., Diagrams of Electrochemical Equilibria. Their

Setting-up and Applications, CEBELOR, Brussels, Belgium, 1982.

6. C. F. Baes, Jr., and R. E. Mesmer, Hydrolysis of Cations, Wiley, New York, NY, 1976.

7. H. C. Helgeson, T. H. Brown, and R. H. Leeper, Handbook of Theoretical Activity

Diagrams Depicting Chemical Equilibria in Geologic Systems Involving an Aqueous
Phase at One Atm. and 0°-300°C, Freeman, Cooper & Co., San Francisco, 1969.

8. W. Stumm and J. J. Morgan, Aquatic Chemistry, 2nd ed., Wiley, New York, 1981.

9. T. S. Bowers, K. J. Jackson, and H. C. Helgeson, Equilibrium Activity Diagrams, for

Coexisting Minerals and Aqueous Soluiton at Pressures and Temperatures to 5kB and
600°C, Springer-Verlag, New York, NY, 1984.

10. C. I. House, "Potential-pH Diagrams and their Appliction to Hydrometallurgical

Systems", in G. A. Davies, ed., Separation Processes in Hydrometallurgy, Ellis
Horwood, Chichester, U. K., 1987, pp. 3-19.

11. J. D. Hem. "Stability Field Diagrams as Aids in Iron Chemistry Studies", J. Am. Water
Works Assoc., 53, 211-232 (1966).

12. E. Peters, "Direct Leaching of Sulfides: Chemistry and Applications", Metall. Trans. B,
7, 505-517 (1976).

13. D. Langmuir, "Uranium Solution-Mineral Equilibria at Low Temperatures with

Applications to Sedimentary Ore Deposits", Geochim. Cosmochim. Acta, 42, 547-569
(1978).

14. K. Osseo-Asare, and T. H. Brown, "A Numerical Method for Computing

Hydrometallurgical Activity-Activity Diagrams", Hydrometallurgy, 4, 217-232 (1979).

15. K. Osseo-Asare, "Application of Activity-Activity Diagrams to Ammonia

Hydrometallurgy 4: Fe-NH3-H2O, Fe-NH3-H2O-CO3 and Fe-NH3-H2O-SO4 Systems
at 25°C", Trans. IMM, 90, C159-C163 (1981).

Osseo-Asare Aqueous Processing 48

 16. K. Osseo-Asare, "Solution Chemistry of Tungsten Leaching Systems", Metall. Trans. B,
13, 555-564 (1982) .

17. T. Xue and K. Osseo-Asare, "Heterogeneous Equilibria in the Au-CN-H2O and Ag-CN-
H2O Systems", Metall. Trans. B, 16, 455-463 (1985).

18. C. M. Jantzen, "Effects of Eh on Borosilicate Waste Glass Durability", Adv. Ceram., 8,

385-393 (1985).

19. K. Osseo-Asare, F. J. Arriagada and J. H. Adair, "Solubility Relationships in the

Coprecipitation Synthesis of Barium Titanate: Heterogeneous Equilibria in the Ti-Ba-
C2O4-H2O System", in Ceramic Powder Science II, G. L. Messing, E. R. Fuller and H.
Hausner, eds., American Ceramic Society, Westerville, OH, 1988, pp. 47-53.

20. T. Xue and K. Osseo-Asare, "Heterogeneous Equilibria in the Ru-H2O, Ru-Cl-H2O and
Ru-S-H2O Systems", J. Less-Common Metals, 152, 103-114 (1989).

21. K. Osseo-Asare, "Solution Chemistry and Separation Processes in Precious and Rare
Metal Systems", in A. E. Torma and I. H. Gundiler, eds., Precious and Rare Metal
Technologies, Elsevier, New York, 1989, pp. 113-135.

Osseo-Asare Aqueous Processing 49

CHAPTER 6 PROBLEMS

6.1. Using the data in Table P6.1, show by means of appropriate clearly labeled sketches, the stability
boundaries of the following pairs of species:

(a) Fe/Fe2+ (d) Fe3+/Fe2O3

(b) Fe2+/Fe3+ (e) Fe3+/Fe3O4
(c) Fe2O3/Fe3O4

Present your answers in a pε-pH coordinate system. Show all your calculations and explain your choice of
specific stability domains.

Table P6.1

Reaction logK
Fe = Fe2+ + 2e- 16.17
Fe2O3 + 2e- + 6H+ = 2Fe2+ + 3H2O 26.93
Fe3O4 + 2e- + 8H+ = 3Fe2+ + 4H2O 36.81
Fe3+ + e- = Fe2+ 13.04

6.2. (a) The oxygen reduction reaction can be written for acidic solutions as

1/2O2(g) + 2H+ + 2e- = H2O logK = 41.56 (1)

What is the standard reduction potential (Eho) for this reaction?

(b) A smart hydrometallurgist has proposed that metallic gold can be precipitated from aqueous
chloride solution by treatment of the solution with graphite. On the basis of the data presented
below, explore the feasibility of this idea with the aid of (a) suitable predominance area
diagram(s). State all your assumptions clearly.

C + 3H2O = H2CO3(aq) + 4H+ 4e- logK = -15.68

-
Au + 4Cl- = AuCl4 + 3e- logK = -50.82

6.3. Using the data provided in Problem 2, and a pε-pH coordinate system, show by means of appropriate
clearly labeled sketches, the stability boundaries of the following pairs of species:

(a) O2(1 atm)/H2O

(b) C/H2CO3(aq)

-
(c) Au/AuCl4

6.4. In the Zn-H2O system,

a) What are the conditions of pε and pH under which each of the following is the predominant or
stable form of zinc: Zn2+ , Zn, ZnO? Assume a zinc ion activity of unity and use the following
data:

ZnO(s) + 2H+ = Zn2+ + H2O logK = 11.2

Osseo-Asare Aqueous Processing 50

 Zn2+ + 2e- = Zn(s) logK = -26

Present your results in terms of a pε-pH diagram with -30 < pε < 30 and 0 < pH <14.

b) From part (a), specify the predominant zinc species under the following conditions:

Condition pH Eh Predominant Species

(i) 2 0.5 ?
(ii) 7 0.5 ?
(iii) 2 -1.0 ?
(iv) 7 -1.0 ?
(v) 12 -1.0 ?

6.5. It is desired to use ammonia as a leaching reagent for waste zinc dust (mainly zinc oxide) obtained from a
zinc smelter. Given that the maximum dissolved zinc expected is 1 molar, what conditions of Eh and pH
will you recommend?

Hint: Calculate and plot the Eh-pH diagram (-2V < Eh < 2V, 0 < pH < 14) for the Zn-H2O-NH3 system.
Use the data provided in Problem 6.4a above with the additional reactions:

2+
Zn2+ + 4NH3 = Zn(NH3)4 logK = 9.6
+
NH4 = NH3 + H+ logK = -9.25

Note that when pH > 9.25, dissolved ammonia is predominantly in the form of NH3, and when pH < 9.25,
+
dissolved ammonia is in the form of NH4 .

6.6. Prepare an Eh-pH diagram for the Ni-H2O system using the data provided in Table P6.6.
Use the range -2.0 < Eh(volt) < 2.0 and 0 < pH < 14. Assume dissolved nickel is at unit activity.

Table P6.6

Selected thermodynamic data for the Ni-H2O system at 25°C

Reaction logK

Ni = Ni2+ + 2e- 7.99

NiO + 2H+ = Ni2+ + H2O 12.45
Ni3O4 + 8H+ + 2e- = 3Ni2+ + 4H2O 65.43
NiO2 + 4H+ + 2e- = Ni2+ + 2H2O 53.39
Ni2O3 + 6H+ + 2e- = 2Ni2+ + 3H2O 58.32
Ni(OH)2(s) + 2H+ = Ni2+ + 2H2O 12.73

6.7. Prior knowledge of the solution chemistry of the Mn-H2O system indicates that in the ranges -1.5 <
Eh(volt) ≤ -0.5, and 6.0 < pH < 14.0, the stable manganese-containing species are Mn2+, Mn, and
Mn(OH)2(s). Prepare an Eh-pH diagram for this system using the thermodynamic data provided below.
Assume {Mn2+} = 1.0.

Osseo-Asare Aqueous Processing 51

 Mn = Mn2+ + 2e- logK = 40.29

Mn(OH)2(s) + 2H+ = Mn2+ + 2H2O logK = 15.35

6.8. "Dissolved carbon dioxide" is present in aqueous solution as a variety of aqueous species depending on the
- 2-
pH: As carbonic acid (H2CO3(aq)), as the bicarbonate ion (HCO3 ), and as the carbonate ion (CO3 ).
Using the data provided below, determine:

(a) The species distribution as a function of pH. Use the range 0<pH<14

(b) The stability field of the dissolved carbon-containing species in terms of a log[C] versus pH
- 2-
diagram, where [C] = [H2CO3(aq)] + [HCO3 ] + [CO3 ]

-
H2CO3(aq) = H+ + HCO3 logK = -6.35
- 2-
HCO3 = H+ + CO3 logK = -10.33

6.9. Table P6.9 presents selected thermodynamic data for the C-H2O system. On the basis of these data,
prepare an Eh-pH diagram in the range 0<pH<14, -2<Eh(V)<2. Include the water stability limits in your
diagram. Indicate all your calculations and justify your line elimination. Assume all dissolved carbon is at
unit activity.

Table P6.9

Reaction logK
2-
C + 3H2O = CO3 + 6H+ + 4e- -32.36
-
H2CO3(aq) = H+ + HCO3 -6.35
- 2-
HCO3 = H+ + CO3 -10.33

6.10 Refractory (i.e., difficult to process) gold ores are often carbonaceous. It is believed that a portion of the
carbonaceous matter in the ore behaves like activated carbon and contributes to the poor gold recovery by
-
adsorbing gold cyanide complexes (Au(CN)2 ) from solution. Consider a leaching system containing
carbonaceous gold ore in cyanide solution. The pH is 9.0 and air is used as the oxidant. The Eh in this
system is controlled by the oxidation of carbon. Will the gold be soluble (as the aurous cyanide complex)
under these conditions? Use the results obtained in Problem 6.9. Additional data are presented below.

Au+ + e- = Au Eho = 1.68V

-
Au+ + 2CN- = Au(CN)2 logK = 38.3

6.11. Table P6.11 presents selected thermodynamic data for the Ag-CN-H2O system.

Table P6.11

Reaction logK

Osseo-Asare Aqueous Processing 52

 Ag+ + e- = Ag 13.51
Ag+ + HCN(aq)= AgCN(s) + H+ 6.45
Ag2O + 2H+ = 2Ag+ + H2O 12.64
Ag2O + 2H+ + 2e- = 2Ag + H2O 39.66
AgCN(s) + e- + H+ = Ag + HCN(aq) 7.06
Ag2O + 2HCN(aq) = 2AgCN(s) + H2O 25.54

Determine the relative stability lines in terms of pε-pH coordinates for the pairs of species indicated below:

(a) Ag/Ag+ (d) Ag2O/Ag

(b) Ag2O/Ag+ (e) AgCN(s)/Ag
(c) AgCN(s)/Ag+ (f) AgCN(s)/Ag2O

Assume [Ag+] = 10-4 M, [HCN] = 10-3 M.

6.12. The following relative stability lines have been determined for the systems (a) and (b) respectively:

-
(a) Ag2O3/Ag/Ag(CN)2

-
Ag2O3→Ag(CN)2 if pε < 37.47 - 1.5 pH
Ag2O3→Ag if pε < 23.32 - pH
-
Ag→Ag(CN)2 if pε > -4.97

-
(b) AgCN(s)/Ag/Ag(CN)2

AgCN(s) →Ag if pε < 10.06 - pH

-
Ag→Ag(CN)2 if pε> 13.45 - 2pH
-
AgCN(s) →Ag(CN)2 if pH > 3.39

Perform the relevant line eliminations and obtain the overall stability diagram for each system.
Justify in detail (i.e., in writing!) the rationale behind your line eliminations.

6.13. Table P10.13 presents a selection of thermodynamic data for the Fe-CN-H2O system. On the basis of
these data, generate an Eh-pH diagram for this system in the range: 10 < pH < 14.0 and -1.0 < Eh(volt) < -
4-
0.6. Assume {Fe2+} = {Fe(CN)6 } = 10-4, {CN-} = 10-3.

Table P6.13

Reaction logK
4-
Fe2+ + 6CN- = Fe(CN)6 35.40
Fe = Fe2+ + 2e- 16.17
Fe(OH)2(s) + 2H+ = Fe2+ + 2H2O 12.90
Fe3O4 + 2e- + 8H+ = 3Fe2+ + 4H2O 36.81

Osseo-Asare Aqueous Processing 53

6.14. Gold is extracted from its ores as a result of the ability of metallic gold to form the auro-cyanide complex
-
Au(CN)2 in aerated alkaline solutions:
-
Au + 2CN- + 1/4O2(g) + 1/2H2O = Au(CN)2 + OH-

(a) Prepare an Eh-pH diagram for the Au-CN-H2O system using the thermodynamic data presented
below:

Au = Au+ + e- logK = -28.59

Au(OH)3(s) + 2e- + 3H+ = Au+ + 3H2O logK = 45.28
-
Au(CN)2 = Au+ + 2CN- logK = -39.44

-
Assume {Au(CN)2 } = 10-4, and {CN-} = 10-3. Confine your diagram to the ranges -2V<Eh<2V and 10
< pH < 13.

(b) What would be the Eh of the Au-CN-H2O system when pH = 10 and the auro-cyanide complex
-
Au(CN)2 at an activity of 10-4, is in equilibrium with Au(OH)3(s) in a cyanide solution
containing {CN-} = 10-3?

6.15 Ocean floor manganese nodules are of commercial interest because of their Cu, Ni and Co content. The
main metaliferous minerals are believed to be hydrous manganese and iron oxides (MnOOH, FeOOH).
The valuable metals are incorporated into the crystal structure of these hydrous oxides and thus, in order to
recover the contained Cu, Ni and Co, the hydrous oxides have to be decomposed. Kennecott's Cuprion
process uses cuprous ions in ammoniacal carbonate solution (as the cuprous ammine complex,
Cu(NH3)2+) to decompose the manganese oxide to manganese carbonate (MnCO3(s) ). The
oxide/carbonate transformation causes the contained Cu, Ni, Co to be released into the aqueous solution.
In this process, the cuprous ammine is converted to the cupric ammine complex (Cu(NH3)42+).

(a) Using the data given in Table P6.15, show that the chemical equation which represents the
Cuprion process is:

+ 2-
MnOOH(s) + Cu(NH3)2 + 3H+ + 2NH3 + CO3 =
2+
MnCO3(s) + Cu(NH3)4 + 2H2O logK = 34.78

(b) Is the conversion of MnOOH to MnCO3 a reduction or an oxidation process? Justify you answer
with a pertinent chemical equation.

2-
(c) If pH = 11, free ammonia {NH3} = 1, and {CO3 } = 1, what is the minimum cuprous to cupric
ratio required for the Cuprion process?

Osseo-Asare Aqueous Processing 54

 Table 6.15

Reaction logK

Cu+ = Cu2+ + e- -2.64

2+
Cu2+ + 4NH3 = Cu(NH3)4 13.00
+
Cu+ + 2NH3 = Cu(NH3)2 10.6
Mn2+ + 2H2O = MnOOH + e- + 3H+ -25.70
2+
Mn2+ + 4NH3 = Mn(NH3)4 1.30
2-
Mn2+ + CO3 = MnCO3(s) 9.30

6.16 An experimental study is being undertaken by one of the engineers in your company on the solubility of
manganese carbonate in aqueous solutions which contain no ammonia. Preliminary results presented to the
engineer by the technician working on the project indicate that in the pH range investigated (4 to 10.5), the
solubility depends less and less on pH as the pH is increased. The experiments were done under conditions
where the total dissolved CO2 (i.e., [CO32-] + [HCO3-] + [H2CO3(aq)])) was always fixed at a constant
value of 1 mol/liter. The engineer is puzzled by these results and questions the competence of her
technician. You overhear their heated arguments in the corridor. The engineer notices you standing by the
coffee machine, she yells to the technician to go back to the lab and repeat the experiments, and she calls to
you to please come to her office. She is fed up with such a lousy technician, she announces to you, closing
her door at the same time. She has a request for you.. She understands you took a course in aqueous
processing at Penn State. Would you be kind enough to analyze the manganese carbonate problem from
"first principles"? Your reputation is at stake. You agree to look at the problem for her. Armed with
Table P6.15 and the additional data provided below, you sit yourself down in your office, your calculator
in your hand. After a few minutes of quick calculations, you arrive at your answer. What kind of
calculations did you do? Do you have good or bad news for your colleague?

-
H2CO3(aq) = H+ + HCO3 logK = -6.35
- 2-
HCO3 = H+ + CO3 logK = -10.33

6.17. It is well-known that solid silver cyanide, AgCN(s), is stable only under acidic conditions. There is a
dispute raging in your lab. One of your colleagues, Dr. Mary Certain, has identified Ag+ to be the
predominant silver species in equilibrium with AgCN(s) and 10-3 M free cyanide. On the other hand, Mr.
-
No Kidding claims that his superior analytical technique has enabled him to identify Ag(CN)2 as the
relevant silver species, not Ag+. As the only qualified aqueous technologist in the neighborhood, you have
been requested by your manager to settle this dispute. With the aid of the thermodynamic data presented
below and a solubility diagram (log[Ag] versus pH), resolve this conflict. Consider the range 0 < pH <4, -
6 < log[Ag] < -3. Use the scale 0.5 units of log[Ag] to 2 cm, 0.5 pH to 2 cm. Ignore activity coefficients.

AgCN(s) = Ag+ + CN- logK = -15.66

-
Ag(CN)2 = Ag+ + 2CN- logK = -20.40
H+ + CN- = HCN(aq) logK = 9.21

Osseo-Asare Aqueous Processing 55

 +
6.18 Table P6.18 summarizes the stability relations describing the equilibrium condition in the Fe-NH4 - H2O
system in the range 8.1 < pH < 9.1, -18 < pε < 0. Using these data, prepare a pε-pH diagram for this
+
system for the conditions {NH4 } = 1.0, {Fe} = 10-4.

Table P6.18

+
Reaction General Equation ({NH4 } = 1.0)

2+ 2+
Fe→Fe(NH3)2 pε>0.055 - pH + 1/2 log{Fe(NH3)2 }
2+ 2+
Fe→Fe(NH3)4 pε>8.55 - 2pH + 1/2 log{Fe(NH3)4 }
Fe→Fe(OH)3(s) pε>-0.54 - pH
2+ 2+ 2+ 2+
Fe(NH3)2 →Fe(NH3)4 log{Fe(NH3)2 }>16.98 + log {Fe (NH3)4 } - 2pH
2+ 2+
Fe(NH3)2 →Fe(OH)3(s) pε>-0.65 - pH - log{Fe(NH3)2 }
2+ 2+
Fe(NH3)4 →Fe(OH)3(s) pε>-17.63 + pH - log{Fe(NH3)4 }

Use the range: -18 < pε < 0, 8.1 < pH < 9.1

6.19. You are an employee of the consulting firm HYDROMET SYSTEMS, Inc. A lab report prepared for your
client, RECYCLEMET, by METPROC, Inc., indicates that the solubility of ferric hydroxide decreases
with increasing pH. On the basis of this report, a process scheme has been developed to control iron
solubility in ammoniacal solutions. To the surprise of RECYCLEMET engineers, the pilot plant tests show
a trend which is opposite to that given them by METPROC, Inc. Now your company has been hired by
RECYCLEMET to take another look at their iron control problem. You have been provided with the
+
following process data: An aqueous ammoniacal solution has a pε of -5.0 and contains 1.0 mol/L NH4 .
+
On the basis of the thermodynamic data provided below, prepare a solubility diagram for the Fe - NH4 -
H2O system in the range 8.1 < pH <9.1 , -5.0 <log{Fe} < -3.0. With the aid of this diagram, provide an
explanation for RECYCLEMET'S pilot plant experience. Should they sue METPROC?

Hint: You can safely assume that Fe2+ concentration is negligible under the specified process
conditions.

Fe(OH)3(s) + e- + 3H+ = Fe2+ +3H2O logK = 15.63

2+ +
Fe(NH3)2 + 2H+ = Fe2+ + 2NH4 logK = 16.28
2+ +
Fe(NH3)4 + 4H+ = Fe2+ + 4NH4 logK = 33.26

Osseo-Asare Aqueous Processing 56