metals

Article
The Eh-pH Diagram and Its Advances
Hsin-Hsiung Huang
Received: 29 July 2015; Accepted: 28 December 2015; Published: 14 January 2016
Academic Editors: Suresh Bhargava, Mark Pownceby and Rahul Ram

Metallurgical and Materials Engineering, Montana Tech, Butte, MT 59701, USA; hhuang@mtech.edu;
Tel.: +1-406-496-4139; Fax: +1-406-496-4664

Abstract: Since Pourbaix presented Eh versus pH diagrams in his “Atlas of Electrochemical Equilibria
in Aqueous Solution”, diagrams have become extremely popular and are now used in almost
every scientific area related to aqueous chemistry. Due to advances in personal computers, such
diagrams can now show effects not only of Eh and pH, but also of variables, including ligand(s),
temperature and pressure. Examples from various fields are illustrated in this paper. Examples
include geochemical formation, corrosion and passivation, precipitation and adsorption for water
treatment and leaching and metal recovery for hydrometallurgy. Two basic methods were developed
to construct an Eh-pH diagram concerning the ligand component(s). The first method calculates
and draws a line between two adjacent species based on their given activities. The second method
performs equilibrium calculations over an array of points (500 ˆ 800 or higher are preferred), each
representing one Eh and one pH value for the whole system, then combines areas of each dominant
species for the diagram. These two methods may produce different diagrams. The fundamental
theories, illustrated results, comparison and required conditions behind these two methods are
presented and discussed in this paper. The Gibbs phase rule equation for an Eh-pH diagram was
derived and verified from actual plots. Besides indicating the stability area of water, an Eh-pH
diagram normally shows only half of an overall reaction. However, merging two or more related
diagrams together reveals more clearly the possibility of the reactions involved. For instance, leaching
of Au with cyanide followed by cementing Au with Zn (Merrill-Crowe process) can be illustrated
by combining Au-CN and Zn-CN diagrams together. A second example of the galvanic conversion
of chalcopyrite can be explained by merging S, Fe–S and Cu–Fe–S diagrams. The calculation of
an Eh-pH diagram can be extended easily into another dimension, such as the concentration of
a given ligand, temperature or showing the solubility of stable solids. A personal computer is capable
of drawing the diagram by utilizing a 3D program, such as ParaView, or VisIt, or MATLAB. Two 3D
wireframe volume plots of a Uranium-carbonate system from Garrels and Christ were used to verify
the Eh-pH calculation and the presentation from ParaView. Although a two-dimensional drawing
is still much clearer to read, a 3D graph can allow one to visualize an entire system by executing
rotation, clipping, slicing and making a movie.

Keywords: Pourbaix diagram; Eh-pH diagram; Eh-pH applications; ligand component; equilibrium
line; mass balance point; Gibbs phase rule; 3D Eh-pH diagrams; ParaView; VisIt; MATLAB

1. Introduction
All Eh-pH diagrams are constructed under the assumption that the system is in equilibrium with
water or rather with water’s three essential components, H(+1), O(´2) and e(´1); the oxidation states
are presented using Arabic numbers with a + or a ´ sign. The diagrams are divided into areas, each
of which represents a locally-predominant species. Eh represents the oxidation-reduction potential
based on the standard hydrogen potential (SHE), while pH represents the activity of the hydrogen ion
(H+ , also known as a proton). An Eh-pH diagram can describe not only the effects of potential and pH,

Metals 2016, 6, 23; doi:10.3390/met6010023 www.mdpi.com/journal/metals

Metals 2016, 6, 23 2 of 30
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butand
alsopH,
of complexes,
but also also of temperature
of complexes,
complexes, and pressures.
temperature By convention,
and pressures.
pressures. Eh-pH diagrams
By convention,
convention, always show
Eh-pH diagrams
diagrams always the
and pH, but temperature and By Eh-pH always
thermodynamically-stable
show the
show the thermodynamically-stable area
thermodynamically-stable area of water by
area of two
of waterdashed
water byby twodiagonal
two dashed lines.
dashed diagonal
diagonal lines.lines.
Two Twotypical
typical Eh-pH Eh-pH diagrams,
diagrams, both
bothbased
basedon thermodynamic
on
Two typical Eh-pH diagrams, both based on thermodynamic data from thermodynamic data
data fromfrom the
the
theNBSNBS
NBS database
database[1],
database are
[1],
[1],
presented.
are Figure
presented. 1
Figureshows 1 an
shows Eh-pH
an Eh-pH diagram
diagram for one
for onecomponent
component (excluding
(excluding
are presented. Figure 1 shows an Eh-pH diagram for one component (excluding three essential H(+1), three
three essential
essential H(+1),
H(+1),
O(´2)
O(−2)
O(−2) andand
and e(´1)e(−1)components)
e(−1) components)of
components) ofmetal,
of metal, in
metal, in this
in case manganese,
this case
this manganese,Mn,
manganese, Mn,while
Mn, whileFigure
while Figure22 2is
Figure isisthat
that
that ofof
of another
another
another
component
component
component of of of mineral
mineral
mineral acidacidphosphorus,
acid phosphorus,P.P.
phosphorus, P.Both
Bothdiagrams
Both diagrams show
diagrams that
show that oxidized
thatoxidized
oxidizedspeciesspecies reside
speciesresidereside inin
in high
high
high
Eh
Eh Eh areas,
areas, whilewhile reduced
reduced species
species are
are inin low
low EhEh areas.
areas. The
The metal diagram
diagram
areas, while reduced species are in low Eh areas. The metal diagram starts, at the left edge, from starts,
starts, at
atthe
the left
leftedge,
edge, from
from
metal ions (Mn2+ )2+
2+) at low pH, which progressively react with OH´ as pH increases totoproduce
produce metal
metal
metalions
ions(Mn (Mn at
) atlowlowpH, pH,which
whichprogressively
progressively reactreact with OH -- as
with OH aspHpHincreases
increasesto produce metal
metal
hydroxides
hydroxides
hydroxides (Mn(OH)
(Mn(OH)
(Mn(OH) ) or oxides.
2 )2)ororoxides.
2 The
oxides.The diagram
The diagram for the
diagram for the mineralmineral acid
mineralacid starts,
acidstarts, again
starts,again from
againfrom
fromthe the left,
theleft, with
with
left, with
acid
acid
acid (H
(H3(HPO PO
33PO ) 44)) and
and and progressivelydeprotonates
progressively
progressively deprotonatesdue
deprotonates dueto
due toreactions
to reactionswith
reactions with OH
with OH´ totofinally
-- to finally
finally produce
produce
produce phosphate
phosphate
phosphate
4
ion
ionion (PO
(PO 3-) at high pH. Figure 1 also illustrates the tendencies to transition between species.
3´43-
(PO 4 4 ) )at athigh
high pH.pH. Figure 1 also also illustrates
illustratesthe thetendencies
tendenciestototransition
transition between
between species.
species.

Figure
Figure
Figure 1. Eh-pH
Eh-pH
1. 1. diagramofof
diagram
Eh-pH diagram ofaaaMn–water
Mn–watersystem.
Mn–water system.Dissolved
system. Dissolved manganese
Dissolved manganese concentration,
manganese concentration, [Mn]
[Mn]===0.001
concentration,[Mn] 0.001 M.
0.001M.
M.

Figure
Figure 2. Eh
2. Eh
Figure 2. Eh
pHpH diagram
diagram
pH diagram ofa aaP-water
ofof P-watersystem.
P-water system.Dissolved
system. Dissolved phosphorus
Dissolved phosphorus species,
phosphorus species, [P]
[P]===0.001
species,[P] 0.001 M.M.
0.001
M.
Metals 2016, 6, 23 3 of 30

Scope of the Paper

This paper illustrates some ways to improve a basic Eh-pH diagram for better visualization of
species and stability regions. The demonstrated methods are all calculated and constructed with
an ordinary PC, without a high-end graphics card, using Windows 7 or a higher version. All diagrams
can be obtained in a short time. The fundamentals underlying the calculations are briefly described
and/or available in the literature and listed as references. Discussions include:

1. Examples of applications: geochemical formation, corrosion and passivation, leaching and metal
recovery, water treatment precipitation and adsorption.
2. Development of equilibrium line and mass balance point methods to handle ligand component(s):
the theory, illustration and result comparison are presented; both methods satisfy the Gibbs phase
rule derived for the Eh-pH diagram.
3. Examples by merging two or more diagrams for better illustration of the overall reactions involved
in a process.
4. Demonstrations using a third party program to produce 3D diagrams with the addition of a third
axis. The axis can represent the solubility of stable solids, ligand concentration or temperature.
Two 3D wireframe volume plots of the Uranium-carbonate system based on a classic Garrels and
Christ [2] work were used to verify the Eh-pH calculation and the presentation from ParaView.

This paper is not intended to discuss the following topics in detail:

1. Comparison among existent computer programs listed from the literature that directly or
indirectly construct an Eh-pH diagram.
2. Effects from temperature, pressure, ionic strength and surface complexation for
aqueous chemistry.
3. The algorithm and flow sheet to construct the diagram used by the author: they are available and
referenced elsewhere; no source codes of the programs are presented.
4. Comparison or comments on third party 3D programs used by the author.

Note: The diagrams shown in this paper are solely for illustration. Unless specified, all were
constructed at a temperature of 25 ˝ C and zero ionic strength. The molarity is used for a dissolved
species as [species], and Σcomponent is used to represent the sum of all mass from one component.
Various thermodynamic databases were used as was convenient. Except as noted for 3D plots, all
diagrams were constructed by STABCAL [3] running on the Windows operating system using win8.1
64 bit, Pentium i7, 4.3 GHz with 16 GB RAM hardware, and 1680 ˆ 1050 resolution monitor.

2. Crucial Developments of the Eh-pH Diagram

Chapter 2 of the Pourbaix Atlas [4] presented the method of calculation and the procedure of
the construction of an Eh-pH diagram. The process was relatively simple since only one component
was considered.
Garrels and Christ [2] dedicated a full chapter to the Eh-pH diagrams. Several diagrams related
to geochemical systems were not only presented, but also explained. They laid out a procedure to
construct the diagrams when ligand(s) were involved, such as illustrated in the Fe–S and Cu–Fe–S
systems. They also presented two 3D wireframe volume diagrams for the Eh-pH-CO2 system, which
will be discussed later in this paper.
A crucial development in constructing an Eh-pH diagram was in deciding how to handle a system
when a ligand component was involved. Two completely different approaches were evolved.

2.1. Development of the Equilibrium Line Method

The equilibrium line method was originally used by Pourbaix for simple metal-hydroxide systems.
Each line equation is derived from an electrochemical and/or acid-base reaction between species.
Metals 2016, 6, 23 4 of 30

Garrels and Christ used Fe–S as an example to show that the same procedure presented by
Pourbaix could be applied to a multicomponent system. Basically, it involved two separate steps:
domain areas of ligand S were first constructed, then all Fe species (including Fe–S complexes) were
distributed in each isolated area of the ligand species. Huang and Cuentas [5] presented a computer
algorithm to construct this type of diagram using an early personal computer.

2.2. Development of the Mass Balance Point Method

Forssberg et al. [6] constructed several Eh-pH diagrams related to chalcopyrite, CuFeS2 , by
performing equilibrium calculations for the whole system at once at each given Eh and pH. By doing
so, the Cu:Fe:S ratio could be strictly maintained to 1:1:2 at all points. They used the SOLGASWATER
program developed by Eriksson [7] to perform the calculation. This point-by-point mass balance
method identifies the predominant species at each given point of Eh and pH. Points of the same species
were combined into an area for the final diagram. The SOLGASWATER program used free energy
minimization, which is commonly used for equilibrium calculation. Woods et al. [8] also presented
diagrams for the Cu–S system using SOLGASWATER.
The mass balance method can also be computed considering the law of mass action
(Huang et al. [9]). This approach simultaneously solves all equations, equilibria and mass balances, at
each given point of Eh and pH. As with the free energy minimization method, the final diagram has to
be plotted by grouping calculated results together. presented later, was reconstructed using the law of
mass action for Cu–S and matched with from Woods et al. [8].
Besides matching the mass input, these diagrams reveal the presence of multiple solids as
restricted only by the Gibbs phase rule. The key to the success of using the point-by-point method,
however, is the resolution of the grids used in the calculation. Except for 3D diagrams, all mass balance
diagrams in this paper were constructed using grids of at least 400 ˆ 800.

3. Applications for the Diagrams

Eh-pH diagrams are widely used in many areas where an aqueous system is affected by
oxidation-reduction and/or acid-base reactions, ligand complexation, temperature or pressure.
The following three examples are presented to illustrate these effects.

3.1. Geochemical Formation

Copper porphyry ore deposits occur throughout the world and are very important sources of
copper, silver and gold. These deposits initially consist of disseminated sulfide minerals in a rock
matrix, but near-surface weathering oxidizes the sulfides and leaches dissolved metals from the
residual mass. These leached metals in solution percolate downward and are often reprecipitated in
an enrichment zone overlying unreacted sulfide protore. The near-surface weathered, oxidized portion
of the deposit corresponds to the oxidizing region of an Eh-pH diagram, while the non-oxidizing
reduced enrichment zone corresponds to the reducing diagram region. Figure 3 is a geologic sketch of
an idealized porphyry deposit versus the depth from the surface, while Figure 4 is a copper Eh-pH
diagram in which iron, sulfur and carbonate, besides copper, are considered in the calculations.
The minerals predicted in the diagram, solely from thermodynamic considerations, correspond
extremely well with minerals observed in these deposits and with the relationships between these
minerals. In the oxidized and weathered zone, the original copper and iron sulfides are not stable,
while copper carbonates (antlerite, malachite, azurite) and oxides (tenorite, cuprite) form instead.
In the enrichment zone, the copper-only sulfides covellite (CuS) and chalcocite (Cu2 S) are dominant,
with native copper seen to occur in both oxidized and enriched zones.
Metals 2016, 6, 23 5 of 30
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Figure 3. Illustrated copper ore deposit for comparison to the Eh-pH diagram to the right (Dudas et al. [10]).
Figure 3. Illustrated copper ore deposit for comparison to the Eh-pH diagram to the right
(Dudas
Figure et al. [10]).copper ore deposit for comparison to the Eh-pH diagram to the right (Dudas et al. [10]).
3. Illustrated

Figure 4. Eh-pH diagram Cu–CO2–Fe–S in water. pCO2 = 0.1 atm, [S] = 0.01 M, [Fe] = [Cu] = 0.001 M.
Species were taken from the LLnL database [11].

Another geochemical example is the Eh-pH diagram modeling metamorphic conditions. In

Figureto
order
Figure 4.show
4. Eh-pH
Eh-pH the effect ofCu–CO
diagram
diagram high pressure,
Cu–CO 2–Fe–S ina water.
database such
pCO as SUPCRT
2 = 0.1 atm, [S] =(Johnson et al.=[12])
0.01 M, [Fe] [Cu]is=required.
0.001 M.
2 –Fe–S in water. pCO2 = 0.1 atm, [S] = 0.01 M, [Fe] = [Cu] = 0.001 M.
See the
Species reference
were taken from
from Kontny
the LLnL et al. [13]
database
Species were taken from the LLnL database [11]. for a
[11]. Fe–S diagram at 300 °C and 1500 bars pressure or
Huang [14] for more calculations and examples using SUPCRT-related databases.
Another geochemical example is the Eh-pH diagram modeling metamorphic conditions. In
Another geochemical example is the Eh-pH diagram modeling metamorphic conditions. In order
order to show the effect of high pressure, a database such as SUPCRT (Johnson et al. [12]) is required.
to show the effect of high pressure, a database such as SUPCRT (Johnson et al. [12]) is required. See the
See the reference from Kontny et al. [13] for a Fe–S diagram at 300 °C and 1500 bars pressure or
reference from Kontny et al. [13] for a Fe–S diagram at 300 ˝ C and 1500 bars pressure or Huang [14] for
Huang [14] for more calculations and examples using SUPCRT-related databases.
more calculations and examples using SUPCRT-related databases.
Metals 2016,
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3.2. Corrosion
3.2. Corrosion and
and Passivation
Passivation
Metallic corrosions
Metallic corrosions areare widespread
widespread problems
problems of of great
great importance
importance in in virtually
virtually all
all physical
physical
3.2. Corrosion
structures. and Passivation
structures. Corrosion
Corrosion chiefly
chiefly occurs
occurs whenwhen metal
metal electrochemical
electrochemical dissolution
dissolution is is favored.
favored. One
One way
way to to
protect
protect the
the metal
metal from
from corrosion
corrosion is
is to
to form
form a
a passivated
passivated layer,
layer, which
which may
may simply
simply
Metallic corrosions are widespread problems of great importance in virtually all physical be
be a
a metal
metal oxide.
oxide.
Some metal
Some metal
structures. oxides,chiefly
oxides,
Corrosion suchoccurs
such as PbO,
as PbO, exhibit
whenexhibit relatively high
relatively
metal electrochemical high solubility
solubility
dissolution and provide
and
is favored.provide
One way little
little
to
corrosion
corrosion protection.
protection.
protect the metal from corrosion is to form a passivated layer, which may simply be a metal oxide. Some
The
metalThe distribution-pH
distribution-pH
oxides, diagram
such as PbO,diagram (Figure 5)
(Figure
exhibit relatively 5) shows
shows
high the concentrations
the
solubility concentrations of dissolved
of
and provide little dissolved
corrosionPbPb species, as
species,
protection. as
wellThe
well as the
as the solubility
solubility of
of PbO,
PbO, versus
versus pH.
pH. Formation
Formation of
of metal-carbonate,
metal-carbonate, as
as shown
shown
distribution-pH diagram (Figure 5) shows the concentrations of dissolved Pb species, as well in
in the
the Eh-pH
Eh-pH
diagram
diagram of Figure
of Figure
as the solubility 6, offers
6,
of PbO,offers aa wider
versus wider passivation
passivation
pH. Formation region.
ofregion. Both diagrams
Both diagrams
metal-carbonate, werein
were
as shown constructed
constructed using
the Eh-pHusing the
the
diagram
LLnL
LLnL [11]
[11] database.
database. Pourbaix
Pourbaix in
in his
his lectures
lectures [15]
[15] presented
presented a
a similar
similar case
case for
for using
using
of Figure 6, offers a wider passivation region. Both diagrams were constructed using the LLnL [11] CO
CO to
22 to passivate
passivate
Zn metal.
Zn metal.Pourbaix in his lectures [15] presented a similar case for using CO to passivate Zn metal.
database. 2

Figure5.
Figure
Figure 5.Solubility
5. Solubilityof
Solubility of PbO
of PbO(shaded)
(shaded)versus
(shaded) versuspH.
versus pH.PbO
pH. PbOdoes
PbO does not
does notprovide
providegood
provide goodcorrosion
good corrosionprotection,
corrosion protection,even
protection, even
even
atelevated
at
at elevatedpHs.
elevated pHs.
pHs.

Figure6.
Figure 6. Eh-pH
6. Eh-pH of
Eh-pH of the
of the PbCO
thePbCO –water system.
PbCO33–water system. [Pb]
[Pb] == 11 ×× 10
10−6−6 and
and [CO
and33]][CO
´6 [CO == 0.001
0.001 M. Pb
M. Pb carbonate
carbonate phases
phases
Figure 3 –water system. [Pb] = 1 ˆ 10 3 ] = 0.001 M. Pb carbonate
do provide
do provide
phases corrosion
corrosion
do provide resistance.
resistance.
corrosion resistance.
Metals 2016, 6, 23 7 of 30
Metals 2016, 6, 23 7 of 30

3.3. Water Treatment and Adsorption

3.3. Water
WaterTreatment
discharge andstandards
Adsorptionalmost always include concentration limits for the acid, base and
heavy metals.
Water When feasible,
discharge standards precipitation
almost always of a solid,
include followed by a liquid-solid
concentration limits forseparation is usually
the acid, base and
the preferred means of achieving these limits, but often, stringent standards
heavy metals. When feasible, precipitation of a solid, followed by a liquid-solid separation is usually are difficult, if not
impossible,
the preferredtomeans
comply of with by this
achieving means.
these Adsorption
limits, but often,onto metal standards
stringent oxides/hydroxides sometimes
are difficult, if not
provides an alternative means of removing these metals from the discharge
impossible, to comply with by this means. Adsorption onto metal oxides/hydroxides sometimes solution. The adsorption
of arsenic
provides an(As) by ferrihydrite
alternative means ofisremoving
demonstratedthese in Figure
metals from7 using data from
the discharge Nishimura
solution. et al. [16]. For
The adsorption of
this particular experiment, the initial conditions were As = 37.5 mg/L with a Fe/As
arsenic (As) by ferrihydrite is demonstrated in Figure 7 using data from Nishimura et al. [16]. For this mole ratio of 10.
The sourceexperiment,
particular of ferric ironthe
was dissolved
initial Fe2(SO
conditions 4)3:5H2O.
were ΣAs = 37.5 mg/L with a Fe/As mole ratio of 10.
The species
The source of ferricconsidered and their
iron was dissolved Fe2thermodynamic
(SO4 )3 :5H2 O. values were also taken from the LLnL
database [11]. The equilibrium calculation included
The species considered and their thermodynamic values adsorption using
were a surface complexation
also taken from the model.
LLnL
Potentially adsorbed species onto ferrihydrite are three arsenates,
database [11]. The equilibrium calculation included adsorption using a surface complexation one arsenite, two sulfates,
model.
hydrogen ion
Potentially and hydroxide.
adsorbed species onto Their equilibrium
ferrihydrite constants,
are three logKone
arsenates, adsint, were obtained from Dzombak
arsenite, two sulfates, hydrogen
andand
ion Morel [17]. In order
hydroxide. to better
Their fit the experimental
equilibrium constants, logK data, some modifying
int , were obtained changes
from were
Dzombakmade:and
ads
Morel [17]. In
1. Type 2 order to better for
site density fit the experimental
ferrihydrite data,
was some modifying
changed from 0.2changes
to 0.3 were
molemade:
As/mole Fe
1. due to2 co-precipitation,
Type site density for ferrihydrite was changed from 0.2 to 0.3 mole As/mole Fe due
to co-precipitation,
2. The logK1int for adsorbed species ≡FeH2AsO4 was changed from 29.31 to 31.67,
2. int for adsorbed species ”FeH AsO was changed from 29.31 to 31.67,
3. TheThe logK
adsorbed
1 species ≡FeAsO42− and its2logK34int = 21.404 were added and
3. The adsorbed species ”FeAsO4 2´ and its logK0 3 int = 21.404 were added and
4. Solid scorodite (FeAsO4:2H2O) and its ΔG 25C = −297.5 kcal/mole were included with the
4. Solid scorodite (FeAsO4 :2H2 O) and its ∆G0 25C = ´297.5 kcal/mole were included with the
LLnL dbase.
LLnL dbase.
Figure 7 is the resulting distribution-pH diagram, of the same type as Figure 5, for arsenate
Figure 7 is the resulting distribution-pH diagram, of the same type as Figure 5, for arsenate
As(V). The adsorption model nicely matches the experimental data, demonstrating effectively what
As(V). The adsorption model nicely matches the experimental data, demonstrating effectively what
the arsenic removal should be. The adsorption of arsenite As(III), while not shown, also matches the
the arsenic removal should be. The adsorption of arsenite As(III), while not shown, also matches the
experimental data. Figure 8 is presented to illustrate the Eh-pH diagram for the As–Fe–S–water
experimental data. Figure 8 is presented to illustrate the Eh-pH diagram for the As–Fe–S–water system
system constructed using the mass-balanced (600 × 800 grids) method. The areas in light blue show
constructed using the mass-balanced (600 ˆ 800 grids) method. The areas in light blue show solids
solids and adsorbed species to a dissolved concentration less than 0.1 ppm.
and adsorbed species to a dissolved concentration less than 0.1 ppm.

Figure7. Distribution
Figure 7. Distribution of vs.As(V)
of As(V) pH diagram whendiagram
vs. pH Fe/As = 10. Asterisks
when are experimentally-observed
Fe/As = 10. Asterisks are
values. Drinking water standard
experimentally-observed values.from EPA (2001).
Drinking water standard from EPA (2001).
Metals 2016, 6, 23 8 of 30
Metals 2016, 6, 23 8 of 30

Figure8.8. Eh-pH
Figure Eh-pHofofAs–Fe–S
As–Fe–Swater
waterwhere
wherethe
themole
moleratio
ratioofofFe/As
Fe/As == 10.
10. The colored
colored area
area indicates
indicates less
less
than0.1
than 0.1ppm
ppmconcentration
concentrationof
ofAs
Asby
byadsorption.
adsorption.

3.4. Hydrometallurgical
3.4. HydrometallurgicalLeaching
Leachingand
andMetal
MetalRecovery
Recovery
Three applications
Three applications for
for hydrometallurgy
hydrometallurgy are
are presented
presented in
in more
more detail
detail later
later in
in the
the section
section titled
titled
“Enhancingthe
“Enhancing theEh-pH
Eh-pHDiagrams
DiagramsbybyMerging
MergingTwo
TwoororMore
MoreDiagrams”.
Diagrams”.These
Theseare:
are:
1.
1. Cyanidation of
Cyanidation of Au
Au and
and cementation
cementation with
withZnZnMetal,
Metal,
2. Cementation of copper with elemental Fe, and
2. Cementation of copper with elemental Fe, and
3. Galvanic conversion of chalcopyrite with Cu metal with two construction methods for Eh-pH
3. Galvanic conversion of chalcopyrite with Cu metal with two construction methods for Eh-pH
diagrams to handle ligand components.
diagrams to handle ligand components.
4. Descriptions
4. Descriptions and
and Comparison
Comparison between
between These
These Two
Two Crucial Methods
Crucial Methods

4.1. Equilibrium
4.1. Equilibrium Equations
Equations for
for Eh-pH
Eh-pHDiagrams
Diagrams
The chemical
The chemical equation
equation between
between Species
Species A
A and
and BB in
in the
the water
water system,
system, with
with or
or without
without electron
electron
involvement,can
involvement, canbe
beexpressed
expressedas:
as:
aA + cC ↔ bB + dD + hH+ + wH2O (+ne−) (1)
aA ` cC Ø bB ` dD ` hH+ ` wH2 O p`ne´ q (1)
Species C and D are ligand and complexes produced with ligand. The stoichiometric coefficient
of a Species C and
species is D as
taken arepositive
ligand and
if it complexes producedside
is on the right-hand withofligand. The stoichiometric
the equation, and vice versa. coefficient
Species
of
H a, species
+ H2O and is etaken
- mayasnot
positive
alwaysif be
it isononthe
theright-had
right-hand side
side of of
thethe equation,
equation. and vicesoversa.
Because manySpecies H+ ,
equations
H ´
2 O species
and and e aremayinvolved
not always be performing
while on the right-had side of the
equilibrium equation.for
calculations Because so many
an Eh-pH equations
diagram, and
it is easier
species
to use the free energy of formation of each involved species, ΔGi , then to calculate the free energy to
are involved while performing equilibrium calculations for
0 an Eh-pH diagram, it is easier of
use as, energy of formation of each involved species, ∆Gi 0 , then to calculate the free energy of
the free
reaction
reaction as,
ΔGrex =ÿ ∑(υi × ΔGi0)0 (2)
∆Grex “ pυi ˆ ∆Gi q (2)
where υi represents the stoichiometric coefficient of species i.
where υi represents the stoichiometric coefficient of species i.
Depending on whether or not the reaction involves an electron and/or hydrogen ion, the
Depending on whether or not the reaction involves an electron and/or hydrogen ion, the
equations are:
equations are:
The Nernst equation for oxidation-reduction reaction with or without acid-base:
The Nernst equation for oxidation-reduction reaction with or without acid-base:
Metals 2016, 6, 23 9 of 30

« ˜ ¸ ff
lnp10qRT
0 tBub tDud
Eh “ Eh ` ˆ log ´ hpH (3)
pn ˆ Fq tAua tCuc

∆Grex
where Eh0 “ , where R is the universal gas constant, 8.314472(15) J/(K¨ mol); T is in kelvins; F is
pn ˆ Fq
the Faraday constant 96,485.3399(24) J/(V¨ equivalent); and {A} and the others species are defined as the
activities of Species A. The activities of solid and liquid are normally assumed to be one; gas is taken
as the atmosphere (atm). The activity of an aqueous solution is the multiplication of the concentration
in mol/L, symbolized as [A], with its activity coefficient. The coefficient can be computed from one
of the appropriate models. Without having the acid-base, the “hpH” term in the equation will be
dropped out.
The equilibrium equation for acid-base reaction without redox reaction:
« ˜ ¸ ff
1 tBub tDud ∆Grex
pH “ ˆ log ` (4)
h tAua tCuc lnp10q ˆ RT

The equation for reaction involves neither an electron nor a hydrogen ion:
˜ ¸
tBub tDud ∆Grex
log Q ´ log K “ log ` (5)
tAua tCuc lnp10q ˆ RT

Species A will be favored if logQ ´ logK is positive, and vice versa.

As mentioned earlier, two different approaches may be used to construct an Eh-pH diagram.
One is to calculate equilibrium equations between pairs of species and to construct the diagram
by plotting the resulting equilibrium lines. The other is to perform equilibrium calculations from
all involved species at each point in a grid, then selecting the predominant species at each point.
Regardless of which method is used, these equilibrium equations have to be satisfied.

4.2. Line Method Using Equilibrium Concentration [5]

The diagram is constructed by computing the equilibrium between two adjacent species from their
activities. The concentration or activity of aqueous species has to be given. Figure 9 shows the Eh-pH
diagram for Cu at three different concentrations. The case where a ligand component is also involved
is demonstrated in Figure 10, for the Cu–S–water system using [S] = 0.001 and [Cu] = 0.001 mol/L.
The areas of predominance for the various ligand S species (labeled in light blue) were first constructed.
The distribution of Cu species, including Cu–S complexes, in each S domain (such as the area of H2 S
shaded with light blue) was then constructed. The final diagram of Cu species was determined by
combining all of the areas from S ligands. It should be noted that the total concentration of ΣS may
change depending on whether or not Cu is complexed with S. When Cu species are not complexed
with S, ΣS would be 0.001 mol/L, as described. However, when Cu species are complexed with S, as
in the formation of CuS, ΣS will be the molar sum of the S concentration plus the CuS concentration,
which will be equal to 0.002 mol/L. In such a case, the mass of total S may not be constant, as
originally assigned.
Metals 2016, 6, 23 10 of 30
Metals2016,
Metals 2016,6,6,23
23 10ofof30
10 30

Figure
Figure
Figure 9.Eh-pH
Eh-pH
9. 9.Eh-pH ofofof Cu-waterconstructed
Cu-water
Cu-water constructedby
constructed bythe
theline
the linemethod
line methodwhere
method where three
wherethree concentrations
threeconcentrations ininin
concentrations log
log scale
scale
log scale
are
are plotted.
plotted. Data
Data taken
taken from
from NBS
NBS
are plotted. Data taken from NBS [1]. [1].
[1].

Figure
Figure
Figure 10.
10.10. Eh-pH
Eh-pH
Eh-pH ofofof Cu(main)–S(ligand).
Cu(main)–S
Cu(main)–S (ligand).The
(ligand). Theline
The linemethod
line methodplots
method plots the
plotsthe ligand
ligand
the first,
first,
ligand shown
shown
first, ininblue
shown blue
in color.
color.
blue color.
The
The
The distribution of
distributionofofCu
distribution Cu species
Cuspecies for
speciesfor each
foreach domain
each domain
domain of of S is
of SS is then
is then determined.
thendetermined.
determined.

4.3.Point-by-Point
4.3. Point-by-PointMethod
MethodUsing
UsingMass
MassBalance
Balance[9,18]
[9,18]
4.3. Point-by-Point Method Using Mass Balance [9,18]
Inthis
In thismethod,
method,mass massbalances
balancesareareconsidered
consideredand andcalculated
calculatedwith
withall
allof
ofthe
theequilibria
equilibriafrom
fromallallof
of
Incomponents
this method,
thecomponents
mass balances are considered andUnlike
calculated with all ofwhere
the equilibria from all of
the atatonce
oncefrom
fromevery
everypoint
pointofofthe
thegrid.
grid.Unlike theline
the linemethod
methodwhere theconcentration
the concentration
theor
components
activity of at once from
of aqueous
aqueous everyispoint
species of thethis
specified, grid.method
Unlike requires
the line method
knowing where the concentration
the total
total mass of each or
of each
or activity species is specified, this method requires knowing the mass
activity of aqueous
component. species is specified,
Thecalculation
calculation thisonly
requiresnot
not method requires
satisfying knowing
allequilibrium
equilibriumtheequations,
total massbutof each component.
alsomatching
matching
component. The requires only satisfying all equations, but also
The
allcalculation
allofofthe
themassrequires
massbalances. not
balances.Theonly satisfying
Theresults
resultsare all equilibrium
aresorted
sortedout
outin equations,
inorder
orderto to plot but
plotthe also matching
thediagram
diagramfor all
foreach of the mass
eachspecific
specific
balances. The
component.This
component. results
Thistype are
typeofsorted out
ofdiagram in order to
diagramisisparticularlyplot the diagram
particularlyimportant
importantfor for
forEh-pH each specific
Eh-pHdiagrams, component.
diagrams,which
whichinclude This
includesolids type
solids
Metals 2016, 6, 23 11 of 30
Metals
Metals 2016,
2016, 6,
6, 23
23 11
11 of
of 30
30

with
with composition
of diagramcomposition
is particularlyratios
ratios that
that are
important close
are for
close to
Eh-pHto mineral
mineral formation
which ratios
formation
diagrams, ratios (such
include (such as 3:1:4
aswith
solids mole
mole ratios
3:1:4composition for
ratiosratios
for
thatenargite
enargite
are close Cu 33AsS
Cuto AsS 44))
mineral formation ratios (such as 3:1:4 mole ratios for enargite Cu3 AsS4 )
Mass
Mass
Mass inputs,
inputs,
inputs, including
includingmasses
including masses
massesof of ligands,
ofligands,
ligands, areare crucial
crucial for
are crucial for determining
determiningcritical
determining criticalareas
critical areasof
areas ofofthese
these
these
diagrams.
diagrams.
diagrams. Figures
Figures
Figures 111111 and
andand 1212
12 illustrate this
illustratethis
illustrate for
thisfor the
forthe Cu–S–water
Cu–S–water system
theCu–S–water system(data
system (datafrom
(data fromNBS
from NBS[1]).
NBS [1]).Figure
[1]). Figure
Figure 11
1111
shows
shows
shows the
the case
case where
thecase whereSS is
where Sis stoichiometrically
stoichiometrically
is stoichiometrically slightly
slightly less
less than
slightly copper,
thanless thani.e.,
copper, i.e., Cu
Cu == 0.001
copper, i.e., and
0.001 and
ΣCu S
S=== 0.0009
0.001 M,
0.0009 M,
and
while
while Figure
Figure 12
12 shows
shows the
the case
case where
where S
S is
is slightly
slightly in
in excess.
excess. The
The higher
higher
ΣS = 0.0009 M, while Figure 12 shows the case where S is slightly in excess. The higher mass of mass
mass of
of SS leads
leads to
to a
a larger
larger
area
area of
S leads of predominance
to larger area offor
apredominance for CuS.
CuS.
predominance for CuS.

Figure
Figure 11.11.
Figure 11. Mass-balanced
Mass-balanced
Mass-balanced Eh-pH diagram
Eh-pHdiagram
Eh-pH for
diagramfor the
forthe Cu–S–water
Cu–S–water system
theCu–S–water systemwith
system withcopper
with copperslightly
copper slightly in excess.
inin
slightly excess.
excess.
ΣCuCu
Cu == 0.001
MM
0.001
= 0.001 M and
and
and S
ΣSS===0.0009
0.0009 M.
0.0009M.
M.

Figure
Figure 12. Mass-balanced
Mass-balanced Eh-pH
Eh-pH diagram
diagram for
for the
the Cu–S–water
Cu–S–water system
system with
Figure 12. 12.
Mass-balanced Eh-pH diagram for the Cu–S–water withcopper
systemwith copper slightly
copperslightly in
in deficit.
slightly deficit.
in deficit.
Cu
Cu == 0.001
0.001 M and S
M and S == 0.0011
0.0011 M.
M.
ΣCu = 0.001 M and ΣS = 0.0011 M.
Metals 2016, 6, 23 12 of 30

Metals2016,
Metals 2016,6,6,23
23 12of
12 of30
30
4.4. Differences and Comparison between the Methods
4.4. Differences
4.4. Differences and
and Comparison
Comparison between
between the
the Methods
Methods
Different results of the two methods can be seen by comparing diagrams constructed within the
Different results
Different resultsofof the
the two
two methods can can be be seen
seen by
by comparing
comparing diagrams
diagrams constructed
constructed withinwithin the the
Cu–S system, with sulfate speciesmethods
not shown due to unfavorable kinetics (Woods et al. [8]). Figure 13
Cu–S
Cu–S system,
system, with
with sulfate
sulfate species
species not
not shown
shown due
due to
to unfavorable
unfavorable kinetics
kinetics (Woods
(Woods et
et al.
al. [8]).
[8]).
was constructed by the equilibrium line method where [Cu] = 0.118 and [S] = 0.059, and Figure 14 was
Figure 13
Figure 13 was
was constructed
constructed by by thethe equilibrium
equilibrium line method method where [Cu] [Cu] = 0.118
0.118 and and [S] == 0.059,
0.059, and
constructed by the mass-balanced point methodline where ΣCu where= 0.118 and =ΣS = 0.059. [S] Free energyand data
Figure
Figure 14
14fromwas constructed
was constructed by the mass-balanced point method where ΣCu = 0.118 and ΣS == 0.059.
0.059.
were taken Woods et al.by [8].theCrucial
mass-balanced
differences point
canmethod
be seenwhere
in theΣCu = 0.118
general areaandof ΣS
Cu–S solids.
Free energy
energy datadata were
were taken
taken from
from Woods
Woods et et al.
al. [8].
[8]. Crucial
Crucial differences
differences can
can be
be seen
seen in in the
the general
general areaarea
As Free
can
of
be seen
Cu–S
from
solids. As
Figure
can be
13, even
seen from
though
Figure
theeven
13,
concentration
though the
ratio of Cu/S
concentration
isratio
specified
of Cu/S
asistwo to one,
specified
of Cu–S solids. As can be seen from Figure 13, even though the concentration ratio of Cu/S is specified
CuS,asnottwoCu S, is CuS,
to 2one,
one, the predominant
not CuCu22S,
S, is
is thespecies.
the predominant species.species.
as two to CuS, not predominant
TheThe mass-balanced
mass-balanced point
point calculation
calculation involved
involved points on
points onon aaa 400
400
400 ׈ 800 grid
× 800
800 gridtotoaaprecision
precisionofof
´ The
10 mass-balanced point calculation involved points grid to a precision of
1 ˆ110 , butbuttook
tookless
lessthan
thanthree minutes for
for aa PC from
from creating
creatingaaworksheet
worksheetfor forinput
inputtotoplotting
plottingthe the
1 ××10 10−10 ,, but three minutes
minutes for a PC
PC
−10
took less than three from creating a worksheet for input to plotting the
finalfinal
diagram.
diagram.
final diagram.

Figure13.
Figure 13. Eh-pH
Eh-pHdiagram
diagram for
forthe
the Cu–S–water
Cu–S–watersystem
system constructed
constructed by
by the equilibrium
equilibrium linemethod.
method.
Figure 13. Eh-pH diagram for the Cu–S–water system constructed bythe
the equilibriumline
line method.

Figure
Figure 14.
14.14.
Figure Eh-pH
Eh-pH
Eh-pH diagram
diagram for
diagram for
for theCu–S–water
the
the Cu–S–watersystem
Cu–S–water systemconstructed
system constructedby
constructed by the
bythe mass-balance
themass-balance point-by-point
mass-balancepoint-by-point
point-by-point
method.
method.
method. This
This
This diagram
diagram
diagram matches Figure
matchesFigure
matches 5 of Wood
Figure55ofofWood et al.
Woodetetal. [8].
al.[8].
[8].
Metals 2016, 6, 23 13 of 30
Metals 2016, 6, 23 13 of 30

The
The equilibrium
equilibrium line
line method
method was favored in the past due to its relative ease of construction.
When diagrams
When diagrams were
were constructed
constructed using
using manual
manual calculation
calculation (as
(as by
by Pourbaix),
Pourbaix), thethe equilibrium
equilibrium line
line
method
method was
was the
the only
only practical
practical approach.
approach. As
As greater
greater computational
computational power
power became
became available,
available, the
the
mass-balanced point-by-point
mass-balanced point-by-pointmethod
method came
came into
into favor.
favor. The
The following
following list
list includes
includes some
some areas
areas where
where
the mass
the mass balance
balance method
method should
shouldbe beconsidered
consideredover
overthe
theline
linemethod.
method.
1.
1. When the
When the exact
exact composition
composition of of the
the system
system isisneeded:
needed: Examples
Examples include
include leaching
leaching and
and flotation
flotation
studies. See
studies. See Huang
Huang and
and Young
Young[18][18]for
formore
moreexamples.
examples.TheThe Eh-pH
Eh-pHdiagram
diagramof ofenargite
enargite(Cu
(Cu33FeS
FeS44))
(Figure 15) was constructed using data collected by
(Figure 15) was constructed using data collected by Gow [19]. Gow [19].
2.
2. When aa system
When system isis required
required to to specify
specify total
total concentration,
concentration, not
not equilibrium
equilibrium concentration
concentration
nor activity.
nor activity.
3.
3. When
When thethe adsorption
adsorption byby solids,
solids, such
such asas ferrihydrite,
ferrihydrite,isisconsidered
considered(refer
(referto
toFigure
Figure8).
8).
4.
4. When multiple
When multiple phases
phases of
of aa solid
solid need
need toto be
be shown:
shown: Figure
Figure 1616 was
was constructed
constructed by
by showing
showing the
the
coexistence of schwertmannite with various forms of jarosites in Berkeley pit water. Water
coexistence of schwertmannite with various forms of jarosites in Berkeley pit water. Water samples
samples were taken and analyzed from 1987 to 2012 by the Montana Bureau of Mines and
were taken and analyzed from 1987 to 2012 by the Montana Bureau of Mines and Geology [20],
Geology [20], and the thermodynamic data for the solids species were regression estimated
and the thermodynamic data for the solids species were regression estimated by Srivastave [21].
by Srivastave [21].
5. A diagram will most likely be mass balanced if a speciation program, such as PHREEQC
5. A diagram will most likely be mass balanced if a speciation program, such as PHREEQC
(USGS) [22], was used to construct it. Results from the program were collected manually or
(USGS) [22], was used to construct it. Results from the program were collected manually or
electronically, then combined into an Eh-pH diagram.
electronically, then combined into an Eh-pH diagram.

Figure 15. Mass balanced Eh-pH diagram for the enargite Cu3AsS4 system. The mass ratio is 0.75:0.25:1
Figure 15. Mass balanced Eh-pH diagram for the enargite Cu3 AsS4 system. The mass ratio is 0.75:0.25:1
for Cu, As and S. The diagram shows only the copper species in acid solution.
for Cu, As and S. The diagram shows only the copper species in acid solution.
Metals 2016, 6, 23 14 of 30
Metals 2016, 6, 23 14 of 30

Figure
Figure 16.16. Mass
Mass balancedEh-pH
balanced Eh-pHdiagram
diagram for
for the
the Fe–K–S
Fe–K–S system
system at at 77 °C.
˝ C.This
Thisdiagram
diagramshows
showsthethe
coexistence
coexistence among
among schwertmannite,K-jarosite
schwertmannite, K-jarosite and
and KH-jarosite.
KH-jarosite. **represents
representsthe thedata
dataanalyzed
analyzedfrom
from
thethe sampled
sampled water.
water.

Both methods, however, can produce identical diagrams under the following conditions:
Both methods, however, can produce identical diagrams under the following conditions:
1. A one-component system, such as Figure 1 for Mn and Figure 2 for P,
1. 2. A one-component
The concentration system, such
of ligand as Figure 1 for
component(s) Mn and
is much Figure
greater 2 for
than theP,main component, such as
2. The concentration
metal corrosion by ofsea
ligand component(s)
water, and is much greater than the main component, such as
3. metal
Gas corrosion
is the onlyby
ligand, such as
sea water, the Fe–CO2(g) system.
and
3. Gas is the only ligand, such as the Fe–CO2 (g) system.
4.5. Gibbs Phase Rule Applied to an Eh-pH Diagram
4.5. Gibbs Phase Rule Applied to an Eh-pH Diagram
An Eh-pH diagram constructed using either method must follow the Gibbs phase rule. The
original
An Eh-pHphase diagram
rule equation, P + F = Cusing
constructed + 2, was developed
either methodformust
considerations
follow theof Gibbs
temperature
phaseand
rule.
pressure. It can be refined for use in constructing an Eh-pH diagram by implementing some concepts
The original phase rule equation, P + F = C + 2, was developed for considerations of temperature and
and restrictions.
pressure. It can be refined for use in constructing an Eh-pH diagram by implementing some concepts
Mass-balanced method: This method calculates equilibrium from all components at once.
and restrictions.
The variables are asmethod:
Mass-balanced follows: This method calculates equilibrium from all components at once.
The1.variables
P is theare as number
total follows:of phases = 1 (liquid water) + 1 (gas if considered) + N (maximum number

1. P isofthe
solids/liquids),
total number of phases = 1 (liquid water) + 1 (gas if considered) + N (maximum number
2. of Fsolids/liquids),
is the degree of freedom on the diagram, which is two for an open area, one on a boundary
2. F islinetheand zeroof
degree onfreedom
a triple point,
on the diagram, which is two for an open area, one on a boundary line
3. andC iszero
theon a triple
total numberpoint,
of components = 3 + EC (extra components). Three components are essential
3. C is fortheEh-pH
total number of components
calculation = 3 +system.
in an aqueous EC (extra components).
These are H(+1),Three
O(−2)components
and e(−1). are
Theessential
extra
forcomponents
Eh-pH calculation in an aqueous system. These are H(+1), O(´2) and
include the main component to be plotted, as well as all ligands. e(´1). The extra
components include the main component to be plotted, as well as all ligands.
4. The term of +2 is for temperature and pressure variables. Since both are considered to be
4. The term of +2 is for temperature and pressure variables. Since both are considered to be constant,
constant, +2 will be dropped off. If any system involved a gaseous species, +1 should be used,
+2 will be dropped off. If any system involved a gaseous species, +1 should be used, but it will be
but it will be canceled out with one extra gaseous phase to the equation.
canceled out with one extra gaseous phase to the equation.
The phase rule equation for an Eh-pH diagram, best expressed as the maximum number of solids
The phase rule equation for an Eh-pH diagram, best expressed as the maximum number of solids
plus liquids excluding the liquid phase of water, thus becomes:
plus liquids excluding the liquid phase of water, thus becomes:
Metals 2016, 6, 23 15 of 30

Metals 2016, 6, 23 15 of 30

Nmaxsolid = CC −´FF−´11
Nmaxsolid“ (6)
(6)
Example
Example 1,1, Cu
Cu andand SS two-component
two-component system:
system: The
The incorporation
incorporation of of the
the rule
rule isis illustrated
illustrated in in
Figure 17, in which all solids containing Cu, as well as S components are presented. Since
Figure 17, in which all solids containing Cu, as well as S components are presented. Since the method the method
computes
computes equilibria
equilibria from
fromall
allcomponents
componentsinvolved
involvedat once,CC==33++ 22 and
atonce, and N 5 5– –F F– –1 1oror4 4– –F.F.
maxsolid = =
Nmaxsolid
open area
1a. In an open area of
ofthe
thediagram whereFF==2,2,NN
diagramwhere willwill
maxsolid
maxsolid be equal
be equal to two.
to two. TheThe co-existence
co-existence of twoof
two solids
solids can becanseen
be seen in many
in many placesplaces
on theondiagram,
the diagram,
1b. On a boundary
boundaryline linewhere
whereFF==1,1,NN maxsolid becomes
maxsolid becomesthree. For For
three. instance, while
instance, eacheach
while of the
oflight blue
the light
areas contains
blue areas two two
contains solids, the the
solids, lineline
between
between them
them represents
representsthethepresence
presenceof of three: CuO,
CuO, CuCu22SS
and Cu1.96
1.96S,
S,
1c.
1c. On aa triple
triplepoint
pointwhere
wherethree
threelines meet,
lines meet,F =F0,=N0, = 4. At=the
Nmaxsolid
maxsolid 4. point
At the labeled
point A, for instance,
labeled A, for
even though
instance, even four
though areas
fourmeet, only only
areas meet, threethree
solids are are
solids coexistent
coexistent atatthe
the point: CuO, Cu
point: CuO, Cu1.75 S
1.75S

and Cu1.96 S.
1.96 S.

Example 2,
Example 2, Pb-S-KEX
Pb-S-KEX (potassium
(potassium ethyl
ethyl xanthate)
xanthate) three-component
three-component system:
system: Pb-S-KEX
Pb-S-KEX waswas also
also
used to
used to illustrate
illustrate the
the phase
phase rule.
rule. Figure
Figure 18 18 was
was constructed
constructed using
using data
data taken
taken from
from Pritzker
Pritzker and
and
Yoon [23]. The plot illustrates a small, but intricate area, Eh from ´0.5 to ´0.3 and pH from 10 13,
Yoon [23]. The plot illustrates a small, but intricate area, Eh from −0.5 to −0.3 and pH from 10 to to
with
13, a resolution
with a resolution of 600 × 800.
of 600 A small
ˆ 800. pinkpink
A small areaarea
shows threethree
shows stable solids:
stable PbS, PbS,
solids: Pb and
Pb PbX . This
and 2PbX 2.
number agrees with the phase rule equation for the Eh-pH diagram of N maxsolid = 5 – F, where F is
This number agrees with the phase rule equation for the Eh-pH diagram of Nmaxsolid = 5 – F, where F
equal
is equaltototwo,
two,being
beinginside
insideananopen
openarea.
area.There
Thereareare four
four solids
solids (PbS, Pb, PbX
(PbS, Pb, PbX2 and
and Pb(OH)
Pb(OH)2)) along
along the
the
2 2
line between
line between thisthis pink
pinkarea
areaand
andthethearea
arearight
rightabove
aboveit.it.The
TheNNmaxsolid for all three corners of this area
maxsolid for all three corners of this area
was no greater than five, as described by
was no greater than five, as described by the rule. the rule.

Figure 17.
Figure 17. Mass-balanced
Mass-balancedEh-pHEh-pHdiagram
diagramofofthe
theCu–S–water
Cu–S–watersystem
system toto illustrate
illustrate thethe phase
phase rule.
rule. This
This is
aiszoomed-in
a zoomed-in
detaildetail
from from
FigureFigure 14;solids
14; stable stableinclude
solids elemental
include elemental from the S ΣCu
S from the S component. component.
= 0.118
ΣCuΣS
and = 0.118 and
= 0.059 M.ΣS = 0.059 M.
Metals 2016,
Metals 2016, 6,
6, 23
23 16
16of
of30
30

Figure 18. Mass-balanced Eh-pH diagram of of the

the Pb–S–potassium
Pb–S–potassium ethyl
ethyl xanthate
xanthate (KEX)
(KEX) water
water system.
system.
ΣPb == ΣS == 0.45
0.45 and ΣX == 0.0001
0.0001 M. This zoomed-in detail has a resolution of 600
600 ˆ
× 800 to verify the
Gibbs phase rule.

Equilibrium
Equilibrium line method: Since
line method: Since this
this method
method works
works on on one
one component
component at at aa time,
time,
N maxsolid = 4 – F – 1 = 3 – F. Referring to Figure 13, in any open area of the diagram, Nmaxsolid = 1, which
Nmaxsolid = 4 – F – 1 = 3 – F. Referring to Figure 13, in any open area of the diagram, Nmaxsolid = 1,
means means
which only one solid
only oneissolid
allowed. On anyOn
is allowed. boundary line, Nmaxsolid
any boundary line, N = 2, as shown by the line between
maxsolid = 2, as shown by the line
CuO
betweenandCuOCuS.and
If a CuS.
tripleIfpoint is formed,
a triple point is N maxsolid will be equal to three.
formed, N will be equal to three.
maxsolid

5.
5. Enhancing
Enhancingthe
theEh-pH
Eh-pHPlot
Plotby
byMerging
MergingTwo
Twoor
orMore
More Diagrams
Diagrams
Most Eh-pHdiagrams
Most Eh-pH diagramsindicate
indicate
thethe stability
stability of water
of water bydashed
by two two dashed lines:
lines: this is athis is aexample
typical typical
example of merging two diagrams together. Other examples include showing several
of merging two diagrams together. Other examples include showing several solubilities of solid species solubilities of
solidFigure
(see species9), (see Figure
showing 9), showing
dissolved dissolved
species species in areas
in areas dominated dominated
by solids by solids
and showing and
ligands inshowing
addition
ligands in addition to the main
to the main component (see Figure 10). component (see Figure 10).
An
An Eh-pH
Eh-pH diagram,
diagram, including
including the
the examples
examples listed
listed above,
above, often
often shows
shows only
only half
half of
of aa reaction.
reaction.
To illustrate
To illustrate the
the whole
whole process,
process, merging
merging another
another relevant
relevant diagram
diagram may
may be be necessary.
necessary. The
The combined
combined
diagram
diagram cancan bebe re-plotted
re-plotted or overlaid by
or overlaid by aa graphics
graphics program, such as
program, such as MS
MS PowerPoint.
PowerPoint. It It is
is strongly
strongly
suggested
suggested to use different
to use different colors
colors for
for each
each merged
merged diagram.
diagram.

5.1. Cyanidation of Gold and Cementation with Zn Metal

The combination
combinationofofa Au–CN
a Au–CNdiagram withwith
diagram a Zn–CN diagram
a Zn–CN is shown
diagram is as Figureas19.
shown The up-arrow
Figure 19. The
indicates leaching
up-arrow indicatesofleaching
Au usingofCN
Auas the complexing
using ligand and Oligand
CN as the complexing 2 as the oxidant.
and O 2 as The
the down-arrow
oxidant. The
down-arrow indicates the cementation of Au replaced by Zn metal.
indicates the cementation of Au replaced by Zn metal.

5.2. Cementation
5.2. Cementation of
of Copper
Copper with
with Metallic
Metallic Iron
Iron
Figure 20
Figure shows the
20 shows the combination
combination ofof aa Cu–water
Cu–water diagram
diagram and
and aa Fe-water
Fe-water diagram
diagram and
and illustrates
illustrates
cementation of
cementation ofcopper
copperby byiron
ironmetal.
metal.Additionally,
Additionally, thethe
diagram shows
diagram other
shows reactions
other of interest,
reactions such
of interest,
as those that represent wasteful consumption of iron metal by reactions involving Fe 3+ , O 3+(g) and
such as those that represent wasteful consumption of iron metal by reactions involving Fe , O2(g) 2
H+ (a).HAlthough
and not partnot
+(a). Although of the diagram
part of thecalculations, the rest potential
diagram calculations, thebetween the Cu2+ /Cu–Fe
rest potential between /Fe
2+
the
electrodes
Cu 2+/Cu–Fe is2+also shown. is also shown.
/Fe electrodes
Metals 2016, 6, 23 17 of 30
Metals
Metals2016,
2016,6,6,2323 1717ofof3030

Figure
Figure 19.19.
Figure 19.Combined
Combined
Combined Au–CN
Au–CN
Au–CN and
andandZn–CN
Zn–CN
Zn–CN Eh-pH
Eh-pH
Eh-pH diagrams
diagrams
diagrams would
would
would show
show
show leaching
leaching
leaching and
and
and cementation
cementation
cementation for
for
theforthe gold cyanidation
thecyanidation
gold gold cyanidationprocess.
process.
process.

Figure
Figure
Figure 20.
20.20.Combined
Combined
Combined Cu
Cu and
Cuand Fe
andFe Eh-pH
FeEh-pH diagrams
diagramswould
Eh-pHdiagrams wouldshow
would showthat
show thatreactions
that reactionsoccur
reactions occurduring
occur during
duringcopper
copper
copper
cementation
cementation
cementation using
using
using metallic
metallic
metallic iron.
iron.
iron.

5.3.
5.3.Galvanic
GalvanicConversion
ConversionofofChalcopyrite
Chalcopyritewith
withCopper
CopperMetal
Metal[24] [24]
5.3. Galvanic Conversion of Chalcopyrite with Copper Metal [24]
When
When inin contact
contact with
with CuCu metal,
metal, chalcopyrite
chalcopyrite reacts reacts cathodically
cathodically inin an an effect
effect known
known asas
When in contact with Cu metal, chalcopyrite reacts cathodically in an effect known as
galvanic
galvanicconversion:
conversion:
galvanic conversion:
10CuFeS
10CuFeS2 2(chalcopyrite)
(chalcopyrite)++24H24H+ +++8e8e− −==2Cu
2Cu5FeS
5FeS4 4++8Fe
8Fe2+2+++12H
12H2S2S (7)
(7)
+ ´ 2+
10CuFeS2 pchalcopyriteq ` 24H ` 8e “ 2Cu 5 FeS 4 ` 8Fe ` 12H 2 S (7)
2Cu
2Cu5FeS
5FeS4 4(bornite)
(bornite)++6H
6H+ +++2e
2e− −==5Cu
5Cu2S2S++2Fe
2Fe2+2+++3H
3H2S2S (8)
(8)
2Cu5 FeS4 pborniteq ` 6H+ ` 2e´ “ 5Cu2 S ` 2Fe2+ ` 3H2 S (8)
Metals 2016, 6, 23 18 of 30

An anodic reaction takes place on the metallic copper as:

Metals 2016, 6, 23 18 of 30
Metals 2016, 6, 23
2Cu ` H2 S “ Cu2 S ` 2H+ ` 2e´ 18 of 30
(9)
An
Ananodic
anodicreaction
reactiontakes
takesplace
placeon
onthe
themetallic
metalliccopper
copperas:
as:
A schematic diagram for all these reactions is shown as Figure 21. In order to present all of the
2Cu
2Cu + H22SS==Cu
Cu22SS++2H
+ +2e− (9)
species involved, three Eh-pH diagrams are+ H
superimposed 2H+and
+2e− shown as Figure 22. (9)
AAschematic
schematicdiagram
diagramfor
forall
allthese
thesereactions
reactionsisisshown
shownas
asFigure
Figure21.
21.In
Inorder
orderto
topresent
presentall
all of
ofthe
the
1. The three
species diagrams
involved, threeused
Eh-pHare: S species
diagrams arein cyan, Fe andand
superimposed Fe–S in red
shown as and Cu–Fe–S
Figure 22. in black.
species involved, three Eh-pH diagrams are superimposed and shown as Figure 22.
2. Areas of predominance are shown as: chalcopyrite in yellow, bornite in gray, chalcocite in light
1.1. The three diagrams used are: SSspecies
speciesin
incyan,
cyan,Fe
Feand
andFe–S
Fe–Sininred
redand
andCu–Fe–S
Cu–Fe–Sininblack.
blue The
andthree
2.2. Areas
diagrams
metallic copper used
in are:
orange. black.
Areas of predominance are shown as: chalcopyrite in yellow, bornite in gray, chalcocitein
of predominance are shown as: chalcopyrite in yellow, bornite in gray, chalcocite inlight
light
3. The blue
down-arrow
and indicates
metallic copper where
in galvanic conversion occurs down from chalcopyrite to bornite
orange.
blue and metallic copper in orange.
and,The
3. finally, to Cu2 S.indicates
The up-arrowgalvanic
indicates where the anodic reaction occurs up from metallic
3. Thedown-arrow
down-arrow indicateswhere where galvanicconversion
conversionoccurs
occursdown
downfrom
fromchalcopyrite
chalcopyriteto
tobornite
bornite
copper
and,to Cu S.
finally, to Cu 2 S. The up-arrow indicates where the anodic reaction occurs up from
2 to Cu2S. The up-arrow indicates where the anodic reaction occurs up from metallic
and, finally, metallic
4. The copper
copperto
diagram Cu
Cu22S.
toindicates
S. that both cathodic and anodic reactions lead to the formation of Cu2 S, and
4.
otherThe
4. The diagram
final species
diagram indicates
matchthat
indicates what
thatboth cathodic
Hiskey
both and
and
cathodic anodic
anodicreactions
Wadsworth
and lead
leadto
tothe
[24] described.
reactions theformation
formationofofCu
Cu22S,
S,and
and
other final species match what Hiskey and Wadsworth [24]
other final species match what Hiskey and Wadsworth [24] described. described.

Figure 21. Schematic diagram of reactions occurring upon galvanic conversion of chalcopyrite with
Figure 21. Schematic diagram
Figure 21. Schematic diagram of of reactionsoccurring
reactions occurring upon
upon galvanic
galvanicconversion
conversionof chalcopyrite withwith
of chalcopyrite
metallic
metalliccopper
copper [24].
metallic copper [24].[24].

Figure
Figure 22. 22.
Figure 22. Combination
Combination
Combinationofofof three
three Eh-pH
threeEh-pH diagrams
diagrams showing
Eh-pHdiagrams showingthe
showing thegalvanic
the galvanic
galvanic conversion reactions
conversion
conversion of
reactions
reactions of of
chalcopyrite
chalcopyrite with
withwith
chalcopyrite metallic
metallic copper.
copper.
metallic copper.
Metals 2016, 6, 23 19 of 30

6. Third Dimension to an Eh-pH Diagram

Metals 2016, 6, 23
Even more information may be shown by adding a third dimension to a base Eh-pH19diagram. of 30

The third
6. Thirddimension
Dimensioncan beEh-pH
to an the simple
Diagramsolubility of solid or an independent variable, such as
temperature or ligand concentration. First, the data needed for a 3D Eh-pH diagram must be calculated.
Even more information may be shown by adding a third dimension to a base Eh-pH diagram.
Thereafter, 3D programs for PC, such as ParaView [25], VisIt [26] or MATLAB [27], combine all of
The third dimension can be the simple solubility of solid or an independent variable, such as
the data into a single diagram. These programs can also provide other functions, such as animated
temperature or ligand concentration. First, the data needed for a 3D Eh-pH diagram must be
rotation, clipping
calculated. and slicing.
Thereafter, This section
3D programs presents
for PC, some
such as 3D examples
ParaView by[26]
[25], VisIt considering
or MATLABextension
[27], of
the Eh-pH
combine all of the data into a single diagram. These programs can also provide other functions, such are
diagram into a third dimension. Data creation and setup input files for a 3D program
briefly
aspresented. Three areas
animated rotation, areand
clipping illustrated:
slicing. This section presents some 3D examples by considering
1. extension
Eh-pH of the
along Eh-pH
with diagram into
the solubility a thirdsolids;
of stable dimension. Data creation
two example and setup
diagrams input files for
are illustrated: a 3D
passivation
program are briefly presented. Three areas are illustrated:
of lead (Figure 6) and adsorption of As(III) and As(V) onto ferrihydrite (Figure 8).
2. 1. Eh-pH
Eh-pH withalong with
an extra theforsolubility
axis ligand CO of stable solids; two example diagrams are illustrated:
2 : two wireframe volume diagrams of Eh-pH-CO2 taken
passivation of lead (Figure 6) and adsorption
from Garrels and Christ [2] are used for verifying of As(III) and As(V)
the results; onto
these ferrihydrite
two are: (Figure 8).
2. Eh-pH with an extra axis for ligand CO2: two wireframe volume diagrams of Eh-pH-CO2 taken
(a) from Garrels
Figure 7.32b:and
in Christ
order [2] are usedthe
to match forgiven ΣCO
verifying the results; these two are:
2 for the third axis, the mass balance method
a. has to be
Figure used;
7.32b: the output
in order to matchof 3D
the given CO2 for the
and discussion forthird
thisaxis,
casethearemass
presented
balancein more has
method detail.
to be used;
(b) Figure the since
7.32a: outputthe
of 3D andaxis
third discussion
is givenforas
this
thecase are presented
pressure of COin more
2 (g), detail.
the equilibrium line
b. method
Figure 7.32a:
can besince the third
applied; axis
the is given
time as thefor
required pressure
the Eh-pHof COcalculation
2(g), the equilibrium
was muchline less.
method
can be applied; the time required for the Eh-pH calculation was much less.
3. Presentation of a system in which two or more solid phases, such as CuS and Cu2 S, can coexist.
3. Presentation of a system in which two or more solid phases, such as CuS and Cu 2S, can coexist.
6.1. Eh-pH with Solubility
6.1. Eh-pH with Solubility
Including the solubility of solids in an Eh-pH diagram can give a much clearer view of what
Including the solubility of solids in an Eh-pH diagram can give a much clearer view of what can
can happen to the solid. The following two diagrams constructed by MATLAB extend the 2D Eh-pH
happen to the solid. The following two diagrams constructed by MATLAB extend the 2D Eh-pH
diagrams presented earlier. In order for MATLAB to plot 3D solubility diagrams, the Eh-pH program
diagrams presented earlier. In order for MATLAB to plot 3D solubility diagrams, the Eh-pH program
needsneeds
to create twotwo
to create files:
files:the
the(name).m filecontains
(name).m file contains instructions
instructions to betoexecuted
be executed by MATLAB,
by MATLAB, and the and
the data
data file contains solubility from each Eh and pH from the grid. A MATLAB plot can showshow
file contains solubility from each Eh and pH from the grid. A MATLAB plot can the the
matching contour (iso-solubility) lines below the 3D
matching contour (iso-solubility) lines below the 3D feature. feature.
Figure 23 is23an
Figure extension
is an extensionof of Figure
Figure 6,6,showing
showing thethe solubility
solubility of Pb(II)
of Pb(II) as the
as the third third dimension.
dimension. The
redareas
The red areas indicate
indicate conditions
conditionswherewherecorrosion
corrosioncancanbe be
expected
expectedto occur. The The
to occur. gulch area area
gulch in yellow
in yellow
indicates
indicates conditions
conditions wherewhere Pb(II)
Pb(II) is is passivatedby
passivated by CO
CO2..
2

Figure 23. The

23. The Eh-pH
Eh-pH plus
plus solubilitydiagram
solubility diagramfor
for Pb–CO
Pb–CO3–water. The yellow gulch area in the middle
Figure 3 –water. The yellow gulch area in the middle
is where Pb(II) is likely passivated by CO3.
is where Pb(II) is likely passivated by CO3 .
Metals
Metals 2016,
2016, 6,
6, 23
23 20 of
20 of 30
30

Figure 24 illustrates the same system as Figure 8, which showed where As(V) and (III) can be
Figureupon
adsorbed 24 illustrates the same
the formation system as Figure
of ferrihydrite. 8, which diagram
The solubility showed where
shows As(V)
whereandthe(III) can
lowest
be adsorbed upon the formation of ferrihydrite. The solubility diagram shows where the lowest
concentrations of As(V) and (III) can be achieved. The deep blue area at the low Eh of the diagram is
concentrations
where of As(V)
arsenic metal and (III)
becomes canand
stable be achieved.
immunized The deep
from blue area at the low Eh of the diagram is
corrosion.
where arsenic metal becomes stable and immunized from corrosion.

log(0.1ppmAs)=-5.8746

-3.5

-4
-2
-4.5

-4
-5
As,log(mol/L)

-6 -5.5

-6
-8
-6.5
-10
15 -7
-1
10 -0.5 -7.5
0
5
0.5
0 1
Eh(Volts)
pH

Figure 24. The Eh-pH

Eh-pH plus
plussolubility
solubilitydiagram
diagramfor
forAs–Fe–water.
As–Fe–water.The
Thevalley area
valley on on
area thethe
leftleft
is where the
is where
greatest
the adsorption
greatest of arsenic
adsorption can can
of arsenic occur.
occur.

6.2. 3D
3D Eh-pH,
Eh-pH, Uranium with 
Uranium with ΣCO
CO22: :Using
Usingthe
theMass-Balance
Mass-BalancePoint
PointMethod
Method
Example system: Figure
Figure 7.23b
7.23b from
from Garrels
Garrels and Christ
Christ [2] is
is one
one of
of the
theearliest
earliest three-dimensional
three-dimensional
diagrams
diagrams for
for the U–CO22–water
–water system.
system. ItIt is
is an
an Eh-pH
Eh-pH diagram
diagram with the concentration of CO22 used
for the third dimension. See See the
the duplicated
duplicated plot plot from
from Figure
Figure 25. InIn it,
it, each
each predominant
predominant species
species is
enclosed by the faces of adjacent
adjacent species.
species. AA semi-transparency
semi-transparency presentation
presentation can can be
be a more advanced
advanced
graphical
graphical method,
method,butbutit ithad not
had been
not developed
been developed at the time.time.
at the A comparison
A comparisonto the to
Garrels and Christ
the Garrels and
Christ plot was generated, considering the same species and their ∆G s (Free energy of formation).
plot was generated, considering the same species and their ΔG 0s (Free0 energy of formation). Other

considerations required
Other considerations are: are:
required
1. One
One species
species in one volume: Since Since total
total carbonate
carbonate is
is given,
given, assuming
assuming total
total CO22 means
means all
carbonates, including
carbonates, including dissolved,
dissolved, solids
solids and
and complexes
complexes with
with U,U, the
the mass-balanced
mass-balanced method method forfor
Eh-pH diagram is used. However, to match the Garrels and Christ plot, only one
Eh-pH diagram is used. However, to match the Garrels and Christ plot, only one single solid insingle solid in
each volume was selected, with no regions of mixed solids allowed.
each volume was selected, with no regions of mixed solids allowed.
2. One missing species: One species on the Garrels and Christ diagram, indicated by a red letter A in
2. One missing species: One species on the Garrels and Christ diagram, indicated by a red letter A
Figure 25, seems to have been mislabeled as UO2 (CO3 )4´ . Judging from its high pH and carbonate
in Figureand
location, 25, being
seemssandwiched
to have been mislabeled
between U(IV) as
andUO 2(CO3the
U(VI), )4−. species
JudgingUO from its high
2 (CO3 )3
pHseems
5´ [28] and
to be a good
carbonate fit. Figure
location, and 26 is the
being regenerated
sandwiched 2D Eh-pH
between diagram
U(IV) and U(VI),using
thelogΣCO
species2UO= ´1 M.3)35− [28]
2(CO

seems to be a good fit. Figure 26 is the regenerated 2D Eh-pH diagram using logCO2 = −1 M.
Metals 2016,6,6,23
Metals 23 21 of 30
21
Metals 2016,
2016, 6, 23 21ofof30
30

Figure 25. 3D
3D diagram after
after Garrels and
and Christ. Label
Label A is
is where the
the questionablespecies
species islocated.
located.
Figure 25. 3D diagram
Figure 25. diagram after Garrels
Garrels and Christ.
Christ. Label A
A is where
where the questionable
questionable species is
is located.

Figure 26.
26. The
The Eh-pH
Eh-pHdiagram
diagramofofUUwith logCO
with 2 = −1.
logΣCO The inclusion
= ´1. of UOof
The inclusion 2(CO
UO3)3(CO 5´ clarifies
5− clarifies a region
Figure 3 )3
Figure 26. The Eh-pH diagram of U with logCO2 = 2−1. The inclusion of UO2(CO3)235− clarifies a region
athat Garrels
region that and Christ
Garrels andmight
Christhave misrepresented.
might have misrepresented.
that Garrels and Christ might have misrepresented.

Example diagrams and conditions: Figures 27–32 are three-dimensional diagrams created using
Example diagrams and conditions: Figures 27–32 are three-dimensional diagrams created using
ParaView (Version 4.3.1) based on the data generated by the STABCAL program. Although the
ParaView (Version 4.3.1) based on the data generated by the STABCAL program. Although the
Metals 2016, 6, 23 22 of 30

Metals 2016, 6, 23 22 of 30
Example diagrams and conditions: Figures 27–32 are three-dimensional diagrams created using
ParaView (Version diagram
complete ParaView 4.3.1) based on such
allows the data generated
functions by the STABCAL
as continuous program.
rotation, clipping andAlthough the
slicing, these
complete
static ParaView
diagrams diagram allows
demonstrate such
the range of functions as continuous
features that rotation,
can be achieved. clipping
A color mapand slicing,
(bar), these
shown in
static diagrams demonstrate the range of features that can be achieved. A color map (bar),
Figure 27, indicates that the names of the species should be added at least once to one of the figures. shown in
Figure 27, indicates that the names
Computational conditional limits include:of the species should be added at least once to one of the figures.
Computational conditional limits include:
 Ranges: Eh = −1 to 0.8, pH = 0 to 14 and logΣCO2 = −6 to −1,
‚ Ranges: Eh =
Grid point: ´1× to
250 2500.8, pH = 0 to 14 and logΣCO2 = ´6 to ´1,
× 250,
‚ Grid point: 250 ˆ 250 ˆ 250,
 Computer: 64 bit, 3.40 GHz, 16 G of RAM,
‚ Computer: 64 bit, 3.40 GHz, 16 G of RAM,
 Program algorithm: mass balance point method using mass action law,
‚ Program algorithm: mass balance point method using mass action law,
‚ Accuracy (sum
Accuracy (sum of
of squared
squared residual)
residual) <1
<1 ˆ
× 10
10´and
−8
8 and

‚ Time to
Time to complete
complete the
the calculation:
calculation: 1:36:25
1:36:25 (h:mm:ss)
(h:mm:ss) from
from i7
i7 PC
PC or
or 2:00:51
2:00:51 from
from i5; contrary to
i5; contrary to
later, which
using the line method, shown later, which took
took less
less than
than 30
30 s.s.

In order for ParaView to plot a 3D diagram, the Eh-pH program needs to create a (name).vtk
file [29] that specifies the type of grid, the values of all X, Y and Z coordinates followed by all of the
plotted for
point data that indicate which species are to be plotted for each
each point
point on
on all
all three
three axes.
axes.

Figure
Figure 27.
27. Eh-pH-logCO
Eh-pH-logΣCO22 of
ofuranium
uranium where
where the
the species
species are
are shown
shown by
by colors.
colors. A
A color
color bar
bar is
is inserted
inserted
to show the corresponding species.
to show the corresponding species.
Metals 2016, 6, 23 23 of 30
Metals
Metals 2016,
2016, 6,
6, 23
23 23
23 of
of 30
30

Figure
Figure 28. The transparent view
Figure28.
28. view of the 3D plot. Each
Each colored
Each colored area
colored area is
area is labeled
is labeled with
labeledwith the
with the name
thename of
name of the
of the species.
the species.
species.

Figure 29.
Figure 29. The
The clip
clip plot
plot shows
shows only
only regions
regions below
below the
the constraint
constraint of
constraint of Eh
of Eh ´0.1
Eh −0.1 V.
−0.1 V.
V.
Metals 2016, 6, 23 24 of 30
Metals 2016, 6, 23 24 of 30

Figure 30. The clip plot shows species below the plane ofof theoretic
theoretic water
water stability
stability between
between H
H22O and
H22(g).
(g). Compare
Compare to
to the
the lower
lower dashed
dashed water
water line in Figure 26 or the lower plane where no species were
shown in Figure 25.

Figure 31. 3D plot that shows the boundaries (contour) between species.
Metals 2016, 6, 23 25 of 30

Metals 2016, 6, 23 25 of 30
Metals 2016, 6, 23 25 of 30

Figure Figure 32. Semi-transparent

plotplot
thatthat showsthe
thestability
stability region
region ofofUO 2(CO 3)2(H 2´ species.
32. Semi-transparent shows UO 2 (CO 3 )22O)
(H22− species.
2 O) 2
Figure 32. Semi-transparent plot that shows the stability region of UO 2(CO3)2(H2O)22− species.

A three-dimensional plot has the great advantage of being able to show the effects of multiple
A three-dimensional
Avariables
three-dimensional plot
at once. Tools,plot
has
suchhas
the
the great
as rotate,great advantage
sliceadvantage
of being
and clip, canofeasily
being able
able to
identify
show
toareas
show the
the effects
effects
of particular
of
of multiple
multiple
interest.
variables
variables at
For aat once.
once. Tools,
complicated Tools, such
such
system, as
as rotate,
however, rotate, slice and
slice and clip, image
a three-dimensional clip, can
can easily
may not easily
identify identify
be as clearareas
as aof areas of particular
particular interest.
two-dimensional
interest. For due
For a complicated
drawing a complicated
system,
to the memory system,
however, however,
a three-dimensional
and screen resolutiona three-dimensional
image
imposed by may not image
an ordinary be PC. Itmay
as clear asnot bewiseas clear
a two-dimensional
is therefore to as
adrawing
two-dimensional
choose or drawing
combine the due
use of to
2D the
and memory
3D to haveandthe screen
best resolution
presentation. imposed
due to the memory and screen resolution imposed by an ordinary PC. It is therefore wise to by an ordinary PC. It is
therefore A
wisesimple
to way
choose to turn
or a set
combine of line-drawn
the use of diagrams
2D
choose or combine the use of 2D and 3D to have the best presentation. and 3Dintotoa three-dimensional
have the best object
presentation.is to arrange
Asix two-dimensional surface plots (two from each of Eh-pH, Eh-ligand and pH-ligand)object into a cube. It
A simple
simple wayway to to turn
turn aa set
set of
of line-drawn
line-drawn diagrams
diagrams into into aa three-dimensional
three-dimensional object is is to
to arrange
arrange
may be necessary to reverse the x- or y-axis direction for this purpose. Simple plastic cubes, intended
six
six two-dimensional
two-dimensional surface plots
surface plots(two(twofrom fromeacheachofofEh-pH,
Eh-pH,Eh-ligand
Eh-ligandand andpH-ligand)
pH-ligand) intointo a cube.
a cube. It
for use with photographs, are readily available. See Figure 33, where the section on the left (three
It may
may bebe necessary
necessary toto reverse
reverse the
the x-x-oror y-axis
y-axis direction
direction for
for this
this purpose.
purpose. Simple
Simple
plots combined) is the top-front view and the section on the right is the bottom-rear view. The two
plastic
plastic cubes,
cubes, intended
intended
for
for use
use with
withphotographs,
sections photographs,
are jointed along are readily
are
the readily
Eh axis,available.
available.
at pH = 14 See See
and Figure
Figure
log ΣCO33, 333,
where M.the
= −1where section theon
the section
Rotating the left
the(three
onsections
right left plots
to (three
combined)
plots combined)is the top-front view
is thea complete
the left will make and
top-frontcube.
view the
Toandsection
show the on the
thesection
continuityright is
on between the
the right bottom-rear
is the
plots, view.
bottom-rear
species The two sections
view. The two
UO2 was purposely
are jointed
sections arealong
colored theblue.
in light
jointed Eh axis,
along the at
EhpH = 14
axis, at and
pH =log14ΣCOand 3log = ´1
ΣCO M.3 =Rotating the rightthe
−1 M. Rotating sections to the left
right sections to
will make a complete cube. To show the continuity between
the left will make a complete cube. To show the continuity between plots, species plots, species UO 2 was purposely
UO2 was purposely colored
in light blue.
colored in light blue.

Figure 33. Combination of six surface plots of the U Eh-pH-logCO2 system to form a cube.

Figure 33.
Figure 33. Combination
Combination of
of six
six surface
surface plots
plots of
of the
the U
U Eh-pH-logΣCO
Eh-pH-logCO22 system to form a cube.
Metals 2016, 6, 23 26 of 30
Metals 2016, 6, 23 26 of 30

6.3.6.3.
3D3D
Eh-pH, Uranium
Eh-pH, Uraniumwith
withPressure
PressureCO
CO22(g): Using the
(g): Using theEquilibrium
EquilibriumLine
LineMethod
Method
Metals 2016, 6, 23 26 of 30
This
Thisexample
exampleused usedFigure
Figure7.32a
7.32afrom
from Garrels
Garrels and Christ
Christ for
for UUwith
withthe
theCOCO system.
system.
22 Since
Since thethe
6.3. 3D Eh-pH, Uranium with Pressure CO2(g): Using the Equilibrium Line Method
extra axis
extra is is
axis thethepressure
pressureofofCOCO2 (g),
2(g),the
the equilibrium line method
equilibrium line methodwas wasused.
used.The
TheEh-pH
Eh-pH program
program took
took
less thanThis
30 example
s to used
create Figure
necessary 7.32a
data from
for Garrels
making and
the Christ for
(name).vtk U with
file for the CO
ParaView.
less than 30 s to create necessary data for making the (name).vtk file for ParaView. Without having 2 system. Since
Without the
having
to to extra
repeat
repeat axis
thethe issame
samethe features
pressure
featuresof CO2(g), the
presented
presented equilibrium
earlier,
earlier, linesemi-transparent
only the
only method was used.surfaces
semi-transparent The Eh-pH
surfaces and program
andthe took
boundaries
the boundaries
less
between
between than 30
species
species s to create
areshown
are necessary
shownon onFiguresdata
Figures 34 for making
34 and 35, the (name).vtk
35 respectively. These file
Thesetwo for ParaView.
twoplots
plotsagree Without
agreewith
with having
thethe
original
original
to repeat
diagram the sameby
presented features
Garrelspresented
and earlier, only the semi-transparent surfaces and the boundaries
Christ.
diagram presented by Garrels and Christ.
between species are shown on Figures 34 and 35, respectively. These two plots agree with the original
diagram presented by Garrels and Christ.

Figure
Figure 34.34. Eh-pH-logpCO
Eh-pH-logpCO 2(g)
2 (g) of uranium
of uranium where
where the species
the species are shown
are shown by colors.
by colors. This diagram
This diagram matches
Figure 34. Eh-pH-logpCO2(g) of uranium where the species are shown by colors. This diagram
matches
Figure Figure
7.32a 7.32a of
of Garrels andGarrels
Christ.and Christ.
matches Figure 7.32a of Garrels and Christ.

Figure 35. 3D plot that shows the boundaries (contour) between species. This diagram used data from
Figure
Figure 3D
35.35. 3Dplot
plotthat
thatshows
shows the
the2boundaries
boundaries (contour) between species. This diagram used data from
the line method where logpCO (g) was given.(contour) between species. This diagram used data from
thethe
line method where logpCO
line method where logpCO (g) was given.
2 2(g) was given.
Metals 2016,
Metals 6, 23
2016, 6, 23 2727
of of
30 30
Metals 2016, 6, 23 27 of 30
6.4. How to Show Two or More Solids in One Area
6.4.6.4.
How to to
How Show
ShowTwo
TwoororMore
MoreSolids
SolidsininOne
OneArea
Area
ParaView is capable of showing areas occupied by more than one solid phase. As with single
ParaView
solid regions,is multi-phase
ParaView capable of of
is capable showing
showing
areas areas
are alsooccupied
areas occupied
colored by
andmore
by more
shownthan one
than
on solid
one
the phase.
solid
color As
phase.
map. with
As
Using single
with
the solid
single
same
regions,
solid multi-phase
regions, areas
multi-phase are also
areas colored
are also and shown
colored and on the
shown color
on map.
the Using
color map.the
conditions as for Figures 11 and 12, Figures 36 and 37 are plotted by ParaView indicating four same
Using conditions
the same
as conditions as
11for
andFigures
for Figuresphases.
two-solid 11 occupied
12, Figures
The areas and
36 12,
andFigures
37
by are
CuS 36plus
andCu
plotted 372SParaView
by are
areplotted by ParaView
indicating
indicated andindicating
in redfour two-solid
pointed to four
phases.
by
Thetwo-solid
areas phases.
occupied
an arrow. The
by CuSareas
plusoccupied
Cu 2 S areby CuS plus
indicated in Cu
red2Sand
are indicated
pointed to in
by red
an and
arrow.pointed to by
an arrow.

Figure 36. ParaView of Cu–S–water, where Cu = 0.001 and S = 0.0009 M. See the 2D plot of
Figure ParaView
36.36.
Figure of Cu–S–water,
ParaView where
of Cu–S–water, ΣCuCu
where = 0.001 and ΣS
= 0.001 and= S
0.0009 M. SeeM.the
= 0.0009 2Dthe
See plot2D
of plot
Figure
of 11
Figure 11 for a comparison.
forFigure
a comparison.
11 for a comparison.

Figure 37. ParaView of Cu–S–water, where Cu = 0.001 and S = 0.0011 M. See the 2D plot of
Figure
Figure
Figure 37.
37.12 ParaView
for of Cu–S–water,
a comparison.
ParaView of Cu–S–water, where ΣCuCu
where = 0.001
= 0.001 and= S
and ΣS = 0.0011
0.0011 M. SeeM.theSee
2Dthe
plot2D
of plot of 12
Figure
Figure 12 for
for a comparison. a comparison.
Metals 2016, 6, 23 28 of 30

7. Summary
An Eh-pH diagram, commonly known as a Pourbaix diagram, is an effective way of presenting
the effects from oxidation-reduction potential, acid and base, complexing ligands, temperature and
pressure for an aqueous system. It can be used in many scientific fields, including hydro- and
electro-metallurgy, geo and solution chemistry and corrosion science. Diagrams describing natural
copper deposits, lead corrosion prevention and arsenic adsorption by ferrihydrite and leaching and
metal recovery were illustrated. The fundamental principles behind the diagram were briefly described.
To handle ligand components for these diagrams, two separate methods developed over time,
the line of equilibrium concentration and the point of complete mass balances, were described and
illustrated. Both satisfy the Gibbs phase rule in their own way of calculation. The comparison and
applications from these two methods are mentioned and illustrated.
Many advances of the Eh-pH diagrams are presented. These are:
Merging diagrams: Most of the Eh-pH diagrams describe only half of the reactions. Merging
several same-sized Eh-pH diagrams together can better illustrate the overall system. Examples include
cyanidation of Au plus cementation with Zn metal, cementation of Cu with metallic Fe and galvanic
conversion of chalcopyrite with metallic Cu.
Creating 3D diagrams: Expanding the Eh-pH program to create data from an extra axis is
relatively simple. However, a more professional third party 3D program is the best choice for
drawing the final diagram. The author has tested ParaView, VisIt and MATLAB for 3D Eh-pH
diagrams. Most of these programs can perform animations, such as rotation, clipping and slicing.
The diagram can be semi-transparent or show the boundary for better illustration. The following
examples are demonstrated:

1. An Eh-pH diagram that shows solubility. Examples include: lead corrosion prevention with
CO2 and concentrations of arsenic adsorption by ferrihydrite; MATLAB was used for more
colorful pictures.
2. An Eh-pH with an independent variable; diagrams created by ParaView were illustrated for its
functionality, and example are:

The mass balance point method for the Uranium system where the extra axis is log(ΣCO3 );
The equilibrium line method for the Uranium system where the third axis is logp(CO2 (g));
The Cu–S system for showing the coexistence of two or more solids in one volume.

When a 3D picture becomes too complex to label all of the species involved, two-variable diagrams
(Eh-pH, Eh-ligand, Eh-temperature or pH-ligand) can be presented side-by-side for clarity.

Acknowledgments: The author would like to thank Dave Tahija, Hecla Greens Creek Mining, for editing this
manuscript and Chen-Luh Lin, Metallurgical Engineering University of Utah, for introducing the use of ParaView.
Thanks to colleagues in the Department of Metallurgical and Materials Engineering at Montana Tech for their
support, in particular Courtney A. Young, Chairman of the Department, for introducing the mass balance method
and encouragement for continuing development of the STABCAL program, and to Steve McGrath for his valuable
discussion on the 3D Uranium-carbonate diagrams from Garrels and Christ.
Conflicts of Interest: The author declares no conflict of interest.

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article distributed under the terms and conditions of the Creative Commons by Attribution
(CC-BY) license (http://creativecommons.org/licenses/by/4.0/).