Eh-pH diagrams

Prakash Singh
University of Allahabad
Introduction
• The use of Eh-pH diagrams in geochemistry is widespread and their
application to many aspects of mineral paragenesis well documented.
• These diagrams have been proven useful for metallurgical purposes,
for predicting species in solutions, for alteration products of ores and
in hydrothermal systems, and many others.
• Eh-pH diagrams are, however, limited in their applicability to many
geochemical processes.
• Most of the chemical reactions such as dissolution and precipitation
of carbonate and silicate minerals, are acid–base processes involving
transfer of protons (H+).
• Oxidation–Reduction reactions (or redox reactions) involve transfer of
electrons (e−) between species having different valence states (or oxidation
numbers), such as Cu+1–Cu2+, Fe2+–Fe3+, Mn2+–Mn3+–Mn4+, U4+–U6+
• The valence state of an element significantly affects its geochemical
behaviour in seawater, surface water, groundwater, and hydrothermal
solutions.
• For example, Fe2+ is much more soluble in aqueous solutions compared to
Fe3+, the higher valence species, but the opposite is the case between U4+ and
U6+.
• Thus, iron is commonly transported as dissolved Fe2+ species in aqueous
solutions but precipitated as a Fe3+-compound.
• By contrast, uranium is transported mostly as dissolved U6+ species but
precipitated as a U4+ compound.
• Oxidation–reduction reactions are important in all geologic processes:
magmatic, diagenetic, metamorphic, chemical weathering (e.g., the familiar
reddish-yellow rust on iron garden tools), and formation of mineral deposits.
Definitions
• Reactions resulting from addition of oxygen (e.g., 2Ni + O2 = 2NiO)
evidently represent oxidation.
• However, a reaction does not have to involve oxygen to qualify as an
oxidation or a reduction reaction.
• Oxidation is defined as a reaction involving the loss of one or more
electrons and reduction as a reaction involving the gain of one or
more electrons.
• Thus, oxidation involves an increase in oxidation state, and reduction
a decrease in oxidation state.
Examples
• When Zinc displaces copper from a solution of copper sulfate
Zn+Cu2+ → Zn2+ + Cu
0 2 2 0

• Zinc is oxidised (change in oxidation from 0-2); Cu is reduced (change

in oxidation from 2-0).
• When chlorine displaces bromine from a solution of sodium bromide
Cl2 + 2Br- → 2Cl- + Br2
0 -1 -1 0

Bromine is oxidised (change in oxidation from -1 to 0); Chlorine is

reduced (change in oxidation from 0 to -1).
• Consider the oxidation of magnetite (Fe2+O.Fe23+O3) to hematite
(Fe23+O3) in the presence of water.

• The essence of this reaction is the oxidation of ferrous ion (Fe2+) to

ferric ion (Fe3+):
• Oxidation: Fe2+ ⇒ Fe3+ + e− reducing agent; electron donor
• As electrons cannot exist in nature as free species, they must be
consumed by some complementary reduction reaction such as:
• Reduction: 2H+ + 2e− ⇒ H2 oxidizing agent; electron acceptor
• An oxidation half-reaction, magnetite (or Fe2+) is the reducing agent or
electron donor (it loses electrons, reduces another species, and gets
oxidized in the process)
• a reduction half-reaction, H+ is the oxidizing agent or electron acceptor (it
gains electrons, oxidizes another species, and gets reduced in the
process).
• In general, metals (elements with low values of electronegativity) are
electron donors.
• Nonmetals (elements with high values of electronegativity) are electron
acceptors.
• Some elements, such as carbon and sulfur, can be either electron donors
or electron acceptors.
• Oxygen is the most common electron acceptor, hence the term oxidation.
• In natural environments, reactions involving loss or gain of electrons do not
occur in isolation because electrons are not released unless they can be
accepted by some other species in the environment.
• Thus, half-reactions are always coupled, with one species getting oxidized
while another species is being reduced.
• The two can be added to represent the whole oxidation–reduction (or
redox) reaction, which for the present example may be written either as
2Fe2+ + 2H+ ⇒ 2Fe3+ + H2
• It can be shown that the free energy change for the full reaction is the sum
of free energy changes for the half reactions.
• As the coupled reaction does not contain any electrons, the value of ∆Gf(e−)
is immaterial; it is conveniently assigned a value of zero
• For a typical oxidation-reduction (from here on called redox) half-cell,
one writes:
reduced species = oxidized species + (n) electrons
• where n is the number of electrons. All such reactions have a certain
standard potential, EO. This parameter is related to the free energy of
the half-cell reaction by:
∆𝐺𝐺𝑓𝑓0 = 𝑛𝑛𝑛𝑛𝐸𝐸 0
• Where, ∆𝐺𝐺𝑓𝑓0 is the Gibbs free energy of the reaction, F is the Faraday
constant, and E0 is the standard potential.
 0
𝑅𝑅𝑅𝑅 ln 𝐾𝐾𝑒𝑒
𝐸𝐸 =
𝑛𝑛𝑛𝑛
• since ΔG = RT In Ke, where R is the gas constant, T is the absolute temperature, and
Ke is the equilibrium constant for a particular reaction. Thus, for a reaction of:
wA+xB = yC+zD+ne-
Reduced Oxidised
species species
(𝐶𝐶)𝑦𝑦 (𝐷𝐷)𝑧𝑧 (𝑒𝑒)𝑛𝑛
𝐾𝐾𝑒𝑒 =
(𝐴𝐴)𝑤𝑤 (𝐵𝐵)𝑥𝑥
• where the terms in parentheses are activities.
• For unit activities, one obtains the simple expression ∆𝐺𝐺𝑓𝑓0 = nEoF from which E0 can
be calculated directly from the knowledge of the free energies of formation of
species A, B, C, D and their operators w, x, y, z.
• The activity of the electron is always taken as unity and its ∆𝐺𝐺𝑓𝑓0 is assumed zero.
• The potential Eh at conditions of other than unit activities of the species
involved can be determined from the Nernst equation,
0
𝑅𝑅𝑅𝑅
𝐸𝐸𝐸 = 𝐸𝐸 + ln 𝐾𝐾𝑒𝑒
𝑛𝑛𝑛𝑛
• Replace ln X=2.3026 𝐥𝐥𝐥𝐥𝐥𝐥 𝟏𝟏𝟏𝟏 𝑿𝑿
0 2.303𝑅𝑅𝑅𝑅 activity product of species in the oxidized assemblage
𝐸𝐸𝐸 = 𝐸𝐸 + log( )
𝑛𝑛𝑛𝑛 activity product of species in the reduced assemblage
• For the Earth’s surface environment we can assume T = 298.15 K (or 25°C).
Substituting the values of T = 298.15, F = 96,485 J volt−1 gram – equivalent−1,
and R = 8.314 J mol−1K−1.
𝑦𝑦 𝑧𝑧 𝑛𝑛
0.0592 (𝐶𝐶) (𝐷𝐷) (𝑒𝑒)
𝐸𝐸𝐸 = 𝐸𝐸 0 + log
𝑛𝑛 (𝐴𝐴)𝑤𝑤 (𝐵𝐵)𝑥𝑥
The Standard Hydrogen Electrode (SHE)
• If a cell is set up in the laboratory based on half reaction
0.5 H2 (g) – H+ + e-
• And conditions a H+ =1 (pH=0) and pH2(g) =1 atm, it would be called
the standard hydrogen electrode.
• If conditions are constant in the SHE, no reaction occurs, but if we
connect to another half cell containing a different solution, electrons
may flow and a reaction may occur.
• Such an electrode can be used as a reference in combination with any
other electrode to complete a circuit and permit a potential to be
measured.
 H2 = 1 atm
• A platinum electrode is inserted into a
solution with a pH = 0 (aH+ = 1), which Platinum
can be prepared by adding approximately electrode
1 M strong acid (such as HCl or HNO3) to
distilled water.
• Then, hydrogen gas at one atmosphere
pressure is bubbled through the solution.
• If the electrode is by itself, nothing will
happen, but if it is connected to another aH+ = 1
electrode, a reaction may occur, a
potential difference may be established
and current may flow.
½H2(g) ↔ H+ + e-
 Electrochemical cell
• SHE (on the left) is connected via
a voltmeter to an electrode based H2 = 1 atm
V
on the ferric(Fe3+)/ferrous(Fe2+) Platinum
electrode
Platinum
electrode
iron redox couple.
• The circuit is completed with the Salt Bridge
device called the salt bridge.
• This electrochemical cell Fe3+
aH+ = 1
suggests a way in which the Fe
2+

redox potential of some unknown

solution relative to the SHE can
be determined. This potential, ½H2(g) ↔ H+ + e-
measured in volts or millivolts. Fe3+ + e- ↔ Fe2+
• The Eh value of an electrode reaction may be positive or negative.
• A positive Eh value implies that the environment is less reducing than the SHE
and, thus, is oxidizing;
• a negative Eh value implies the converse, that the environment is more
reducing
• The Eh of a natural terrestrial environment is largely a function of its organic
matter content.
• The shallow water on an open shelf presents an oxidizing environment
because most organic material, irrespective of the abundance of organisms,
decays to carbon dioxide and water before burial can take place.
• Sedimentary environments in which organic matter is accumulating or has
accumulated in the past through burial (e.g., black shales) are highly reducing,
with Eh values in the range of −0.1 to −0.5 volts (and pH reaching a minimum
of about 4 where decay takes place under aerobic conditions).
 Redox Potential
• Dissolved sulfur is largely in the form of SO42- in the water of the open sea
where conditions are oxidising but chiefly in the form of H2S in the
stagnant bottom waters of enclosed basin.
• The ability of natural environment to oxidise sulfur or bring about any
other oxidation or reduction process is measured by quantity called its
redox potential.
• Redox potential in many ways is similar to pH. It measures the ability of an
environment to supply electrons to oxidising agent or take up electrons
from a reducing agent.
• Just as pH of an environment measures its ability to supply protons
(hydrogen ions) to a base or take up protons from an acid.
pH= − log10 𝑎𝑎𝐻𝐻 +
 Calculation of the ratio of oxidized to reduced
species in an environment of known Eh
• If the measured Eh of the water in a lake is +0.65 volts, what is the dominant
form of the dissolved copper in this water (Cu+ or Cu2+)?
0
• The standard potential 𝐸𝐸𝐶𝐶𝐶𝐶+ ofthe oxidation half-reaction is +0.16 volts
Cu+ ⇒ Cu2+ + e−
2+
0 0.0592 𝐶𝐶𝐶𝐶
𝐸𝐸𝐸 = 𝐸𝐸𝐶𝐶𝐶𝐶 + + log
𝑛𝑛 𝐶𝐶𝐶𝐶+
𝐶𝐶𝐶𝐶2+
=10 8.3
𝐶𝐶𝐶𝐶+
• Thus, practically all the dissolved copper in this water should occur as Cu2+.
Eh–pH stability diagrams
• For the Earth’s surface environment, temperature and pressure can
be assumed as fixed at 298.15 K (25°C) and 1 atm (1 atm = 1.013 bar
≈ 1 bar), so that Eh pH, and solute activities are the most important
variables in oxidation and reduction reactions in such near-surface
aqueous systems.
• It is, therefore, a common practice in geochemistry to depict phase
equilibria in low-temperature aqueous systems on Eh–pH diagrams at
specified solute activities.
• Such diagrams are useful for the interpretation of relative stabilities of
minerals and aqueous species during chemical weathering, and solute
transport in aqueous solutions, especially of elements with more than
one valence state (e.g., Fe, Cu, Mn, Au, Hg, S, etc.).
Stability limits of surface water
• The Eh–pH stability fields of solid compounds and dissolved species in
natural aqueous environments are limited by the stability of water
itself at the Earth’s surface P–T conditions.
• It is a common practice, therefore, to include the stability limits of
water in a Eh–pH diagram.
• The strongest oxidising agent commonly found in nature is the
atmospheric oxygen.
• Stroger agent than this cannot persist because they would react with
water to liberate oxygen.
• The stability field for water at 25°C and 1 bar pressure is defined by the
reaction:
2H2O(liq)=2H2(g)+ O2(g)
• This reaction is the sum of the two half-cells:
• Upper limit:
2H2O = 4H+ +02(g)+4e-
• Lower limit:
H2(g) = 2H+ +2e-
• While water does not enter into half-cell b, it is implied by the presence of
H+.
• ΔGfo of any element in its standard state is zero, and since the ΔGf of both
H+ and e- are zero by convention.
• The upper limit of redox potential is defined by the reaction:
H2O → 0.5O2 + 2H+ + 2e-
• The Eh of the water electrode is given by

• 𝐸𝐸𝐻𝐻𝑜𝑜 𝑂𝑂 (𝑙𝑙) =1.23v

2
• If we take fO2 =0.2 bar, considering that oxygen constitutes about 20%
by volume of the present atmosphere.
𝑢𝑢𝑢𝑢
𝐸𝐸𝐻𝐻 𝑂𝑂 (𝑙𝑙) = 1.22 − 0.059 𝑝𝑝𝑝𝑝
2
• Lower limit is defined by
H2(g)=2H+ + 2e- E0H2g=0.0v
𝑙𝑙𝑙𝑙 0.059 +
0.059
𝐸𝐸𝐻𝐻 (𝑔𝑔) = 0.0 + 2 ∗ log 𝐻𝐻 + log 𝐻𝐻2(𝑔𝑔)
2 2 2
Since the pressure of hydrogen gas in near surface environment cannot
exceed 1atm
𝐸𝐸𝐻𝐻𝑙𝑙𝑙𝑙(𝑔𝑔) = −0.059 𝑝𝑝𝑝𝑝
2
Types of boundaries
• There are actually relatively few types of boundaries in Eh-pH space.
• Those depending only on Eh, but independent of pH (Horizontal to
the X axis)
• Those dependent only on pH, but independent of Eh (Vertical to the X
axis)
• Those dependent on Eh and pH (Sloping line with definite slope)
 Natural waters
• Mine waters, which are usually acidic and oxidizing;
• Rain, which in certain parts of the world is
becoming much more acidic due to the buildup of
CO2 in the atmosphere, and in turn due to fossil
fuel burning, is acidic.
• Stream waters are oxidizing and near-neutral in pH
• Normal ocean water, which in the near-surface to
the surface is oxidizing and in approximate
equilibrium with both CO2(g) and CaCO3(c)
• residual aerated waters in saline environments are
typically oxidizing and basic
• Groundwaters in many instances are near
saturation with respect to CaCO3. They are much
less oxidizing than surface waters, and many
reduction reactions occur in this zone as well.
• Saline waters rich in organic material are reducing
and alkaline
Procedure for construction of Eh–pH diagrams
• For Eh–pH diagram we will compute the stability fields of the two
most important iron oxide minerals, magnetite (Fe3O4) and hematite
(Fe2O3), and the fields of dominance of the two important dissolved
ionic species, Fe2+ and Fe3+.
• We will also take a look at the stability of metallic Fe, only to conclude
that it is not a stable species in the surface aqueous environment.
• For the computations described below, aFe(s) = 1, aFe2O3(s) = 1, and
aFe3O4 (s) = 1 (pure solids in standard state), and aH2O(l) = 1 (almost
pure phase in standard state).
• The thermodynamic data needed for the computations are listed in
Table below.
 1. Fe2+–Fe3+ boundary
• The reaction is independent
of pH and equation yields a
straight line parallel to the
pH-axis.
• Since at any point on the
boundary between the fields
of Fe2+ and Fe3+, aFe2+ =
aFe3+ in the solution, the Eh
coordinate of the boundary
is +0.760 v.
• At any point above this
boundary, aFe3+ > aFe2+ and
at any point below, aFe3+ <
aFe2+.
 Fe3+–Fe2O3 (s) boundary
• This reaction is independent of Eh as
it does not involve transfer of
electrons.
• Therefore, the reaction boundary is
parallel to the Eh axis at a particular
value of pH, which we can determine
from the equilibrium constant of the
reaction.
• Assuming aFe3+ = 10-6, pH = 2.009
• It should be evident from equation
(8.49) that the pH value would be
lower for aFe3+ > 10-6 and higher for
aFe3+ < 10-6
• The oxide minerals become more
soluble when the solution becomes
more acidic
 Fe2+–Fe2O3 (s) boundary
• The boundary, which is a function
of both pH and Eh, is a straight
line that can be plotted easily by
calculating values of Eh for two
arbitrarily chosen values of pH
(e.g., pH = 0 and pH = 10).
 Fe2+–Fe3O4 (s) boundary

• The boundary is a straight line that

can be plotted easily by calculating
Eh for two arbitrarily chosen values
of pH (e.g., pH = 0 and pH = 10).
 Fe3O4 (s) - Fe2O3 (s) boundary

• This straight-line boundary,

which separates the stability
fields of magnetite and
hematite in equilibrium with
water, has the same slope as
the lines defining the stability
limits of water.
 Fe(s)–Fe2+ boundary

• This reaction boundary is

independent of pH and plots as a
straight line parallel to the pH axis.

• For 𝑎𝑎𝐹𝐹𝐹𝐹 2+ = 10−6 the Eh

coordinate for this boundary is
 Fe(s) - Fe3O4 (s) boundary

• The slope of this reaction boundary

is parallel to the Fe3O4 (s)–Fe2O3 (s)
boundary.
• The Fe(s)–Fe2+ and Fe(s)–Fe3O4 (s)
boundaries lie below the lower
stability limit of water, indicating
that metallic iron cannot exist in
equilibrium with Fe2+ or Fe3O4 in
surface aqueous environments at
any pH.