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Chapter 4
OXIDATION/REDUCTION IN AQUATIC
CHEMISTRY

Environmental Chemistry, 9th Edition

Stanley E. Manahan
Taylor and Francis/CRC Press
2010

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Electrochemistry: The area of chemistry that examines
the transformations between chemical and electrical
energy.
Oxidation-reduction (redox) reactions involve an
exchange of electrons between reacting species
Must have both reduction and oxidation happening for the
reaction to occur

REDUCTION – a process in which electrons are gained by an entity

OXIDATION – a process in which electrons are lost by an entity

Reducing agent :donates the electrons and is oxidized

Oxidizing agent : accepts electrons and is reduced

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4.1 The Significance of Oxidation/Reduction
Oxidation/reduction (redox) reactions involve changes in
oxidation states of elements, most easily visualized as a
transfer of electrons
The reaction
Fe + Cd2+ → Fe2+ + Cd
can be obtained by adding the two following half-reactions:
Oxidation: Fe → Fe2+ + 2e-
Reduction: Cd2+ + 2e- → Cd
Overall: Fe + Cd2+ → Fe2+ + Cd
In the above
• Fe is oxidized by losing 2 electrons to yield Fe2+
• Cd2+ ion is reduced by gaining 2e- to give elemental Cd

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Oxidation/reduction reactions are significant in water
Bacterially mediated oxidation of biomass depletes oxygen
• {CH2O} + O2 → CO2 + H2O

Bacterially mediated reduction of solid iron oxides and hydroxides puts

soluble iron in water
• Fe(OH)3(s) + 3H+ + e- → Fe2+(aq) + 3H2O

Microbialy mediated oxidation of ammonium nitrogen produces nitrate,

which can be assimilated by algae
• NH4+ + 2O2 → NO3- + 2H+ + H2O

Two important points regarding oxidation/reduction in water

• Most such reactions mediated by microorganisms
• Close relationship with acid-base, analogies between e- and H+
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 Equilibrium Relationship
Redox reactions involve electron transfer
Ox (oxidized species) + z e- ↔ Red (reduced species)
at equilibrium :
K = [Red]/ [ Ox] [ e-]z
Solving for e- , the electron activity
[ e-] = {[Red]/K[Ox]}1/z
The electron activity is expressed in two ways :

1) As measured potential E= -2.3 R T log [e-]/zF or ΔG=-zF E using the symbol

E (Called redox potential ) , ΔG is the free energy change of the reaction. ΔG= +ve
( reaction not proceed), proceed in the reverse direction.
ΔG = - ve ( reaction proceed)
ΔG= 0 ( reaction in equilibrium)
E units volt or millivolts, z is the number of electron-equivalent per mole.
F is Farady or coulombs per equivalent. 1 F = 96,485 C/mol = 96,485 J/V-mol
If E is positive , the reaction proceeds.
Or
2) Using a logarithmic scale where pE=- log[e-], low pE indicate reducing
conditions, high pE values indicate oxidizing conditions.
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Consider the following reaction
aA +bB ↔ cC + d D
The free energy for this reaction is
ΔG= ΔGo +RT ln [C]C[D]d/ [ A]a[ B]b
where
ΔG : reaction free energy change
ΔGo :standard free energy change
R : gas constant (1.98 cal/mol K) or (8.314 J/mole K)
T : absolute temperature. K.

At equilibrium,
ΔG= 0
ΔGo = - RT ln K

ΔGo= -zFEo
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Figure 4.1 Predominance of various chemical species in a
stratified body of water; conceptually, pE is the negative log
of electron activity.

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4.2 The Electron and Redox Reactions
The reaction 2Fe3+ + H2 ↔ 2Fe2+ + 2H+
can be carried out as two half-reactions in an
electrochemical cell (Figure 4.2)

Half reaction:
Half reaction:
Fe3+ + e- ↔ Fe2+
2H+ + 2e- ↔ H2

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For the electrochemical cell shown in the preceding slide
• The left electrode is the standard hydrogen electrode,
SHE
• Half-reaction: 2H+ + 2e- ↔ H2 E0 = 0.00 volts
• When all reaction participants are at unit activity
(essentially [H+] = 1.00 mol/L, pressure of H2 = 1.00 atm), the
potential of the SHE (E0) is assigned a value of 0.00 volt
• The potential of the right electrode vs. SHE is the
electrode potential, E.
• When Fe3+ and Fe2+ are at unit activity, E is the
standard electrode potential, E0
• Fe3+ + e- ↔ Fe2+ E0 = 0.77 volts

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4.3 Electron Activity and pE
Conceptually the negative log of electron activity, pE
expresses this activity over many orders of magnitude

2H+(aq) + 2e- ↔ H2(g) E0 = 0.00 volts pE0 = 0.00

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4.4 The Nernst Equation
To account the effect of different activities upon electrode
potential.
Fe3+ + e- ↔ Fe2+ E0 = 0.77 volts pE0 = 13.2
For the [Fe3+]/[Fe2+] electrode, which expresses pE as a
function of species concentration, is
[Fe3+] = 2.35 ´ 10-3 M [Fe2+] = 7.85 ´ 10-5 M
Nernst Equation : E =Eo+2.3 RT/nF log [Fe3]/[Fe2]
= Eo+0.0591/n log [Fe3]/[Fe2]
Or

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4.5 Reaction Tendency: Whole Reaction from Half-
Reactions 22
For the overall electrode reaction in the electrochemical cell
shown in Figure 4.2
2(Fe3+ + e- ↔ Fe2+) E0 = 0.77 volts
-(2H+ + 2e- ↔ H2) E0 = 0.00 volts
2Fe3+ + H2 ↔ 2Fe2+ + 2H+) E0 = 0.77 volts
The positive value of E0 for the overall reaction indicates
that it goes to the right
• H2 reduces Fe3+ to Fe2+

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4.6 The Nernst Equation and Chemical Equilibrium
Consider the system
illustrated in Figure 4.3
Cu2+ + 2e- ↔ Cu pE0 = 5.71
-(Pb2+ + 2e- ↔ Pb pE0 = -2.13)

Cu2+ + Pb ↔ Cu + Pb2+ pE0 = 7.84

The equilibrium constant for this
reaction is

When pE = 0, the system is at equilibrium

Log K = 15.7 In general, log K = npE0 23

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4.7 The Relationship of pE to Free Energy
∆G = -2.303nRT(pE)
∆G0 = -2.303nRT(pE0)

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4.8 Reactions in Terms of One Electron-Mole
Writing oxidation/reduction reactions on the basis of one
electron-mole enables their comparison on a common basis
• Especially significant for free energy comparisons
Consider the reaction
NH4+ + 2O2 ↔ NO3- + 2H+ + H2O pE0 = 5.85
The N atom changes oxidation state from -3 to +5
corresponding to a transfer of 8 electrons, so the reaction
in terms of 1 mole of electrons is
1/ NH + + 1/ O ↔ 1/ NO - + 1/ H+ + 1/ H O pE 0 = 5.85
8 4 4 2 8 3 4 8 2
∆G0 = -2.303RT(n) (pE0)
For a reaction written as one electron-mole (n = 1)
• ∆G0 = -2.303RT(pE0) • pEo is related to K, log K = pE0
Note Table 4.1 of important half-reactions written for 1
electron-mole and their pE0 values 25
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4.10 pE Values in Natural Water Systems
pE values can be calculated from the species in water at
equilibrium.
Consider pH 7.00 water in equilibrium with atmospheric
oxygen (0.21 atm partial pressure)
1/ O + H+ + e- ↔ 1/ H O pE0 = 20.75
4 2 2 2

Substituting 0.21 for O2 pressure and [H+] = 1.00 ´ 10-7 M

• pE = 13.8
Consider anoxic water at pH 7.00 in which the pressures of
CH4 and CO2 are equal

1/8 CO2+H++e-↔1/8CH4+1/4H2O

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Discussion of Iron pE-pH Diagram
• Equations for constructing the diagram are in text
• Dashed lines are thermodynamic limits of water stability
• Fe3+ is stable in a small region at high pE and low pH
(such as acid mine water in contact with the atmosphere)
• Fe2+ ion is stable over a relatively large range of pH and
relatively low pE often encountered in groundwater and
anoxic water in the bottom of bodies of water; bringing this
water into contact with the atmosphere results in
precipitation of Fe(OH)3
• Solid Fe(OH)3 predominates over a very large region
reflecting the very low solubility's of iron(III) hydroxides and
oxides
• Solid Fe(OH)2 has a limited region of stability;
in most aquatic systems FeS or Fe(CO3) are the iron(II)
compounds found in this region 48
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4.12 Humic Substances as Natural Reductants
Humic substances (see Chapter 3) may function as
reducing agents in natural water systems
• May be due to the quinone/hydroquinone group

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4.14 Corrosion
Corrosion takes place when an electrochemical cell is set
up on the surface of a metal, M
• Metal oxidized at the anode: M → M2+ + 2e-
• Several possible cathodic reactions often involving
oxygen species
O2 + 2H2O + 4e- → 4OH-
O2 + 4H+ + 4e- → 2H2O
O2 + 2H2O + 2e- → 2OH- + H2O2
• Oxygen may accelerate corrosion by participating in
cathodic reactions
• In some cases oxygen inhibits corrosion by forming
protective oxide coatings
• Bacteria are commonly involved in corrosion and set up
electrochemical cells in which corrosion occurs. 50
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Example
The equilibrium constant for the reaction
Ni(s) + Hg2Cl2(s) 2Hg(l) + 2Cl-(aq) + Ni2+(aq)

is 1.8 × 1019 at 298K.

What is the value of the standard cell potential E°cell for this reaction?

ΔG° = -RT ln K
= - (8.314 J K-1 mol-1) (298 K) ln (1.8 × 1019)
= - 109847.8 J mol-1
= - 1.098 × 105 J mol-1

ΔG° = -n F Eo cell F = 9.65E4 C/mol e-

Ecell = -ΔG°
nF
= -(-1.098 × 105 J mol-1) = 0.57 J/C = 0.57 V
(2 mole e-) (96500 C/mol e-)
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Example

• Copper metal can be oxidized in a solution to form copper(I) oxide.

What is the half-reaction for this process? Cu(s) Cu2O(s)

1. Balance all atoms except H and O 2Cu(s) Cu2O(s)

1. Balance oxygen by adding water 2Cu(s) +H2O(l) Cu2O(s)

1. Balance hydrogen by adding H+(aq) 2Cu(s) +H2O(l) Cu2O(s) + 2H+(aq)

2. Balance charge by adding electrons 2Cu(s) +H2O(l) Cu2O(s) + 2H+(aq) + 2 e-

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Example

Will the following reaction occur spontaneously at 250C if

[Fe2+] = 0.60 M and [Cd2+] = 0.010 M ?
Fe2+ (aq) + Cd (s) ↔ Fe (s) + Cd2+ (aq)
Oxidation: Cd → Cd2+ + 2e- E= 0.4 V

Reduction: 2e- + Fe2+ → Fe E= - 0.44 V

E0 = -0.04 V

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 The interrelationship of ∆G°, Ecell, and K.

Reaction Parameters at the Standard State

∆G°
Reaction at standard-
∆G° K E°cell state conditions
<0 >1 >0 spontaneous
0 1 0 at equilibrium
>0 <1 <0 Non spontaneous

Ecell K

RT ln K
Ecell =
nF

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 Water Electrolysis (Splitting Water Using Electricity)

TWO TYPES OF CELLS

• Voltaic cell: does work by releasing free energy from a
spontaneous reaction to produce electricity such as a battery.
- A voltaic cell uses a spontaneous redox reaction (∆G < 0) to generate
electrical energy.
- The system does work on the surroundings.
• Electrolytic cell : does work by absorbing free energy from a
source of electricity to drive a non-spontaneous reaction such as
electroplating.

- A electrolytic cell uses electrical energy to drive a nonspontaneous reaction

(∆G > 0).
- The surroundings do work on the system.

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• Electrolysis is splitting (lysing) of a substance or
decomposing by forcing a current through a cell to
produce a chemical change for which the cell
potential is negative.

• In voltaic cells i.e. cells with Ecell > 0 and ∆G < 0

spontaneous reactions.
• For the cells where Ecell < 0 and ∆G > 0 that are non-
spontaneous reactions and require electricity for the
reactions to take place.

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A voltaic (Galvanic) cell can power an electrolytic cell

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Purpose : Production Of Hydrogen

Energy Density
(Mega Joules per kilogram)
Li-ion Battery 0.54
Gasoline 46.9
Hydrogen 120.0
~ 220 times more energy than batteries
~ 2.6 times more energy than gasoline
NO AVAILABLE SOURCE OF HYDROGEN
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• Hydrogen generation can be accomplished via traditional DC electrolysis
of aqueous solutions at temperatures less than about 100 oC.
• However, electrolysis of stream can also be accomplished at higher
temperatures at the cathode of electrolytic cells utilizing solid membranes.
• Hydrogen production via the conventional electrolysis largely depends
upon the availability of cheap electricity (e.g. , from hydroelectric
generators).
• Only about 5 % of the world hydrogen production is via electrolysis.
• The only complete hydrogen production process that is free of CO2
emissions is water electrolysis (if the electricity is derived from nuclear or
renewable fuels).
• However, 97% of the hydrogen currently produced is ultimately derived
from fossil energy.

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 Low temperature water electrolysis
H 2 O(l / g ) → 0.5O2 + H 2
• The reversible electrical potential(minimum cell voltage) (ΔG/nF = -Erev) to split the O-H
bond in water is 1.229 V.
Erev= -ΔG/nF, ΔG= (Gf,H2+0.5Gf,o2-Gf,H2O)
• In addition, heat is needed for the operation of an electrolysis cell.
• If the heat energy is supplied in the form of electrical energy, then the thermal
potential is 0.252 V (at standard conditions), and this voltage must be added to Erev
(i.e., add entropic term TΔS to ΔG).(ΔG= ΔH-TΔS )
• The (theoretical) decomposition potential for water at standard conditions (for ΔH ≈
ΔHo) is then 1.480 V. (Eth= ΔH/nF)
• Anode and cathode reactions for electrolysis (see next figure) :
1
Anode : 2OH − → O2 + H 2O + 2e − (2.1)
2
Cathode : 2 H 2O + 2e − → H 2 + 2OH − (2.2)
Overvoltage is the additional voltage needed (above that predicted by
E°values) to produce gases at metal electrodes
Overvoltage needs to be taken into account when predicting the products of
electrolysis for aqueous solutions. Overvoltage is 0.4 – 0.6 V for H2(g) or O2(g).
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Electrolysis of water

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Stoichiometry of electrolysis: Relation between
amounts of charge and product
• Faraday’s law of electrolysis relates to the
amount of substance produced at each
electrode is directly proportional to the
quantity of charge flowing through the cell
(half reaction).
• Each balanced half-cell shows the relationship
between moles of electrons and the product.

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 Application of Faraday’s law

1. First balance the half-reactions to find number of

moles of electrons needed per mole of product.
2. Use Faraday constant (F = 9.65E4 C/mol e-) to find
corresponding charge.
3. Use the molar mass of substance to find the charge
needed for a given mass of product.
– 1 ampere = 1 coulomb/second or 1 A = 1 C/s
– Axs=C

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 Stoichiometry of Electrolysis
• How much chemical change occurs with the flow of a given current for a
specified time?
• current and time → quantity of charge →
• moles of electrons → moles of analyte →
• grams of analyte

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Electroplating of a spoon.

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 Fuel Cell
• In a fuel cell, also called a flow cell, reactants enter the cell and products
leave, generating electricity through controlled combustion.
• Reaction rates are lower in fuel cells than in other batteries, so an
electrocatalyst is used to decrease the activation energy.

Anode (oxidation): 2H2(g) → 4H+(aq) + 4e-

Cathode (reduction): O2(g) + 4H+(aq) + 4e- → 2H2O(g)
Overall (cell) reaction: 2H2(g) + O2(g) → 2H2O(g) Ecell = 1.2 V

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