ELECTROCHEMISTRY
Deals with chemical changes produced by an electric
current and with the production of electricity by chemical
reactions
All electrochemical reactions involve transfer of electrons
and are redox (oxidation-reduction) reactions
Electrochemical reactions take place in electrochemical
cell (an apparatus that allows a reaction to occur through
an external conductor)
ELECTROCHEMICAL CELLS
Two types:
1. Electrolytic cells: - these are cells in which an external
electrical source forces a nonspontaneous reaction to
occur
(one common process is called electrolysis)
(not to be covered here)
2. Voltaic cells: - also called galvanic cells. In these
cells spontaneous chemical reactions generate
electrical energy and supply it to an external circuit
(corrosion and fuel cells are examples)
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ELECTRODES
(as also covered earlier)
Electric current enters and exits the cell by electrodes electrodes are surfaces upon which oxidation or reduction
half-reactions occur
Two kinds of electrodes:
GALVANIC CELLS
Cells in which spontaneous reactions produces electrical
energy
The two half-cells are separated so that electron transfer
occurs through an external circuit
Each half-cell contains the oxidized and reduced forms of
species in contact with each other
Half-cells linked by a piece of wire and a salt bridge
Salt bridge
Zn Zn 2+ (1.0 M) Cu
2+ (1.0
M) Cu
Electrode
Species (with
concentrations) in
contact with electrodes
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(oxidation, anode)
2(Ag+ + e- Ag)
(reduction, cathode)
2Ag+ + Cu Cu2+ + Ag
Cu |Cu2+(1.0 M) ||Ag+(1.0 M) | Ag
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The standard equilibrium cell potential (Ecell) is for the cell operating
under standard state conditions
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EQUILIBRIUM POTENTIAL
When we immerse a metal in solution, there will be a tendency for the
metal to react with the solution, either with metal atoms dissolving as
cations or cations already in the solution depositing as metal atoms:
Zn Zn2+ + 2eZn2+ + 2e- Zn
As a result of these reactions, the metal will tend to accumulate a
negative or positive charge. The build-up of this charge on the metal will
change its potential in such a way as to inhibit the reaction generating
the charge until the potential reaches a value at which the rates of the
two reactions are equal and opposite. This is known as the equilibrium
potential, and is the potential the metal will adopt in the solution in the
absence of any other reactions.
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p.s. If the equation is to be used for determining the equilibrium potential for a half
cell rxn, then the half cell rxn is to be written in reduction form or the (-) sign in
the equation is to be replaced by (+) sign in case the half cell rxn is written in
oxidation form.
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Notation: E for the overall cell rxn, e for the half-cell rxns
p.s. If the equation is to be used for determining the equilibrium potential for
a half cell rxn, then the half cell rxn is to be written in reduction form or
the (-) sign in the equation is to be replaced by (+) sign in case
the half cell rxn is written in oxidation form.
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ACTIVITY
Activity of a dissolved species A (A) is equal to its concentration in
moles per 1000 grams of water (molality) multiplied by the activity
coefficient, f.
Activity coefficients are extensively tabulated in numerous chemical
and electrochemical handbooks.
Activity of a gas is approximated at ordinary pressures by its partial
pressure in atmospheres (atm).
The activities of pure solids and water are set equal to unity in
aquaeous solutions.
At 25C, 2.303RT/F = 0.0592 V equivalent
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ACTIVITY (Cont.)
Activity Coefficients of Strong Electrolytes (M=molality)
[Corrosion and Corrosion Control, H. H. Uhlig and R. W. Revie, John Wiley & Sons, 1985.]
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ACTIVITY (Cont.)
Activity Coefficients of Strong Electrolytes (M=molality)
[Corrosion and Corrosion Control, H. H. Uhlig and R. W. Revie, John Wiley & Sons, 1985.]
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ACTIVITY (Cont.)
Activity Coefficients of Strong Electrolytes (M=molality)
[Corrosion and Corrosion Control, H. H. Uhlig and R. W. Revie, John Wiley & Sons, 1985.]
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PREDICTION OF SPONTANEITY
1. First write the half-cell rxn with the more positive (less
negative) E for the reduction-cathodic along with its half
cell electrode potential
2. Write the other half-cell rxn as an oxidation-anodic and
include its half cell electrode potential
3. Balance the electron transfer
4. Obtain the cell rxn by adding the reduction and oxidation
half-cell rxns.
5. Determine the overall cell potential, Ecell, from
Ecell= Ecathode- Eanode
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Ecell < 0
EXAMPLE PROBLEM 1
Notation: e for the half-cell rxns, E for the overall cell rxn.
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EXAMPLE BROBLEM 2
Notation: E for the overall cell rxn, e for the half-cell rxns
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EXAMPLE PROBLEM 3
Notation: e for the half-cell rxns, E for the overall cell rxn.
Assuming standard states for all reactants and products, determine the
spontaneous direction of the following reactions by calculating the cell potential:
CuCl2 + H2 = Cu + 2HCl
CuCl2 + H2 Cu + 2HCl
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Note that the sign notation used in the text is different and
confusing.
The text uses
E = ec + ea
which is actually identical to the notation presented above
since the text takes ea as the negative value of the anode
half-cell electrode potential.
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EXAMPLE PROBLEM
(Prb. 2.15 in Principles and Prevention of Corrosion, Denny Jones, 1996)
A corrosion potential of -0.229 V versus SCE was measured for a corroding alloy. What
is the potential versus (a) SHE, (b) Ag/AgCl (saturated), (c) Cu/saturated CuSO4?
(a)
(b)
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Potential
O2 is stable
H2O is stable
2H+ + 2e- = H2
H2 is stable
0
14
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Potential
Equilibrium for
Zn2+ + 2OH- Zn(OH)2
ZnO22stable in
solution
Zn(OH)2
stable
solid
Zn2+ stable
in solution
Equilibrium for
Zn + 2OH- Zn(OH)2 + 2eEquilibrium for
Zn + 4OH- ZnO22- + 2H2O + 2e-
Zn metal
stable
Equilibrium for
Zn(OH)2 + 2OH- ZnO22- + 2H2O
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Equilibrium for
Zn Zn2+ + 2e-
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Potential
2.0
1.6
1.2
0.8
0.4
0.0
-0.4
-0.8
-1.2
-1.6
Corrosion
Passivity
Corrosion
Corrosion is possible,
but likely to be stifled by
solid corrosion product
Immunity
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Corrosion is thermodynamically impossible
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2H+ + 2e- H2
Potential
14
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2.0
1.6
1.2
0.8
0.4
0.0
-0.4
-0.8
-1.2
-1.6
Cu oxides
stable
Cu2+ stable
in solution
Potential
No - hydrogen evolution
only occurs below the
potential for copper
corrosion
Cu metal stable
0
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2.0
1.6
1.2
0.8
0.4
0.0
-0.4
-0.8
-1.2
-1.6
Cu oxides
stable
Cu2+ stable
in solution
Potential
Cu metal stable
0
14
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Potential
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Potential
14
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Potential
14
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Potential
Al3+
Al2O3
AlO2-
Al
0
14
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EXAMPLE PROBLEM
(Prb. 2.10 in Principles and Prevention of Corrosion, Denny Jones, 1996)
Using the Pourbaix diagram for nickel, give the anodic and cathodic reactions on Ni
in water for the following conditions, assuming activity of 10-6 for all soluble species:
(a) deaerated pH 2, (b) deaerated pH 10, (c) aerated pH 2, aerated pH 10.
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eo=-0.31 V
Prbs. 3, 5, 6 of Chapter 2
in Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996.
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References
Corrosion and Corrosion Control, H. H. Uhlig and R. W. Revie, John Wiley &
Sons, 1985.
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