Chemical vs.

Electrochemical
Reactions
Chemical reactions are those in which elements are
added or removed from a chemical species.

Electrochemical reactions are chemical reactions in

which not only may elements may be added or removed
from a chemical species but at least one of the species
undergoes a change in the number of valance electronS.

Corrosion processes are electrochemical in nature.

 2
Chemical Corrosion

Chemical corrosion: Removal of atoms from a material by virtue of

the solubility or chemical reaction between the material and the
surrounding liquid.

EXAMPLES:
Dezincification: A special chemical corrosion process by which both
zinc and copper atoms are removed from brass, but the copper is
replated back onto the metal.

Graphitic corrosion: A special chemical corrosion process by which

iron is leached from cast iron, leaving behind a weak, spongy mass of
graphite.
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Photomicrograph of a copper deposit in brass, showing the effect of

dezincification (x50).
 Electrochemical Corrosion 4

Electrochemical corrosion - Corrosion produced by the

development of a current in an electrochemical cell that removes
ions from the material.

Electrochemical cell - A cell in which electrons and ions can flow by

separate paths between two materials, producing a current which,
in turn, leads to corrosion or plating.

Oxidation reaction - The anode reaction by which electrons are

given up to the electrochemical cell.

Reduction reaction - The cathode reaction by which electrons are

accepted from the electrochemical cell.
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The components in an electrochemical cell: (a) a simple electrochemical cell and

(b) a corrosion cell between a steel water pipe and a copper fitting.
 6

The anode and cathode reactions in typical electrolytic corrosion cells:

(a) the hydrogen electrode, (b) the oxygen electrode, and (c) the water electrode.
Electrochemistry

Thermodynamics at the electrode

 Redox (Review)

Oxidation is...
Loss of electrons
Reduction is...
Gain of electrons
Oxidizing agents oxidize and are reduced
Reducing agents reduce and are oxidized
Redox Review (Cu-zn)
Zn displaces Cu from CuSO4(aq)
In direct contact the enthalpy of reaction is dispersed as
heat, and no useful work is done

Redox process:
Zn is the reducing agent
Cu2+ is the oxidizing agent

2
Zn(s) Zn (aq) 2e
Cu 2 (aq) 2e Cu( s)
 Separating the combatants

Each metal in touch with a solution of its own ions

External circuit carries electrons transferred during the redox process
A salt bridge containing neutral ions completes the internal circuit.
The energy released by the reaction in the cell can perform useful work
like lighting a bulb
Labelling the parts
 Cell notation

Anode on left, cathode on right

Electrons flow from left to right
Oxidation on left, reduction on right
Single vertical = electrode/electrolyte boundary
Double vertical = salt bridge

Anode: Cathode:
Zn Zn2+ + 2e Cu2+ + 2e Cu
 Odes to a galvanic cell
Cathode
Where reduction occurs
Where electrons are
consumed
Where positive ions migrate
to
Has positive sign
Anode
Where oxidation occurs
Where electrons are
generated
Where negative ions migrate
to
Has negative sign
 The role of inert electrodes

Fe(s) 2Fe3 (aq) 3Fe2 (aq)

Not all cells start with elements as the redox agents

Consider the cell

Fe can be the anode but Fe3+ cannot be the cathode.

Use the Fe3+ ions in solution as the cathode with an inert metal such as Pt
Anode Catho
de

Oxidati Reduct
on ion
 Connections: cell potential and free
energy

The cell in open circuit generates an electromotive force (emf) or

potential or voltage. This is the potential to perform work
Energy is charge moving under applied voltage

1J 1C 1V
Relating free energy and cell
potential
The Faraday :
F = 96 485 C/mole

Standard conditions (1 M, 1 atm, 25C)

G nFE
G nFE
 Standard Reduction Potentials

The total cell potential is the sum of the potentials for the
two half reactions at each electrode
Ecell = Ecath + Ean

From the cell voltage we cannot determine the values of

either we must know one to get the other

Enter the standard hydrogen electrode (SHE)

All potentials are referenced to the SHE (EH=0 V)

 Unpacking the SHE

The SHE consists of a Pt electrode in contact with

H2(g) at 1 atm in a solution of 1 M H+(aq).
The voltage of this half-cell is defined to be 0 V.

An experimental cell containing the SHE half-cell

with other half-cell gives voltages which are the
standard potentials for those half-cells
Ecell = 0 + Ehalf-cell
 Zinc half-cell with SHE
Cell measures 0.76 V
Standard potential for
Zn(s) = Zn2+(aq) + 2e : 0.76 V
 Where there is no SHE
In this cell there is no SHE and the measured voltage is 1.10 V

2 2
Zn Zn (aq) C u (aq) Cu
2 2
Zn( s ) Cu (aq) Zn (aq) Cu ( s )
Zn(s) Zn 2 (aq) 2e, E o 0.76V
2
Cu (aq) 2e Cu(s), E 0.34V o
Standard reduction potentials

Any half reaction can be written in two ways:

Oxidation:
M = M+ + e (+V)
Reduction:
M+ + e = M (-V)
Listed potentials are standard reduction potentials
 Applying standard reduction
potentials
Consider the reaction
Zn(s) 2 Ag (aq) Zn 2 (aq) 2 Ag (s)

What is the cell potential?

The half reactions are:
Ag (aq) e Ag ( s) Zn( s ) Zn 2 (aq) 2e

E = 0.80 V (-0.76 V) = 1.56 V

NOTE: Although there are 2 moles of Ag reduced for each

mole of Zn oxidized, we do not multiply the potential by 2.
 Extensive VS intensive
Free energy is extensive property so need to multiply by no of moles
involved

G nFE
But to convert to E we need to divide by no of electrons involved

E G
nF
E is an intensive property
 The Nernst equation
Working in nonstandard conditions

G G RT ln Q

nFE nFE RT ln Q

E E RT ln Q
nF

E E 0.0592 log Q
n
 Summary 27

Electrode potential - Related to the tendency of a material to

corrode. The potential is the voltage produced between the material
and a standard electrode.

emf series - The arrangement of elements according to their

electrode potential, or their tendency to corrode.

Nernst equation - The relationship that describes the effect of

electrolyte concentration on the electrode potential in an
electrochemical cell.

Faradays equation - The relationship that describes the rate at

which corrosion or plating occurs in an electrochemical cell.
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

28

The half-cell used to measured the

electrode potential of copper under
standard conditions. The electrode
potential of copper is the potential
difference between it and the standard
hydrogen electrode in an open circuit.
Since E0 is great than zero, copper is
cathodic compared with the hydrogen
electrode.
29
 Example
30
HalfCell Potential for Copper
Suppose 1 g of copper as Cu2+ is dissolved in 1000 g of water to produce an
electrolyte. Calculate the electrode potential of the copper half-cell in this
electrolyte.
The atomic mass of copper is 63.54 g/mol.
Example 22.1 SOLUTION
From chemistry, we know that a standard 1-M solution of Cu2+ is obtained when we
add 1 mol of Cu2+ (an amount equal to the atomic mass of copper) to 1000 g of
water. The atomic mass of copper is 63.54 g/mol. The concentration of the solution
when only 1 g of copper is added must be:

From the Nernst equation, with n = 2 and E0 = +0.34 V:

 31

Polarization

Polarization - Changing the voltage between the anode and cathode

to reduce the rate of corrosion.

Activation polarization is related to the energy required to cause

the anode or cathode reaction
Concentration polarization is related to changes in the
composition of the electrolyte
Resistance polarization is related to the electrical resistivity of
the electrolyte.
 32

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Photomicrograph of intergranular corrosion in a zinc die casting. Segregation of

impurities to the grain boundaries produces microgalvanic corrosion cells (x50).
 Corrosion Cells

Galvanic cell (Dissimilar electrode cell) dissimilar metals

Salt concentration cell difference in composition of aqueous
environment
Differential aeration cell difference in oxygen concentration
Differential temperature cell difference in temperature
distribution over the body of the metallic material
 Dissimilar Electrode Cell

When a cell is produced due to two

dissimilar metals it is called dissimilar
electrode cell
Dry cell
Zn anode Cu cathode

Local action cell HCl Solution

A brass fitting connected to a steel pipe

A bronze propeller in contact with the

steel hull of a ship
 Differential Temperature Cell
This is the type of cell when two identical electrodes are
immersed in same electrolyte, but the electrodes are
immersed into solution of two different temperatures

This type of cell formation takes place in the heat

exchanger equipment where temperature difference
exists at the same metal component exposed to same
environment

For example for CuSO4 electrolyte & Cu electrode the

electrode in contact with hot solution acts as cathode.
Salt Concentration Cell
Differential Aeration Cell
Corrosion at the bottom of the
electrical poles
Local Action Cell