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CMT555

Electrochemical & Corrosion Science

CHAPTER 1
ELECTROCHEMICAL NATURE OF AQUEOUS
CORROSION

ELECTROCHEMISTRY
What is electrochemistry?
Electrochemistry is a branch of chemistry that
deals with the interconversion between electrical
energy and chemical energy.
Electrical Chemical
The conversion takes place in an electrochemical
cell.

REDOX REACTIONS
In an electrochemical cell, there are two halfreactions (redox processes) occur at two different
electrodes:
Reaction

Electrode
Cathode

Reduction
(Gain of electron)

Anode

Oxidation
(Loss of electron)
* Remember:
OIL RIG

Example 1:

Half-reaction
Anode:

Zn( s ) Zn(2aq

2
e
)

(oxidation)

Cathode:
(reduction)

Overall:

2 H (aq) 2e H 2 ( g )

Zn( s ) 2 H (aq) Zn(2aq


) H 2( g )

A summary of redox terminology


Process
OXIDATION
One reactant loses electrons.
Reducing agent is oxidized.
Oxidation number increases.

REDUCTION
Other reactant gains electrons.
Oxidising agent is reduced.
Oxidation number decreases.

Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)


Zinc loses electrons.
Zinc is the reducing agent and become
oxidized.
The oxidation no. of Zn increases from
0 to +2.

Hydrogen ion gains electrons.


Hydrogen ion is the oxidizing agent
and becomes reduced.
The oxidation no. of H decreases from
+1 to 0.

Oxidising agent: ?
Reducing agent:?

Electron acceptor
Electron donor

When a piece of zinc is placed in an aqueous


solution of copper(II) sulphate, brown solids
(copper metal) will form and collect at the
bottom of the container. The blue colour of
the solution slowly fades, and the piece of zinc
gets smaller.

In the reaction, the zinc metal gives up


electrons and slowly dissolves:
Zn Zn2+ + 2e The electrons are taken up by the Cu2+ ions in
the solution, and get deposited as copper:
Cu2+ + 2e- Cu
In the process, zinc gets oxidised while the Cu2+
ions get reduced.
Zn + Cu2+ Zn2+ + Cu

In the reaction, zinc supplies electrons to Cu2+


ions. Hence, zinc is the reducing agent. Cu2+
ions accept electrons from zinc. Hence, the Cu2+
ions is the oxidising agent.
In a redox reaction, the reducing agent
undergoes oxidation, while the oxidising agent
undergoes reduction.
oxidation

Zn + Cu2+ Zn2+ + Cu
reducing
agent
oxidising
agent

reduction

Balancing Redox Equations using Halfreactions


This method divides the overall redox reaction
into oxidation and reduction half-reactions.
Since neither oxidation nor reduction can
actually occur without the other, we refer to
the separate equations as half-reactions.

The general rule involves the following:


1.
2.

Divide the reaction into two half-reactions.


Balance each half reaction separately.

a) Balance atoms other than O & H in each half-reaction


separately.
b) Balance O by adding H2O to the opposite side.
c) Balance H by adding H+ as appropriate.
d) Balance the charge by adding e-. For example, if the
reactant side of the equation has a total charge of +3, the
product side must also equal +3.
e) Balance the charges of the two half-reactions by
multiplying appropriately.
3.

4.

Add two half-reactions together and balance the final equation by


inspection.
Cancel the electrons on both sides.

Example 2:
Consider the following reaction:

MnO4 Cl Mn Cl2
Reduction

MnO4 Mn

Oxidation

Cl Cl2

1) MnO4 Mn 2

1) 2Cl

2) MnO Mn 2 4 H O
4
2

2) ..........

3) 8H MnO4 Mn

4 H 2O

3) ..........

4) 5e 8H MnO4 Mn 2 4 H 2O

5) 10e 16 H 2MnO4 2Mn

Cl2

8 H 2O

4)

2Cl Cl2 2e

5)

10Cl 5Cl2 10e

Finally, combine half-reactions and cancel


terms:

10e 16 H 2MnO4 10Cl


2

2Mn 8H 2O 5Cl2 10e

16H 2MnO4 10Cl 2Mn 8H 2O 5Cl2

Exercise 1
Balance the following equations:
(a)

(b)

(c)

2
7

Cr2O Fe

Cr

Fe
2
4

Cl2 SO2 Cl SO

C H 2 SO4 CO2 SO2

ELECTROCHEMICAL CELL
Oxidation-reduction or redox reactions take
place in electrochemical cells.
There are several types of electrochemical cells:
1. Galvanic/voltaic/chemical cell/daniel cell
2. Electrolytic cell
3. Concentration cell

There are 4 essential components in a cell:


1.
2.
3.
4.

Anode
Cathode
Ionic conductor (electrolyte)
Metallic conductor (electrical connection)

Galvanic Cells
Spontaneous chemical reaction which
generates electrical energy
Chemical energy Electrical energy

In the cell reaction the difference in chemical


potential energy between higher energy
reactants and lower energy products is
converted into electrical energy.

A common galvanic cell is shown below:

Electrolytic Cells
Electrical energy is used to bring about a nonspontaneous reaction.
Electrical energy Chemical energy
This type of cell is formed when an external
source of electrical energy is introduced into the
system.

In the cell reaction electrical energy from an


external power supply converts lower energy
reactants into higher energy products.

A common electrolytic cell is shown below:

Similarities between Galvanic Cell and


Electrolytic Cell
1. Both involve redox reactions.
2. Anode is the site of oxidation.
3. Cathode is the site of reduction.
4. Involve the flow of electrons from the
Anode to the Cathode.
5. Both can have a salt bridge (for the passage of
ions so as to maintain electrical neutrality).

Differences between Electrolytic Cell and Galvanic Cell


Galvanic cell

Electrolytic cell

1. Chemical energy
Electrical energy

1. Electrical energy
Chemical energy

2. Spontaneous reaction

2. Non-spontaneous reaction

3. Positive terminal of a cell 3. Positive terminal of a cell is


is cathode
anode
Negative terminal of a
Negative terminal of a cell
cell is anode
is cathode
4. G < 0

4. G > 0

Cell Notation
Cell notation in chemistry is a shorthand way of
expressing a certain reaction in an
electrochemical cell.

Components of
anode compartment
(oxidation half-cell)
LEFT SIDE

Components of
cathode compartment
(reduction half-cell)

RIGHT SIDE

Cell Notation
Electrode
(s)

Electrolyte
(aq)

Zn Zn

Electrolyte
(aq)

Cu

Oxidation

Reduction

Phase boundary (aqueous/solid)


Salt bridge or porous partition

Electrode
(s)

Cu

Concentration Cells
A galvanic cell in which both compartments have
the same material but at different concenration.
The electrons flow in the direction that tends to
equalize concentrations.

Concentration Cell

Diluted solution

Concentrated solution

[Zn2+] in the two compartments are different, 1.0


M and 0.1 M, respectively.
The cell will try to equalize the [Zn2+] in the two
compartments by transfering electrons from:
Compartment containing 0.1 M Zn2+ to the one
containing 1.0 M Zn2+ (left to right).

The electron transfer will produce more Zn2+ in the


left compartment and consume Zn2+ (to form Zn) in
the right compartment.

CELL POTENTIAL
Electron flows from the anode to the cathode
because there is a difference in electrical
potential energy between the electrodes.
The difference in electrical potential between
the anode and the cathode is measured by a
voltmeter.
The voltage across the electrodes of a cell is
called the cell voltage or cell potential or
electromotive force (emf) (E)

STANDARD ELECTRODE POTENTIAL


According to the IUPAC convection, all half-cell
reactions are written as REDUCTION.
The standard electrode potential is sometimes
called as standard reduction potential or standard
redox potential.
The electrode potential measured under
standard-state conditions is called standard
electrode potential, E measured in volts.

Conditions for the measurement of the


electrode potential have to be standardised.
The standard-state conditions are:

Temperature (T) fixed at 25C or 298 K


Pressure (P) fixed at 1 atm or 101 kPa
Concentration of aqueous ions fixed at 1.0 M

The absolute value of the standard electrode


potential of an electrode system cannot be
measured.
The value can be determined if a particular
electrode is chosen as the standard or
reference electrode and all other electrode
systems are measured against this standard
electrode.

The standard hydrogen electrode (SHE) was


chosen by IUPAC as the reference electrode
for all measurements of E.

The standard reference half-cell is a standard


hygrogen electrode, which consists of a specially
prepared platinum electrode immersed in a 1 M
aqueous solution of a strong acid, H+ (aq) [or
H3O+ (aq) ], through which H2 gas at 1 atm is
bubbled.
2H (aq;1M ) 2e H 2 ( g;1atm)

Ereference = 0.00 V

E for the hydrogen electrode is arbitrarily


fixed at 0.00 V.

Tables of Standard Electrode Potentials for


Half-Reactions allow us to determine the
voltage of electrochemical cells.

These tables compare the ability of different


half-reactions to compete for electrons
(become reduced).
Since the values are given in their ability to be
reduced, the bigger the E, the easier they are
to be reduced.

Selected Standard Electrode Potentials (298K)

F2(g) + 2e
2F(aq)
Cl2(g) + 2e
2Cl(aq)
MnO2(g) + 4H+(aq) + 2e
Mn2+(aq) + 2H2O(l)
NO3-(aq) + 4H+(aq) + 3e
NO(g) + 2H2O(l)
Ag+(aq) + e
Ag(s)
Fe3+(g) + e
Fe2+(aq)
O2(g) + 2H2O(l) + 4e
4OH(aq)
Cu2+(aq) + 2e
Cu(s)
2H+(aq) + 2e
H2(g)
N2(g) + 5H+(aq) + 4e
N2H5+(aq)
Fe2+(aq) + 2e
Fe(s)
2H2O(l) + 2e
H2(g) + 2OH(aq)
Na+(aq) + e
Na(s)
Li+(aq) + e
Li(s)

Eo(V)
+2.87
+1.36
+1.23
+0.96
+0.80
+0.77
+0.40
+0.34
0.00
0.23
0.44
0.83
2.71
3.05

strength of reducing agent

strength of oxidizing agent

Half-Reaction

Example 3:
If copper and hydrogen half-cells are joined
together, we find that the copper half-cell will
gain electrons from the hydrogen half-cell:
Cu 2 aq 2e Cus

2H

aq 2e

H 2aq

E 0.34V
E 0.00V

Since both half-reactions cannot undergo


reduction, we must reverse the equation of
the reaction that will undergo OXIDATION.

Cu

aq

2e Cu s

E 0.34V

Reduction

H 2 g 2H

aq

Oxidation

2e

E 0.00V

Calculating Voltages of Electrochemical


Cells
Before calculating the voltage of a cell you
must first determine which half-cell will be
oxidized and which one will be reduced.

cell

cathode

anode

Example 4
Zinc copper electrochemical cell
From Table of Standard Electrode Potential:

Cu 2 aq 2e Cu s
Zn

aq

2e Zn s

E 0.34V
E 0.76V

In the Table, all reactions are written as reduction


reactions.
The E values indicate which half-reaction is
better at competing for electrons.

Since the copper half-reaction has a larger


value for E than the zinc half-reaction, copper
will be reduced, forcing zinc to be oxidized.
So we reverse the zinc equation.
We can then add the two equations together to
get the full redox reaction and determine the
voltage of the cell.

Cu 2 aq 2e Cu s

0.34V
0.76V

Zn s Zn 2 2e
Cu

aq

Zn s Zn

aq

Cu s

A positive value of E indicates a


spontaneous reaction
A negative value of E indicates a
non-spontaneous reaction

1.10V

Exercise 2
Predict the spontaneity of the following
reactions:
a) Reduction of Sn2+ to Sn by Mg
b) Oxidation of Cl- to Cl2 by acidified Cr2O72-

SPONTANEITY OF REDOX REACTIONS


In an electrochemical cell, chemical energy is
converted to electrical energy.
Electrical energy in this case is the product of
the emf of the cell and the total electrical
charge (in coulombs) that passes through cell:

W=QE
unit: W = Joules (J)
Q = Coulombs (C)
E = Volts (V)

The total charge is determined by the number of moles of


electrons (n) that pass through the circuit.
By definition: total charge = nF (Q = nF)
1F = 96500 C/mol
The measured emf is the max. voltage that the cell can
achieve. This value is used to calculate the maximum
amount of electrical energy that can be obtained from the
chemical reaction.
This energy is used to do electrical work (wele), so
wmax = wele
= -nFEcell

wmax = is the max. amount of work that can be done.

Gibbs Free Energy (G)


The Gibbs free energy (G) represent the max.
amount of useful work that can be obtained from a
reaction.
G is the negative value of the max. electrical work:
G = Wmax
= -nFEcell
For reactions in which reactants and products are in
their standard states,
G = -nFEcell

Spontaneous reaction: G = negative


Ecell = positive
Non-spontaneous reaction: G = positive
Ecell = negative

Applications of Thermodynamics to
Corrosion
G = -nFEcell

A definite relation between the free energy


change and the cell potential of an
electrochemical reaction.

G is used to predict the spontaneous direction


of any electrochemical reaction.
The sign of G is the most important factor to
indicate whether or not the reaction is
spontaneous.

In any electrochemical reaction, the most


negative (active) half-cell tends to be oxidized
and the most positive (noble) half-cell tends
to be reduced.
From the rule:
All metals with potentials more negative
(active) than hydrogen will tend to be
corroded by acid solutions.

However Cu, Ag, Hg, Pt and Au are not


corroded in acid solutions.
But if dissolved oxygen is present, there is a
possibility of corrosion to occur for Cu and Ag
due to oxygen reduction.
Cu and Ag tend to corrode spontaneously in
the presence of oxygen.

Example 5
i) Cu + H2SO4 No reaction
(Cu/Cu2+ > positive than H2/H+)
ii) 2Cu + 2H2SO4 + O2 2CuSO4 + 2H2O
(O2/H2O > positive than Cu/Cu2+)

Exercise 3
1. Would it be possible to store a silver spoon in
a zinc nitrate solution?
2. Would it be possible to store a silver nitrate
solution in a copper container?
3. Calculate the standard free-energy change
for the following reaction at 25C:
2

2 Au( s ) 3Ca (1M ) 2 Au (1M ) 3Ca( s )


Zn( s ) 2HCl( aq) ZnCl2 H 2 ( g )
Is these reaction spontaneous?

Nernst Equation

Used when all or some of the components are under


non-standard-state conditions.

Shows how the cell potential depends on the


concentrations of the cell components.

Ecell E

Ecell E

cell

RT

ln Q
nF

cell

2.3RT

log Q
nF

Ecell E

cell

0.0592

log Q
n

Where R = universal gas constant


(8.314472 J K-1 mol-1)
T = temperature (K)
F = Faraday constant (96500 C mol-1)
n = no. of electron
Q = reaction quotient

product
Q
reac tan t

Cell Potential and the Nernst


Equation
The Nernst equation can be used to calculate
the cell potential of electrochemical cells which
are not under standard conditions.
Consider the galvanic cell operate at 25C:
Zn (s) Zn2+ (1.8 M) Cu2+ (0.2 M) Cu (s)

Exercise 4
Predict whether the following reaction would
proceed spontaneously as written at 298 K:
Co(s) + Fe2+ (aq) Co2+ (aq) + Fe(s)
given that
[Co2+] = 0.15 M and [Fe2+] = 0.68 M.

Equilibrium Constants
For a general cell reaction:

aA bB cC dD
where a, b, c, and d are the stoichiometric
coefficients for the reacting species A, B, C, and D.
For the reaction at a particular temperature:
c

[C ] [ D]
K a b
[ A] [ B]

where K is the equilibrium constant.

At equilibrium, there is no net transfer of


electrons, so E = 0 and Q = K.

Applying these conditions to the Nernst equation


(valid at 25C)
0.0592
Ecell E cell
log Q
n
0.0592

0 E cell
log K
n

n( E cell )
log K
0.0592

Therefore,

K ?

Example 6
Calculate the equilibrium constant, K, for the
following reaction:

Sn

2 Ag Sn

2 Ag

Relationship of Gibbs Free Energy


and Nernst Equation
Consider a redox reaction of type:
aA bB cC dD

The free energy change, G, is given by


thermodynamic equation:
G G RT ln Q
Where Q = reaction quotient

C D

a
b
A B
c

= [Product]
[Reactant]

Because G = -nFE and G = -nFE, the


equation can be expressed as
nFE nFE RT ln Q

Dividing the equation through by nF, we get


RT
EE
ln Q (Nernst Equation)
nF

Using the base-10 logarithm of Q


0.0592
EE
log Q
n

The interrelationship of Go, Eo, and K.


Go

Go

Go = -nFEocell

Eo

Eocell

Reaction at
standard-state
conditions
spontaneous

<0

>1

>0

at equilibrium

>0

<1

<0

nonspontaneous

Go = -RT lnK

cell

Eocell = RT lnK
nF

cell

0.0592

log K
n

(at 298 K)

HOMEWORK

1. Calculate E and Ecell for the following cell


reactions.
a. Mg s Sn 2 ( aq) Mg 2 aq Sn s

Mg 0.045M , Sn 0.035M
2

3
2
3
Zn

2
Cr

3
Zn
(
aq
)
aq 2Cr s
s
b.

Cr 0.010M , Zn 0.0085M
3

2. What is the emf of a cell consisting of a Pb2+/Pb


half-cell and a Pt/H+/H2 half-cell if [Pb2+] = 0.10
M, [H+] = 0.050 M and PH2 = 1.0 atm?

3. Calculate the emf of the following


concentration cell:

Mgs Mg

0.24M Mg 0.53M Mgs

READ on batteries topic


-dry cell battery
-mercury battery
-lead storage battery
-solid state lithium battery

Solubility Product Constant


When a sparingly soluble salt (a salt which has
very low solubility in water) is added a little at a
time to water, a saturated solution is eventually
formed.
That is, the solution is in equilibrium with excess
undissolved solid.
When a saturated solution of silver chloride is in
contact with solid silver chloride, the following
equilibrium is established.

AgCl (s) Ag (aq) Cl (aq)

The product of the concentration of silver ions


and chloride ions is known as the solubility
product (Ksp) of silver chloride.
K sp [ Ag ][Cl ]

The solubility product of a sparingly soluble salt


is defined as the product of the concentration of
the ions in a saturated solution of the salt,
raised to the power of the stoichiometric
coefficient of the respective ions.

Example 7
1.

NiS (s) Ni (aq) S (aq)

K sp [ Ni 2 ][S 2 ]

2
2
K

[
Pb
][
Cl
]
2. PbCl 2 (s) Pb (aq) 2Cl (aq) sp

3. Ca3 ( PO4 )2 (s) 3Ca3 (aq) 2PO43 K sp [Ca 2 ]3[ PO43 ]2

For a sparingly soluble salt AxBy, the Ksp is given


by:
y

Ax By (s) xA (aq) yB (aq)


K sp [ A y ]x [ B x ] y
The value of Ksp changes when there is a change
in temperature.
Generally, the higher the value of Ksp, the higher
the solubility.

Example 8
Write down the expression for the solubility
product for the following salts.
a)
b)
c)
d)

Pb(OH)2
Ag2CrO4
Al(OH)3
MgF2

Example 9
Calculate the solubility products of the salts from
the data below:
a) The solubility of silver chloride in water is
1.453 x 10-3 g dm-3.
b) The solubility of silver sulphate in water is 1.5 x
10-2 mol dm-3.

Solubility Product and Precipitation


When an aqueous solution of calcium nitrate is
added to an aqueous solution of sodium
sulphate, one of the products is calcium
sulphate, a sparingly soluble salt.
Ca( NO3 ) 2 (aq) Na2 SO4 (aq) CaSO4 (s) 2 NaNO3 (aq)

Whether a precipitate of CaSO4 will be formed


or not depends on the concentration of the Ca2+
ions and SO4- ions in the mixture.

If,
[Ca2+][SO42-] > Ksp : precipitation will occur
[Ca2+][SO42-] < Ksp : no precipitation takes place

Example 10
25.0 cm3 of 1.0 x 10-5 mol dm-3 silver nitrate is
added to 25.0 cm3 of 1.0 x 10-5 mol dm-3 sodium
chloride.

Common Ion Effect

Consider a saturated solution of silver chloride:

AgCl (s) Ag (aq) Cl (aq)


If a little sodium chloride is added to the above
solution, according to Le Chateliers Principle, the
equilibrium will shift to the left to get rid of some of
the Cl- ions added.
Hence, the amount of solid silver chloride will
increase.
In other words, the solubility of silver chloride is
decreased by the addition of sodium chloride
(which contains the Cl- ions).
This phenomenon is known as the common ion
effect.