Kinetics & Equlibria

6.

REDOX EQUILIBRIA

If zinc rod is placed into a solution containing zinc ions, an equilibrium will be set up between them.
There is a tendency for zinc atoms on the surface of the rod to be attached into the solution and they
enter as atoms. The electrons left behind when a zinc atom is transformed into positive ion remain on
the rod. The immediate environment of the rod suffers an increase in positive charge owing to the
extra zinc ions.

2e +

2n 2+ (aq)

+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
ZnSO4 (aq) Solution +
Zn (s)

+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+

Zn2+

For this metal the equilibrium lies to the left. Electrons remain on rod, 2n 2+ go into solution as
positive change.
Other metals dipping into solutions of their ions under a similar but opposite change. The positive
change stay on the metal rod and the elections go into solution e.g.
Cu(s)

Cu2+ (aq) + 2e-

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Kinetics & Equlibria

+
Cu 2+
Cu (s)

+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+

2e

Positive ions leave the solution and cling on to the metal and attract electrons out of the rod.

+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+

2e-

CuSO4 (aq) Solution

The equilibrium lies to the right. The potential difference between the strip of metal and the solution
depends on the nature of the metal and on the concentration of the ions involved in the equilibrium a
the metal surface. Zinc requires a more negative potential than copper since it has a greater tendency
to dissolve as ions.
The two metals zinc and copper in solution of their ions may be combined as follows to make a
Daviell cell. The metals will be called electrodes, each in a separate half- cell.
The half-all with the most negative electrode potential should always be shown as the left hand cell.
This is why the cell with zinc half-cell on the left hand side, and the copper on the right.

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Kinetics & Equlibria

+
+ 1.10 V

Zn Electrode (-ve)

Cu Electrode (+ve)
e- Flow

Salt Bridge

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Kinetics & Equlibria

Zinc Sulphate Solution

1 mol dm-3

Positive Half Cell On

Right

Negative Half Cell On

Left
The above assemble is now called and electrochemical cell for a Zn/Cu combination.
The electromotive force (e. m.f) of the cell is a measure of the tendency of electrons to flow through
the external circuit.
Standard (e.m.f) is given by symbol E and is measured by the standard hydrogen electrode (S.H.E)
ESHE = 0.000 V
EH+/H2 = 0.000 V

or

The standard hydrogen electrode (S.H.E)

The S.H.E consists of a hydrogen gas bubbling over a platinum electrode immersed in a solution of
hydrochloric acid. At standard conditions, the hydrogen must be

atm (101.325KPa) and

acid must be 1 mol dm-3

Temperature should be 250C (298K). The platinum chloride is usually called platinum black. This acts
as a catalyst to allow equilibrium between gas and solution to be established quickly.

H2 at 1
atm

Temp 25 oC

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Kinetics & Equlibria

1 mol dm-3 HCl

Pt Electrode
Coated With Pt
Black
A Standard hydrogen electrode (S.H.E)
The reaction that takes place in the S.H.E is
2H+(aq) + 2e-

H2(g)

Under standard conditions the e.m.f of the S.H.E is defined to be exactly zero.
ESHE

0.000 V

Standard Electrode Potential

Having established the standard, the S.H.E can now be used to measure e.m.f of metals, etc.

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Kinetics & Equlibria

+
- 0.76 V
Zn Electrode (+ve)
-

e Flow
H2 1 atm

Salt Bridge

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Kinetics & Equlibria

Pt.

Zinc Sulphate Solution

1 mol/dm-3

HCl
1 mol dm-3

An assemble for measuring standard electrode potential of zinc.

At standard condition zinc should be dipped into 1 mol dn-3 solution of zinc ions. The S.H.E is on the
left. The two half cells are connected by a salt bridge. A typical salt bridge is made by dissolving
potassium chloride in a jar. The mixture is then filled in a U-tube which sets into a jelly. The salt
bridge allows for positive and negative ions to travel into the solutions and so keep the charge
balance.
Now
ECell
ECell

Eright - Eleft

= EZn2+/zn - EH+/H2

But EH+/H2 = 0.000V

So, ECell = EZn2+/zn
Now Zn is connected to the positive terminal of the voltmeter with gives a reading. This means than
Zinc is negative compared to S.H.E
ECell = EZn2+/zn
EZn2+/zn = -0.76V
This figure is known as the standard electrode potential of Zinc.
The standard electrode potential of many other half cells can be measured in a similar way. The more
negative the value of the standard electrode potential, the greater the tendency of for a metal to give
up its electrons, and the stronger is its reducing power. Conversely, the more positive the value of E ,
the greater the oxidizing power.
Reaction
H+(aq)

e-

E/V
Li(s)

-3.03

Ca2+(aq) + 2e-

Ca(s)

-2.87

Zn2+(aq) +

2e-

Zn(s)

0.76

2H+(aq) +

2e-

H2(g)

0.00

Strongest reducing agents

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Cu2+(aq) +

2e-

Cu(s)

+0.34

Ag+(aq) +

e-

Ag(s)

+0.80

Weakest reducing agents

Some standard electrode potentials at 250C

Combining Half Cells

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Kinetics & Equlibria

Negative Terminal
(Black)

Positive Terminal
(Red)

Voltmeter

+ 1.10 V

Zn Electrode (-ve)

Cu Electrode (+ve)
e- Flow

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Kinetics & Equlibria

Salt Bridge

Zinc Sulphate Solution

1 mol dm-3

Copper Sulphate Solution

1 mol dm-3

Negative Half Cell On

Left

Positive Half Cell On

Right

A Daniel cell made by joining zinc in zinc Sulphate half-cell with a copper in copper (II) Sulphate
half-cell
ECell

=
=
=
=
=

Eright ECell ECu2+/Cu

+0.34 1.10V

Eleft
ECell
- EZn2+/Zn
(-0.76)

Another example of combination of copper and silver half cells. They both have positive standard
electrode potential but the silver is more positive than the copper.
Therefore the copper half-cell should be on the left hand side.
ECell

= EAg+/Ag - ECu2+/Cu
= 0.80 V - (+0.34 * V)
= 0.80 V - 0.34 V
= 0.46 V
Quick way of writing Cells
Negative half
cell
(a)

Zn(s) Zn2+(aq)
1 mol dm-3

Cu2+(aq)
1 mol dm-3

Cu(s)

The vertical broken line represents a barrier (porous pot)

(b)

Zn(s)

Zn2+(aq)
1 mol dm-3

KCl Cu2+(aq)
1 mol dm-3

Cu(s)

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Kinetics & Equlibria

Between the two cells is a salt bridge

(c) Most important half-cell is S.H.E
pt(s)

H2(g)
1 atm

H+(aq)
1 mol dm-3

Pb2+(aq)
Pb(s)
1 mol dm-3

(d) Calomel electrode. Sometimes used as substitute for S.H.E

pt(s)

H2(g)
1 atm

H+(aq)
1 mol dm-3

Cl-(aq)
1 mol dm-3

Hg(l)

Ions of the Same Element in Different Oxidation State

An element can have a standard electrode potential for equilibrium between different oxidation stats.
The standard electrode potential of the system, say, Fe 3+/Fe2+ can be measured by the use of saturate
calomel electrode.

V
Platinum
Wire
Iron Rod
Saturated
Solution
of KCl &
Hg2Cl2
Solutions
of Fe3+ (aq)
1 mol dm-3
& Fe2+ (aq)
1 mol dm-3

Porous
Plug

Solid
Calomel
Hg2Cl2

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Kinetics & Equlibria

Hg

Apparatus for measuring the standard electrode potential for an element in different oxidation state.
ECell = EFe3+/Fe2+ - E(Calomel)
0.526 V = EFe3+/Fe2+ - 0.245 V
EFe3+/Fe2+ = 0.771 V

Feasibility of a Reaction
When two electrods combine to form a cell, the value of E for the cell must be positive if the cell
reaction is to happen spontaneously. For example when copper and silver are in contact with solution
of their ions, two equilibria are set up:
Cu2+ (aq) + 2e-

Cu (s) ; Eo = 0.34 V.

Ag+ (aq) + e-

Ag (s) ; Eo = +0.80 V

So that Eo shall have a positive value, the reaction that take place is:
Ag+ (aq) + e-

Eo = +0.80 V

Ag (s) ;
Cu2+ (aq) + 2e- ;

Cu (s)

Eo = -0.34 V

Total:
Cu (s) + 2Ag+ (aq)
Eo =
=

Cu2+ (aq) + 2Ag (s) ;

+0.80 0.34
+0.46 V

In solution containing Ce4+, Ce3+, Fe3+ and Fe2+ are mixed, the redox equilibria in solution are:
Fe3+ (aq)

+ e-

Fe2+ (aq)

; Eo = +0.77 V

Ce4+ (aq)

+ e-

Ce3+ (aq)

; Eo = +1.45 V

The redox reaction that takes place is that for which E o is positive, i.e.
Ce4+ (aq)
Eo =

+ Fe2+ (aq)

Ce3+ (aq)

+ Fe3+ (aq)

1.45 V 0.77 V

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Kinetics & Equlibria

+0.68 V

A redox reaction will go almost to completion between two redox systems which differ by 0.3V or
more in their electrode potential.
N.B. A cell reaction can happen of Eo for the cell is positive and the cell reaction can go to completion
if Eo > 0.3V.

Variation of Electrode Potential With Concentration

The value of the electrode potential, E of a metal depends on:
Standard electrode potential
On temperature
And on concentration of metal ion in solution
The electrode potential increases with concentration of metal ions.
In general
E = Eo + (0.0592 / z) log [10N]
Where z is the charge on the metal ion. For zinc electrode this is
E = Eo + (0.0592 / 2) log [Zn2+ (aq)]
For a reaction:
Mn+ (aq) + ne-

M (s)

The standard free energy change is Go

-nFEo

(Where n is the number of electrons and F is Faradays constant)

Example
Eo = +0.34 V at 298K for the electrode reaction:
Cu2+ (aq) + 2e-

Cu (s)

The value of Go is given by:

Go

Cu (s)

-2 * 96500 * (-0.34)

65.6 KJ mol-1
Cu2+ (aq) + 2e- ;

Eo = -0.34 V

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Kinetics & Equlibria

Energy Storage Devices

Lead Acid Battery

In a lead acid storage batter, anodes made of Pb alternate with cathode of Pb coated with PbO 2.
The batter consists of 6 2V cells connected in series. Each cell consists of two lead plates dipping
into a 30 % solution of sulphuric acid. One plate is coated with lead (IV) oxide, PbO2. The lead plate
and the lead (IV) oxide have different electrode potentials so when they are connected a current flows
between them. The electrode processes are:
Positive Plate:
PbO2 (s)

4H+ (aq)

+ SO42- (aq) + 2e-

PbSO4 (s) + 2H2O (l)

Negative Plate
Pb(s) + SO42- (aq)

PbSO4 (s) + 2e-

The electrons produced are used to do work e.g. make the lights, etc.
An alternator reverses the reaction and converting PbSO 4 back to PbO2 and Pb. The charging and
discharging is an ongoing process, but does not last indefinitely since the acid decomposes, the plate
changes their structure and the battery loses its efficiency.

Fuel Cell
A fuel cell is a cell which converts the chemical energy of a continuous supply of reactants into
electrical energy. The most well known type of fuel cell generates electricity from hydrogen and
oxygen using platinum electrodes and a solution of alkali.
At the negative electrode, electrons are released through the reaction.
2H2 (g)

+ 4OH- (aq)

4H2O (l)

+ 4e-

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Kinetics & Equlibria

The electrons released travel to the positive terminal where oxygen is used up.
O2 (g)

+ 2H2O (l) + 4e-

4OH- (aq)

Overall the change is:

2H2 (g)

+ O2 (g)

2H2O (l)

Not only does the cell produce a reliable supply of electricity, it also produces water. Both features
have given hydrogen oxygen fuel cells a use in space exploration.

Porous Carbon Electrode

Containing Nickel
O2 + H2O + 2e-

H2 + 2OH-

2H2O

2OH-

2e-

Hydrogen & Oxygen Fuel Cell

The two gases are fed in separately and oxidized and reduced at the electrode. Hot KOH completes
the circuit. H2O (g) evaporates continuously.

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