EMF of cells and relationship to

thermodynamic parameters
 Typical Voltaic/Galvanic Cell
Voltmeter

2e- 2e-

Voltaic Cells: electrochemical cells in which electricity is

generated as a result of spontaneous chemical reactions.
Notation: Zn/Zn2+ // Cu2+/Cu
N.B. The flow of electric current is taken opposite to the flows of electrons 2
It consists of 2 half cells in electrical contact through a Salt bridge
When an external circuit is completed, e-s flow from Zn to Cu, so,
At the anode
• The electrode is made of Zn metal
• The electrolyte is a Zn2+ solution (e.g. ZnSO4)
• Zn metal loses e-s & is oxidized to Zn2+(aq)
• Electrode is eroded during the process and loses
Mass
•Electrons lost by Zn metal passes to the cathode

At the cathode
• The electrode is made of Cu metal
• The electrolyte is a Cu2+ solution
• Cu2+ gains e-s & is reduced to Cu metal
• Copper is deposited on the electrode and it gains
mass (since electrons are gained by Cu2+ to form Cu)
• Cu is said to be at a +ve electrode potential wrt Zn since e-s flow to it
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 Salt bridge and its function
 It’s usually an inverted U-tube filled with concentrated
solution of inert electrolyte.

The essential requirements of the electrolyte are:

a) The mobility of the anion and cation of the electrolyte
should be almost same.
b) The ions of the electrolyte are not involved in
electrochemical change.
c) The ions do not react chemically with the species of the cell.

 Examples of salts like KCl, KNO3, etc. are used.

The saturated solutions of these electrolytes are prepared
in agar jelly or gelatin. The jelly keeps the electrolyte in
semi-solid phase and thus prevents mixing.
 The important functions of the salt bridge

a) The salt bridge allows the flow of ions but prevents the
mixing of the different solutions that would allow
direct reaction of the cell reactants.
b) Salt bridge completes the electrical circuit.
c) Salt bridge maintains electrical neutrality of two half cell
solution.
The accumulation of charges in the two half cells
*Accumulation of extra positive charge in the solution around
the Anode according to the release of Zn2+ in excess (bc of loss
of e-s) and (NO3- neutralizes excess cations)
*Accumulation of extra negative charge in the solution around
the Cathode due to excess of SO42- ) (NB: Cu becomes Cu) is prevented
2+

by using salt bridge, which provides a passage for the flow of

the charge in the internal circuit. (K+ neutralizes excess anions)
 Electrode Potential
 The flow of electric current in an electrochemical cell indicates
that a potential difference exists between two electrodes

If the metal has relatively high tendency to get oxidized, its atom will lose
electrons readily and form Cu2+ ions, which go into the solution. The
electrons lost on the electrode would be accumulated on the metal electrode
and the electrode acquires a slight negative charge with respect to the
solution. Some of the Cu2+ ions from the solution will take up electrons and
become Cu atoms. After some time, an equilibrium will be established as:

When such an equilibrium is attained, it results in separation of charges

(negative on the electrode with respect to the solution).
Similarly, if the metal ions have relatively greater tendency to get
reduced, they will take electrons from the electrode. As a
result, a net positive charge will be developed on the electrode
with respect to the solution. This will also result into
separation of charges (positive on the electrode with respect to
the solution).

Due to separation of charges between the electrode and the

solution, an electrical potential is set up between metal
electrode and its solution.

The electrical potential difference set up

between the metal and its solution is known
as ELECTRODE POTENTIAL
The electrode potential may be of two types:

1. Oxidation potential:
The tendency of an electrolyte to lose electrons
or to get oxidized
e.g. E= +0.76 V

2. Reduction potential. The tendency of an electrode

to gain electrons or to get reduced.
e.g. E= -0.76 V (reverse of the oxn
potential)
 EMF or Cell Potential of a Cell
The maximum difference between the electrode potentials of the two electrodes
constituting an electrochemical cell is known as EMF or Cell potential of a
cell. This acts as a driving force for the cell reaction expressed in volts.
It is equal to the reduction potential for the substance that actually undergoes
reduction minus the reduction potential of the substance that undergoes oxidation.

i.e

OR Ecell = Ered + Eox , where sign of potential is changed

Thus, emf of a cell may be defined as the potential difference between
two electrodes of the cell when either no or negligible current is allowed
to flow in the circuit.
 Standard electrode potential
Since a half cell in an electrochemical cell can work only in
combination with the other half cell and does not work
independently, it is not possible to determine the absolute
electrode potential of an electrode. We can, therefore, find only
the relative electrode potential.

This difficulty can be solved by selecting one of the electrodes as a

reference electrode and arbitrarily fixing the potential of this
electrode as zero.

For this purpose, reversible hydrogen electrode has been

universally accepted as a reference electrode. It is called standard
hydrogen electrode (S.H.E) or normal hydrogen electrode
(N.H.E.) (H+(aq)/H2(g))
The electrode potential of an electrode can be determined by
connecting this half cell with a SHE which (under agreed
standard conditions) is given a Eθ value of zero

The electrode potential of a metal electrode as determined with

respect to a standard or normal hydrogen electrode is called
standard electrode potential (E0)
Standard electrode potentials are always associated with the
reduction occurring at the electrodes.

oxidation reduction
It is not always convenient to use SHE as reference electrode
because of experimental difficulties in its preparation and use.

N.B. The standard electrode potentials given in the following

table are measured in their standard states when the
concentration of the electrolyte solutions are fixed as 1M
and temperature is 298 K.
 Application of the Electrochemical series/Standard reduction potential

1. Relative strengths of oxidizing and reducing agents.

The substances which have lower reduction potentials are stronger reducing agents
while have higher reduction potentials are stronger oxidations agent.
2. Calculation of the E.M.F. of the cell.
E0cell = E0(cathode) - E0(anode) (or addn if potential sign is changed)

3. Predicting feasibility of the reaction.

In general, a red-ox reaction is feasible only if the species to release electrons must
have lower reduction potential as compared to the species which is to accept
electrolytes.

4. To predict whether a metal can liberate hydrogen from acid or not.

In general, only those metals which have negative values of reduction potentials , - E0
values can liberate hydrogen from the acid.
 Calc. Standard Cell potential of a cell
• Split the cell reaction into half-reactions
• Look up Eθ in a standard table and identify the redn. and oxidation
reaction and write against each half reaction
• Eθred = half cell potential of the reduction reaction
• Eθox = half-cell potential of the oxidation reaction
• OR
• Change the reduction equation θ
(from tables) of the half-cell
reaction withθ lower value of E to an oxidation equation. The
sign of the E value will also change
• Balance the number of electrons θin the two half equations
(NOTE, this does not affect the E since it is an intensive
property)
• Add up the two half equations and do the same to the Eθ
• Eθtot = Eθred + Eθox , where Eθtot (or Eθcell) is the standard cell voltage
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Spontaneity of Redox Reactions
Recall: Gibbs Free Energy Change in a cell;
G = H  TS
ΔG = Gibbs’ energy change
ΔH = enthalpy change
T = temperature and
ΔS = entropy change
Note: Maximum useful workdone by a system at constant
pressure = ΔG
Workdone by a system is negative
For electrochem., Wmax = Welec.
 ΔGθ = -wmax = -nFEθtot
wmax = maximum amount of work reactant can produce
n = number of moles of electrons transferred in balanced equation
F = Faraday’s constant (96485 C.mol-1)
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Spontaneity of Redox Reactions
ΔGθ = -wmax = -nFEθtot
Deductions:
- A positive Eθtot means a negative ΔGθ and a spontaneous
forward reaction

- A negative Eθtot means a positive ΔGθ and a non-

spontaneous forward reaction

- A zero Eθtot means the cell is in equilibrium and there is no

net reaction in either direction
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Standard cell potential and Equilibrium constant Keq
Recall from Thermodynamics:

Also, that
2.303RT
Re-arrange to get: E0  log K
nF
At standard conditions, T= 250C/298K, R=8.314 Jmol-1K-1, F=96485
C/mol of e-
0.0592
E 0
cell  log K
n

K is equil constant or setup for calc - prod/reactants

[C ]c [ D]d
Example aA +bB cC + dD K
[ A]a [ B]b
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 Dependence of emf on Concentration

• Everything we have done so far has been with a

standard cell.
• If an electrode is a measure of the extent to which
concentration in a half cell differs from an equil value;
then concentration will affect equil and vary electrode
potential.
• Electrode potential is there4 dependent on
concentration. Further from equil, greater potential
(higher voltage).
• Remember E from table is for standard conditions. If
concentrations are not std concentrations, then the
cell potential must be corrected.
• Basically, the potential for non std cell will be equal to
the std cell potential with a correcting factor for
nonstd concentrations. The basic equation is as
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follows:
 The Nernst Equation
• The Nernst equation shows relationship between E0 and
concentration of reactants. Consider a reaction:
[C ]c [ D]d
aA + bB → cC + dD K
[ A]a [ B]b

From Thermodynamics, G= G0 + RTlnK OR, G= G0 + 2.303 RT logK

G= -nFEcell; G0= -nFE0cell

-nFEcell = -nFE0cell + RT lnK

Divide through by (-nF)
RT ln K 2.303RT log K
Ecell  Ecell 
0
or Ecell 
0

nF nF

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 The Nernst Equation
[C ]c [ D]d
• Inserting K: K
[ A]a [ B]b
RT [C ]c [ D]d RT oxidized RT n
Ecell  E
0
cell  ln or E 0
cell  ln or E 0
cell  ln M
nF [ A]a [ B]b nF reduced nF

Ecell = Eθcell -
•

Ecell = potential under non-standard conditions

Eθcell = potential under standard conditions
RT/F = 0.0592
n = the number of moles of electrons, and
[ ] = concentrations
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