ELECTROCHEMISTRY – 2

Title: EMF series, Reference electrodes

Learning Objective : To understand the
significance of EMF series, construction
and working of reference electrodes.
PRIMARY REFERENCE ELECTRODE
– SHE
For assigning a value to hydrogen
electrode (HE), the conditions which
affect the potential are standardized.
•The molar concentration of the
hydrogen ions is fixed as unity.
•Temperature unless otherwise
specified is taken to be 25oC or 298 K.
•Pressure of hydrogen gas is fixed as
one atmosphere.
The surface of platinum should be
pure and fresh and to ensure this
platinized platinum foil is taken.
Under these standard conditions, the H 2  2 H   2e 
hydrogen electrode, HE becomes
standard hydrogen electrode (SHE)
and its potential is arbitrarily fixed to
be zero.
 Reference Electrode

There are some problems faced with standard

hydrogen electrode.
•Setting up of SHE is very cumbersome and tedious.
•Platinum electrode is highly prone to get poisoned by
traces of impurities in hydrogen gas. Hence hydrogen
gas passed must be in a high state of purity.
•Reproducibility is of low order.

Hence other electrodes, whose potential will not vary

with use, are developed, which are called secondary
reference electrodes.

Very widely used secondary reference electrodes are

•Calomel
•Silver/silver chloride electrodes.
Calomel electrode

Applying Nernst equation,


Hg 2Cl2 ( s )  ( Hg 2Cl2 aq )  Hg 2  2Cl 

Hg 2Cl2 ( s )  Hg 2  2Cl 
−
++ ¿+2 𝑒 ⇔2 𝐻𝑔¿
𝐻𝑔 2
− −
𝐻 𝑔 2 𝐶 𝑙2 (𝑠)+2 𝐶 𝑙 ⇔ 2 𝐻𝑔+2 𝐶 𝑙

Ecalomel = E0calomel + 0.059 log [Hg2Cl2(s)]

2 [Hg]2[Cl]2
[Hg2Cl2(s)] = 1; [Hg] = 1
Rearranging
Ecalomel = E0calomel – 0.059 log[Cl-]
Silver-Silver chloride electrode

AgCl ( s )  e   Ag  Cl 

E = E0 + 0.059 log [AgCl(s)]

1 [Ag][Cl–]

= [AgCl(s)] = 1; [Ag] = 1

E = E0– 0.059 log [Cl-]

Standard reversible potentials (reduction) E0 values
Species in equilibrium E0 Volts Species in equilibrium E0 Volts
Li+/Li –3.01 Cu++/Cu+ 0.15
K+/K –2.92 AgCl/Ag + Cl– 0.22
Ba++/Ba –2.90 Cu++/Cu 0.34
Ca++/Ca –2.87 O2/OH- 0.401
Na+/Na –2.713 Cu+/Cu 0.52
Mg++/Mg –2.38 I2/I- 0.536
Al+++/Al –1.66 Fe+++/Fe++ 0.77
Mn++/Mn –1.18 Hg22+/Hg 0.798
Cr2+/Cr –0.913 Ag+/Ag 0.799
Zn++/Zn –0.763 Hg++/Hg 0.858
Cr3+/Cr –0.744 Br2 (l) /Br 1.065
Fe++/Fe –0.44 Cr6+/Cr3+ 1.23
Cr3+/Cr2+ –0.407 Pt++/Pt 1.2
Cd++/Cd –0.402 Cl2(g)/Cl– 1.358
Co++/Co –0.28 Au3+/Au+ 1.4
Ni++/Ni –0.257 Au3+/Au 1.5
Sn++/Sn –0.14 Au+/Au 1.7
Pb++/Pb –0.126 H2/H– 2.2
Fe+++/Fe –0.037 F2(g)/F– 2.87
H+/H 0.0
Significance of the EMF series:

•The sign of the potential indicates the

spontaneity of the reaction. If it is positive the
reaction occurs from left to right spontaneously
i.e., reduction is favoured. If it is negative,
oxidation is spontaneous.

•When the potential of Mg electrode is compared

with that of SHE, it is less reducing or more
oxidizing to the extent of 2.38 volts. If the two are
coupled in a cell, Mg will undergo oxidation and
hydrogen ion reduction.
Mg  Mg    2e 


2H  2e   H 2
•When any two electrodes are combined in this
series, one with a lower reduction potential
(higher oxidation potential) undergoes oxidation
and the other with a higher reduction potential,
undergoes reduction.

•One with a higher oxidation potential displaces

the one lower in the series, with less oxidation
potential. Iron dipped in copper sulphate
solution, displaces copper from the solution.

•When the potential difference between two

electrodes is large, the oxidation and reduction
occur readily.
 Mg  Mg    2e 

•If SHE is combined with copper electrode

which is more reducing, the spontaneous cell
reaction is oxidation in SHE and reduction in
copper electrode.

H 2  2H  2e 

Cu    2e   Cu
•For metals whose oxidation potentials are very
high compared to SHE, such as K, Li, Ba, Ca and
Na an equilibrium in aqueous solution is not
attainable. ΔG is highly negative and the
oxidation occurs extremely fast and irreversibly.
For these electrodes Eo values are obtained
indirectly from thermodynamic data.

•Due to the above said fact, sodium reacts with

water very fast, displacing hydrogen.
Na  H 2O  NaOH  1 / 2 H 2

As a redox couple,

Na  Na   e 
H   e   1 / 2 H 2 or

H 2 O  e   1 / 2 H 2  OH 
•The amount of hydrogen ion present in water is very
low, 10-7 gm.eqts / L. The oxidizing power of Na, Li or
K is so high to initiate the reduction of this H + or
reduction of water.

•Down the series, Mg, Al, Zn, Fe, do not undergo

oxidation so fast in water. But in dilute acid where H +
concentration is more, redox couples are set up and
the metals dissolve displacing hydrogen.

•But nickel and lead which are above SHE, do not

displace hydrogen even from dilute acids. The
threshold energy requirement is high and the
difference in potential with SHE, is not high enough
to initiate the reaction. Metals below SHE, as
expected do not displace hydrogen from acids.
 Spontaneity of the cell reaction
For any spontaneous reaction, it has already been
seen that the free energy change must be negative. i.e.,
wmax =nFEcell
ΔG= wmax
Work is expressed as a negative number because
work is being done by a system (an electrochemical cell
with a positive potential) on its surroundings.
ΔG = - nEF

At standard conditions, ΔGo=−nFEocell

ΔG - free energy change; ΔG o = free energy change at standard

condition
n - number of electrons involved in the change.
F - Faraday.
E - cell potential ; Eocell = cell potential at standard conditions
For any electrochemical reaction, when E is
positive, ΔG becomes negative and the reaction is
favored from left to right. When E is negative, ΔG
is positive and the reaction is favoured in the
other direction.

Problem:
Find the free energy change at 25 oC for the cell
reaction for the following electrochemical cell
where Eocell = + 0.281 volts :
Cu | Cu2+(1 M) || Ag+(1 M) | Ag.
Solution:
ΔG o = - nFEocell
ΔGo = - (2 mol e-)(96,485 C/mol e-)(0.281 J/C)
ΔGo = - 54,200 J or - 54.2 kJ
Equilibrium constant and cell potential

The product of the cell potential and the total

charge is the maximum amount of energy
available to do work, which is related to the
change in free energy that occurs during the
chemical process.
ΔGo=−nFEocell

At equilibrium Q = K. Substituting in K for Q, and

the values for R, T, and F, we get
Problem:
Find the value of the equilibrium constant at 25 oC for the
cell reaction for the following electrochemical cell where
Eoreduction = + 0.799 V; Eooxidation = - 0.518 V.

Cu | Cu2+(1 M) || Ag+(1 M) | Ag.

Solution:
2 Ag+(aq) + 2 e- 2 Ag(s) Eoreduction = + 0.799 V
Cu(s) Cu2+(aq) + 2 e- Eooxidation = - 0.518 V

2 Ag+(aq) + Cu(s) 2 Ag(s) + Cu2+(aq) Eocell = + 0.281 V

HW problem:
The following two half-reactions are used to form
an electrochemical cell:
Oxidation:
SO2(g) + 2 H20(ℓ) → SO4-(aq) + 4 H+(aq) + 2
e- E°ox = -0.20 V
Reduction:
Cr2O72-(aq) + 14 H+(aq) + 6 e- → 2 Cr3+(aq) + 7
H2O(ℓ) E°red = +1.33 V
What is the equilibrium constant of the combined
cell reaction at 25 oC ?
Thank you