Electrochemistry is a branch of chemistry which deals

with the properties and behavior of electrolytes in solution

and inter-conversion of chemical and electrical energies.
• An electrochemical cell can be defined as a single
arrangement of two electrodes in one or two electrolytes
which converts chemical energy into electrical energy or
electrical energy into chemical energy.

• It can be classified into two types:

 Galvanic Cells.
 Electrolytic Cells.
Galvanic Cells:

A galvanic cell is an electrochemical cell that produces

electricity as a result of the spontaneous reaction
occurring inside it. Galvanic cell generally consists of
two electrodes dipped in two electrolyte solutions
which are separated by a porous diaphragm or
connected through a salt bridge. To illustrate a typical
galvanic cell, we can take the example of Daniel cell.
Daniel Cell.
At the anode: Zn → Zn 2+ + 2e-

At the cathode: Cu 2+ + 2e- → Cu

Net reaction: Zn(s)+Cu 2+ (aq)→ Zn 2+ (aq)+ Cu(s)

An electrolytic cell is an electro –chemical cell in
which a non- spontaneous reaction is driven by
an external source of current although the
cathode is still the site of reduction, it is now the
negative electrode whereas the anode, the site
of oxidation is positive.
 Representation of galvanic cell.

• Anode Representation:
Zn│Zn2+ or Zn ; Zn2+
Zn │ ZnSO4 (1M) or Zn ; ZnSO4 (1M)
• Cathode Representation:
Cu2+/Cu or Cu2+ ;Cu
Cu2+ (1M) ; Cu or CuSO4(1M)/Cu
• Cell Representation:
Zn │ ZnSO4 (1M)║ CuSO4(1M)/Cu
 Liquid Junction Potential.

• Difference between the electric potentials developed in

the two solutions across their interface .
Ej = Ø soln, R - Ø soln,L
Eg: *Contact between two different electrolytes
(ZnSO4/ CuSO4).
*Contact between same electrolyte of different
concentrations(0.1M HCl / 1.0 M HCl).
 Salt Bridge.

• The liquid junction potential can be reduced (to about 1 to

2 mV) by joining the electrolyte compartments through a
salt bridge.
 Functions Of Salt Bridge.

It provides electrolytic contact between the two

electrolyte solutions of a cell.

It avoids or at least reduces junction potential in galvanic

cells containing two electrolyte solutions in contact.
 Emf of a cell.

• The difference of potential, which causes a current to flow

from the electrode of higher potential to one of lower
potential.
Ecell = Ecathode- Eanode
• The E Cell depends on:
the nature of the electrodes.
temperature.
concentration of the electrolyte solutions.
Standard emf of a cell(Eo cell) is defined as the emf
of a cell when the reactants & products of the cell
reaction are at unit concentration or unit activity,
at 298 K and at 1 atmospheric pressure.
The emf cannot be measured accurately using a voltmeter :

As a part of the cell current is drawn,thereby causing a

change in the emf.

As a part of the emf is used to overcome the internal

resistance of the cell.
The emf of the cell Ex is proportional to the length AD.
Ex α AD

The emf of the standard cell Es is proportional to the length AD1.

Es α AD1

Ex ═   AD
Es AD1

Ex = AD x Es
AD1
 Standard Cell.
It is one which is capable of giving constant and reproducible
emf.
It has a negligible temperature coefficient of the emf.
The cell reaction should be reversible.
It should have no liquid junction potential.

Eg: Weston Cadmium Cell. The emf of the cell is 1.0183 V at 293 K
and 1.0181 V at 298 K.
 Sealed wax

Cork
Saturated solution of
• Weston Cadmium
CdSO4.8/3H O Cell
2 CdSO4.8/3H2O
crystals

Cd-Hg Paste of Hg2SO4

12-14%
Cd Mercury, Hg
Cell representation:
Cd-Hg/Cd2+, Hg2SO4/Hg

At the anode:

Cd (s) → Cd2+ + 2e-

At the cathode:

Hg2SO4(s) + 2e- → 2 Hg (l)+ SO42-(aq)

Cell reaction:

Cd + Hg22+ → Cd2+ + 2Hg

Origin of single electrode potential.

Consider Zn(s)/ ZnSO4

Anodic process: Zn(s) → Zn2+(aq)
Cathodic process: Zn2+(aq) → Zn(s)

 At equilibrium: Zn ↔ Zn
(s)
2+
(aq)

Metal has net negative charge and solution has equal positive
charge leading to the formation of an Helmholtz electrical layer.
 Single electrode potential.

Electric layer on the metal has a potential Ø (M).

Electric layer on the solution has a potential Ø (aq)
• Electric potential developed between the electric double
layer existing across the electrode /electrolyte interface
of a single electrode or half cell.
De-electronation Electronation

Helmholtz double layer

 MEASUREMENT OF ELECTRODE
POTENTIAL.

It is not possible to determine experimentally the

potential of a single electrode.
It is only the difference of potentials between two
electrodes that we can measure by combining them to
give a complete cell.
By arbitrarily fixing the potential of reversible hydrogen
electrode as zero it is possible to assign numerical values
to potentials of the various other electrodes.
 Sign Of Electrode Potential.

 The electrode potential of an electrode:

Is positive: If the electrode reaction is reduction when
coupled with the standard hydrogen electrode
Is negative: If the electrode reaction is oxidation when
coupled with standard hydrogen electrode. According
to latest accepted conventions, all single electrode
potential values represent reduction tendency of
electrodes.
when copper electrode is combined with SHE, copper electrode acts as
cathode and undergoes reduction hydrogen electrode acts as anode.

H2(g) → 2H+ +2e- (oxidation)

Cu2+ +2e- → Cu (reduction)

Hence electrode potential of copper is assigned a positive sign. Its

standard electrode potential is 0.34 V.
When zinc is coupled with S.H.E. zinc electrode acts as
anode and hydrogen electrode acts as cathode.
Zn → Zn2+ +2e-
2H+ + 2e-→ H2.
Hence, electrode potential of zinc is negative. The
standard electrode potential of zinc electrode is -0.74 V.
 Nernst Equation.

It is a quantitative relationship between electrode

potential and concentration of the electrolyte species.
Consider a general redox reaction:
Mn+(aq) + ne- → M(s) ----(1)
We know that, ΔG =-nFE ----- (2)
ΔGo=-nFEo-----(3)
ΔG =ΔGo +RT ln K
 ΔG =ΔGo +RT ln K
ΔG =ΔGo +RT ln[M]/[Mn+]-----(4)
-nFE= -nFEo + RT ln [M]/[Mn+]----(5)
E= Eo – RT/nF ln 1/[Mn+]------(6)
E=Eo- 2.303 RT/nF log 1/[Mn+]---(7)
At 298K,
E= Eo-0.0592/n log 1/[Mn+]-------(8)
 1. A galvanic cell consists of copper plate immersed in 10
M solution of CuSO4 and iron plate immersed in 1M FeSO4

at 298K. If E0cell=0.78 V, write the cell reaction and calculate

E.M.F. of the cell.

Solution:

Cell reaction:

Fe + Cu2+ ↔ Fe2+ + Cu

ECell= E0Cell-0.0592/2 log [Fe2+ ]/[Cu2+]

ECell= 0.78 + 0.0296 log 10/1

=0.8096V
Calculate E.M.F. of the zinc – silver cell at 25˚C when
[Zn2+ ] = 1.0 M and [Ag+] = 10 M (E0cell=1.56V at 25˚C).
Write the cell representation and cell reaction
• Zn/ Zn ((1M)//Ag (10M) /Ag
2+ +

• Cell reaction:
Zn + 2Ag+ ↔ Zn2+ + 2Ag
ECell= E0Cell-0.0592/2 log [Zn2+ ]/[Ag+]2

ECell= 1.56 + 0.0592 log 10/1.0

=1.6192 V
 The emf of the cell

Mg│ Mg 2+ (0.01M)║ Cu 2+ /Cu is measured to be 2.78 V at 298K.

The standard eletrode potential of magnesium electrode is

-2.37 V. Calculate the electrode potential of copper electrode
Cell reaction:

Mg + Cu2+ ↔ Mg2+ + Cu
E= Eo-0.0592/n log 1/[Mn+]
EMg= EoMg-0.0592/2 log 1/[Mg2+]
=-2.4291V
Ecell=ECu-EMg
2.78 = ECu-[-2.429]
ECu =2.78-2.429
=0.3509 V
 The emf of the cell

Cu│ Cu 2+ (0.02M)║ AgNO3 /Ag is measured to be 0.46 V at 298K.

The standard eletrode potential of copper electrode is 0.34 V

and silver is 0.81. Calculate the concentration of silver nitrate
solution.
 Energetics of Cell Reactions.

Net electrical work performed by the cell

reaction of a galvanic cell:
W= QE ------(1)
Charge on 1 mol electrons is
F(96,500)Coulombs.
When n electrons are involved in the cell reaction,
the charge on n mole of electrons = nF
 Q = nF

Substituting for Q in eqn (1)

W = nFE ----------(2)

The cell does net work at the expense of

- ΔG accompanying. ΔG = -nFE

- ΔG = nFE
According to Gibbs – Helmholtz equation the change in
free energy, ΔG, enthalpy ΔH and entropy ΔS,
accompanying a reaction at a constant temperature, T are
related as

∆G = ΔH – TΔS (1)
Differentiation of equation (1) w.r.to temperature T at
constant pressure P yields

[δ(∆G)/ δT]P = [δ(∆H)/ δT]P - T [δ (ΔS)/ δT)P - ΔS (2)

But from the Kirchhoff equation, the
variation of ∆H of a reaction with
temperature at constant pressure is equal to
∆Cp of the system. We can write it as
[δ (∆H)/ δT]P = ΔCP (3)
and the variation of ∆S of a reaction with
temperature at constant pressure is equal to
∆ CP / T.
i.e. [δ (ΔS)/ δT]P = ΔCP/T (4)
Substituting equations (3) & (4)in equation (2).
[δ (ΔG)/ δT]P = ΔCP – TΔCP/T – ΔS
[δ (ΔG)/ δT]P = - ΔS ----------- ---------------->(5)
Substituting equation(5) in equation (1) we get Gibbs
– Helmholtz equation.
ΔG = ΔH + T [δ(ΔG)/ δT]P ------------------>(6)
The relation between emf, E and free energy change,
of a galvanic cell.
ΔG = -nFE --------------- ----------------------->(7)
Differentiation of equation(7) w.r.t. T at constant
P.
[δ (ΔG)/ δ T]P = -nF (δ E/ δT)P ----------->(8)
Substitution of (7) & (8) in 6 gives
-nFE = ΔH – nFT (δ E/ δT) P
i.e. ΔH = nFT (δ E/ δ T)P – nFE or
ΔH = nF[T(δ E/ δT)P –E] ----------------->(9)
 This gives enthalpy change in Joules of a cell
reaction of a galvanic cell in terms of its emf, E in
volts, temperature coefficient of emf, in volts K-1, no.
of electrons, n taking part in the cell reaction &
Faraday constant in coulombs.
Problem: Emf of Weston Cadmium cell is 1.0183 V at 293 K and
1.0l81 V at 298 K.
Calculate ∆G, ΔH and ΔS of the cell reaction at 298 K.

Solution:- ∆G: ∆G = - n FE
n = 2 for the cell reaction; F = 96,500 C E= 1.0181 V at 298 K
∆G = -2 x 96,500 x 1.0181 J = -196.5 KJ
• ∆H: ∆H = nF [ T (δE /δT)P – E]
• (δE/δT)p = 1.0181 – 1.0183 / 298-293 = -0.0002 / 5
• = -0.00004VK-1
• T = 298 K
• ∆H = 2 x 96,500 { 298 x (-0.00004) – 1.0181)
• = -198. 8 KJ
• ΔS: ΔS = nF (δE / δT) P
• = 2 x 96,500 x (-0.00004) = -7.72JK-1
3. The emf of the cell
Cd/ CdCl2.2.5 H2O(sat’d) // AgCl (s) / Ag
is 0.6753 V and 0.6915 V at 298 K and 273 K respectively.
Calculate ∆H , ∆S and ∆G at 298 K.
 Classification of Electrodes.

Gas electrode ( Hydrogen electrode).

Metal-metal insoluble salt (Calomel electrode).
Ion selective electrode.(Glass electrode).
 Gas electrode.

• It consists of gas bubbling over an inert metal wire or foil

immersed in a solution containing ions of the gas.
• Standard hydrogen electrode is the primary reference
electrode, whose electrode potential at all temperature is
taken as zero arbitrarily.
Construction.
Representation: Pt,H2(g)/ H+
Electrode reaction: H+ + e- 1/2 H2(g)
The electrode reaction is reversible as it can undergo either
oxidation or reduction depending on the other half cell.
If the concentration of the H+ ions is 1M, pressure of H2 is 1atm
at 298K it is called as standard hydrogen electrode (SHE).
Usage of platinised platinum electrode is caused by several
factors:
• Necessity to employ electrode with very large area.
• The greater the electrode area, the faster electrode kinetics.
• Necessity to use electrode material which can absorb
hydrogen at its interface. This factor also improves electrode
kinetics.
 Applications.

To determine electrode potential of other unknown

electrodes.
Electrode potential of Hydrogen Electrode is given as
follows:
 E=Eo -2.303 RT/nF log [H2]1/2/[H+]
= 0 -0.0591 log 1/[H+]
= -0.0591pH.
To determine the pH of a solution.

Cell Scheme: Pt,H2,H+(x)// SHE

The emf of the cell is determined.
E (cell) = E (C) – E(A)

= 0 – (- 0.0592 pH)
E (cell) = 0.0592 pH
pH = E(cell)/ 0.0592
 Limitations.

Construction and working is difficult.

Pt is susceptible for poisoning.

Can not be used in the presence of oxidizing agents.

 Metal –metal salt ion electrode.

• These electrodes consist of a metal and a sparingly

soluble salt of the same metal dipping in a solution of a
soluble salt having the same anion.
Eg: Calomel electrode.
Ag/AgCl electrode.
Construction.
Representation: Hg; Hg Cl / KCl
2 2

It can act as anode or cathode depending on the nature of the other

electrode.
As anode: 2Hg + 2Cl → Hg Cl + 2e
-
2 2
-

As Cathode: Hg Cl + 2e → 2Hg + 2 Cl

2 2
- -
E = Eo – 2.303 RT/2F log [Cl-)2

= Eo -0.0591 log [Cl-] at 298 K

Its electrode potential depends on the concentration of KCl.
Conc. of Cl- Electrode potential
0.1M 0.3335 V
1.0 M 0.2810 V
Saturated 0.2422 V
 Applications.

• Since the electrode potential is a constant it can be used

as a secondary reference electrode.
• To determine electrode potential of other unknown
electrodes.
• To determine the pH of a solution.
Pt,H2/H+(X) // KCl /Hg2Cl2,Hg
pH = [E(cell) – 0.2422]/ 0.0592
 Ion Selective Electrode.

It is sensitive to a specific ion present in an electrolyte.

The potential of this depends upon the activity of this
ion in the electrolyte.
Magnitude of potential of this electrode is an indicator
of the activity of the specific ion in the electrolyte.
*This type of electrode is called indicator electrode.
• The hydration of a pH sensitive glass membrane involves an ion-
exchange reaction between singly charged cations in the
interstices of the glass lattice and protons from the solution.
H+ + Na+ Na+ + H+
Soln. glass soln. glass
Eg = Eog – 0.0591 pH
• Glass Electrode:`
Scheme of typical pH glass electrode
1. a sensing part of electrode,
2. a bulb made from a specific glass
sometimes electrode contain small amount

of AgCl precipitate inside the glass

electrode
3 internal solution, usually 0.1M HCl for pH
electrodes
4.internal electrode, usually silver chloride
electrode or calomel electrode
5.body of electrode, made from non-
conductive glass or plastics.
6.reference electrode, usually the same type
as 4
7.junction with studied solution, usually made
from ceramics or capillary with asbestos
or quartz fiber.
 Electrode Potential of glass
electrode.
The overall potential of the glass electrode has three components:

 The boundary potential Eb,

 Internal reference electrode potential Eref.
 Asymetric potential Easy.- due to the difference in response of the
inner and outer surface of the glass bulb to changes in [H+].
Eg = Eb + Eref. + Easy.
Eb = E1 – E2
= RT/nF ln C1 – RT/nF ln C2
= L + RT/nF ln C1
Eb depends upon [H+]
Eg = Eb + EAg/AgCl + Easy.
= L + RT/nF ln C1 + EAg/AgCl + Easy.
= Eog + RT/nF ln C1
= Eog + 0.0591 log [H+]
Eg = Eog – 0.0591 pH.
• Advantages:
1. It can be used without interference in solutions
containing strong oxidants, strong reductants, proteins,
viscos fluids and gases as the glass is chemically robust.
2. It can be used for solutions having pH values 2 to 10.
With some special glass (by incorporation of Al2O3 or
B2O3) measurements can be extended to pH values up
to 12.
3. It is immune to poisoning and is simple to operate
4. The equilibrium is reached quickly & the response is
rapid
5. It can be used for very small quantities of the solutions.
Small electrodes can be used for pH measurement in one
drop of solution in a tooth cavity or in the sweat of the skin
(micro determinations using microelectrodes)
6. If recently calibrated, the glass electrode gives an accurate
response.
7. The glass electrode is much more convenient to handle than
the inconvenient hydrogen gas electrode.
Disadvantages:
The bulb of this electrode is very fragile and has to be
used with great care.

The alkaline error arises when a glass electrode is

employed to measure the pH of solutions having pH
values in the 10-12 range or greater. In the presence of
alkali ions, the glass surface becomes responsive to
both hydrogen and alkali ions. Low pH values arise as a
consequence and thus the glass pH electrode gives
erroneous results in highly alkaline solutions.
 The acid error results in highly acidic solutions
Measured pH values are high.
Dehydration of the working surface may cause erratic
electrode performance. It is crucial that the pH
electrode be sufficiently hydrated before being used.
When not in use, the electrode should be stored in an
aqueous solution because once it is dehydrated,
several hours are required to rehydrate it fully.
As the glass membrane has a very high electrical
resistance (50 to 500 mΩ), the ordinary potentiometer
cannot be used for measurement of the potential of the
glass electrode. Thus special electronic potentiometers
are used which require practically no current for their
operation.
 Standardization has to be carried out frequently
because asymmetry potential changes gradually
with time. Because of an asymmetry potential, not
all glass electrodes in a particular assembly have the
same value of EoG . For this reason, it is best to
determine EoG for each electrode before use.
The commercial verson is moderately expensive
 Limitations.

The bulb is very fragile and has to be used with great

care.
In the presence of alkali ions, the glass surface
becomes responsive to both hydrogen and alkali ions.
Measured pH values are low.
In highly acidic solutions measured pH values are high.
When not in use, the electrode should be stored in an
aqueous solution.
 Applications.

• Determination of pH:
Cell: SCE ║Test solution / GE
E cell = Eg – Ecal.
E cell = Eog – 0.0591 pH – 0.2422

pH = Eog -Ecell – Ecal. / 0.0591

 Problems

The cell SCE ΙΙ (0.1M) HCl Ι AgCl(s), Ag

gave emf of 0.24 V and 0.26 V with buffer having pH value
2.8 and unknown pH value respectively. Calculate the pH
value of unknown buffer solution. Given ESCE= 0.2422 V
Eog= 0.0592pH +Ecell + Ecal.
= 0.0592x2.8 +0.24 + 0.2422
=0.648 V
pH = Eog -Ecell – Ecal. / 0.0592
= 0.648 -0.26-0.2422/0.0592
= 2.46
 CONCENTRATION CELLS.

 Two electrodes of the same metal are in contact with

solutions of different concentrations.
Emf arises due to the difference in concentrations.
Cell Representation:
M/ Mn+[C1] ║ Mn+ [C2 ] /M
Construction.
• At anode: Zn →Zn2+(C1) + 2e-
• At cathode: Zn2+(C2) + 2e-→ Zn
• Ecell = EC-EA
= E0 + (2.303RT/ nF)logC2- [E0+(2.303RT/nF)logC1]
• Ecell = (0.0591/n) log C2/C1
Ecell is positive only if C2 > C1
Anode - electrode with lower electrolyte concentration.
Cathode – electrode with higher electrolyte
concentration.

Higher the ratio [C2/C1] higher is the emf.

Emf becomes zero when [C1] = [C2].
 Problems

• Zn/ZnSO (0.001)||ZnSO (‘x’ M)/Zn is 0.09V at 25˚C. Find

4 4

the concentration of the unknown solution.

Ecell = 0.0591/n log C2/C1
0.09 =(0.0591/2) log ( x / 0.001)
x =1.097M
2. Calculate the valency of mercurous ions
with the help of the following cell.
Hg/ Mercurous || Mercurous /Hg
nitrate (0.001N) nitrate (0.01N) when the emf
observed at 18˚ C is 0.029 V
Ecell=(2.303 RT/nF) log C2/C1
Ecell=(2.303 RT/nF) log C2/C1

0.029 = 2.303RT/n) log (0.01/0.001)

0.029 =0.057 x 1/ n
n = 0.057/0.029 =̃ 2
Valency of mercurous ions is 2, Hg2 2+
 Concentration cell with transference

Consider a concentration cell formed  by combining two hydrogen gas

(1atm) electrodes in contact with HCl solutions of different
concentrations, which are in direct contact.
 
Pt, H2(g), HCl(a1) : HCl(a2), H2(g), Pt

 At anode, ½ H2(g) → H+(a1) + e- ----- (1)

 At cathode, H+(a2) + e- → ½ H2(g) ----- (2)

Thus H+ ions are generated at the left hand electrode and
consumed at the right hand electrode as the current flows. Since
the solutions are in direct contact with each other, the ions are
free to move from one solution to the other when current flows
through the cell. Since anions move in the direction opposite to
that in which cations move, Cl- ions migrate from right to left.
Let t be the transport number of Cl ion and
-
- t+ (=1-
t-) that of H+ ion in HCl. Then for 1F of electricity passing
through, t- F will be carried by Cl- ions and t+ F by H+ ions.
According to Faraday’s second law, t- equivalent of Cl-
ions will be transferred from the solution of activity a2 to
the solution of activity a1. This may be represented as

 t- Cl- (a-)2 → t- Cl- (a-)1 (3)

  t+ equivalent of H+ ions will be transferred from the

solution of activity a1 to that of a2 which is represented
as
  t+ H+ (a+)1→ t+ H+ (a+)2 (4)
 
The net result for flow of 1F electricity is
At anode:
Gain of 1 gram equivalent of H+ ions in anodic
reaction (1) = Loss of t+ gram equivalent of H+ ions (4)
Therefore, net gain of H+ ions = (1-t+) gram
equivalent =t- gram equivalent
 At the same time,
Net gain of Cl- ions = t- gram equivalent (3)
At cathode:
Loss of 1 gram equivalent of H+ ions in cathodic
reaction (2) = gain of t+ gram equivalent of H+ ions (4)
Therefore, net loss of H + ions = (1-t+) gram equivalent =t- gram
equivalent
At the same time,
Net loss of Cl- ions = t- gram equivalent (3)
 Thus for every 1F of electricity, there is net transfer of t gram
-
equivalent of H+ ions and t- gram equivalent of Cl- ions from the
solution in which activity of HCl is a2 to that in which activity of HCl is
a1.

 These changes are represented as

t- H+ (a+)2 → t- H+ (a+)1
t- Cl- (a-)2 → t- Cl- (a-)1
 The EMF of concentration cell with transport is
 E = t- RT ln (a+)2 + t- RT ln (a-)2
F (a+)1 F (a-)1
If (a )
± 1and (a±)2 are the mean ionic activities of the two
hydrochloric acid solutions, it follows that
 (a±)12 = (a+)1(a-)1 and (a±)22 = (a+)2(a-)2
 Therefore,

E = = t- RT ln (a±)22 = 2 t- RT ln (a±)2
F (a±)12 F (a±)1
 Knowing that activity of a univalent electrolyte, a, is
a = (a±)2

 E = t RT ln a
- 2

F a1
Where a2 and a1 are activities of HCl at the cathode and
anode respectively.
 Conclusion

Concentration cell without transference : For the flow of one

faraday of electricity, the overal reaction is the transfer of 1
mole of HCl from a solution of activity a2 to activity a1.
Concentration cell with transference : For the flow of one
faraday of electricity, there is a net transfer of t- gram
equivalent of H+ ions and t- gram equivalent of Cl- ions from
right to left i.e from the solution in which activity of HCl is a2
to that in which activity a1.
 Liquid Junction Potential

The equation derived for the emf of a concentration cell

with transference includes the potential at the junction of
the two solutions are indirect contact with each other does
not include the liquid junction potential. These equations
may be reproduced as
• Ew.t = 2 t- RT ln (a±)2
F (a±)1
•E w.o.t = t- RT ln (a±)2
F (a±)1
Hence, liquid junction potential El is given by
• E= E
l w.t –Ew.o.t = (2t—1) RT ln (a±)2
F (a±)1

• E = (t -t
l - + ) RT ln (a±)2
F (a±)1
 Problems
1. Calculate the liquid junction potential at 25 ◦ C between two
solutions of HCl having mean ionic activities of 0.01 and
0.001, respectively.The transport number of H+ (t+) ion in
HCl may be taken as 0.83

Solution: t + = 0.83 so that t- = 1-t+= 0.17

(a±)1 = 0.01 ; (a± )2 = 0.001
El = (t- -t +) RT ln (a±)2
F (a±)1
= (0.17 -0.83) 0.0591 log (0.001/0.01) = 0.039 volt
2. Calculate the liquid junction potential associated with
the following cell at 25◦C:
Ag(s), AgCl(s), HCl (m1= 1.0 ; √1= 0.809 : HCl (m2= 0.05 ; √2=
0.830, Ag Cl(s), Ag (s) if the transport number of H+ is 0.83.

Solution: t + = 0.83 so that t- = 1-t+= 0.17

E = (t -t
l - ) RT ln (a±)2 = (t- -t +) RT ln (√2 m2/ √2 m2)
+

F (a±)1 F
= (0.17-0.83)x 0.0591 log (0.83 x 0.05/0.809x1.0)
= 0.05 volt