Type of electrodes:

The potential of an electrode changes with change in the activity of

the electrolyte.
Potentiometric method
Direct Potentiometric method
Potentiomtric titrations
A Calibration Curve by varyichange in EMF of an electrolytic
ing the conc. of an active species cell measured through the addition
may be derived and from
of a titrant
that curve an unknown conc.
E=Eo 0.0591\n log [Red]\[ox]
of the active sp. is deterimned.
Ex. Agno3 vs Nacl titration
ph meter is a potentiometer in A species of interest is titrated
which potential is measured
against a suitable titrant and
in terms of ph.
equivalence point is obtained.

Equipment required for potentiometric measurements:1. Reference electrode

2. Indicator electrode
3. Potential measuring device
Indicator Electrode:-

two types

1. Metal Indicator Electrode

2. Membrane Electrode
(i) Metal Indicator Electrode of Ist Kind for cations:Electrode of this type are reversible with respect to the ions of the
metal phase. It consists of a metal in contact with a solution of its
own ion.

Examples:
Zinc rod in ZnSo4 solution
Cu rod in CuSo4 solution
Ag rod in AgNo3 solution
(ii) Metal Indicator Electrodes of IInd type for anions
These electrodes consists of a metal coated with a
layer of its spraingly soluble salt dipped in a solution
of a soluble salt having same anion.
Example:silver-silverchloride eletrode, calomel electrode
Silver silverchloride electrode:- It is consists of a silver
wire coated with a layer of silver chloride inserted in
a solution of KCl of HCl of known concentration.

At the Ag/AgCl solution inter face the electrochemical

equilibrium is
AgCl(s) + e
Ago +ClIn addition there is chemical equilibrium---AgCl(s)
Ag+ + ClSchematic representation of electrode:Ag, AgCl(s) ; KCl (aq)
The electrode is reversible with respect to Cl- ion.
Calemal Electrode :- It consists of mercury, solid mercurous
chloride and a solution of KCl.
Schematic representation:Hg, Hg2Cl2(s); KCl (solution)

If electrode reaction is reduction, Hg++ ions given by sparingly

soluble Hg2Cl2 get dischanged at electrode. So more Hg2Cl2 would
pass into solution and the conc. of Cl- ion increases.
Hg++(aq)+2eHg2Cl2 (s)

2Hg(l)
Hg2++ (aq) + 2Cl (aq)

If electrode reaction is oxidation, then it liberate electrons and

send Hg++ ions in solution. The Hg++ ions combine with Cl- ions
(furnished by KCl) forming sparingly soluble Hg2Cl2. So conc. Of
Cl- ions decreases in solution.
2Hg(l)

Hg2 ++ (aq)+ 2e-

Hg2++ (aq) + 2Cl- (aq)

Hg2Cl2(s)

Electrode reaction is--Hg2Cl2(s)+2e2Hg (l)+2Cl- (aq)

So electrode is reversible with respect to Cl- ion
Electrode of this kind can be used for direct determination of the
activity of either the metal ions the anion in the coating, also used
as indicator electrode to follow titration involving either.

Thind type:- This type of electrode consists of a metal, one of its

insoluble salts, another insoluble salt of another metal having
same anion and solution of any soluble salt of the latter having
same cation
Pb PbC2O4(S) CaC2O4(S) CaCl2(aq)
Lead Ist Dissolves to form Pb++ ions with the liberation of 2
electrons. The lead ions then Combine with C2O4-- ions to form
insoluble lead oxalate
Pb
Pb++ + 2ePb++ + C2O4- PbC2O4 (s)
The removal of C2O4-- ions from solution results in dissolving of
Calcium oxalate which ionises to maintain the equilibrium
CaC2O4(s)
Ca++ + C2O4-Pb + CaC2O4
PbC2O4+ Ca++ + 2eThe system behaves as an electrode reversible with respect to
Ca++ ions.

Metal Indicator Electrode of third kind---Pb PbC2O4 CaC2O4 CaCl2

Pb
Pb+++ 2ePb++ + C2O4-PbC2O4
CaC2O4
Ca2+ + C2O4-Pb +CaC2O4

Pb C2O4 + Ca2+ + 2e-

Metal Indicator Electrode of third kind---Pb PbC2O4 CaC2O4 CaCl2

Pb
Pb+++ 2ePb++ + C2O4-PbC2O4
CaC2O4
Ca2+ + C2O4-Pb +CaC2O4

Pb C2O4 + Ca2+ + 2e-

Electrode of the 4th kind or oxidation Reduction electrode

(Inert electrode): The term oxidation-reduction electrode is used for those
electrodes in which the potential is developed due to the
presence of ions of same substance in two different oxidation
states.
It is set up by inserting an unattackable metal (Platinum or
gold) in an appropriate solution.
When platinum wire is inserted in a solution containing Fe++
and Fe+++ ions or Sn++ and Sn++++ ions or Ce+++ and Ce++++ ions,
the wire acquires potential. The potential at electrode arises
due to tendency of ions in one oxidation state to change in to
more stable oxidation state.
Electrode reactions--Fe+++ (aq) + eFe++ (aq)
Sn++++(aq) + 2eSn++ (aq)
Ce++++ (aq) +eCe+++ (aq)

 The function of Pt wire is to pick up the electrons and to

provide electrical Contact to the electrode.
Quinhydrone electrode Oxidation reduction electrode
It consists of a platinum wire placed in a solution containing
hydroquinone (QH2) and quinone(Q) in equimolar amounts.
Electrode reaction--O=
=O + 2e- + 2H+
HO= O =OH
quinone
Hydroquinone
Scematic representation of electrode ----Pt, Q, QH2; H+ (aq)
It is reversible with respect to H+ ions.

CONCENTRATION CELLS

In galvanic cells electrical energy arises from chemical

reactions
In concentration cells EMF arises not due to any chemical
reaction but due to transfer of matter from one half cell to
other because of the difference in concentration of the species
involved.
Concentration cell one of two types Electrode Concentration cells
Electrolyte concentration cells
Electrode Concentration cells - In these cells, two like
electrode at different concentrations are dipped in the same
solution.
ex. Two hydrogen electrodes at unequal gas pressures
immersed in the same solution of H+ ions constitute an
electrode-concentration cell.

Schematic Representation
Pt; H2(P1) Solution of H+ ions, (ex. HCl)
Reactions:-

R.H.E :

2H+ + 2e-

L.H.E:

H2 (P1)

Overall:

H2 (P1)

H2 (P2); pt

H2 (P2)
2H+ + 2e-

H2(P2)

Reaction is independent of the conc. of electrolyte. At moderate

pressures H2 considered as ideal gas.
So Ratio of activities = Ratio of gas pressures.
So nernst equation -E=Eo 0.591/2 log (P2/P1) at 25oC
By definition Eo=0
E= - 0.02955 log P2/P1 = 0.02955 log P1/P2

2ndexample- An amalgam with two different concentrations of

the same metal.
Hg- Pb(C1), PbSO4 (soln.), Hg-Pb(C2)
Electrode Reactions:
R.H.E.

Pb++ + 2e-

Pb(C2)

L.H.E.

Pb(C1)

Pb++ + 2e-

Overall

Pb(C1)

Pb(C2)

EMF of the Cell

E = ER EL

E = (E0Pb- 0.0591/2 log C2) (E0Pb - 0.0591/2 log C1)

= 0.0591/2 log C1/C2 = 0.02955 log C1/C2
If C2< C1, EMF is positive , process spontaneous i.e. lead will
go spontaneously from high conc. to low conc. amalgam.

Electrolyte Concentration cells- In these cells two electrodes of the

same metal are dipped in the solutions of metal ions of different
concentrations and hence of different activities.
Zn, Zn++ (a+)1

Zn++ (a+)2, Zn

Both electrodes of zinc metal are in contact with solution of Zn++

ions, but the conc. and activities of ions are different.
Activities of zinc ions in two electrolytes (a+)1 and (a+)2
The two electrolytes (ZnSO4) Solutions separated from salt
bridge
Reactions
R.H.E. :
Zn++ (a+)2 + 2eZn(s)
Reduction
L.H.E. :
Zn (s)
Zn++ (a+)1 + 2eOxidation
Overall:
Zn++ (a+)2
Zn++ (a+)1
The net process involves transfer of 1 mole of Zn++ ions from the

Acc. to Nernst equation - Reduction potentials of RHE & LHE

ER = Eoel RT/nF ln 1/(a+)2 = Eoel + RT/nF ln (a+)2

---(1)

EL= Eoel RT/nF ln 1/(a+)1 = Eoel + RT/nF ln (a+)1

---(2)

ECell = ER EL = RT/nF ln (a+)2/(a+)1

----(3)

For the process to be feasible, EMF should be +ve. Hence

(a+)2 > (a+)1
a = ym
E Cell = RT/2F ln y2m2/y1m1

y1 & y2 - activity coefficients of the electrolytes

Other example of conc. Cell--Pt, H2(g), H+(a+)1 ll H+(a+)2, H2(g),Pt

1atm
1atm
Both Hydrogen electrodes are in contact with H+ ions of
different activities. The two solutions of HCl are separated
by a salt bridge.
Reactions-R.H.E. : H+ (a+)2 + e H2 (g)
Reduction
L.H.E. : H2(g)
H+(a+)1 + eOxidation
Overall: H+ (a+)2
H+(a+)1
ECell = ER EL
= [Eoel RT/F ln 1/(a+)2] [Eoel RT/F ln 1/(a+)1]
= RT/F ln (a+)2/(a+)1
For E to be +ve (a+)2 Should be greater than (a+)1

Types of Electrolyte concentration Cells--Electrolyte conc. Cells in which solutions of the same electrolyte
of different conc. are used are of two types
1. Concentration cells without transference
The two electrolytic solutions are not in direct contact with
each other. So transference of ions does not take place
directly.
solutions ore separated by salt bridge.
2. Conc. Cell with transference.
The two solutions are in direct contact.
Transference of ions take place directly.

Concentration Cells Without Transference.

Concentration cells already discussed( Zn and H) separated by
salt bridge are concentration cells without transference.
But some other means can also be used to keep the solutions apart
and bringing the transference of ions indirectly.
Ex. Pt, H2 (g), HCl (a1) AgCl(s), Ag
1atm
Suppose : activity of H+ ions ---- (a+)1
activity of Cl- ions ----(a-)1
R.H.E. --- Reduction half Cell reaction
AgCl (s ) + eCl- (a-)1 + Ag (s)----------- (1)
L.H.E.--- Oxidation Half Cell reaction
H2(g)
H+ (a+)1 + e-------------- (2)

Net reaction (1) + (2)

H2(g) + AgCl (s)

H+ (a+)1 + Cl- (a-)1 + Ag (s ) -----(3)

Same cell with activity of HCl solution a2--Pt, H2(g), HCl (a2) AgCl (s), Ag
1atm
Net Cell reaction
H2 (g) + AgCl (s)

H+(a+)2 + Cl- (a-)2 + Ag (s) -----(4)

Now the two cells are connected in such a way that they send
current in opposite derection
Pt, H2(g),HCl (a1), AgCl (s), Ag Ag, AgCl (s), HCl (a2), H2(g),pt.
1atm
1atm

for the passage of 1 faraday of electricity, overall reaction of

combined Cell ------ 4 - 3
H+ (a+)2 + Cl- (a-)2
H+(a+)1+ Cl- (a-)1
So, for the passage of 1 faraday of electricity, the overall reaction
is the transfer of 1 mole of H+ and Cl- ions or 1 mole of HCl from
the solution of activity a2 to that of activity a1
EMF of Cell
Ew.o.t. = RT/F ln (a+)2/(a+)1 + RT/F ln (a-)2/(a-)1
= RT/F ln (a+)22/(a+)21
= 2RT/F ln (a+)2/(a+)1
(a+ )1 & (a+ )2 -- Mean ionic activities of the electrolyte in 2 solutions
Ew.o.t. = (RT/F) ln (a2/a1)
a1 & a2 activities of HCl in two solutions
Transfer of electrolyte from one to another solution takes place

If middle electrode Ag, AgCl(s) is withdrawn then two solutions

of HCl will be in direct contact and cell becomes conc. Cell
with transference.
So conc. cell with transference in which the electrodes one
reversible with respect to cations (H+ ions) can be converted in
conc. Cell without transference by interposing another
electrode which is reversible with respect to anions (Cl- ions in
this case).
Another Example--(1)Zn, ZnSO4(a1), PbSO4(s), Pb,PbSO4(s), ZnSO4(a2),Zn
Electrodes are reversible with respect to cation.
(2) Ag, AgCl(s), HCl(a1), H2(g), HCl(a2), AgCl(s), Ag
The end electrodes are reversible with respect to Cl-ions while
the intermediate electrode is reversible with respect to H+ions.

Concentration Cell with Transference.----Concentration cell formed by combining two hydrogen gas
electrodes in contact with HCl solutions of different
concentrations. The two solutions are in direct contact with
each other :
Pt, H2(g), HCl(a1) : HCl(a2), H2(g), Pt
1atm
H+ :
1atm
ClThe reaction on the left involves oxidation and that on the
right involves reduction.
The following changes are involved for the flow of one faraday
of electricity:
Left hand electrode :

1/2H2(g)

Right hand electrode : H+ (a+)2 + e-

H+(a+)1 + e- -------(1)
1/2H2(g) --------(2)

H+ ions are generated at LHE and consumed at RHE as the

current follows.
Solutions are in direct contact with each other, ions are free to
move from one solution to another when current flows through
the cell.
H+ ions move from the solution on left hand side to that on the
right hand side.
Since anions move in direction opposite to that of cations move,
Cl- ions migrate from right to left.
Pt, H2(g), HCl(a1) : HCl(a2), H2(g), Pt
1atm
:
1atm
H+
Cl-

 If t- is the transport number of Cl- ion and t+ (= 1- t-) for H+

ion in HCl

For one faraday of electricity passing through, t

faraday will be carried by Cl- ions and t+ faraday by H+ ions.

According to Faradays second law, t- equivalent of Cl- ions

will be transferred from the solution of activity a 2 to the

solution of activity a1.

t- Cl- (a-)2

t- Cl- (a-)1

-------------- (3)

At the same time, t+ equivalent of H+ will be transferred from

the solution of activity a1 to that of activity a2
t+ H+ (a+)1

t+ H+ (a+)2 -------------- (4)

The net result for the flow of one faraday of electricity is Left hand electrode
Gain of 1 gram equivalent of H+ ions by process (1)
1/2H2(g)

H+(a+)1 + e-

Loss of t+ gram equivalent of H+ ions by process (4)

t- H+ (a+)1
t- H+ (a+)2
Therefore, Net gain of H+ ions = (1 - t+) gram equivalent
= t- gram equivalent
At the same time,
Net gain of Cl- ions = t- grams equivalent by process (3)

Right hand electrode

Loss of 1 gram equivalent of H+ ions by process (2)
Gain of t+ gram equivalent of H+ ions by process (4)
Therefore, Net loss of H+ ions = (1 - t+) gram equivalent
= t- gram equivalent
At the same time,
Net gain of Cl- ions = t- grams equivalent by process (3)
Thus, for every one faraday of electricity ,
there is net transfer of t- gm equivalent of H+ ions and t- gm
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 of HCl is a1.

t- H+ (a+)2
t- Cl- (a-)2

t- H+ (a+)1
t- Cl- (a-)1

The EMF of concentration cell with transference--Ew.t.= t- RT/F ln (a+)2/(a+)1 + t- RT/F ln (a-)2/(a-)1 -------(5)
(a+)1 and (a+)2 --- mean ionic activities of 2 HCl solutions.
(a +)12 = (a+)1 (a-)1 and (a+)22 = (a+)2 (a-)2
So eq. (5) may be written as
Ew.t. = t- RT/F ln (a+)22/(a+)12

---------------------(6)

Activity of uni-univalent electrolyte is given by------a = (a+)2

Ew.t. = t- RT/F ln a2/a1

Reference Electrodes ----- The electrodes of standard potential

with which we can compare the potentials of an other electrode, is
called a reference electrode.
Ex.(1). SHE--- whose electrode pot at all temp. is taken as zero.
(2) Calomel electrode Mercury-mercurous chloride electrode.
The potential of the calomel electrode on the Hydrogen scale has
been found to very with the conc. Of the KCl solution.
The reduction potentials for the various KCl concentration at 25 oC
are

KCl conc.

0.1N(

1N(none)

Saturated

EP in volt.

0.3335

0.2810

0.2422

Electrode Reaction Hg Cl2(s) + 2eHg(l) + 2Cl-(Oa)

The pot of this electrode (due to reduction of Mercurous ion to
mercury) is eanal to end of cell.
Pt H2(atm) H+(1m) KCl (o.1N
)
Hg2 Cl2 Hg

Liquid Junction Potential

When two salt solutions of different concentration are placed
in contact with one another,the ions from the concentrated
solution will tend to diffuse in to dilute one.
The rate of diffusion of each ion is approximately proportional
to the speed of the ion in electric field.
Suppose positive ion moves with a greater speed than the
negative ion. It means that the positive ion from the conc.
solution will diffuse ahead of the ve ion in the dilute solution.
Thus dilute solution becomes positively changed with respect to

Suppose the negative ion moves faster. It means that negative

ion will diffuse rapidly in dilute solution than the positive ion
and the dilute solution gets a negative change.

In both cases, an electrical double layer is set up at the

junction of the two solutions and thus a potential difference is
setup at this junction.

This potential difference developed at the junction of two

solutions of different concentration is termed as liquid liquid
junction potential (LJP).

(1) If two liquid one moving with the same speed, there will not
be any liquid liquid junction potential.
(2) The liquid-liquid junction potential is due to the different
migration velocities of the two ions.
(3) Magnitude of liquid-liquid junction potential depends on the
relative speed of the ions.