ELECTRO CHEMISTRY.

References:

1.Physical Chemistry by P. Atkins, J.D. Paula

2.Engg.Chemistry by Jain and Jain
3.Principles of Physical Chemistry by Puri and Sharma
4.Engg. Chemistry ( Vol I & II) by J.C. Kuriacose and J Rajaram

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. Eg.: Daniel cell.

Daniel Cell.

Representation of galvanic cell.

Anode Representation:

ZnZn2+ 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

ELECTROLYTIC CELL
An electrolytic cell is an electro chemical cell in which
a non- spontaneous reaction is driven by an external
source of current.

LIQUID JUNCTION POTENTIAL

Potential difference across the interface of

the two electrolytes.

Ej = soln, R - soln,L
The junction potential contributes to the

cell emf.
Generally, junction potentials are of the

order of magnitude 10 to 30 mV.

Salt Bridge.
The liquid junction potential can be reduced (to about 1 to 2
mV) by joining the electrolyte compartments through a salt
bridge.

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 of a galvanic cell can not be measured accurately using a

voltmeter

Ex AD
Es AD1
Ex AD
Es AD1
Ex = AD x Es
AD1

Weston Cadmium Cell

Sealed wax

Cork
CdSO4.8/3H2O
crystals

Cd-Hg
12-14%
Cd

Soturated solution of
CdSO4.8/3H2O

Paste of Hg2SO4
Mercury, Hg

Capable of giving constant and reproducible

emf.
Negligible temperature coefficient of the emf.
Cd (s) Cd2+ + 2e- (At negative electrode)
Hg2SO4(s) + 2e- 2 Hg (l) + SO42-(aq) (At positive
electrode)

Energetics of Cell Reactions.

G = -nFE ( in k cal)

H = nF[T( E/ T)P E]

S = nF (E/ T)P

Single electrode potential.

Electric layer on the metal has a potential
(M).
Electric layer on the solution has a potential
(aq)
Electric potential difference between the
electric double layer existing across the
electrode /electrolyte interface of a single
electrode or half cell.

De-electronation

Electronation

Helmholtz double layer

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.

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)

At 298K,
E= Eo-0.0592/n log 1/[Mn+]

Classification of Electrodes.
Gas electrode ( Hydrogen electrode)
Metal-metal insoluble salt (Calomel electrode).
Ion selective electrode.(Glass electrode).

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.
The crystal structure of
calomel(Hg2Cl2), which has limited
solubility in water (Ksp = 1.8 1018).

 Representation: Hg; Hg2Cl2 / KCl

IAs anode: 2Hg + 2Cl- Hg2Cl2 + 2e As Cathode: Hg2Cl2 + 2e- 2Hg + 2 Cl-

E= 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.

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.

Composition of glass
membranes
70% SiO2
30% CaO, BaO, Li2O, Na2O,
and/or Al2O3

The overall potential of the glass electrode has three components:

The boundary potential Eb
Internal reference electrode potential Eref.
Asymetric potential Easy.

Eg = Eb + Eref. + Easy.
Glass electrode is mainly used in the determination of pH of a
solution.

Applications.
Determination of pH:

Cell: SCE Test solution / GE

E cell = Eg Ecal.
E cell = Eog 0.0592 pH 0.2422
pH = Eog -Ecell Ecal. / 0.0592

Problems
The cell SCE (0.1M) HCl 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

POTENTIOMETRIC TITRATION
Titrations carried out using potentiometric indicators are

normally referred to as potentiometric titrations.

involves the measurement of electrode potentials between

indicator electrode and reference electrode, with the addition of

titrant.
The electrode reaction is,
Mn+ + ne------>M
As the concentration of Mn+ changes, the EMF of the cell also
changes correspondingly.
Types of potentiometric titrations:
1) Acid-base titrations.
2) Redox titrations.
3)Precipitation titrations.

1) Acid-base titrations. These titrations are based on the

neutralization reaction that occurs between an acid and a base,
when mixed in solution.
Common indicators, their colours, and the pH range in which they
change colour,
When more precise results are required, or when the titration
constituents are a weak acid and a weak base, a pH meter or a
conductance meter are used.

Measurement of Potential
To measure a potential we need to create a voltaic cell containing
two electrodes, one of which is the indicator electrode and one
of which is the reference electrode. We measure the voltage
of the cell which is giving a reading of the potential of the
indicator electrode relative to the reference electrode. This
potential can be related to the analyte activity or
concentration via the Nernst equation.

basic
potentiometric cell

General Principles
Reference electrode | salt bridge | analyte solution | indicator electrode
Eref Ej Eind

Ecell = Eind Eref + Ej

Reference cell :(fixed potential)

a half cell having a known electrode potential
Indicator electrode:
has a potential that varies in a known way
with variations in the concentration of an analyte

Determination of pH:

Cell: SCE Test solution / GE

E cell = Eg Ecal.
E cell = Eog 0.0592 pH 0.2422
pH = Eog -Ecell Ecal. / 0.0592

Procedure
.The combined electrode is standardised by dipping in the buffer
solution of known pH.
.The emf of the cell containing the initial solution is determined.
.Relatively large amounts of the titrant solution are added until
the equivalence point is approached.
.The emf is determined after each addition.
.The approach of the end point is indicated by a somewhat more
rapid exchange of emf.
Then
fresh
and
.Thus again
the pilot
runsolution
is madeistotaken
locate
theinend point.
the vicinity of the end point, equal
increments (0.1or 0.05ml) of titrant is
added to locate where exactly the
equivalence point lies.

Graph of voltage against volume added can be drawn and the end
point of the reaction is half way between the jump in voltage.
Equivalent point or End point

Volume of NaOH,mL

The equivalence
point is the point
on the curve with
the
maximum
slope
Titration

curve

Volume of NaOH,mL

The maximum
point is the
equivalence point

Derivative of
Titration Curve

For example;
CH3COOH + NaOH- CH3COO- + Na+ + H2O

Background
Consider the following graph:

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Background
Consider the following graph:

In this region H+ dominates, the small change in pH is the

result of relatively small changes in H+ concentration.
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Background
Consider the following graph:

In this region, relatively small changes in H+ concentration

cause large changes in pH, The midpoint of the vertical
region is the equivalence point.
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Background
Consider the following graph:

In this region OH- dominates, the small change in pH is the

result of relatively small changes in OH- concentration.
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Advantages

1.The apparatus required is generally inexpensive,

reliable and readily available.
2. It is easy to interpret titration curves
3. The method can be used for colored solutions.
4. The method is applicable for analysis of dilute
solutions
5. Several components can be titrated in the same
solution without the possibility of indicators interfering

CONDUCTOMETRIC TITRATION
Conductance measurements are frequently employed to find the
end points of acid-alkali and other titrations.
The principle involved is that electrical conductance depends
upon the number and mobility of ions.

Conductance of electrolyte is directly propotional to:

1.Mobility of ions
2.No. of ions present in unit volume.
Conductance of the titrating solution varies due to two reasons,
namely:
1.Dilution
2.Replacement of molecular species by ionic species or one ionic
species by another

The concentration of the titrant must be 10 times as the solution being titrated. This is done to keep
the volume changes small.

Consider the titration of a strong acid(HCl) with a strong

base(NaOH).
The acid is taken in the conductivity vessel &
the alkali in the burette.
The concentration of the titrant must be 10 times as the
solution being titrated. This is done to keep the volume
changes small.
The conductance of hydrochloric acid is due to the presence of
hydrogen and chloride ions. As alkali is added gradually, the
hydrogen ions are replaced by slow moving sodium ions, as
represented below:
H+ (aq) + Cl- (aq) + Na+ (aq) + OH- (aq) Cl- (aq) + Na+ (aq) + H2O(l)
(unionised)

Hence, on continued addition of sodium hydroxide, the

conductance will go on decreasing until the acid has been
completely neutralized. The solution at neutralization ie. at end
point containing only sodium and chloride ions., will have
minimum conductivity.
Any subsequent addition of alkali will result in introducing fast
moving hydroxyl ions. The conductance , therefore , after
reaching a certain minimum value, will begin to increase.Thus a
V-shaped graph is produced.

Strong acid x Strong base HCl

Vs NaOH

Strong acid x Weak base ( HCl x NH4OH)

When NH4OH is added to HCl, the conductivity decreases
because of replacement of highly conducting H+ ions by less
conducting NH4+ ions. After the equivalence point is reached,
the conductance remains almost constant, since the excess of
NH4OH added, does not ionize in presence of NH4Cl. (Common
ion effect)
H+ + Cl- + NH4+ + OH- NH4Cl + H2O

Vol. of NH4OH

When weak acid(CH3COOH ) is titrated with NaOH, the

conductivity decreases initially. (the anion formed suppresses the
ionization of the weak acid, This is because the conversion of the non conducting
weak acid into its conducting salt. The 2 opposing effects act here- decrease due to
common ion effect and increase due to formation of conducting salt.) . the

conductance increases with the further addition of NaOH due to

the formation of Na+ & CH3COO- .
CH3COO- + H+ + Na+ + OH- CH3COO- + Na+ + H2O
When the neutralization of acid is complete, further addition of
NaOH produces excess of OH- & the conductance of the solution
increases more rapidly.
Weak acid X Strong base
(CH3COOH x NaOH)

Weak acid x Weak base (CH3COOH x NH4OH)

The conductance decreases initially and then increase, the reason
being the same as in the previous titration. After the end point an
excess of NH4OH solution has little effect on the conductance as
its dissociation is suppressed by ammonium salt in the solution.

ADVANTAGES

1.They can be used in the case of colored liquids where ordinary

indicators cannot work
2.They can be used for the analysis of dilute solutions and also
for v. weak acids.
3.It is not necessary to measure the actual conductance value
because we can use any quantity that is proportional to it. Eg.
The reading on a Wheatstone bridge. This can be directly
plotted against the volume of the titrant.

DISADVANTAGES
1.It becomes less accurate and less satisfactory with increasing
total electrolytic concentration. Actually, the change in
conductance due to addition of titrant can become largely
masked by high salt concentrations in the solution being
titrated; under these circumstances, the method cannot be
used.
2.Although the method is potentially adaptable to all types of
volumetric reactions, the number of useful applications to redox
systems is limited. The reason for this is that the substantial
excess of hydronium ion typically needed for such reactions
tend to mask conductivity changes associated with volumetric
reaction.

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+/M[C2]

Construction.

At anode: Zn Zn2+(C1) + 2eAt cathode: Zn2+(C2) + 2e- Zn

Ecell = EC-EA

= E0 + (2.303RT/ nF)logC2[E0+(2.303RT/nF)logC1]
Ecell = (0.0592/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].

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, H2(g) H+(a1) + e- (1)
At cathode, H+(a2) + e- H2(g) (2)

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.

Transport number: The fraction of the total

current carried by each ion is called its
transport number.
Transport number of the cation,t+=Current carried by the
cation/Total current=u+u+ + u-

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 Clions and t+ F by H+ ions.
According to Faradays 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 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 cathode,
Net gain of Cl- ions = t- gram equivalent (3)
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

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)1 and (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
F (a)12

Problems
Zn/ZnSO4(0.001M)||ZnSO4(x)/Zn is 0.09V

at 25C. Find the concentration of the

unknown solution.

Ecell = 0.0592/n log C2/C1

0.09 =(0.0592/2) 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+

Hiii
Why don't you hear more about negative pH?
It's possible. If the molarity of hydrogen ions is greater than 1,
you'll have a negative value of pH.
For example, you might expect a 12 M HCl solution to have a pH
of -log(12) = -1.08.
Even strong acids don't dissociate completely at high
concentrations. Some of the hydrogen remains bound to the
chlorine, making the pH higher than you'd expect from the acid
molarity. Because there are so few waters per acid formula unit,
the influence of hydrogen ions in the solution is enhanced.
We say that the effective concentration of hydrogen ions (or the
activity) is much higher than the actual concentration. The usual
general chemistry text definition of pH as -log [H+] (negative the
logarithm of the hydrogen ion molarity) is better written as pH = +

Extra slide: Not necessary

The Second
Derivative of
Titration Curve

0 crossing is the
equivalence point