Electrochemistry

Session

Electrochemistry - 1
INTRODUCTION:

Electro chemistry is the branch of chemistry which deals

with transformation of electrical energy into chemical
energy vice versa.
• Electrochemistry serves as an interface between chemistry and everyday life.
When we switch on calculator, a computer, a radio,start a car, use mobile
phone , use a digital watch, and so on we are depending upon the
electrochemical reactions occurring in the cells or batteries.
A number of Electro chemical industries have been established on the concept
of electrochemistry:
• Electro refining(Cu), Electro plating(Ni, Cr, Au,Ag) ,Fused electrolysis(Al,
Mg,Na), Electro thermal(CaC2,Graphite,SiC) , Electrolytic furnacing (Alloy
steels) , Chemical to electrical Conversion (batteries, fuel cells), Gas phase
electric discharge(O3)
In addition to the above industries, the chemical Engineer uses Electro
chemical principle in dealing with corrosion phenomena.
 Electric power conversion in
electrochemistry
Electrolysis / Power consumption

Electric Chemical
Power Reactions

Electrochemical battery / Power generation

Types of Electrolytes(Strong and
Weak)

Strong electrolytes are highly ionized in solution.

Examples : HCl, H2SO4, NaOH, KOH etc

Weak electrolytes are only feebly ionized in solution.

Examples : H2CO3, CH3COOH, NH4OH etc
Conductors:
 The substances which allow the passage
of electric current are called as
conductors.
 These are of two types:
1) Metallic conductors/ Electronic
Conductors
2) Electrolytic conductors/ Electrolytes
1.Metalic conductors(Electronic
conductors):
 The substances which conduct electricity under the influence of an
applied electric potential and that the electricity is carried
extensively by the electrons.
 The flow of electricity does not cause any physical or chemical
change in the metallic conductors.
 As the temperature increases in a metal the kinetic energy of the
electrons increases that is the electrons move around a lot more ,
which results in many collisions between electrons since they colloid
with each other a lot when the temperature is high it is harder for the
electrons to move through the metal and hence the metallic
conduction decreases.
 Metallic conduction is not restricted to pure metals ,for it is a
property possessed by most alloys , graphite , certain solid salts
and oxides.
 2.Electrolytic conductors:
 Free ions are responsible for electrolytic conductors .
 Electrolytic solutions and molten salts conduct electricity

through the migration of ions.

 When the current is passed through an electrolytic solution changes

occur in the composition of the electrolyte.

 With increasing of temperature resistance decreases and

conductance increases.
 Increase in the temp reduces the resistance by reducing the
extent of solvation of ions inter ionic forces , and viscosity of the
medium. The ultimate result is that the conductance ,specific or molar ,
equivalent conductance increase with increase in temperature.
 Resistance:
Property of hindering the flow of electricity is called
resistance. Longer the wire greater the electrical resistance
than shorter one.

For a conductor of uniform cross section(a)

and length(l); Resistance R,

l l
R l and R  R  
a a
a
Unit of resistant is Ohm.
Where  is resistivity or l
specific resistance and its unit is rho.
Conductance
The reciprocal of the resistance is called conductance. It is
denoted by C.

C=1/R

Conductors allow electric current to pass through them.

Unit of conductance is ohm-1 or mho or Siemen(S)

 Specific Conductnce:
It is the reciprocal of specific resistance
of an electrolyte.
1
Specific conductance 

a
But ρ = R


K 
a.R
 
K    x Conductance
a
l/a is known as cell constant

Cell constant: for given cell with fixed electrodes (l/a)is a constant
called the cell constant.
Unit of specific conductance is ohm–1cm–1
SI Unit of specific conductance is Sm–1 where S is Siemen
Equivalent conductance : Equivalent conductance is defined
as the conductance of all the ions produced by one gram
equivalent of an electrolyte in a given solution of volume V.
 /\ eq =v x specific conductance of 1cm3 solution (k)

/\ eq= KV = K × 1000/N

         Where N = normality

                The unit of equivalent conductance is ohm-1 cm2 equi-1.
Molar conductance
The molar conductance is defined as the conductance of
all the ions produced by ionization of 1 g mole of an
electrolyte when present in V mL of solution. It is denoted
by.

Molar conductance     Λ m = k ×V  

                              
Λ m = k × 1000/M

It’s unit is ohm- cm2 mol-1.

Effect of Dilution on Conductance:

Equivalent and molar conductance both increase with dilution

and reaches a maximum value at infinite dilution. Increasing
temperature reduces the resistance, there by increasing
conductance. Hence equivalent conductance and molar
conductance increases with increasing of temperature.

Specific conductance decreases with increase in dilution

because with increasing of dilution , the no. of ions present per
centimeter cube of electrolyte decreases.
 K C l ( s t r o n g e le c t r o ly t e )

C H 3 C O O H ( w e a k e le c t r o ly t e )

c o n c (moles
Dilution e n t r a t/i olitn , ( m o l e L – 1 ) 1 /2
Kohlrausch’s law of independent
migration of ions:
 At infinite dilution when dissociation complete (m) , the
molar conductivity of an electrolyte is expressed as the
sum of the contributions from its individual ions.
 It is applicable to dilute solutions of strong electrolytes at
equivalent concentration as well as at infinite dilution.

Λ ∞ m = v + λ∞ + + v - λ∞ -

v+ and v- are the number of cations and anions respectively as

per above formula for unit of electrolyte
λ∞+ and  λ∞- are the molar conductivities of the
cation and anion at infinite dilution respectively
Applications of Kohlrausch's law

 Determination of molar conductance at infinite

dilution of weak electrolytes

 Determination of the degree of dissociation of a

weak electrolyte

 Determination of the solubility of a sparingly

soluble salt
APPLICATIONS OF KOHLRAUSCH LAW
 1) Determination of molar conductivities of weak
electrolytes:
The optimum molar concentration of weak electrolytes cannot be
determined by direct extrapolation method. However the same
can be obtained indirectly by applying kohlrausch’s law. let us
find the optimum conductance of acetic acid.
CH3 COOH + NaCl  CH3COONa +HCl
From the value of of Λ∞ m HCl Λ ∞m CH3COONa and Λ ∞m NaCl
the value of Λ ∞m CH3COOH can be calculated.

Λ ∞CH3 COOH =  Λ ∞CH3COONa +  Λ ∞HCI  -  Λ ∞NaCI

= λ∞m ( CH3COO-)+ λ∞m ( Na+) + λ∞m (H+)+ λ∞m (Cl-) -
λ∞m ( Na+) - λ∞m (Cl-)
= λ∞m (H+)+ λ∞m ( CH3COO-)
= Λ ∞CH3 COOH
Illustrative Example
Equivalent conductance of NaCl, HCl
and CH3COONa at infinite dilution are
128, 425 and 91.5 ohm–1 cm2
respectively.Calculate the equivalent conductance
of C2H5COOH.

Solution:

Λ ∞CH3 COOH =  Λ ∞CH3COONa +  Λ ∞HCI  -  Λ ∞NaCI

= 91.5 + 425 – 128
= 388.5 ohm–1 cm2
2)Determination of degree of dissociation :
Degree of dissociation is the fraction of the total number of
molecules dissociated into ions.
Degree of dissociation (∞) = No. of molecules dissociated in to ions
Total no. of molecules present
No. of molecules dissociated is directly proportional to
conductivity of the molecules.
No. of molecules dissociated in to ions Λ cm ( molar conductivity
at a particular concentration.
Total no. of molecules Λ ∞m (molar conductivity at infinite dilution)

∞(degree of dissociation) = Λ cm / Λ ∞m
3) Determination of solubility of sparingly soluble salt :
The solubility of a sparingly soluble salts such as silver chloride,
silver chromate, lead sulphate, barium sulphate etc…can be
determined from conductance values because of inability to
give rise to ions.

The solubility S in mole equivalent/ liter is related to equivalent

conductance Λ∞ m and specific conductivity k

The concentration of sparingly soluble salt is the solubility of the

salt.
hence Λ∞ m = K X 1000
S
 Difference between Electrolytic cell and
Electrochemical cell:
 Electrolytic cell – anode is positive
 Electrochemical cell (galvanic)- anode is negative
 Oxidation always happens at the anode ,reduction always happens at the
cathode, that is independent if cell is Electrolytic cell or Electrochemical cell.
The electrons are always going to be moving from the anode to the cathode.
If the cell is spontaneous, as galvanic is, it makes sense that the electrons
will be moving towards positive electrode, the cathode is positive while for
electrolytic, which is not spontaneous, an electron is actually being forced to
move towards a negative pole ,hence the cathode is negative.
 In the voltaic cell, the current flows from positive electrode (+) to the
negative electrode (-) outside the cell .
 In the electrolytic cell the currents flows from positive electrode to the
negative electrode inside the cell.
 Voltaic cell can become an electrolytic cell by use of an external voltage
greater than the voltaic cell voltage and imposed in opposite direction.
ELECTROCHEMICAL CELLS/GALAVANIC
CELL:

 An Electrochemical cell is a device in which a redox

reaction is utilized to get electrical energy
Ex: Daniel cell

Daniel cell consists of zinc and copper

electrodes. Zn electrode is dipped in ZnSO4
solution & Cu is dipped in CuSO4 solution.
Zn --> Zn2+ + 2e- Cu2+ + 2e- --> Cu
wire
wire
eeleleccttro Reduction
rons
ns Cathode
Oxidation
Anode Zn
Zn salt
salt
bridge
bridge
Cu
Cu Positive

Negative

<--Anions
2+ Cations--> 2+
Zn
Zn2+ions
ions Cu
Cu2+ions
ions

•Electrons travel thru external wire.

Salt bridge allows anions and
cations to move between electrode
compartments.
Cell reaction:
At Anode
Oxidation takes place: Zn  Zn2+ + 2e-
At Cathode
Reduction takes place: Cu2+ + 2e-  Cu
The over all reaction is:
Zn + CuSO4  ZnSO4 + Cu
The two solutions separated by a porous
membrane, a current is seen to be flow on
connecting the two wires externally.
The cell function due to dissolution of zinc and
the simultaneous deposition of copper.

The over all reaction is:

Zn + CuSO4  ZnSO4 + Cu
The cell may be represented as:
Zn/ZnSO4 // CuSO4/Cu
Uses of salt bridge:
 If you have no salt bridge, eventually all of
the electrons from anode are going to move
into the cathode and have zero electrons
flow.
 It completes the circuit by connecting the
electrodes at the electrode side.
 It maintains electrical change neutrality in
both the compartments during cell operation
by selectively providing anions to anode and
cations to cathode.
EMF:
 In an electrochemical cell the potential difference across
the electrodes operates as a driving force for the flow of
electrons in one direction and there by making current to
flow in opposite direction and is known as cell
potential/electromotive force(emf). It can be expressed in
terms of both reduction potential and oxidation
potential.In terms of tendency to gain electron, i.e.,
reduction potential of the cathode remains at higher
potential. On the other hand , with respect to tendency to
lose electron i.e., oxidation potential of the anode
remains at higher potential
 In terms of reduction potential
 E o Cell = E o cathode –E o anode or E o Right – E o Left
 In terms of oxidation potential
 E o Cell = E o anode - E o cathode
 EMF of the total cell is equal to the sum of
oxidation potential and reduction potential of the
right hand electrode minus left hand electrode.
 Ecell = ER –EL
 Generally electrode potential refers toyhe reduction potential.
for examlple: ER of Cu+2 / Cu = 0.337V
EL of Zn / Zn+2 = -0.763V
Ecell = ER –EL
=0.337-(-0.763)
=0.337+0.763
=1.1V
 Generally reduction potential can be expressed in terms of oxidation potential
With negative symbol before it. For ex the oxidation potential of Cu +2 / Cu = -0.337V
But when it is substituted in the place of reduction it mustbe substituted with out negative
symbol.
for examlple: ER of Cu+2 / Cu = -0.337V
EL of Zn / Zn+2 = +0.763V
Ecell = ER +EL
= 0.763-(-0.337)
= 0.763+0.337
=1.1V
According to IUPAC convention the standard reductionpotentials alone are the standard
potentials.
Direction of spontaneous reaction:
If Ecell > 0 ,the cell reaction has a tendency to go from left to right. If however the Ecell <
0 the cell reaction will have a tendency to go from right to left.the reaction is
spontaneous or feasible only when Ecell is postive for that case standard free energy
of the reaction (ΔG0 ) would be negative (ΔG0 = nFE0).
Cell formulation/Cell notation:
 A short hand notation for representing a
cell is called cell formulation
 In this notation the state of the element ,a
single stroke for separation of two different
phases, a double stroke for separation of
the two electrodes.
 Standard hydrogen electrode(SHE), standard calomel electrode(SCE).

Eg; H2(g) / Pt/H+(1M) // Cu+2(1M) / Cu (s)

SHE anode SCE cathode
NERNST EQUATION:
The theoretical relation ship b/w the electro chemical reaction and
the corresponding cell e.m.f, this relation ship is generally known
as nernest equation.
Consider a galvanic cell
a A +bB  c C + d D here a,b,c,d are represent the number
of moles of A,B,C,D respectively, the nernest equation is

Ecell =RT/n F ln K - RT/n F ln [C]c[D]d / [A]a[B]b

Here Ecell = e.m.f of the cell,

R= gas constant,
T = Aboslute Temperature,
n= Number of electrons involved in the cell reaction
F= no. of faradays of current passed,
K = equilibrium constant,
RT/n F ln k = standard e.m.f of the Eocell
 Ecell = Eo cell - RT/n F ln [C]c[D]d / [A]a[B]b (or)

 Ecell = Eo cell - 2.303 RT/ nF log [C]c[D]d / [A]a[B]b

 where T=298 K, R=8.314 K-1 mol -1, F=96457 C by

substituting the values in above equation

 Ecell = Eo cell - 0.05916/ n log [C]c[D]d / [A]a[B] b

 Where n= no of electrons participating the elecrtode
reaction.

 Standard cell e.m.f equal to cell e.m.f when the

activities of both reactants and products is equal to
unity.
Applications of Nernst Equation:
 It can be used to study the effect of electrolyte
concentration on electrode potential
 E= E- RT/nf ln(1/Mn+ )
 Determination of unknown concentration of one
species in a cell is possible with the help of
nernst equation, provided Ecell and concentration
of other ionic species are known.
 The pH of a solution can be calculated from the
measurement of EMF and nernst equation
 Nernst equation can also be used for finding the
valency of an ion or the number of electrons
involved in the electrode reaction.
Classification of electrodes :
a) Gas electrode. Eg: hydrogen electrode.
b) metal-metal ion electrode. Eg: Cu+2 /Cu.
c) Redox electrode. (Quinhydrode electrode)
d) Metal-metal insoluble salt electrode. Eg: calomel electrode
e) Ion selective Electrode.
(a) Gas electrode (H2 electrode)
In this electrode , a gas is brought in contact with its own
ions in the solution such as hydrogen electrode.
 Pure hydrogen gas is bubbled into a solution of 1 M Hcl along
‘Pt’ electrode coated with platinum black. A platinum black placed
in the solution at atmospheric pressure as shown in the diagram.
Generally the electrode is fitted into a tube. The tube will
have two circular small holes. This tube is immersed in the acid
solution such that one half of the circular hole is exposed to air and
other half is in the solution.
The following equilibrium exists at the electrode
Pt foil absorbs part of hydrogen gas and the rest
comes out through the holes. So, there will be equilibrium
between the H2 and H+ions.

H2 2H+ + 2e-
When it acts as cathode, reduction takes place
2H+ +2e-  H2
Applying Nernst equation with n = 1,
EH2/H+ = E0H2/H+ - 0.0591/2 log[H+]2
Since E0 H2/H+is standard hydrogen potential = 0.00 v
EH2/H+ = - 0.0591 log[H+]
EH2/H+ = 0.0591 pH
Advantage:

It gives satisfactory results in the entire pH

range.
Limitations :

•The hydrogen gas used must be pure, because

the impurities can easily absorb on the Pt surface
•It is very difficult to maintain unit activity of
hydrogen ion in the solution.
b)Metal ion electrode (Zn/Zn+2)
This electrode consists of a metal immeresed in a solution
containing its own ions such as zinc electrode.
 At anode:

At cathode:
Zn+2 + 2e-  Zn(s)
E Zn/Zn+2 = E0 Zn/Zn+2 – 0.0591/ 2 log Zn+2
c)Quinhydrone electrode: (Redox electrode)
 This is a redox electrode reversible to protons &
often replaces the hydrogen electrode
 This is 1:1 molar mixture of quinone &
hydroquinone
 Electrode consist of a Pt electrode dipped in a
test solution which is saturated with quinhydrone
 The electrode reaction is given by

+ 2H+ + 2e-
 Q + 2H+ + 2e-  QH2
 (quinone) ( hydroquinone)

 The electrode potential at 25oc is given by

E Pt/Q,,H+,QH2 = E0 Pt/Q,H+,QH2 – 0.0592/2 log [QH2 ] / [Q][H+]2

 Since Q,,QH2 are in equimolar amounts i.e. [ Q]= [QH2 ]

 So, E=E0 - 0.0592 log [H+]

 EQ,QH2 = E0 Q,QH2 + 0.0592 p H
Advantages:
•Easy to set up no need to remove air
•The equilibrium is achieved faster than the hydrogen gas electrode
•pH values of solutions containing reducible substances like Cu 2+, unsaturated
acids can be measured, where hydrogen electrode cannot be used
Limitations:
•Electrode cannot be used at pH values greater than 8
•The electrode fails in presence of strong oxidizing and reducing agents (fe +2
mno2
 d.Metal – Metal insoluble salt
electrode(SCE)
Reference Electrode:
These type of electrodees consists of a metal,aninsoluble salt of the same metal
a solution of a soluble salt with common anion.
The electrode of standard potential with which we can compare the potentials of
unknown electrodes is called reference electrode.
Best example for primary reference electrode is Standard Hydrogen Electrode,
because its electrode potential at all temperatures is taken as zero.
However, in view of difficulties in setting up of hydrogen electrode, secondary
reference electrodes are used.

Metal- Metal insoluble salt electrode Ex: SCE (Standard Calomel Electrode)
Calomel electrode is the (Hg-Hg2Cl2) electrode. It is very simple to
construct, free from surface sensitivity and accurate to use even in normal
laboratory.
It consists of a glass tube with two side tubes each side. Mercury of high
purity is placed at the bottom of the tube and connected to the circuit by
means of a Pt wire sealed in glass tube. The surface of mercury is covered
with a paste of calomel (Hg2Cl2) and mercury in KCl solution. The calomel
electrode is only used as reducing electrode.
The corresponding electrode reaction is

Hg2Cl2 + 2e-  2Hg + 2 Cl-

The Nernst equation will be

EHg2Cl2|Cl- = E0 Hg2Cl2|Cl- – 2.303RT/2F log [Cl-]2

= E0 Hg2Cl2|Cl- – 0.0591 log [Cl-] at 25 0C

The electrode potential depends on the [Cl-].

For 0.1 M KCl EHg2Cl2|Cl- = 0.335V

1.0 M KCl EHg2Cl2|Cl- = 0.2810V

Saturated KCl EHg2Cl2|Cl- = 0.2422V

e.Ion selective electrode.
(glass electrode)
An Ion-selective electrode is a sensor which converts the activity
of a specific ion dissolved in a solution into an electrode potential,
which can be measured by some potentiometric device (Voltmeter
or pH meter).
Glass electrode is made up of glass tube ended with glass bulb
which is sensitive to protons. The inside of the electrode is filled
with buffer solution of chlorides in which Ag wire covered with
AgCl immersed. The surface of the glass is protonated by both
internal and external solution i.e., both sides of the glass are
charged by protons, which causes a potential difference.
At 25 0C the Nernst equation is given by

EG = E0G - 0.0591 log [H+]

EG = E0G + 0.0591pH
For the determination of pH, an SCE electrode is immersed as a
reference electrode in the buffer solution of HCl.
The e.m.f. of the cell is given by
Ecell = ESCE – Eglass
= 0.2422v – [E0G + 0.0591pH]
pH = 0.2422v – E cell - E0G
0.0591v
 Different types of ion-selective electrodes have been
developed the above principle.
1) glass electrodes for the determination of cations
other than H+ Ex: Na+ ,Ag+ / Pb+2 , Cd+2.
2) Solid state electrodes Ex: fluoride selective
electrode Ex: LaF3 crystals
3) liquid-ion exchange membrane electrodes &
heterogeneous membrane electrodes
Ex: potassium selective electrode based on
salinomycine as an ion exchange agent.
4) Gas sensing electrodes
glass electrodes with high selectivity for cations such as
Na+,NH4+,Ag+ & Li+ consists glass membranes whose composition
determines the selectivity to individual cations.