ELECTROCHEMISTRY

Electrochemistry is the branch of

chemistry that deals with the relation
between chemical action and
electricity
 Electrochemical Reactions

In electrochemical reactions, electrons are

transferred from one species to another
 Electron Transfer Reactions
 Electron transfer reactions are oxidation-reduction or redox
reactions.
 Results in the generation of an electric current (electricity) or be
caused by imposing an electric current.
 Therefore, this field of chemistry is often called
ELECTROCHEMISTRY.
 Terminology for Redox Reactions
 OXIDATION :loss of electron(s) by a species; increase in
oxidation number; increase in oxygen.

 REDUCTION: Gain of electron(s); decrease in oxidation

number; decrease in oxygen; increase in hydrogen.

 OXIDIZING AGENT: Electron acceptor; species is reduced.

 REDUCING AGENT: Eelectron donor; species is oxidized.

LEO = Loss of Electron is Oxidation

Oxidation and Reduction with respect to Oxygen Transfer
Oxidation is the gain of oxygen.
Reduction is the loss of oxygen.

Oxidation and Reduction with respect to Hydrogen Transfer

Oxidation is the loss of hydrogen.
Reduction is the gain of hydrogen.

Oxidizing and Reducing Agents

Oxidizing agents give oxygen to another substance.
Reducing agents remove oxygen from another substance.

Oxidizing and Reducing Agents

Oxidizing agents add oxygen to another substance
or remove hydrogen from it.
Reducing agents remove oxygen from another substance
or add hydrogen to it.
 OXIDATION-REDUCTION REACTIONS

Direct Redox Reaction

Oxidizing and reducing agents in direct contact.
Cu(s) + 2 Ag+(aq) ---> Cu2+(aq) + 2 Ag(s)
 Electrical Conductance

Conductors are classified as

(a)Metallic conductors or electronic conductors

(b) Electrolytic conductors
 What is electrolyte?
Any substance that produce ions when dissolved
in a solvent (usually water) is an electrolyte.
Types of electrolytes
Strong electrolyte
Weak electrolyte
 Strong Electrolytes
Strong electrolytes are substances that only exist
as ions in solution.
They completely dissociate to their ions when
dissolved in solution.
Ionic compounds are typically strong electrolytes.
Strong acids, strong bases and salts are strong
electrolytes.
 they are good conductors because they break
down well and produce many ions in solution
They conduct electricity when molten or in
aqueous solution.
Example: Hydrochloric acid, Sodium chloride

HCl  H 2O  H 3O   Cl 

 
NaCl  H 2O  Na  Cl
 Weak Electrolytes
A weak electrolyte only partially dissociates in
solution and produces relatively few ions (exist
in water as a mixture of individual ions and
incontact molecules).
Weak acids and weak bases are weak
electrolytes.
do not conduct electricity so well because fewer
ions are produced in solution.
They conduct electricity weakly.
Example: Acetic acid, ammonia

 
CH 3COOH  H 2O  CH 3COO  H


NH 3  H 2O  NH 4  OH 
Types of Electrolytes

1.Strong electrolytes (completely dissociate e.g. HCl, HNO3,

NaOH, NaCl, KCl

2. Weak electrolytes (do not undergo complete dissociation e.g.

CH3COOH, NH4OH, HCOOH
Mechanism of electrolytic conduction and electrolysis of
molten NaCl

Electrolytic cell

Na+  +  e-          Na (-)cathode).

 

2Cl-  -  2e-          Cl2 (chlorine gas at the (+)anode).

 
Electrolytic Conductance
Electrolysis of molten sodium chloride
NaCl   ↔ Na+ + Cl-

At cathode [Reduction Reaction]  At Anode [Oxidation]

Na+ + e- → Na                      Cl- → Cl + e-
                      
 Specific conductance or conductivity
 The resistance of any conductor varies directly as its length (l) and
inversely as its cross sectional area (a), i.e.,

R α l/a or R = ρ l/a  , Here ρ = specific resistance

[ Resistance offered by a substance of 1 m length and 1 m2 cross-section]
   If l = 1 m and a = 1 m2, then
R = ρ  [ρ unit is ohm-meter ]         
Reciprocal of specific resistance is specific conductance               
Κ= 1/ρ, Κ = kappa - the specific conductance          
ρ = R.a/l So K = l/ R.a

K = l/a×C (l/a = cell constant and 1/R is Conductance)

Specific conductance = cell constant x Conductance
The unit of specific conductance (k) is ohm-1 m-1.
 Specific conductance or conductivity
Specific conductance is the conductance of a solution
placed between two electrode of 1m2 cross section
and placed 1 m apart.

Ohm-1 or mho is called S (Siemens)

 Equivalent conductance (/\)
Equivalent conductance is the conductance of solution
containing 1 gram equivalent of an electrolyte dissolved
into V ml of the solution.
/\ = KV
In case, if the concentration of the solution is c g
equivalent per liter, then the volume containing 1 g
equivalent of the electrolyte will be 1000/C.
So equivalent conductance
                                                                                 
/\ = 1000 k /C
         Where C
= Concentration
                The unit of equivalent conductance is ohm-1 m2 equi-1.
 Molar conductance
 The molar conductance is defined as the conductance of all
the ions produced by ionization of 1 mole of an electrolyte
when present in V mL of solution. It is denoted by.
Molar conductance     Λ = k ×V  
                              
Where V is the volume in mL containing 1 mole of the
electrolyte. If c is the concentration of the solution in g mole
per litre, then
Λ = k × 1000/M
It units are ohm-1 m2 mol-1.
              
 Equivalent conductance =  (Molar conductance)/n
         Where            n = (Molecular mass) / (Equivalent mass)
Molar Conductance
Conductance of an electrolytic solution due to all the ions obtained
from 1 mole of electrolyte at a given concentration.
Unit: Sm2/mol

Equivalent Conductance
Conductance of an electrolytic solution due to all the ions obtained
from 1 gram-equivalent mass of the electrolyte at a given
concentration
Unit: Sm2/equivalent.

Cell Constant is the ratio of the distance between electrodes to the

cross-sectional area
Cell constant = l/a
 For Numerical

ρ = Specific Resistance, 1/ ρ = k = Specific Conductance

R= Resistance, 1/R = C = Conductance
Cell Constant = l/a

Specific conductance K = l/R.a

Equivalent conductance /\ = 1000 k/ c [Where k is in ohm-1
m-1 ] and conc is in Moles/ Litre (M)/ N.
Q: Calculate the specific conductance of a solution placed
between two electrodes
1.63x10-2 m apart and having cross –section area 3.996x
10 -4 m2. Resistance is 17.69 ohm ?

Ans: 2.30 S/m

Q: If a solution of 0.0469 M concentration has
a resistance 60.2 ohm and cell constant
89.6 m-1, what is it’s molar conductance and
equivalent conductance?

At 298K, the specific conductance of 0.1 N NaCl is 1.1

S/m. Calculate the equivalent conductance at the same
temperature?
Electrochemical Cells

The devices which convert electrical energy into chemical energy or vice
versa are called electrochemical cells. Based on the activity taking place in
them, these devices are classified into two major categories:

1.Electrolytic cells.
2.Galvanic (voltaic cells): These are further divided into

•chemical cells;
•concentration cells.

The devices in which chemical changes occur in the presence of applied

electrical energy are referred as electrolytic cells. The devices in which
electrical energy is generated on account of the chemical reactions occurring
in them are known as galvanic cells.

In Galvanic cell = Chemical reaction change to electrical energy,

In Electrolytic cell = Electrical energy changes to chemical energy
 Electrode Potential

Origin of Electrode Potential

Origin of electrode potential (oxidation) Origin of electrode potential

(reduction)

Zn is leaving the electron

on the metal rod Zn+2 is taking the e from the metal rod to
So (-) charge on metal rod. Zn+2 become Zn, So (+) charge on metal rod. Zn+2
goes to solution, solution becomes (+) is coming out of solution so SO4 -2 ion
excess in solution. So solution is (-).
Oxidation Potential
If oxidation occurs at the electrode, at equilibrium the potential of the
electrode can be termed as oxidation potential. For the zinc electrode, the
reaction can be represented as:

Reduction Potential
If reduction occurs at the electrode, at equilibrium the potential of the
electrode is referred to as reduction potential. For the zinc electrode, the
reaction can be represented as:

Standard Electrode Potential (E0)

If is defined as the potential that exists between the metal or the gas and its
aqueous solution of unit concentration at 298 K when the sum of all partial
pressures of the gaseous reactants and products, if any, is equal to 1 atm
pressure.
 Galvanic Cells

+
anode - cathode
oxidation reduction

spontaneous
redox reaction
 Galvanic Cells
The difference in electrical potential between
the anode and cathode is called:
• cell voltage
• electromotive force (emf)
• cell potential

Cathode + in Galvanic cell

Cathode – in Electrolytic cell
Cell Diagram

Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)

[Cu2+] = 1 M & [Zn2+] = 1 M

Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)

Anode Cathode CAR = Cathode
(Oxidation) (Reduction) Reduction
 What is salt bridge?

Salt bridge is usually an inverted U-tube filled with

concentrated solution of inert electrolytes. An inert

electrolyte is one whose ions are neither involved in any

electrochemical change nor do they react chemically

with the electrolytes in the two half-cells. Generally

salts like KCl, KN03, NH4N03, etc., are used

Significance of salt bridge:
The following are the functions of the salt bridge:
 For continuous generation of electrical energy
 It connects the solutions of two half-cells and completes the
cell circuit.
 It prevents transference or diffusion of the solutions from one
half-cell to the other.
(i) Salt bridge is U – shaped glass tube filled with a gelly like substance, agar
– agar (plant gel) mixed with an electrolyte like KCl, KNO3, NH4NO3 etc.
(ii) The electrolytes of the two half-cells should be inert and should not react
chemically with each other.
(iii) The cation as well as anion of the electrolyte should have same ionic
mobility and almost same transport number, viz.  etc.

(iv) The following are the functions of the salt bridge,

(a) It connects the solutions of two half - cells and completes the cell circuit.

(b) It prevent transference or diffusion of the solutions from one half cell to the

other.

(c) It keeps the solution of two half - cells electrically neutral.

 EMF
Electromotive force is known as the difference in the
potential of the electrodes.

In spontaneous reaction, change in free energy

decreases.

Larger the decrease in free energy, greater would be the

EMF.
Electrochemical Conventions and Notations

1.There are two electrodes in a galvanic cell. Each of these electrodes is

referred to as a half cell.
2.If reduction occurs at an electrode, it is called a reduction electrode or a
positive electrode.
3.If oxidation occurs at an electrode, it is called an oxidation electrode or a
negative electrode.
4.Oxidation and reduction potential values of an electrode are numerically the
same, with opposite signs.
5.As per IUPAC, the potential of an electrode is always expressed as reduction
potential only, irrespective of the reactions occurring at the electrode.
6. The interphase across which a potential develops is denoted by either a
single vertical line (|) or a semicolon (;).

7. Representation of a cell will have the oxidation electrode (anode) on the

LHS and the reduction electrode (cathode) along the RHS.

8. The EMF of a cell is represented as:

EMF of the Cell and Free Energy Change

For spontaneous reaction = E cell must be

positive
 T = In Kelvin

Equation 19.6 NERNST EQUATION

Replacing the value of R, T and F

Q = Conc of pdt/ Conc of Reactant E = E0 – 0.0591/n Log Q

Q: Calculate the electrode potential of copper, if the
concentration of CuSO4 is 0.206 M at 23.1 degree C.
Given that E0 Cu2+ /Cu = + 0.34 V.

Q: Calculate the EMF of the following Zn-Ag cell at

22.3 degree Celsius, if the conc of ZnSO4 and Ag NO3
are 0.191 M and 0.0289M, respectively. Given that E0
Zn2+ /Zn = -0.76 V and E0 Ag+ /Ag =+0.8 V.
Q: Calculate the concentration of NiCl2 in the nickel
electrode having a potential of -0.16942 V at 24.9 °C.
Given that E0 Ni2+ /Ni = -0.14 V.

Q: Calculate the standard electrode potential of lead

electrode, if the electrode potential is -0.18025V at
301 K and a concentration of Pb2+ solution is 0.0096V.
Q: For the cell Zn/Zn2+ (a =10-4 M)II Mg2+ (a =10-3M)I Mg, the standard
reduction potential for Zn and Mg electrodes are -0.764 V and -2.364 V
respectively,
(a)Write the half cell reaction and overall cell reaction
(b) Find E° cell and Gibbs free energy and predict if the cell reaction is
spontaneous or not.

Q: Calculate the potential of copper-silver cell if Ag+ = 1x10-3 M and

Cu+2 = 1x10-4 M. The standard reduction potentials of silver and copper
electrode are 0.8 V and 0.3 V respectively. The cell reaction is given by
WE NEED A REFERENCE ELECTRODE
Standard Hydrogen Electrode.

Reduction and oxidation both are possible

Single Electrode Potential.
REMEMBER
 REMEMBER

 E0 can be calculated directly from the given value, E value can be calculated from Nernst
equ.
 For a reaction to be spontaneous the E value should be positive.
 EMF Series/ Electrochemical
Series

A serial arrangement of metallic elements or ions

according to their electrode potentials determined
under specified conditions; the order shows the
tendency of one metal to reduce the ions of any other
metal below it in the series.
Electrochemical Series

When the electrodes are arranged in the increasing order of their standard
reduction potential values, the series so formed is termed as electrochemical
series.
EMF and Potential Difference

The terms EMF and potential difference are used indiscriminately, but there is
a clear distinction between them. Differences between EMF and potential
difference
 Remember this points before solving numerical

1. If Cu+2/Cu = +0.34 V, Cu/Cu+2 = -0.34 V

2. If the temperature is 25 0 C ( or if the temperature is not mentioned y then
consider it to be 25 0 C, then use this formula –

3. If the temperature is something other than 25 0 C, then use this formula-

T = In Kelvin

4. E0 (Standard emf) of each half cell will be given directly in the question. You can
calculate E0 of the reaction directly from the E0 values given in the question. [E0 ca - E0

an ]. [E0 should be at 250 C , conc = 1 M].

5. But E must be calculated using Nernst equation.
6. If E is (+) then the reaction is spontaneous.
7. If the cell representation is given like this –
then oxidation occurs in left side and reduction on right side.
8. If the cell representation is not given, then the oxidation happens in that half cell
which has lower E0 value .
Concentration Cell

It is a galvanic cell that generate electrical energy at the

expense of chemical energy (same species is present all
around in a cell but at different concentration.
 Fe+2/ Fe= -0.44 V

Ag+/ Ag = 0.8 V

What will be E0 and E for the cell?

Cr+3/ Cr = -0.74 V
Ni+2/ Ni = 0.25 V What is E and
E0
Reversible and Irreversible electrochemical
cells:

Cells produce electricity when electrochemical reactions take place in the

cell.  If the cell is reversible (like a lead-acid car battery, or a nickel
cadmium battery) you can use a higher voltage to force current
backwards through the battery, causing the reverse electrochemical
reactions to occur, recharging the battery.  Regular and alkaline dry cell
batteries also produce electricity via electrochemical reactions, but if you
force current backwards through them, different reactions take place and
the battery heats up, explodes, or just quits working.
Reversible electrochemical cells are the cells
whose cell reactions can be get reversed when an external emf
greater than its capacity is applied. (A cell which obeys
thermodynamic conditions of reversibility is known as reversible
cells)
For example: Daniel cell with Capacity 1.1 V, when an external
emf of 1.1 V is applied, the cell reaction stops.

Zn + Cu+2  Zn+2 + Cu

But when an increased amount of emf greater than 1.1 V is

applied, the cell reaction is get reversed.

Zn+2 + Cu -------> Zn + Cu+2

A cell of this type can be termed as Reversible cell.

Irreversible electrochemical cells are the cells whose cell
reactions can not be get reversed when an external EMF greater than its
capacity is applied. (A cell which does not obey thermodynamic conditions
of reversibility is known as irreversible cells). For example, a cell which has
Zn as an anode and Ag as a cathode with sulphuric acid as an electrolyte.
The cell reaction at the anode is (Zn/H+/Ag)

Zn (s) ----------> Zn+2 (aq) + 2e-

In the presence of electrolyte (H2SO4)

Zn + 2H+ ----------> Zn+2 + H2

The cell reaction at the cathode is

2 Ag + 2e- ----------> 2 Ag

When an external EMF applied to the cell, the chemical reactions are not
reversed because one of the products of the reaction H2 gas is escaped
from the reaction system.
 Concentration Cell
Concentration cell is a galvanic cell in which both electrode contains
same material and same electrolyte but with different concentration.