ELECTROCHEMISTRY

Electrochemistry is that branch of chemistry which deals with the study of production of electricity
from energy released during spontaneous chemical reactions and the use of electrical energy to
bring about non-spontaneous chemical transformations.
The arrangements used to bring about these conversions are called electrochemical cells. There
are two types of electrochemical cells:
1. Galvanic cells or voltaic cells. 2. Electrolytic cells.
The three main aspects of study in the branch of electrochemistry are :
1. Galvanic cells or voltaic cells. 2. Electrolytic cells. 3. Electrolytic conduction.
GALVANIC CELLS
A device which is used to convert chemical energy produced in a reaction into electrical energy is
called a galvanic cell or voltaic cell.
Considering a Daniel cell,

It consists of two half-cells. The half-cells on the left contains a zinc metal electrode dipped in
ZnSO4solution. The half-cell on the right consists of copper metal electrode in a solution
CuSO4. The two rods are connected by a wire and the two solutions are connected by a salt
bridge.
When the zinc and copper electrodes are joined by wire, the following observations are made:
● There is a flow of electric current through the external circuit.
● The zinc rod loses its mass while the copper rod gains in mass.
● The concentration of ZnSO4 solution increases while the concentration of copper sulphate
solution decreases.
● The solutions in both the compartments remain electrically neutral.
At the zinc electrode, the zinc metal is oxidized to zinc ions which go into the solution. The electrons
released at the electrode travel through the external circuit to the copper electrode where they are
used in the reduction of Cu2+ ions to metallic copper which is deposited on the electrode.
At the zinc rod, oxidation occurs. It is the anode of the cell and is negatively charged while at copper
electrode, reduction takes, place; it is the cathode of the cell and is positively charged.
Therefore the electrons flow from zinc to copper in the external circuit. The current flows in the
opposite direction.
The oxidation of zinc into its ions produces excess of Zn 2+ ions in the left beaker and the reduction
of Cu2+ ions to copper atoms leaves excess of sulphate ions in the right beaker. To maintain electrical
neutrality in the two beakers, the ions move through the salt bridge. This completes the inner circuit.
The half-cell in which oxidation taking place is called oxidation half-cell and , the half-cell in which
reduction occurs is called reduction half-cell .
Oxidation half reaction, Reduction half reaction Net reaction

Zn(s) → Zn2+(aq) + 2e- Cu2+(aq) + 2e- → Cu (s) Zn(s) + Cu2+ (aq) → Zn2+(aq) + Cu(s)

Daniel cell has an electrical potential of 1.1 V.

ELECTRODE POTENTIAL
The electrical potential difference set up between the metal and its ions in the solution is called
electrode potential.
Oxidation potential : The tendency of an electrode to undergo oxidation ie; to lose electrons is
known as oxidation potential.
Reduction potential :The tendency of an electrode to undergo reduction ie; to gain electrons is
known as reduction potential. According to IUPAC convention, the reduction potential alone be
called as the electrode potential unless it is specifically mentioned.
Standard electrode potential : The potential difference developed between metal electrode and
solution of ions of unit molarity (1M) at 1 atm pressure and 25°C (298 K) is called standard
electrode potential.
It is denoted by E°.

Reference Electrode
It is not possible to determine the absolute value of electrode potential. For this a reference electrode
[NHE or SHE] is required. The electrode potential is only the difference of potentials between two
electrodes that we can measure by combining them to give a complete cell.
The electrode of known potential is called reference electrode. It may be primary reference
electrode like hydrogen electrode or secondary reference electrode like calomel electrode.

Standard hydrogen electrode (SHE) Standard hydrogen electrode (SHE). also known as normal
hydrogen electrode (NHE), consists of platinum wire, carrying platinum foil coated with finely
divided platinum black. The wire is sealed into a glass tube placed in beaker containing 1 M HCl.
The hydrogen gas at 1 atm pressure is bubbled through the solution at 298K. Half-cell is pt H2 (1
atm) H+ (1 M)

. In SHE, at the surface of platinum, either of (he following reaction can take place)

2H+(ag) + 2e– → H2 Reduction

H2(g) → 2H+(ag) + 2e– Oxidation
The electrode potential of SHE has been fixed as zero at all temperatures

Electromotive Force (emf) of a Cell

It is the difference between the electrode potentials of two half-cells and cause flow of current
from electrode of higher potential to electrode at lower potential.

Standard emf of a cell,

Electrochemical Series
It is the arrangement of electrodes in the increasing order of their standard reduction
potentials.
Standard Electrode Potential at 298 K
EFFECT OF ELECTROLYTE CONCENTRATION AND TEMPERATURE ON THE ELECTRODE
POTENTIAL (NERNST EQUATION FOR ELECTRODE POTENTIAL)

The relationship between the concentration of ions and electrode potential is given by Nernst
equation.

For a electrochemical cell,

Concentration of pure solids and liquids is taken as unity.

NERNST EQUATION FOR THE EMF OF A CELL

Equilibrium constant from Nernst equation

In a Daniel cell , the reaction Zn + Cu2+→ Zn2+ + Cu takes place and as time passes the
concentration of Zn2+ keeps on increasing and the concentration of Cu2+keeps on decreasing.
After some time there is no change in the concentration of Cu2+ and Zn2+ ions and the voltmeter
gives zero reading. At this point of time equilibrium has been reached.

But at equilibrium,

The equation can be rewritten as

ELECTROCHEMICAL CELL AND GIBBS ENERGY OF THE REACTION

When a cell reaction takes place, electrical energy is produced. The electrical work done by
system results in decrease in free energy of the system.
Electrical work done = Decrease in Gibbs free energy
The electrical work done in one second is equal to electrical potential of the cell multiplied by
quantity of electricity flowing in the circuit.
For n moles of electrons transferred in the cell reaction, the quantity of electricity flowing is nF
Electrical work done = nFEcell
Δ G = -nFEcell
r

If the concentration of all the reacting species is unity, then E cell = E0 cell and we have
Δ G0 = -nFE0cell
r

We know that
E0cell= RT ln Kc
nF
Substituting this value, we get ΔrG0= - RT ln Kc or Δ G0= - 2.303RT log Kc
r

CONDUCTANCE OF ELECTROLYTIC SOLUTIONS

Any substance or material, which permits the passage of electricity through it, can be termed as a
conductor. On the other hand, any substance which resists the flow of electricity through it is
termed as an insulator.

Types of Conductors

Generally, science divides conductors into two broad categories. The division of conductors or
conductance is based on the decomposition of electricity when it passes through a given
conductor. Based on the nature of decomposition, conductors could be classified into the
following two categories:

sl Metallic conductors Electrolytic conductors

no

1 Flow of electricity takes place without Flow of electricity takes place accompanied by the
the decomposition of the substance decomposition of the substance.

2 Flow of electricity is due to the flow of Flow of electricity is due to the movement of ions.
electrons

3 The resistance offered by a metal is due The resistance offered is due to inter-ionic
to vibrating kernels. attractions, viscosity of solvent etc.

4 The electrical conduction decreases with The electrical conduction increases with increase
increase of temperature. This is because of temperature. This is because of the increase in
the kernels start vibrating which produce dissociation or decrease in inter ionic attractions.
hindrance in the flow of electrons.

FACTORS AFFECTING ELECTROLYTIC CONDUCTION

Following factors affect the level of Electrolytic conduction:

● Nature of the electrolyte: Strong electrolytes ionize almost completely in the solution and
hence conduct electricity to a large extent where as weak electrolytes ionize to a small extent
in the solution and hence conduct electricity to a small extent.

● Size of the ion produced and their salvation: Greater the size of ions or greater the
solvation of the ions ,less is the conductance.

● Nature of the solvent and its viscosity: Electrolytes ionize more in a polar solvent. Hence
greater the polarity of the solvent greater is the ionization and hence greater is the
conductance. Greater the viscosity of the solvent lesser is the conductance.
 ● Concentration of the solution: Higher the concentration of the solution, lesser is the
conduction.

● Temperature: On increasing the temperature the dissociation increases and hence conduction
increases.

ELECTRICAL RESISTANCE AND CONDUCTANCE

Electrical resistance
o It is denoted by the symbol ‘R’.
o It is measured in a unit called ohm (Ω) with the help of a Wheatstone bridge
o The electrical resistance is directly proportional to its length, and inversely proportional to its
area of cross section, A.

o In the equation the constant of proportionality denoted by called rho is called resistivity.
o It is measured in units called ohm metre.
o Resistivity is defined as the resistance of a conductor whose length is 1 cm and area of cross
section is 1cm2 .
Electrical conductance
o The reciprocal of of electrical resistance is known as conductance.

o It is measured in a unit called Siemens represented by the symbol ‘S’

o It is equal to ohm–1 also known as mho or Ω –1.

conductivity or specific conductance

The reciprocal of resistivity is known as conductivity or specific conductance.It is denoted by
kappa.

We know that G=I/R and G* = l/A

Therefore = G X l/A or
= G X G*
Specific conductance = Conductance × cell constant
Unit of specific conductance:
Conductivity of a solution can be defined as the conductance of a solution of 1 cm length and
having 1cm2 as the area of cross section OR
 Conductivity of a solution is defined as the conductance of 1cm3 of the solution of the
electrolyte. The unit of conductivity is Scm-1 or Sm-1..
Molar conductivity
Molar conductivity of a solution is defined as the conductance of all the ions produced from
one mole of the electrolyte dissolved in V cm3 of the solution when the electrodes are one cm
apart and the area of the electrodes is so large that the whole of the solution is contained
between them. It is usually represented as Λm.
Λm =κ V or Λm = κ x 1000
M
Where κ is the conductivity , V is the volume of the solution containing one mole of the
electrolyte and M is the molarity.
The unit is Scm2mol-1 or Sm2mol-1

1 Sm2mol-1 = 104 Scm2mol-1

VARIATION OF CONDUCTANCE, CONDUCTIVITY AND MOLAR CONDUCTIVITY WITH

CONCENTRATION OR DILUTION
❖ The conductance of a solution is due to the presence of ions in the solution. The greater
the number of ions in the solution, greater is the conductance .As on dilution, more ions
are produced in the solution, the conductance increases on dilution.
❖ Conductivity of an electrolyte decreases with dilution because the number of ions
present per cm3 of the solution becomes less and less on dilution.
❖ Molar conductivity of an electrolyte increases with dilution since this is a product of
conductivity and volume V of the solution containing one mole of the electrolyte .As the
decreasing value of conductivity is more than compensated by the increasing value of
volume, molar conductivity increases with dilution.
VARIATION OF MOLAR CONDUCTIVITY OF A STRONG AND WEAK ELECTROLYTE WITH
CONCENTRATION OR DILUTION
The molar conductivity of an electrolyte vary with concentration according to DEBYE-HUCKEL-
ONSAGER equation :
Λm = Λ0m – A√C
where, A is a constant. It depends upon the type of the electrolyte, nature of the solvent and
temperature and Λ0m is the molar conductivity at zero concentration or at infinite dilution called
limiting molar conductivity.

The curve obtained for a strong electrolyte shows that there is only a small increase in conductance
with dilution. This is because a strong electrolyte is completely dissociated in solution and so the
number of ions remain constant. At high concentrations, the greater inter- ionic attractions retard
the motion of the ions. With dilution, the ions are far apart and the interionic attractions decrease
due to which conductance increases with dilution and approaches a maximum limiting value at
infinite dilution known as limiting molar conductivity. The plot can be extrapolated to zero
concentration get the value of Λ0m.
As a weak electrolyte dissociates only to a lesser extent compared to a strong electrolyte ,the
conductance of a weak electrolyte is lower than that of a strong electrolyte at the same
concentration. The curve obtained for a weak electrolyte shows that there is a large increase in
conductance with dilution. This is because as dilution increases the dissociation of the weak
electrolyte increases and therefore the number of ions in the solution increases .But it does not
reach a limiting value. Hence it is not possible to determine the value of Λ0m value of a weak
electrolyte from the plot. This problem was solved by Kohlrausch law.
KOHLRAUSCH’S LAW
kohlrausch’s law of independent migration of ions states that limiting molar conductivity
of an electrolyte can be represented as the sum of the individual contributions of the anion and
cation of the electrolyte.
Mathematically,

for
If λ°(Na+) and λ°(Cl-) are the limiting molar conductivities of sodium and chloride ions, then limiting
molar conductivity of NaCl is:
Λ°m (NaCl) = λ°(Na+) + λ° (Cl-)
Application:
1) The law is used to calculate the molar conductivity of any electrolyte at zero concentration. For
example, the molar conductivity of acetic acid at zero concentration can be calculated from the
following expression.
By Kohlrausch’s law, we have,

)
2)The value of the dissociation constant of a weak electrolye can be calculated by using
Kohlrauschs law.