Electrochemistry

The study of the processes involved in the inter conversion of electrical energy and
chemical energy is known as electro chemistry.

Electrochemical Cells

An electrochemical cell is a device which converts chemical energy into electrical energy or
electrical energy into chemical energy. Thus, there can be two types of electrochemical cells.
(i) The one which converts chemical energy into electrical energy is called galvanic
cell or voltaic cell.
(ii) The one which converts electrical energy into chemical energy is called electrolytic
cell.
Galvanic cells

Galvanic cell generally consists of two electrodes dipped in two electrolyte solutions which
are connected through a salt bridge. Example Daniel cell.

Construction

Daniel cell consists of two half cells, in one, a zinc electrode is dipped in 1 M ZnSO4
solution and in another, a copper electrode is dipped in 1 M CuSO4 solution. Each electrode is
known as a half cell. The two solutions are inter connected by a salt bridge and the two electrodes
are connected by a wire through the ammeter.

Reaction occurring in the cell

At anode: Oxidation takes place in the zinc electrode by the liberation of electrons, so
this electrode is called negative electrode or anode.

At cathode: Reduction takes place in the copper electrode by the acceptance of

electrons, so this electrode is called positive electrode or cathode.
 Zn → Zn2+ + 2e- (at anode) Oxidation
Cu2+ + 2e- → Cu (at cathode) Reduction
_____________________________________
Cu2+ + Zn ↔ Zn2+ + Cu (net cell reaction)
______________________________________

The electrons liberated by the oxidation reaction flow through the external wire and are
consumed by the copper ions at the cathode.

Salt bridge

The salt bridge is a U-tube, filled with either a jelly containing KCl or NH4NO3 and both
the ends of the U-tube plugged with a porous material.

Functions of salt bridge

(i) It eliminates liquid junction potential

(ii) It provides the electrical continuity between the two half cells.

Electromotive force of the Cell

Current cannot flow from one point to another unless there is a potential difference between
the two points. Hence, a flow of electrons from anode to cathode in a galvanic cell indicates that
the two electrodes have different potentials. "The potential difference between the two electrodes
of a galvanic cell which causes the flow of current from one electrode (higher potential) to the
other (lower potential) is called the electromotive force (emf) of the cell or the cell potential"

𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛

EMF = {𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑜𝑓 𝑟𝑖𝑔ℎ𝑡 ℎ𝑎𝑛𝑑 } − {𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑜𝑓 𝑙𝑒𝑓𝑡 ℎ𝑎𝑛𝑑 𝑠𝑖𝑑𝑒 }
𝑠𝑖𝑑𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑖𝑔ℎ𝑡 − 𝐸𝑙𝑒𝑓𝑡

The emf of a cell depends on the nature of the electrode, temperature and concentration of the
electrolyte solutions. To facilitate comparison of different galvanic cells, their standard emf values,
denoted by Eo.

Standard emf

Standard emf of a cell is defined as the emf of a galvanic cell when the reactants and products of
the cell reaction are at unit concentration or unit activity, at 298 K, 1.0 M of concentration and 1
atm.
A negative value indicates oxidation tendency and a positive value indicates reduction tendency
with respect to hydrogen.
• The metal with lower electrode potential is more reactive and as the electrode potential increases,
the reactivity decreases, and metals with higher electrode potentials are nobler.
• Metals with lower electrode potentials have the tendency to replace metals with higher electrode
potential from their solutions for example, Zn displaces Cu, and Cu displaces Ag
• Metals with negative electrode potentials can liberate hydrogen from acidic solutions
Electrode Potential

It is known that metal atoms have a tendency to go into solution as metal ions. Electrode
potential is a measure of the tendency of metal atoms to go into solution as metal ions. When a
metal strip (M), immersed in a solution of its own ions (Mn+), either of the following three
possibilities occurs

(i) A metal ion (Mn+) may collide with the electrode and undergo no change.
(ii) A metal ion (Mn+) may collide with the electrode, gain ‘n’ electrons and converted
into a metal atom (M) (the ion reduced)
(iii) A metal atom on the electrode (M) may lose ‘n’ electrons to the electrode and enter
the solution as Mn+ (the metal is oxidized).

Standard Electrode potential

When the half reaction’s potential is measured under standard conditions namely at 298 K,
1.0 M of concentration and 1 atm the reduction potential is called ‘Standard reduction potential’.
Standard reduction potentials are also called ‘Standard electrode potentials’.

Types of electrodes

i) Metal-Metal ion electrode: An electrode of this type consists of a metal

dipped in a solution containing its ions.
Ex- Zn/Zn2+, Cu/Cu2+ etc.

ii) Metal-Metal salt ion electrode: These electrodes consist of a metal is in

contact with a sparingly soluble salt of the same metal dipped in a solution
containing anion of the salt.
Example-Calomel (Hg|Hg2Cl2|Cl- , Silver- Silver salt electrode (Ag| AgCl |Cl-

iii) Gas electrode: Gas electrode consists of a gas bubbling about an inert
metal wire, immersed in solution containing ions to which the gas is reversible. The metal provides
electrical contact and facilitates the establishment of equilibrium between the gas and its ions.
Example-Hydrogen electrode (Pt|H2|H+) , Chlorine electrode (Pt|Cl2|Cl-)