Electrochemistry

Electrochemistry is that branch of chemistry which deals with the relationship between
chemical energy and electrical energy.

Electrolysis

The passage of an electric current through an electrolyte with subsequent migration of charged
ions to the negative and positive electrodes.

Electrolyte

A solution containing free ions that are carriers of electric current.

An electrolyte is a compound that ionizes when dissolved in suitable ionizing solvents such as
water. This includes most soluble salts, acids, and bases. Some gases, such as hydrogen
chloride.

Electrolytes

Electrolytes are chemical compounds which conduct electricity either in the fused or in an
aqueous solution state and which undergo chemical decomposition due to flow of current
through it.

Examples
Acid solutions - HCl, HNO3
Alkaline solutions - KOH, NaOH
Ionic salt solutions - PbBr2 , CuSO4

Strong Electrolytes Weak Electrolytes

Allows a large amount Allows a small amount of
of
electricity to flow electricity to flow through
through
them Them

Are completely Are partly dissociated

dissociated

Solutions contain only Partly ionised and partly

free mobile ions unionised molecules are
 present

Examples Examples
Acids - HCl, HNO3 Acids - Acetic, Oxalic
Bases - NaOH, KOH solution Bases - NH4OH
Salts - CuCl2 , PbBr2 Salts - Na2CO3 , NaHCO3

Electrode

Electrodes are electrical conductors that provide physical interface between electrolyte and the
electrical circuit.

Electrodes allow the electric current to enter or leave the electrolytic solution and aretwo in
number.

An electrochemical cell is a device capable of either deriving electrical energy from chemical
reactions or facilitating chemical reactions through the introduction of electrical energy.

Process of electrolysis

The key process of electrolysis is the interchange of atoms and ions by the removal or addition
of electrons from the external circuit. The desired products of electrolysis are often in a
different physical state from the electrolyte and can be removed by some physical processes.
For example, in the electrolysis of brine to produce hydrogen and chlorine, the products are
gaseous. These gaseous products bubble from the electrolyte and are collected.

2 NaCl + 2 H2O → 2 NaOH + H2 + Cl2

A liquid containing mobile ions (electrolyte) is produced by:

 Solvation or reaction of an ionic compound with a solvent (such as water) to produce

mobile ions.

 Each electrode attracts ions that are of the opposite charge. Positively charged ions
(cations) move towards the electron-providing (negative) cathode, whereas negatively
charged ions (anions) move towards the positive anode.

 At the electrodes, electrons are absorbed or released by the atoms and ions. Those
atoms that gain or lose electrons to become charged ions pass into the electrolyte.
 Those ions that gain or lose electrons to become uncharged atoms separate from the
electrolyte.

At anode → oxidation → loss of electrons

2 Cl – → Cl 2 + 2 e–

At cathode → reduction → gain of electrons

Na + + e– → Na

Faraday's laws of electrolysis

In 1833 M. Faraday studied the quantitative aspects of electrolysis, and postulated two laws
named after him.
Faraday's First Law of Electrolysis
This law states:
The mass of any substance deposited or dissolved at any electrode during electrolysis is
directly proportional to the quantity of electricity passed through the solution.
Mathematically, if “m” gram of any material gets deposited or dissolved when Q coulombs of
electricity is passed, then

m α Q
m=ZQ

But Q = I x t
m =Z I t
Where, Z is the electrochemical equivalent of the substance.
Electrochemical Equivalent
The amount of substance deposited when one coulomb of electric charge is passed through an
electrolyte.
Unit: In SI unit it is expressed in kg/Coulomb.

If I = 1 unit (say, 1 ampere) and t = 1 unit (say, 1 second). Then Z = W, i.e., the electrochemical
equivalent of a substance is equal to the mass of that substance deposited or dissolved, when a
current of one ampere is passed for one second.

The electrochemical equivalents of some common elements are given below.

Faraday's Second Law of Electrolysis
The second law of electrolysis is defined thus:
The masses of different substances, liberated or dissolved by the same amount of electricity
are proportional to their equivalent masses.
Thus, when the same quantity of electricity is passed through a number of electrolytic solutions
connected in series, then the masses of the different materials liberated or dissolved at the
respective electrodes are in the ratio of their equivalent masses.
For example, when the same current is passed through the solutions of sulphuric acid (H 2SO4),
copper sulphate (CuSO4) and silver nitrate (AgNO3) for the same period of time,

Equivalent mass of an element= atomic mass an element/valency of the element

Figure - Experimental set up for the verification of the Second Law of Electrolysis
According to the second law of electrolysis, the same quantity of electricity will produce or
dissolve chemically equivalent amounts of all the substances. Therefore, the same quantity of
electricity is required to liberate or dissolve one equivalent of any material during electrolysis.
This quantity of electricity is called Faraday (F). One Faraday is equal to 96487 coulomb. For the
sake of convenience, we generally use a value 96500 C for the Faraday constant (F).

       Example

 How long has a current of 3 ampere to be applied through a solution of silver nitrate to coat a
metal surface of 80 cm2 with 0.005 cm thick layer? Density of silver is 10.5 g/cm 3.

Solution:             Mass of silver to be deposited

                                 = Volume × density

                                = Area ×thickness × density

Given: Area = 80 cm2, thickness = 0.0005 cm and density = 10.5 g/cm 3

                        Mass of silver to be deposited = 80 × 0.0005 × 10.5

                                                                = 4.2 g

                        Applying to silver E = Z × 96500

                                                Z =  108/96500 g

                        Let the current be passed for r seconds.

                        We know that

                                W = Z × I × t

                        So, 0.42 = 108/96500×3×t

                        or     t = (0.42 × 96500)/(108×3) = 1250.09 second

Example

A 100 watt, 100 volt incandescent lamp is connected in series with an electrolytic cell
containing cadmium sulphate solution. What mass of cadmium will be deposited by the current
flowing for 10 hours?

Solution:             We know that

               Watt = ampere × volt

             100 = ampere × 100

             Ampere = 100/100

             Quantity of charge = ampere × second

                                       = 100/100×10×60×60 coulomb

             The cathodic reaction is

            Cd2+       +     2e-    -->    Cd

           112.4 g      2 × 96500 C

Mass of cadmium deposited by passing  100/100×10×60×60

Coulomb charge = 112.4/(2×96500)×100/110×10×60×60 = 19.0598  g

Example

 In an electrolysis experiment, a current was passed for 5 hours through two cells connected in
series. The first cell contains a solution gold salt and the second cell contains copper sulphate
solution. 9.85 g of gold was deposited in the first cell. If the oxidation number of gold is +3, find
the amount of copper deposited on the cathode in the second cell. Also calculate the
magnitude of the current in ampere.

Solution:             We know that

(Mass of Au deposited)/(Mass f Cu deposited)=(Eq.mass of Au)/(Eq.Mass of Cu)

                        Eq. mass of Au = 197/3 ; Eq. mass of Cu 63.5/2

                        Mass of copper deposited

                        = 9.85 × 63.5/2×3/197 g = 4.7625 g

                        Let Z be the electrochemical equivalent of Cu.

                        E = Z × 96500

                or     Z = E/96500 = 63.5/(2×96500)

                Applying W = Z × I × t

                       T = 5 hour = 5 × 3600 second

                4.7625 = 63.5/(2×96500) × I × 5 × 3600

        or     I = (4.7625 × 2 × 96500)/(63.5 × 5 × 3600) = 0.0804 ampere

Applications of Electrolysis

The phenomenon of electrolysis has wide application. The important ones are:

(1)    Determination of equivalent masses of elements:

According to second law of electrolysis when the same quantity of electronic current is passed
through solutions of salts of two different cells, the amounts of the metals deposited on the
cathodes of the two cells are proportional to their equivalent masses of the respective metals.
If the amounts of the metals deposited on the cathodes be WA and WB respectively, then

WA/WB = (Equivalent mass of A)/(Equivalent mass of B)

Knowing the equivalent mass of one metal, the equivalent mass of the other metal can be
calculated from the above relationship. The equivalent masses of those non-metals which are
evolved at anodes can also be determined by this method.

 (2)    Electrometallurgy:

The metals like sodium, potassium, magnesium, calcium aluminum, etc., are obtained by
electrolytes of fused electrolytes.

Fused electrolyte                                                Metal isolated

NaCl + CaCl2 + KF                                             Na

CaCl2 + CaF2                                                              Ca

Al2O3 + cryolite                                                Al     

MgCi2 (35%) + NaCl (50%) + CaCl2 (15%)             Mg

NaOH                                                              Na

KCl + CaCl2                                                     K

(3)    Manufacture of non-metals:

Non-metals like hydrogen, fluorine, chlorine are obtained by electrolysis.

 (4)    Electro-refining of metals:

The metals like copper, silver, gold, aluminum, tin, etc., are refined by electrolysis.

 (5)    Manufacture of compounds:

Compounds like NaOH, KOH, Na2CO3 KCIO3, white lead, KMnO4, etc., are manufactured by
electrolysis.
(6)    Electroplating:

The process of coating an inferior metal with a superior metal by electrolysis is known as
electroplating.

The aims of electroplating are:

(i)     To prevent the inferior metal from corrosion.

(ii)    To make it more attractive in appearance.

 Process

The object to be electroplated is made the cathode and block of the metal to be deposited is
made the anode in an electrolytic bath containing a solution of a salt of the anodic metal. On
passing electric current in the cell, the metal of the anode dissolves out and is deposited on the
cathode-article in the form of a thin film. The following are the requirements for fine coating:

(i)  The surface of the article should be free from greasy matter and its oxide layer. The surface
is cleaned with chromic acid or detergents.

(ii)  The surface of the article should be rough so that the metal deposited sticks permanently.

(iii)  The concentration of the electrolyte should be so adjusted as to get smooth coating.

(iv)  Current density must be the same throughout.

For Anode Cathode Electrolyte

electroplating
With copper Cu Object CuSO4 + dilute H2SO4

With silver Ag Object KAg(CN)2

With nickel Ni Object Nickel ammonium sulphate

With gold Au Object KAu(CN)2

With zinc Zn Iron objects ZnSO4

With tin Sn Iron objects SnSO4