ELECTROCHEMISTRY

Electrochemistry is that branch of chemistry which deals with the inter-relationship between electrical energy
and chemical changes. It is the study of the production of electricity from energy released during spontaneous
chemical reactions and the use of electrical energy to bring about non-spontaneous chemical transformations.
Redox reactions:
A redox reaction is the reaction which involves both reduction and oxidation simultaneously. In the reaction,
one substance is reduced while the other is oxidized. Oxidation is a reaction which involves loss of electron
and reduction is a reaction which involves gain of electrons.
[OILRIG – Oxidation is Loss of electron and Reduction is Gain of electrons]
The substance that gets oxidized reduces the other substance and is called reducing agent or reductant. The
substance which gets reduced, oxidises the other substance is called oxidizing agent or oxidant.
Zn (s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
A redox reaction is considered to be made up of two half reactions. One involving oxidation and the other
involving reduction. These are called oxidation half reaction and reduction half reaction respectively.
Zn → Zn2+ + 2e- oxidation half reaction
Cu2+ + 2e- → Cu reduction half reaction
2+ 2+
Zn + Cu → Zn + Cu overall reaction
Electrochemical cells
These cells constitute the electrochemical reactions in which chemical energy is converted into electrical
energy. In these cells, spontaneous redox reaction is used to generate an electric current. These cells are also
called galvanic cells [voltaic cell]
Example of a galvanic cell is Daniel cell. It was constructed on the basis of the following spontaneous redox
reaction.
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

 The arrangement consists of two beakers, 1 M ZnSO 4 is taken in one and 1 M CuSO 4 is taken in the
other.
 A zinc rod is dipped in ZnSO4 solution and Cu rod in the CuSO4 solution. These metal rods act as
electrodes.
 The metallic rods in the beaker are connected to an ammeter by means of an insulated wore through a
key. Ammeter is used to know the passage of current which moves in opposite direction to the flow of
electrons.
 The solution in the two beakers are connected by an inverted U-shaped tube called salt bridge. A salt-
bridge is a U-shaped tube containing a concentrated solution of an inert electrolyte like KCl, KNO 3,
K2SO4, NH4NO3, etc. in a jelly like substance called agar agar or gelatin. The jelly keeps the electrolyte is
semi solid form and thus prevents mixing.
The important functions of a salt bridge are:
 Completes the electrical circuit. The salt bridge connects the two solutions of the half cells and their
electrodes are connected by means of a wire. Therefore, salt bridge completes the circuit.
 It maintains electrical neutrality of the two half-cell solutions.
 It allows the movement of ions from one solution to the other without mixing of the two solutions.
  In a salt bridge, the electrolytes such as KCl, KNO 3, NH4NO3, etc. are generally preferred because their
ions have almost equal mobility.
The circuit in a Daniel cell is completed by inserting the key in the circuit. It is observed that electric current
flows through external circuit as indicated by the ammeter. The observations are:
 Zinc rod undergoes oxidation and it gradually loses weight.
 The concentration of Zn2+ in the ZnSO4 solution increases.
 Copper gets deposited on the Cu rod and it gains weight.
 The concentration of Cu2+ in CuSO4 solution decreases.
 There is a flow of electrons in the external circuit from zin rod to the Cu rod. Therefore, current flows
from Cu to Zn. [the flow of electric current is taken opposite to the flow of electrons]
Zn(s) → Zn2+ + 2e [oxidation at anode]
2+
Cu + 2e → Cu(s) [reduction at cathode]
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) [overall reaction]
 The potential (emf) of Daniel Cell is 1.1 V, when the concentration of Zn 2+ and Cu2+ is 1 M.
 When an external opposite potential is applied, we see that the reaction continues to take place till the
opposing voltage reaches continues to take place till the opposing voltage reaches the value of 1.1 V.
 When the external opposing voltage reaches 1.1 V, the cell reaction stops and no current flows
through the cell. There is no chemical reaction.
 When the external opposing voltage is greater than 1.1 V, the cell reactions are reversed. The cell
now becomes as an electrolytic cell.
 To reverse an electrochemical cell, Eext > emf of the cell

Representation of an electrochemical cell [galvanic cell]

 A galvanic cell is represented by writing the anode on the left side and the cathode on the right side.
 Anode is represented by writing metal first and then the cation of the electrolyte, while the cathode is
represented by writing the cation of the electrolyte first and then the metal.
 The metal and the cation are separated by a slash (/).
 The salt bridge is represented by two vertical lines (||). They separate the two half cells.
1. Daniel cell
Zn(s)/Zn2+(s) || Cu2+(aq)/Cu(s)
2. Cu-AgNO3 cell
Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)
Cell notation: Cu(s) / Cu2+(aq) || Ag+(aq) / Ag(s)
3. Ni – AgNO3 cell:
Ni(s) + 2Ag+(aq) → Ni2+(aq) + 2Ag(s)
Cell notation: Ni(s) / Ni2+(aq) || Ag+(aq) / Ag(s)
ELECTRODE POTENTIAL AND EMF OF A GALVANIC CELL
o If a metal ion has relatively higher tendency to get reduced, the following reaction occurs. M n+ ions will
gain electrons from the metal rod. Mn+ + ne- → M. As a result, metal rod will develop a positive charge
with respect to the solution.
o If metal has higher tendency to get oxidized, the following reaction occurs: M → Mn+ + ne-. The
electrons will accumulate on the metal rod which will develop a negative charge. This may attract some
metal ions from the solution which may change into metal atoms.
o The electrical potential difference developed between the metal and its ions in the solution is called
electrode potential.
The electrode potential is of 2 types:
Oxidation potential: The tendency of an electrode to lose electrons or to get oxidized is called it oxidation
potential. Zn → Zn2+ + 2e-
Reduction potential: The tendency of an electrode to gain electrons or to get reduced is called its reduction
potential. Zn2+ + 2e- → Zn
o Oxidation potential is the reverse of reduction potential. Eg., If the reduction potential of Zn is - 0.76 V,
its oxidation potential is + 0.76 V.
o The difference between the electrode potentials of the two electrodes constituting an electrochemical
cell is known as electromotive force or cell potential of a cell. [emf]. This acts as a driving force for the
cell reaction. It is expressed in volts. It is equal to the reduction potential for the substance that
actually undergoes reduction minus the reduction potential of the substance that undergoes oxidation.
Ecell = Ecathode – Eanode
Ecell = Eright – Eleft
o EMF is the potential difference between the two electrodes of the cell when either no or negligible
current is allowed to flow in the circuit.
Eg., for the reaction in Daniel cell, Zn + Cu2+ → Zn2+ + Cu Zn / Zn2+ || Cu2+ / Cu
EZn2+/Zn = - 0.76V; ECu2+/Cu = 0.34 V
Ecell = 0.34 V – (- 0.76 V) = 1.1 V
Difference between EMF and potential difference
EMF Potential difference
1. It is the potential difference between the two It is the difference of the electrode potentials of the
electrodes when no current is flowing in the two electrodes when the cell is sending current
circuit. through the circuit.
2. It is the maximum voltage obtainable from the It is less than the maximum voltage obtainable from
cell. the cell.
3. The work calculated from EMF is the maximum The work calculated from the potential difference is
work obtainable from the cell. less than the maximum work obtainable from the
cell.
4. It is responsible for the flow of steady current It is not responsible for the flow of steady current in
in the cell. the cell.
5. EMF can be measured by potentiometric It can be measured by a simple voltmeter.
method only so that the EMF sent by the
potentiometer source is equal and opposite to
that of the cell and there is no net current
flowing in the circuit. It cannot be measured by
a voltmeter that draws current.

STANDARD HYDROGEN ELECTRODE [SHE]

The exact value of the electrode potential of a single electrode is measured by using some electrode as the
reference electrode. The reference electrode used is called standard hydrogen electrode.

o SHE consists of Pt wire sealed in a glass tube and has a Pt foil attached to it.
 o The foil is coated with finely divided Pt and acts as electrode.
o It is dipped into an acid solution containing H+ ions in 1 M concentration.
o Pure H2 gas at 1 bar pressure is constantly bubbled into solution at constant temperature of 298 K.
o If SHE acts as anode: H2(g) → 2H+(aq) + 2e- [oxidation] reaction takes place.
o If SHE acts as cathode: 2H+(aq) + 2e- → H2(g) [reduction] reaction takes place.
o The electrode is usually represented as: Pt, H2(g) / H+(aq)
o The electrode potential of SHE is taken as zero. E0H+/H2 = 0.0 V

MEASUREMENT OF ELECTRODE POTENTIAL E0

o To determine the electrode potential of any electrode, a cell is set up using this electrode as one of the
electrodes and the second electrode is the standard hydrogen electrode.
o The EMF of the cell is measured. As the emf of the cell is the sum of the oxidation potential of the
electrode when oxidation takes place, and the reduction potential of the electrode when reduction
takes place and one of the electrodes involved is the SHE, for which the electrode potential is taken as
zero, the emf of the cell will directly give the electrode potential of the electrode under investigation.
o The direction of the flow of current further indicates whether oxidation takes place or reduction takes
place with respect to the hydrogen electrode.
o The electrode potential is given positive sign if the electrode reaction involves reduction, when it is
connected to SHE and a negative sign if the electrode reaction involves oxidation when connected to
SHE.
E0Zn/Zn2+ = - 0.76 V and E0Cu2+/Cu = + 0.34 V
o A positive value of ECu2+/Cu indicates that Cu2+ ions get reduced more easily than H+ ions.
o Cu cannot be oxidized to Cu2+ ions in the presence of H+ ions. Hence Cu does not dissolve in HCl.

ELECTROCHEMICAL SERIES
The series in which the electrode potentials are arranged in the increasing order is called electrochemical
series.
A negative E0 means that the redox couple is a stronger reducing agent than H+/H2 couple.
A positive E0 means that the redox couple is a weaker reducing agent than H+/H2 couple.
 APPLICATIONS OF ELECTROCHEMICAL SERIES
1) To compare the relative oxidizing and reducing powers.
 Greater the reduction potential, more easily is the substance reduced., i.e., it is a stronger oxidizing
agent.
 The substance having lower electrode potential has least tendency to get reduced. Hence, they
undergo oxidation and act as a good reducing agent.
2) To compare the relative activities of metals:
 Any element having lower reduction potential can displace anuy element having higher reduction
potential from its salt solution. Eg. E 0Zn/Zn2+ = - 0.76 V, E 0Ag+/Ag = + 0.8 V. Here, Zn is more reactive than ag
and can displace Ag from it salt solution.
3) To calculate the standard EMF of any galvanic cell (E0cell): E0cell = E0cathode – E0anode
4) To predict the spontaneity of a redox reaction:
 If the E0cell is positive, the reaction is spontaneous.
 If E0cell is negative, the direct reactions as given cannot take place. The reverse reaction may occur.
5) To predict the product of electrolysis:
 Any substance having lower E0 becomes the anode and oxidation occurs. Any substance having higher
E0 becomes the cathode and reduction occurs.
 Electrochemical cells are extensively used for determining the pH of a solution, solubility product,
equilibrium constant and other thermodynamic properties and for potentiometric titrations.
 DIFFERENCE BETWEEN ELECTROLYTIC AND ELECTROCHEMICAL CELLS
ELECTROCHEMICAL CELLS ELECTROLYTIC CELLS
1. Chemical energy is converted into electrical Electrical energy is converted into chemical energy.
energy.
2. Free energy change ΔG is negative. Free energy change ΔG is positive.
3. Redox reaction will be spontaneous. Redox reaction is non-spontaneous and takes
plance only when electrical energy is supplied.
4. Two electrodes are usually set up in two Both the electrodes are suspended in the solution
separate beakers. in the same beaker.
5. The electrolytes taken in the two beakers are Only one electrolyte is taken.
different.
6. The electrodes taken are of different materials. The electrodes taken may be of the same or
different materials.
7. The electrode on which oxidation takes place is The electrode which is connected to the negative
the anode [-ve terminal] and the electrode on terminal of the battery is called cathode. The
which reduction takes place is called the cathode cations migrate to it which gains electrons and
[+ve terminals] hence reduction takes place here. The other
electrode is the anode.
8. Salt bridge is needed. Salt bridge is not needed.
9. Anode is negative and cathode is positive. Anode is positive and cathode is negative.
10. Oxidation occurs and anode and reduction at Oxidation occurs at positive electrode and
cathode. reduction at the negative electrode.
11. Electrons move from anode to cathode in the The electrons are supplied by the external battery
external circuit. and enter through cathode and come out through
anode.
12. Electricity is produced. Electricity is consumed.
13. Current flows from cathode to anode. Current flows from anode to cathode.
14. Reversible. Irreversible.

NERNST EQUATION
The concentration of electrolytes used in both the electrodes will affect the potential of the cell. This is
explained using Nernst equation.
For Daniel cell: Zn(s) / Zn2+(aq) || Cu2+(aq) / Cu(s)
Ecell = E0cell – 0.0591 log [Zn2+]
n [Cu2+]
For a general reaction: aA + bB → cC + dD, Nernst equation is given by
Ecell = E0cell – 0.0591 log [C]c[D]d
n [A]a[B]b
Equilibrium constant (Kc): At equilibrium, Ecell = 0.
At 298 K, E0cell = 0.0591 log Kc
n
Electrochemical cell and Gibbs energy of a reaction:
ΔG0 = - nFE0cell
ΔG0 = - 2.303 RT log Kc
CONDUCTANCE OF ELECTROLYTE SOLUTIONS
Substances that allow electricity to pass through them are called conductors and substances that do not allow
electricity to pass through them are called insulators.
 TYPES OF CONDUCTORS
DIFFERENCE BETWEEN METALLIC CONDUCTION AND ELECTROLYTIC CONDUCTION
METALLIC CONDUCTORS ELECTROLYTIC CONDUCTORS
1. Carried out by movement of electrons. Carried out by the movement of ions.
2. Flow of electricity takes place without Flow of electricity takes place accompanied by the
decomposition of the substance. decomposition of the substance.
3. There is no flow of matter. There is flow of matter.
4. Conductivity decreases with increase of Conductivity increases with increase in
temperature. temperature.
5. Electrons flow from negative end to positive Ions move towards oppositely charged electrodes.
end.
6. No change in composition at the electrodes. Chemical change takes place as conduction occurs.

FACTORS AFFECTING ELECTROLYTIC CONDUCTION

NATURE OF THE ELECTROLYTE:
 The conductance of an electrolyte depends on the number of ions present in the solution. Greater the
number of ions, greater is the conductance.
 Strong electrolytes dissociate almost completely into ions in solution. They conduct electricity to a
large extent. i.e. they have high conductance.
 Weak electrolytes ionize to a small extent and give lesser number of ions. Hence, they conduct
electricity to a small extent and they have low conductance.

NATURE OF THE SOLVENT AND ITS VISCOSITY:

 Electrolytes ionize more in polar solvents. Greater the polarity of the solvent, larger is the ionization
and hence greater is the conductance.
 Greater the viscosity of a solvent, lesser is its conductance.
SIZE OF THE IONS PRODUCED AND THEIR SOLVATION:
 If the ions are strongly solvated, their effective size will increase [combination of ions with solvent] and
their conductance decreases.
CONCENTRATION OF THE ELECTROLYTIC SOLUTION:
 Higher the concentration of the solution, lesser is the conductance.
 This is because in a weak electrolyte, the ionization is less whereas in a strong electrolyte, the
interionic attractions are large at higher concentrations.
 Conductance of an electrolyte increases with decrease in concentration or increase in dilution. With
dilution in weak electrolytes, ionization increases and hence conductance increases. For strong
electrolytes, the interionic attractions decrease with dilution and hence conductance increases.
TEMPERATURE:
 With increase in temperature, the conductivity of an electrolyte increases due to decrease in
interactions between ions. The dissociation increases and hence the conduction increases.
RESISTANCE AND RESISTIVITY
It measures the obstruction to the flow of current. The resistance of a conductor is directly proportional to the
length (l) and inversely proportional to the area of cross-section (A).
Rαl ⇒R=ρl where ρ = constant of proportionality called resistivity.
A A
2
If l = 1 cm, A = 1 cm , then R = ρ
Therefore, resistivity or specific resistance is defined as the resistance of a conductor of length 1 cm and area
of cross-section 1 cm2. The unit of ρ is ohm cm [Ω cm]
 CONDUCTANCE AND CONDUCTIVITY
o Conductance is a measure of the ease with which the current flows through a conductor.
o It is expressed as G. It is the reciprocal of resistance. G = 1/R
o Units of conductance is Ω-1 or mho. The SI unit of electrical conductance is Siemens (S). [1 S = 1 Ω -1].
o The inverse of resistivity is called conductivity or specific conductance. It is represented by k (kappa).
G = 1 = 1xA = kA
R ρ l l
2
o If l = 1 cm, A = 1 cm , G = k. Conductivity is the conductance of a solution of length 1 cm and area of
cross-section 1 cm2.
o Unit of Conductivity: Ω-1 cm-1
o Conductivity depends on the nature of the material. Substances having zero resistivity or infinite
conductivity are known as super conductors. Conductivity also depends on the temperature and
pressure at which the measurements are made.
o Metals and their alloys have very large conductivity and are known as conductors.
o Certain non-metals like carbon black, graphite and some organic polymers (polyacetylene, polyaniline,
polypyrrole, polythiophene) are also conducting. Substances like glass, ceramics, etc. have very low
conductivity are called insulators.

MOLAR CONDUCTIVITY
o It is the conducting power of all ions produced by dissolving 1 mole of an electrolyte in solution.
o It is the conductance of the solution containing 1 mole of the electrolyte when placed between two
parallel electrodes 1 cm apart. The molar conductance is the product of the conductivity and volume V
in cm3 of the solution containing 1 mole of the electrolyte.
λm = kV λm = 1000 k where M = molarity
M
o Unit of molar conductance: Ω cm2 mol-1 or S cm2 mol-1
-1

VARIATION OF CONDUCTIVITY AND MOLAR CONDUCTIVITY WITH CONCENTRATION

o The electrolytic conductance decreases with increase in concentration or increases with increase in
dilution. This is because conductance of ions is due to the presence of ions in the solution. Greater the
number of ions, the greater is the conductance.
o Conductivity of electrolytes decrease with decrease in concentration for both weak and strong
electrolytes.
o Molar conductivity increases with the decrease in concentration. i.e. conductivity decreases while
molar conductivity increases with dilution.
o The increase in λm on dilution is due to the fact that it is the product of k and the volume of the solution
containing 1 mole of the electrolyte.
λm = k V
On dilution, k decreases but volume containing 1 mole of an electrolyte increases. The increase in volume on
dilution is much more than the decrease in k. λm increases with dilution.
λm = 1000 k where M is the concentration.
M
It is clear from the equation that λm is inversely proportional to concentration. Hence as concentration
decreases, λm increases.
VARIATION OF λm FOR STRONG ELECTROLYTES
 For strong electrolytes, λm increases slowly with dilution and there is a tendency for λ m to approach a
certain limiting value when the concentration approaches zero [infinite dilution].
The molar conductivity when the concentration approaches infinity dilution is called molar conductivity at
infinite dilution. [λm0]. As c → 0, λm = λm0

 The variation of λm with concentration is given by Debye Huckel Onsager equation:

λm = λm0 – A √c
 The value of constant A for a given solvent and temperature depends on the type of electrolyte, i.e.,
the charges on the anion and cation produced on the dissociation of the electrolyte in the solution.
[NaCl is 1:1 electrolyte, CaCl2 is 2:1 electrolyte and ZnSO4 is 2:2
electrolyte].
All electrolytes of a particular type have the same value of A.

 Using the equation, λm = λm0 – A √c, we can plot a graph taking λm

as y-axis and √c as X-axis, we will get a straight-line graph for
strong electrolyte and the slope of the graph is – A. On
extrapolating to zero concentration we get the intercept. It
corresponds to λm0 of that particular strong electrolyte.
 For strong electrolytes, there is only a small increase in conductance with dilution because a strong
electrolyte is completely dissociated in solution and so the number of ions remains constant. At higher
concentration, the greater inter-ionic attractions retard the motion of ions and therefore, the
conductance falls with increasing concentration. On decreasing the concentration, the ions are far
apart and therefore, inter-ionic attractions are less due to which the conductance increases with
dilution.

WEAK ELECTROLYTES
Weak electrolytes dissociate to a lesser extent than strong electrolyte. λm is low for weak electrolytes as
compared to strong electrolytes.
The variation of λm with √c is very large for weak electrolyte. We cannot obtain λm0 for weak electrolyte from
the graph by extrapolation. The graph is a curve and it is parallel to the Y-axis.
The value of λm0 of weak electrolytes can be obtained by an indirect method based on Kohlraush’s law.
For weak electrolytes, there is a very large increase in conductance with dilution especially near infinite
dilution. This is because, as the concentration of weak electrolyte is reduced, more of it ionizes.

KOHLRAUSCH’S LAW OF INDEPENDENT MIGRATION OF IONS

It states that, “The limiting molar conductivity of an electrolyte can be expressed as the sum of the limiting
ionic molar conductivities of the cation and anion.”
[The λm0 of an electrolyte is the sum of the limiting ionic conductivities of the cation and anion each multiplied
with the number of ions present in one formula unit of the electrolyte.]

λ0+ and λ0- are molar ionic conductivities of cations and anions respectively.
are the number of cations and anions formed from one formula unit of an
electrolyte.
APPLICATIONS OF
KOHLRAUSH’S LAW
1) Calculate λ om of weak electrolytes:
It is not possible to obtain the λ om of a weak electrolyte from the λ m vs √ C graph. To calculate the λ om of a
weak electrolyte, we have to identify some strong electrolytes from which we will be able to obtain the λ om of
a weak electrolyte easily.
o Example: To find the λ om of CH3COOH, we have to select a sodium or potassium salt of acetic acid, a
strong acid and a salt like NaCl or KCl (depending on the acid)
The electrolytes selected are CH3COONa, HCl and NaCl.
λ o CH3COONa = λ oCH3COO- + λ oNa+ à(1)
λ oHCl = λ oH+ + λ oCl- à(2)
λ oNaCl = λ oNa+ + λ oCl- à(3)
λ o CH3COOH = λ o CH3COONa + λ oHCl - λ oNaCl
= λ oCH3COO- + λ oNa+ + λ oH+ + λ oCl- - λ oNa+ - λ oCl-
= λ oCH3COO- + λ oH+

o To find λ oNH4OH, we can take NH4Cl, NaOH, NaCl.

λ oNH4OH = λ oNH4Cl + λ oNaOH - λ oNaCl
λ oH2O = λ oHCl + λ oNaOH - λ oNaCl
2) Calculation of Degree of Dissociation
λm of a weak electrolyte depends upon the degree of dissociation. Higher the degree of dissociation, larger
is the value of λm.
λm = molar conductivity of a solution at any concentration.
λ0m= molar conductivity at infinite dilution.
3) Calculation of Dissociation Constant (K)
Dissociation constant, K = cα2 where c = concentration
1-α
4) Calculation of Solubility of Sparingly Soluble Salts
Sparingly Soluble Salts such as AgCl, PbSO4, BaSO4 etc. dissolve to a very little extent in water. Hence their
solutions are considered as infinite dilute. As their solutions are saturated, their concentration may be taken
equal to their solubility. The solubility can be calculated as follows.
λ0m= k x 1000 = k x 1000
molarity solubility
solubility = k x 1000
 λ 0m
ELECTROLYTIC CELLS AND ELECTROLYSIS
Electrolysis is the process of decomposition of an electrolyte by the passage of electricity through its aqueous
solution or molten (fused) state. It takes place in a cell called electrolytic cell.
Electrolysis involves the following steps:
1) Ionisation or dissociation of electrolytes.
2) Migration of ions to the respective electrodes (oppositely charged)
3) Discharge of ions at the respective electrodes.
Eg:- an electrolytic cell consists of two copper rods dipped in an aqueous copper sulphate solution. When
electric current is applied to the two electrodes, Cu2+ ions discharged at cathode.
Cu
2 +¿¿
+2 e−¿¿ -------->Cu. Therefore, copper metal is deposited at cathode.
2 +¿¿
At the anode, Cu is converted to C u ions. Cu------->C u2 +¿¿+2 e−¿¿
Cu dissolves at anode. Cu is oxidized at the anode, and it is reduced at the cathode.

 By this method we can convert impure Cu to high purity.

 Metals like Mg, Al, Na can be produced on large scale using this method.
 Na and Mg are produced by the electrolysis of their fused chlorides.
 Al is produced by electrolysis of A l 2 O3 in presence of cryolite N a2 Al F 6.
FARADAYS LAWS OF ELECTROLYSIS
Faradays first law of electrochemistry:
It states that the amount of any substance liberated or deposited at any electrode is directly proportional to
the quantity of electricity passing through the electrolyte.
If W gram of any substance is liberated/deposited on passing Q coulomb of electricity, then,
W = ZQ Z=proportionality constant
If current of I ampere is passed for t seconds, then, Q = It ⇒ W = ZIT
If I = 1 A and t = 1s, then, W = Z
The electrochemical equivalent of a substance is defined as the mass of a substance liberated/deposited
when a current of 1 amp is passed for 1 second.
Faraday’s second law of electrolysis:
It states that when the same quantity of electricity is passed through different electrolytic solutions connected
in series, the weight of the substances produced at the electrodes are directly proportional to their chemical
equivalent weights.
Note- [chemical equivalent weight is atomic mass divided by the number of electrons required to reduce the
cation]
Therefore, Weight of A deposited/Weight of B deposited = equivalent mass of A/equivalent mass of B
EXAMPLE: When the same quantity of electricity was passed through CuSO4 and AgNO3 solutions connected in
series,
Weight of Cu deposited/Weight of Ag deposited = equivalent mass of Cu/
equivalent mass of Ag
According to Faraday’s law, the amount of chemical change occurred is the moles of substance deposited or
liberated is proportional to the number of moles of electrons exchanged during the oxidation-reduction
reactions that occur.
The quantity of electricity required to liberate 1.008 g (1 g equivalent) of hydrogen or deposit 108 g of Ag or to
liberate/deposit 1 g equivalent of any substance has been found to be approximately 96500 Coulomb. This
quantity is called Faraday’s constant.
On combining 1st and 2nd law, it is stated that the amount of electricity or charge required for oxidation or
reduction depends on the stoichiometry of the electrode reaction.
EXAMPLE: Ag+ + 1e- à Ag
1 mole of electrons is required for the reduction of 1 mole Ag +.
Charge on 1 electron = 1.6021 x 10-19 C
Therefore, charge on one mole of electron = 1.6021 x 10 -19 x 6.022 x 1023 = 96487 C mol-1 = 96500C = 1 F
Cu2+ + 2e- àCu therefore, 2F electricity is needed.
Al3+ + 3e- àAl therefore, 3F electricity is needed.
PRODUCTS OF ELECTROLYSIS
 The products of electrolysis can be predicted on the basis of electrode potentials of different reactions.
the products of electrolysis depend on the nature of material being electrolyzed and the types of
electrodes used.
 If the electrode is inert, (Pt, Au), it does not take part in the chemical reaction and only acts as a source
of electrons.
 If the electrode is reactive, it takes part in the chemical reaction. the products of electrolysis mainly
depend on the different oxidizing and reducing species present in the electrolytic cell and their
standard electrode potentials.
 The slowness of certain electrode reactions creates electrical resistance at the electrode surface.
Therefore, for the occurrence of such reactions, [liberation of gases] some extra potential or voltage is
required than the
 Theoretical value of their standard electrode potential. this extra voltage required is called over
voltage.
 The ion having low reduction potential goes to the anode and undergoes oxidation.
1) Electrolysis of molten NaCl [common salt]
When electricity is passed through molten NaCl the ions produced are Na +¿¿ and Cl−¿¿
NaCl → Na + Cl
+¿¿ −¿¿

Cathode:
+¿¿
Na + 1e
−¿¿
→ Na
Anode: Cl −¿¿
→ Cl + 1e −¿¿

Overall: 2NaCl → 2Na + Cl 2

Sodium is deposited at the cathode and Cl 2 gas is liberated at the anode.

2) Electrolysis of molten Pb Br2 using Pt electrodes

When electricity is passed through molten Pb Br2 the ions produced are Pb2+¿ ¿and Br−¿¿
Pb Br2 → Pb
2+¿ ¿ −¿¿
+ 2 Br
2 Br → 2Br + 2e
−¿¿ −¿¿
At Anode:
-
2Br → Br2
At cathode: Pb
2+¿ ¿
+ 2e → Pb
−¿¿

Overall reaction: Pb Br2 → Pb + Br2

Lead is obtained at cathode and bromine gas at anode.
3) Electrolysis aqueous NaCl [brine solution]
When electricity is passed through aqueous NaCl, it ionizes as
 NaCl → Na + Cl
+¿¿ −¿¿

H 2O → H +¿¿ + OH −¿¿
At cathode: Na +¿¿ and H +¿¿ can go to the cathode.
The ion having higher Eo goes to the cathode and gets discharged. Eo = - 2.7 V, Eo =0.00 V
+¿¿
Since H has higher Eo , it goes to the cathode. H+ + 2e → H2
+
H ions are produced by the dissociation of water. H2O → H+ + OH-

Therefore, net reaction at the cathode is: H2O + e → ½ H2 + OH-

At anode: Cl- and OH- can go to the anode and get discharged. The ion having lower E0 usually goes to the
anode.
Cl- - e- → ½ Cl E0 = 1.36 V
2H2O → 2H2 + O2 E0 = 1.23 V
The E0 of water is slightly less and therefore, it has more chance to get oxidized. But due to the over potential
of oxygen, it cannot get oxidized at anode. Hence Cl- gets oxidized at anode and Cl2 gas is liberated.
2Cl- → Cl2 + 2e-
Overall reaction: NaCl(aq) + H2O(l) → Na+ + OH- + ½ H2(g) + ½ Cl2(g)
Hydrogen is liberated at cathode and Cl2 at the anode and the solution contains NaOH.

4) Electrolysis of acidulated water:

Pure water is a poor conductor of electricity. Water containing a few drops of acid or alkali becomes a good
conductor.
Reaction at cathode: 2H+ + 2e- → H2
Reaction at anode: 4OH- - 4e → 2H2O + O2
When we add a few drops of H2SO4, before carrying electrolysis, the SO42- ions will also be formed at the anode
along with OH- ions.
H2SO4 → 2H+ + SO42-
SO42- ions will not be released since their E0 is more than that of OH-
Overall reaction: 2H2O → 2H2 + O2
Hydrogen is collected at the cathode and oxygen is obtained at the anode. The volumes of hydrogen collected
is found to be twice the volume of oxygen.

5) ELECTROLYSIS OF COPPER SULPHATE SOLUTION USING INERT ELECTRODES

On passing electricity, aqueous CuSO4 ionises as: CuSO4 → Cu2+ + SO42-
H2O → H+ + OH-
At cathode: Cu and H ions are present near the cathode. The ion having higher E0 goes to the cathode and
2+ +

get discharged. E0Cu2+/Cu = + 0.34 V; E0H+/H2 = 0.0 V

Hence E0Cu2+/Cu is more and is discharged at the cathode. Cu2++ 2e → Cu
Since the E0 of OH- is less than SO42-, it is discharged at the anode.
2H2O → 4H+ + O2 + 4e
Overall reaction: 2CuSO4 + 2H2O → 2Cu + 4H+ + 2SO42- + O2
Copper is deposited at cathode and oxygen is liberated at anode. The electrodes used are inert electrodes
which are not attached by ions. However, if the electrodes are attacked by ions, then the reactions taking
place during electrolysis are different.

6) ELECTROLYSIS OF CUSO4 SOLUTION USING COPPER ELECTRODES

CuSO4 → Cu2+ + SO42-
H2O → H+ + OH-
At cathode: Cu2+ ions discharge and Cu deposits at cathode.
Cu2+ + 2e → Cu
At anode: Unlike electrolysis of copper sulphate using Pt electrodes, no ions are liberated. On the other hand,
anode itself undergoes loss of electrons to form Cu2+ ions which goes into solution.
Cu → Cu2+ + 2e
Hence, Cu is deposited at cathode from the solution and an equivalent amount of copper from the anode
dissolves into solution as Cu2+ ions.
This principle of electrolysis is widely used in electroplating and purification of less reactive metals such as Pb,
Cu, Ag, etc. The impure metal is made the anode that dissolves on passing current and the pure metal is
deposited at the cathode.
HYDROGEN – OXYGEN FUEL CELLS

In H2-O2 fuel cell, H2 is used as a fuel and O2, the

oxidizing agent. The energy produced due to the
combustion of H2 is converted into electrical
energy.

The cell consists of porous carbon electrode

immersed in concentrated NaOH or KOH
solution.

Catalysis like finely divided Pt or Pd metals are

incorporated into the electrodes for increasing
the rate of electrode reactions.

H2 and O2 are bubbled through the porous electrodes into NaOH or KOH solution. H 2 is introduced into the anode where
it is oxidized. O2 is introduced into the cathode where it is reduced.

Anode: 2H2 + 2OH- → 2H2O + 2e

Cathode: O2 + 2H2O + 4e → 4OH-
Overall reaction: 2H2 + O2 → 2H2O

The cell has been used for providing electric power in the Apollo space programme. The weight of the fuel sufficient for
11 days in space was approximately 200 kg. The product of combustion, water was used for drinking by the astronauts.

Advantages of fuel cells:

1. Because of the continuous supply of fuels, such cells never become dead. Such a cell is usually operated at a
temperature of 70 – 1400C and gives a potential of about 0.9 V.
2. The fuel cells convert the energy of a fuel directly into electricity. Therefore, they are more efficient.
3. There is no electrode material to be replaced as in ordinary battery. The fuel can be fed continuously to produce
power.
4. They do not cause any pollution problems like thermal plants which burn fossil fuels like coal, gas, oil, etc.

Difficulties in constructing fuel cells:

1. Providing of contact between the three phases needed in a fuel cell. i.e, gaseous fuel, the liquid electrolyte and
the solid catalyst.
2. The corrosiveness of the electrolytes used.
3. High cost of the catalysts needed for the electrode reactions. [Pt, Pd, Ag, etc.]
4. Problem of handling gaseous fuels at low temperatures or high pressures.

CORROSION
At a particular spot of an object made up of iron, oxidation takes place and the spot behaves as an anode.
At anode: Fe → Fe2+ + 2e
Thus, the metal atoms in the lattice go into solution as Fe 2+ ions leaving the electrons on the metal itself. These electrons
go to another spot on the metal and reduce the atmospheric O 2 to water in the presence of H+ ions. This spot behaves as
the cathode. The water vapours on the surface of the metal dissolve CO 2 and O2 from air. This, the surface of metal is
covered with the solution of CO2 in water. [carbonic acid, H2CO3]

H2O + CO2 → H2CO3 [This acts as an electrolytic solution of the cell]

The carbonic acid dissociates to a small extent. H 2CO3 → 2H+ + CO32-

The H+ ions are obtained either from the dissociation of water or by the dissociation of carbonic acid.
At cathode: 4H+ + O2 + 4e → 2H2O
Oxidation half reaction is: Fe → Fe2+ + 2e E0 = -0.44V
+ 2
Reduction half reaction is: 4H + O + 4e → 2H2O E0 = 1.23 V
Overall reaction is: 2Fe + 4H+ + O2 → 2Fe2+ + 2H2O E0 = 1.67 V

The Fe2+ ions are oxidized further by the dissolved O 2 or atmospheric O2 from air to form ferric oxide with further
production of H+ ions. The ferric oxide then reacts with water (hydration) and forms hydrated ferric oxide which is
known as rust.
4Fe 2+ + O2 + 4H2O → 2Fe2O3 + 8H+
Fe2O3 + xH2O → Fe2O3.xH2O [rust]