3.electrochemistry 2020-21 Except Nerest Equation

3.
Electrochemistry
Electrochemistry is 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 reactions carried out electrochemically can be energy efficient and less polluting.
The basis of these types of process are redox reactions.
Redox reactions
The reactions which involve both oxidation and reduction are called redox reactions. In
these reactions, electrons are transferred from one reactant to another.
Reducing agent or Reductant:
The substance which can lose one or more electrons(i.e., get oxidized) is called Reducing
agent or reductant.
Oxidizing agent or Oxidant:
The substance which can gain one or more electrons (i.e., get reduced) is called Oxidizing
agent or Oxidant.
{“LEOGER” = Loss of Electron is Oxidation and Gain of Electron is Reduction}
Single Electrode (or) Half Cell:
Zinc Electrode:
In a beaker,
Zinc rod is dipped into 1.0 M ZnSO4 solution
Copper Electrode:
In a beaker,
Copper rod is dipped into 1.0 M CuSO4 solution
Salt Bridge:
A salt bridge is an inverted U-tube filled with
concentrated solution of inert electrolytes or salts like KCl,
KNO3, NH4NO3. [For preparing a salt bridge, gelatin or agar-agar is
dissolved in a hot aqueous solution of salts like KCl, KNO3, NH4NO3 and
filled in a U-tube. On cooling the agar-agar solution becomes solid and
is used as salt bridge.]
Class:12 Unit 3: Electrochemistry 2020-21 R .SEKAR, EMBASSY OF INDIA SCHOOL MOSCOW Page 1 of 25
Function of Salt bridge:
i) Connects the two half cells and completes the cell circuit.
ii) Keeps the solutions in the two half cells electrically
neutral.
[Sometimes, both the electrodes dip in the same electrolyte solution
and in such cases we don’t require a salt bridge.]
Electrochemical Cell:
The Electrochemical cells are also called Galvanic cells or Voltaic cells after the names
of the scientists.
A Electrochemical cell convert chemical energy into electrical energy.
Daniel Cell: Daniel Cell:

The arrangement consists of two
beakers,
Anode one of which a Zinc rod is dipped into 1.0
M ZnSO4 solution and the other a Copper
rod is dipped into 1.0 M CuSO4 solution.
It has electrical potential equal to 1.1 V.
(i) Cu2+ + 2e→Cu(s) (reduction half reaction)

(ii) Zn(s) →Zn2+ + 2e– (oxidation half reaction)
Overall reaction is
Zn(s) + Cu2+(aq) →Zn2+ (aq) + Cu(s)
The copper electrode may be called the
reduction half cell and the zinc electrode,
the oxidation half-cell.
Cathode These two portions of the cell are also
called half-cells or redox couples.
Functioning of Daniell cell when external voltage Eext opposing the cell potential is applied:
Case I:
Case II:
Case III:
Electrode potential:
A potential difference develops between the electrode and the electrolyte which is called
electrode potential.
Standard electrode potential:
When the concentrations of all the species involved in a half-cell is unity then the
electrode potential is known as standard electrode potential.
Standard reduction potentials are now called standard electrode potentials.
The potential difference between the two electrodes of a galvanic cell is called the cell
potential and is measured in volts.
Conventional Current flow

Electron flow
Zn 2+(1M) Zn 2+(1M)
Anodoic Anodoic
Electrolyte Electrolyte
Zn Salt bridge Cu
Anode Cathode
Oxidation takes place Reduction takes place
(-)ive (+)ive
Left Right
Distinction between emf and Potential difference:
EMF Potential difference

1. It is the difference in the electrode It is the difference in the electrode
potentials when no current flows potentials when current is flowing
through the cell. through the cell.
2. It is the maximum voltage which can be It is less than the maximum voltage
obtained from the cell. which can be obtained from the cell.
3. It is responsible for the flow of steady It is not responsible for the flow of
current. steady current.
4. It can be measured by a potentiometer. It can be measured by voltmeter.
Cell potential :
The cell potential is the difference between the electrode potentials (reduction
potentials) of the cathode and anode. It is called the cell electromotive force (emf) of the
cell when no current is drawn through the cell.
Ecell = Eright – Eleft i.e., Ecell = ECathode – EAnode
Refer: Text Book

Measurement of Electrode Potential :
The potential of individual half-cell cannot be measured.
Standard Hydrogen Electrode (SHE).
-Nernst Equation - Nernst Equation for Daniell cell
Equilibrium Constant from Nernst Equation
Electrochemical Cell and Gibbs Energy of the Reaction

************************
Conductance of Electrolytic Solutions
Metallic and Electrolytic conductance:
Non-Conductors (or) Insulator : The substances which do not allow the

passage of electric current are called Non-Conductors or Insulators.
Conductors: The substance which allow the passage of electric current are
called Conductors.
Example: Metals , Semi-metals or Metalloids and Alloys
Super Conductors:
Substance have zero resistivity or infinite conductivity are called Super
Conductors.
Earlier, only metals and their alloys at very low temperatures (0 to 15 K) were
known.
Nowadays a number of ceramic materials and mixed oxides are also show
superconductivity at temperatures as high as 150 K.
Types of conductors:
1.Metallic conductors or Electronic Conductors:
Metallic substances which allow the electricity to pass through them without
undergoing any chemical change.
The flow of electric current through metallic conductors is due to the flow
of electrons in the metal atoms.
Metallic conductors depends on:
i)the nature and structure of the metal
ii)the number of valence electrons per atom
iii)the density of metal and
iv)temperature (Decreases with increase in temperature)
(Exception: Certain non-metals like carbon black, Graphite and some organic
polymers are also electronically conducting)
2.Electrolytic conductors or Electrolytes :

The substances which allow the pass through them in their molten state or in
the aqueous solutions and undergo chemical decomposition are called
electrolytic conductors.
The flow of current through an electrolytic solution is called electrolytic
conduction.
Factors influencing Electrolytic conduction:
(i) the nature of the electrolyte added
(ii) size of the ions produced and their solvation or Hydration of ions.
(iii) the nature of the solvent and its viscosity
(iv) concentration of the electrolyte
(v) temperature (it increases with the increase of temperature).
Non-Electrolytes:
The substances, which do not conduct electricity either in their molten state
or through their aqueous solutions are called Non-Electrolytes.
Difference between metallic and Electrolytic Conduction
Sl.No. Metallic conduction Electrolytic conduction
1 Due to the movement of Due to the movement of ions
electrons
2 No change in their chemical Decomposition of electrolyte
properties takesplace
3 It does not involve transfer of It involves transfer of matter
matter
4 Metallic conduction decreases Electrolytic conduction
with increase in temperature increases with increase in
temperature
5 The conductivity is generally The conductivity is generally
high low
Classification of Electrolytes:
All electrolytes do not ionize to the same extent in solution. On the basis of
ionization electrolytes are divided into two types.
Strong Electrolytes and Weak Electrolytes.
Strong Electrolytes:
The electrolytes which undergo complete dissociation are called Strong
Electrolytes.
Example: NaCl, KCl, NaOH, NH4Cl ,Salts, etc.,
Weak Electrolytes: The electrolytes which do not undergo complete

dissociation are called Weak Electrolytes.
Example: CH3COOH, H2CO3, NH4OH, etc.,
Degree of Dissociation (or) Degree of Ionisation: In Weak Electrolytes, an

equilibrium is established between the unionized electrolyte and the ions in
the solution. The extent of ionization of a weak electrolyte is expressed in
terms of degree of ionisation .
Number of molecules of electrolyte which split into ions
Degree of Dissociation( α) = -----------------------------------------------------------
Total number of molecules of electrolyte
For Strong electrolyte α is almost equal to one. α =1
For Weak electrolyte α is smaller than one. α < 1
Ohm’s Law: Like metallic conductors, electrolytic solutions obey Ohm’s Law.
“Current flowing through a conductor is directly proportional to the
potential difference across it”
ie., V α I or V = IR where V is the potential difference (in Volts). I is
the current strength( in amperes) and R is the proportionality constant.
Resistance: It measures the obstructions to the flow of current.
R α l/A (or) R = ρ . l/A Where ρ(rho) is called
specific resistance (or) Resistivity.
R is measured in ohm (Ω) which in terms of SI base units is equal to
(kg.m2)/(s3 A2). It can be measured with the help of a Wheatstone bridge.
Resistivity or Specific Resistance: [IUPAC recommends Resistivity]

“The resistance of a conductor of 1cm length and having area cross section
equal to 1 cm2 ”. A= 1cm, l = 1cm2
ρ = R . A/l ohm. cm2/cm = ohm. cm
Its SI units are ohm.metre(Ωm). But quite often ohm.cm(Ωcm) is used.
Conductance: It is a measure of the ease with which current flows through a
conductor.
It is expressed as ’G’. It is inverse of the resistance,
i.e., G = 1/R ohm-1(or) mho. Ω-1. [In SI unit, 1 ohm-1 = 1S] Siemens
=1/ ρ . A/l
G = k. A/l
Conductivity(or) Specific Conductance:
The inverse of resistivity is called conductivity(or) Specific Conductance).
It is represented by the symbol ‘k’ (kappa).
“The conductance of a solution of 1 cm length and having 1 cm2 as the area of

cross-section”. (or)
“Conductance of one centimeter cube of a solution of an electrolyte”
k = 1/ ρ ohm-1.cm-1 (or) Ω-1cm-1(or) S.m-1
Molar Conductivity (or) Molar Conductance:
“The conducting power of all the ions produced by dissolving one mole of an
electrolyte in solution”. It is denoted as Λm (Lambda).
Λm = k/C where C is the molar concentration.
If C is in the units of Molarity,
Then, Λm = [ k x1000]/C where C is the Molarity.
Measurement of the Conductivity of Ionic Solutions:
We know that accurate measurement of an unknown resistance can be
performed on a Wheatstone bridge.
However, for measuring the resistance of an ionic solution we face two
problems.
Firstly, passing direct current (DC) changes the composition of the solution.
(It causes electrolysis of the solution)
Secondly, a solution cannot be connected to the bridge like a metallic wire or
other solid conductor.
The first difficulty is resolved by using an alternating current (AC) source of
power.
The second problem is solved by using a specially designed vessel called
conductivity cell. Conductivity cell
Two different types of conductivity cells
It consists of two platinum electrodes coated with platinum black (finely
divided metallic Pt is deposited on the electrodes electrochemically).
These have area of cross section equal to ‘A’ and are separated by distance ‘l’.
Therefore, solution confined between these electrodes is a column of length l
and area of cross section A.
The quantity l/A is called cell constant denoted by the symbol, G*.
The cell constant is usually determined by measuring the resistance of the

cell containing a solution whose conductivity is already known. For this
purpose, we generally use KCl solutions whose conductivity is known
accurately at various concentrations and at different temperatures.
Conductivity Conductance(G) x Cell Constant Since, G = 1/R
(or)
The conductivity of solutions of different electrolytes in the same

solvent and at a given temperature differs due to charge and size of the ions
in which they dissociate, the concentration of ions.
In the above equation, if ‘κ’ is expressed in S m–1 and the concentration, c in
mol m–3 then the units of Λm are in S m2 mol–1.
Wheatstone Bridge
AC
Apparatus for measuring conductance of a solution
R2 R1
=
R4 R3
R1 X R4
R2 =
R3
Variation of Conductivity and Molar Conductivity with Concentration
*Upon dilution, Specific conductance or conductivity decreases while molar

conductivity increases.
Reason for conductivity decrease :
“The number of ions per unit volume that carry the current in a solution
decreases on dilution”.
The conductivity of a solution is the conductance of one unit volume of
solution kept between two platinum electrodes with unit area of cross section
and at a distance of unit length.
i.e., G=k. 1 Since A =1cm2 and l = 1 cm . [unit volume]
Reason for molar conductivity increases:
Molar conductivity of a solution at a given concentration is the

conductance of the volume V of solution containing one mole of
electrolyte kept between two electrodes with area of cross section A and
distance of unit length.
Since l = 1 and A = V (Volume containing 1 mole of electrolyte)
Molar conductivity increases with decrease in concentration. This is because

the total volume, V, of solution containing one mole of electrolyte also
increases.
Also, decrease in ‘κ’ on dilution of a solution is more than compensated by
increase in its volume.
Limiting molar conductivity : When concentration approaches zero, the
molar conductivity is known as limiting molar conductivity and is represented
by the symbol Λm°.
Variation of Molar Conductivity with Concentration for Strong Electrolyte
:
In case of strong electrolytes, the ionisation is already complete. With

dilution, the interionic forces decrease. Therefore, the ionic mobility
increases leading to small increase in the value of molar conductivity.
For strong electrolytes, Λ increases slowly with dilution and can be

represented by the equation:
Λm = Λm° – A.√c {This equation is known as Debye Huckel Onsagar Equation}
we obtain a straight line by extrapolation, the limiting molar conductance (
Λm°) can be obtained and slope equal to A.
The value of the constant ‘A’ for a given solvent and depends on the type of
electrolyte.
NaCl, CaCl2, MgSO4 are known as 1-1, 2-1 and 2-2 electrolytes respectively.
All electrolytes of a particular type have the same value for ‘A’.
Variation of Molar Conductivity with Concentration for Strong Electrolyte

:
In case of weak electrolyte, the extent of dissociation is very small.

Therefore, the molar conductivity is low as compared to that of strong
electrolytes. Dissociation increases with dilution. As a result, the value of Λm
increases with dilution. Since there is an enormous increase in ionisation upon
dilution, there is large increase in the value of Λm when the solution is very
dilute. This has been depicted in the curve. In case of weak electrolyte, the
limiting value of the molar conductance (Λm°) cannot be achieved since the
dissociation of electrolyte is never complete.
Kohlrausch law of independent migration of ions :
Kohlrausch determined the molar conductance at infinite dilution(Λm°)

for certain pair of strong electrolyte at 298 K. From the value of strong
electrolytes, he put forward Kohlrausch Law . It can be states as:
“At infinite dilution when the dissociation is complete, each ion of the
electrolyte makes a definite contribution of its own towards the molar
conductivity of the electrolyte”. (or)
“The limiting molar conductivity of an electrolyte (Λ° m) is the sum of limiting molar
conductivities of cation (λ°+) and anion (λ°-). Λ° m = ٧+ λ° + + ٧-λ°-
Where ٧+ and ٧- are no. of cation and no of anions formed on dissociation respectively.
The law 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.
Limiting molar conductivity for sodium chloride is
Λm°
Where, ƛ°Na+ and ƛ°Cl – are limiting molar conductivity of the sodium and
chloride ions respectively.
Λm°
Application of Kohlrausch’s Law:
1.Calculation of Molar Conductance at Infinite Dilution for Weak Electrolytes
2. Calculation of Degree of Dissociation of Weak Electrolytes:
Degree of Dissociation
.
3. Calculation of Dissociation Constant of Weak Electrolytes:
Dissociation Constant(Ka)
Λm°
Λm°
Λm°
Electrolytic Cells and Electrolysis:

Difference between Electrochemical cell and Electrolytic Cell :
Electrochemical cell or Galvanic cell or Electrolytic Cell
Voltaic Cell
A device in which electrical energy is A device in which electrical energy is
produced from chemical reaction.
used to bring about a chemical reaction.
E.g. Daniel cell, dry cell, leads storage E.g. Electrolysis of molten NaCl,
battery. Electrolysis of dil. Aq. H2SO4 sol. using
Pt electrodes.
Daniel cell : Zn (s) | Zn 2+ (aq) || Cu 2+ (aq) | Cu (s) E0cell = 1.10 V
Electrode potential: the potential difference between electrode (metal) and the
electrolyte (metal ion solution).
Cell potential: the potential difference between the two electrodes of a galvanic cell.
Ecell = Ecathode – Eanode
EMF (electromotive force) of cell: the potential difference between the two
electrodes when no current is drawn (flowing) through the cell.
S H E (standard hydrogen electrode):

It is used as a reference electrode to measure the standard electrode potential
of the other electrode by assigning standard electrode potential of SHE is zero.
[E0 H+ = zero].
It consists of a platinum electrode (foil) coated with finely divided
platinum dipped in an acidic solution with 1 M H +(aq) ion and pure hydrogen gas (at 1 bar)
is bubbled through the solution.
H (aq) | H2 (g) | Pt (s)
Nernst equation: It shows the relationship between the electrode potential

(electrode)
and concentration of the solution.
For the electrode reaction. Mn+ (aq) + ne- M (s)
RT M s
E electrode = ln
nF M n( )
E0electrode –
aq
( )
E electrode (at 298 K)= E0electrode – 0.059 log
n
[Since [M (s)] =1 ]
For cell, E cell at 298 K = E0 cell - 0.059 log [products]
Or emf n n [reactants]
E.g. for cell reaction Cu (s) + 2 Ag + aq 2e- Cu2+ (aq) + 2 Ag (s)
E cell = E0 cell - 0.059 log [Cu2+] [Ag (s)] 2
2 [Cu (s)] [Ag +] 2
Where E0cell = E0 cathode– E0anode = E0Ag + /Ag – E0Cu+2/Cu [Ag (s)] and [Cu (s)] = 1
Relationship between standard cell potential (E0cell) and equilibrium constant ( Kc)
E0 cell = 2.303 RT log KC
nF
At 298 K E0 cell = 0.059 log KC
Relationship between E cell and Gibbs energy (∆rG)

∆rG = - nF E0 cell
∆rG0 = -nF E0cell (at 250C or 298K 1 atm)
Relationship between ∆rG and equilibrium constant KC

∆rG0 = - 2.303 RT log KC
Maximum work = ∆rG0
Electrolysis: At cathode, when there is competition between many cations or much
reduction reaction the reduction with higher E0 value is preferred .Similarly, the oxidation
reaction with lower E0 value is preferred.
Faradays laws:
First law: the amount of substance formed (m) or chemical reaction occurs at any electrode
is
directly proportional to quantity of electricity (Q) passed through the electrolyte.
m=zQ Where Z=electrochemical equivalent.
Q = I t where Q = quantity of electricity in coulombs (C), I = current in ampere(A) and t =
time
in (s)
Second law: When the same quantity of electricity is passed through the different
electrolytic
solutions, the amount of different substance liberated are directly proportional to their
chemical
equivalent weights.
Faraday: The charge on one mole of electrons is called one faraday (1F) and its value is
96478 C
mol-1 or approximately 96500 C mol-1
Products of electrolysis depend on

(i) the nature of material being electrolysed and
(ii)the type of electrodes being used.
If the electrode is inert (e.g., platinum or gold), it does not
participate in the chemical reaction and acts only as source for
electrons. On the other hand, if the electrode is reactive, it
participates in the electrode reaction. Thus, the products of
electrolysis may be different for reactive and inert electrodes.
(iii)The products of electrolysis depend on the different oxidizing and
reducing species present in the electrolytic cell and their standard
electrode potentials.
Moreover, some of the electrochemical processes although feasible,
are so slow kinetically that at lower voltages these don’t seem to take
place and extra potential (called overpotential) has to be applied, which
makes such process more difficult to occur.
Application of electrochemical series

1. The substance which has higher standard electrode potential (E0 value) is stronger
oxidizing
agent or has greater tendency to get reduced.
2. The substance which has lower standard electrode potential (E0 value) is stronger
reducing
agent or has greater tendency to undergo oxidation.
Class:12 Unit 3: Electrochemistry 2020-21 R .SEKAR, EMBASSY OF INDIA SCHOOL MOSCOW Page 20
of 25
Primary Cells: In these the reaction occurs only once and battery then becomes dead
after use over a period of time. It cannot be recharged and reused again.
E.g. dry cell, mercury cell
Dry cell (leclanche cell)
(1.) Anode- Zn container.
(2.) Cathode- graphite rod surrounded by powered MnO2 and carbon. Electrolyte- a moist
paste of NH4Cl and ZnCl2.
Anode: Zn(s) → Zn 2+ (aq) + 2e-
Cathode: MnO + NH
2 4+ + 1e- → MnO (OH) + NH 3
Cell potential: nearly 1.5V.
Mercury cell
Anode – Zn-Hg amalgam
Cathode - A paste of HgO and carbon Electrolyte - a paste of KOH and ZnO
Anode: Zn (Hg) + 2OH- → ZnO(s) + H2O + 2e
Cathode: HgO(s) + H2O + 2e → Hg (l) + 2OH-
Overall cell reaction: Zn (Hg) + HgO(s) → ZnO(s) + Hg (l)
Cell potential is 1.35V
Secondary batteries:
After use, they can be recharged by passing current through it in opposite direction and so
they can be reused again. E.g. Lead storage battery, nickel- cadmium cell.
Lead Storage Battery

Secondary Batteries (Rechargeable)
Nickel Cadmium Cell
Lead storage battery: anode – Pb plate
Cathode – grid of lead packed with PbO2.
Electrolyte – 38% solution f sulphuric acid (1.3 g / ml)
Anode: Pb(s) + SO4 2- (aq) → PbSO4 (s) +2e-
Cathode: PbO2 (s) + SO4 2- (aq) + 4 H +(aq)+2e- → 2 PbSO4 (s) + 2 H2O (l)
Overall cell reaction: Pb(s) + PbO2 (s) + 2 H2SO4 → 2 PbSO4 (s) + 2H2O(l)
used in automobiles and inverters. On recharging the battery, the above reaction is reversed.
Nickel- Cadmium cell:

Anode: Cd Cathode: Ni(OH)3
Overall cell reaction,
Cd (s) + 2 Ni (OH) 3 (s) → CdO (s) + 2Ni (OH) 2 (s) + H2O (l)
nickel cadmium cell has longer life than the lead storage cell but more expensive to
manufacture. H2O
H2 O2
Fuel Cells: galvanic cells which convert the energy of combustion of fuels like
hydrogen, methane directly into electrical energy.
E.g. Hydrogen – Oxygen Fuel Cell

Hydrogen and oxygen are bubbled through porous carbon electrode into concentrated
aqueous
sodium hydroxide solution. To increase the rate of electrode reaction catalysts like
palladium or
platinum are used.
Anode: 2 H (g) + 4 OH- (aq) → 4 H O (l) + 4e

2 2
cathode: O2 (g) + 2H2O (l) + 4e → 4 OH-(aq)

overall cell reaction: 2 H2 (g) + O2 (g) → 2H2O (l)
Advantages:
1. High efficiency
NaOH (aq)
2. Continuous source of energy
3. Pollution free.
Carbon Electrode Filled

With
Pt/Pd
Corrosion: formation of oxides or other salt of metal on the surface of metallic

objects
when exposed to air or water. E.g. rusting of iron, tarnishing of silver.
Rusting Of Iron: Corrosion of iron is known as rusting. Rust is hydrated ferric oxide,
Fe O .X
2 3
H2O. It is an electrochemical phenomenon. At a particular spot oxidation takes place, which acts
as
Anode: 2Fe (s) → 2Fe2+ +4e E0 red = - 0.44V

Electrons released at anode move through the iron metal and go to another spot and
reduce the
oxygen in presence of H + ion.
Cathode: O2 (g) + 4 H + (aq) + 4e → 2H2O (l) E0 red = +1.23V

Overall reaction: 2Fe (s) + O2 (g) + 4 H + (aq) → 2Fe2+ (aq) + 2H2O (l)
E0 cell = +1.67V
Methods Of Preventing Corrosion:

(1). Galvanization: the process of coating Zinc over iron
(2). Cathodic protection or sacrificial electrode: In this method more reactive metal like
Mg
(or) Zn are made as sacrificial anode and are connected to iron pipe or tank.
Difference between:
Electrochemical cell or Galvanic cell or
Voltaic Cell
Electrolytic Cell
A device in which electrical energy is
produced from chemical reaction.
A device in which electrical energy is used to
bring about a chemical reaction.
E.g. Daniel cell, dry cell, leads storage battery. E.g. Electrolysis of molten NaCl, Electrolysis
of dil. Aq. H2SO4 sol. using Pt electrodes.
Daniel cell : Zn (s) | Zn 2+ (aq) || Cu 2+ (aq) | Cu (s)
E0cell = 1.10 V
Electrode potential: the potential difference between electrode (metal) and the
electrolyte (metal ion solution).
Cell potential: the potential difference between the two electrodes of a galvanic cell. E
cell = Ecathode - Eanode
EMF (electromotive force) of cell: the potential difference between the two electrodes
when no current is drawn (flowing) through the cell.
S H E (standard hydrogen electrode): It is used as a reference electrode to measure the
standard electrode potential of the other electrode by assigning standard electrode potential of S
H E is zero. [E0 H+ = zero]. It consists of a platinum electrode (foil) coated with finely divided
platinum dipped in an acidic solution with 1 M H + (aq) ion and pure hydrogen gas (at 1 bar)
is bubbled through the solution.
H (aq) | H2 (g) | Pt (s)
Electrolysis: At cathode, when there is competition between many cations or much
reduction reaction the reduction with higher E0 value is preferred .Similarly, the oxidation
reaction with lower E0 value is preferred.
Faradays laws:
First law: the amount of substance formed (m) or chemical reaction occurs at any electrode is
directly proportional to quantity of electricity (Q) passed through the electrolyte.
m = z Q Where Z=electrochemical equivalent.
Q = I t where Q = quantity of electricity in coulombs (C), I = current in ampere(A) and t = time
in (s)
Second law: When the same quantity of electricity is passed through the different electrolytic
solutions, the amount of different substance liberated are directly proportional to their chemical
equivalent weights.
Faraday: The charge on one mole of electrons is called one faraday (1F) and its value is 96478 C
mol-1 or approximately 96500 C mol-1
Application of electrochemical series
1. The substance which has higher standard electrode potential (E0 value) is stronger oxidizing
agent or has greater tendency to get reduced.
2. The substance which has lower standard electrode potential (E0 value) is stronger reducing
agent or has greater tendency to undergo oxidation.
Page 58 / 249
Primary Cells: In these the reaction occurs only once and battery then becomes dead
after use over a period of time. It cannot be recharged and reused again.
E.g. dry cell, mercury cell
Dry cell (leclanche cell)
(1.) Anode- Zn container.
(2.) Cathode- graphite rod surrounded by powered MnO2 and carbon. Electrolyte- a moist
paste of NH4Cl and ZnCl2.
Anode: Zn(s) → Zn 2+ (aq) + 2e-
Cathode: MnO2 + NH4+ + 1e- → MnO (OH) + NH3
Cell potential: nearly 1.5V.
Mercury cell
Anode – Zn-Hg amalgam
Cathode - A paste of HgO and carbon Electrolyte - a paste of KOH and ZnO
Anode: Zn (Hg) + 2OH- → ZnO(s) + H2O + 2e
Cathode: HgO(s) + H2O + 2e → Hg (l) + 2OHOverall
cell reaction: Zn (Hg) + HgO(s) → ZnO(s) + Hg (l)
Cell potential is 1.35V
Secondary batteries:
After use, they can be recharged by passing current through it in opposite direction and so
they can be reused again. E.g. Lead storage battery, nickel- cadmium cell.
Lead Storage Battery
Secondary Batteries (Rechargeable)
Nickel Cadmium Cell

Lead storage battery:
anode – Pb plate
Cathode – grid of lead packed with PbO2.
Electrolyte – 38% solution f sulphuric acid (1.3 g / ml)
Anode: Pb(s) + SO4 2- (aq) → PbSO4 (s) +2e-
Cathode: PbO2 (s) + SO4 2- (aq) + 4 H +(aq)+2e- → 2 PbSO4 (s) + 2 H2O (l)
Overall cell reaction: Pb(s) + PbO2 (s) + 2 H2SO4 → 2 PbSO4 (s) + 2H2O(l)
used in automobiles and inverters. On recharging the battery, the above reaction is reversed.
Nickel- Cadmium cell:
Anode: Cd Cathode: Ni(OH)3
Overall cell reaction,
Cd (s) + 2 Ni (OH) 3 (s) → CdO (s) + 2Ni (OH) 2 (s) + H2O (l)
nickel cadmium cell has longer life than the lead storage cell but more expensive to
manufacture.
Fuel Cells: galvanic cells which convert the energy of combustion of fuels like hydrogen,
Page 59 / 249
methane directly into electrical energy.
E.g. Hydrogen – Oxygen Fuel Cell
Hydrogen and oxygen are bubbled through porous carbon electrode into concentrated aqueous
sodium hydroxide solution. To increase the rate of electrode reaction catalysts like palladium or
platinum are used.
H2O
Anode: 2 H2 (g) + 4 OH- (aq) → 4 H2O (l) + 4e
cathode: O2 (g) + 2H2O (l) + 4e → 4 OH-(aq)
overall cell reaction: 2 H2 (g) + O2 (g) → 2H2O (l) H2 O2
Advantages:
1. High efficiency NaOH (aq)
2. Continuous source of energy
3. Pollution free.
Carbon Electrode Filled With
Pt/Pd
Corrosion: formation of oxides or other salt of metal on the surface of metallic objects
when exposed to air or water. E.g. rusting of iron, tarnishing of silver.
Rusting Of Iron: Corrosion of iron is known as rusting. Rust is hydrated ferric oxide, Fe2O3.X
H2O. It is an electrochemical phenomenon. At a particular spot oxidation takes place, which acts
as
Anode: 2Fe (s) → 2Fe2+ +4e E0 red = - 0.44V
Electrons released at anode move through the iron metal and go to another spot and reduce the
oxygen in presence of H + ion.
Cathode: O2 (g) + 4 H + (aq) + 4e → 2H2O (l) E0 red = +1.23V
Overall reaction: 2Fe (s) + O2 (g) + 4 H + (aq) → 2Fe2+ (aq) + 2H2O (l)
E0 cell = +1.67V
Methods Of Preventing Corrosion:
(1). Galvanization: the process of coating Zinc over iron
(2). Cathodic protection or sacrificial electrode: In this method more reactive metal like Mg
(or) Zn are made as sacrificial anode and are connected to iron pipe or tank.
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3.

The basis of these types of process are redox reactions.

Single Electrode (or) Half Cell:

Zinc rod is dipped into 1.0 M ZnSO4 solution

Copper rod is dipped into 1.0 M CuSO4 solution

Daniel Cell: Daniel Cell:

(i) Cu2+ + 2e→Cu(s) (reduction half reaction)

Standard reduction potentials are now called standard electrode potentials.

Conventional Current flow

Distinction between emf and Potential difference:

EMF Potential difference

Refer: Text Book

-Nernst Equation - Nernst Equation for Daniell cell

Equilibrium Constant from Nernst Equation

Electrochemical Cell and Gibbs Energy of the Reaction

Non-Conductors (or) Insulator : The substances which do not allow the

2.Electrolytic conductors or Electrolytes :

Weak Electrolytes: The electrolytes which do not undergo complete

Degree of Dissociation (or) Degree of Ionisation: In Weak Electrolytes, an

Resistivity or Specific Resistance: [IUPAC recommends Resistivity]

“The conductance of a solution of 1 cm length and having 1 cm2 as the area of

The cell constant is usually determined by measuring the resistance of the

Conductivity Conductance(G) x Cell Constant Since, G = 1/R

The conductivity of solutions of different electrolytes in the same

*Upon dilution, Specific conductance or conductivity decreases while molar

Reason for conductivity decrease :

i.e., G=k. 1 Since A =1cm2 and l = 1 cm . [unit volume]

Reason for molar conductivity increases:

Molar conductivity of a solution at a given concentration is the

Since l = 1 and A = V (Volume containing 1 mole of electrolyte)

Molar conductivity increases with decrease in concentration. This is because

by the symbol Λm°.

In case of strong electrolytes, the ionisation is already complete. With

For strong electrolytes, Λ increases slowly with dilution and can be

Variation of Molar Conductivity with Concentration for Strong Electrolyte

In case of weak electrolyte, the extent of dissociation is very small.

Kohlrausch law of independent migration of ions :

Kohlrausch determined the molar conductance at infinite dilution(Λm°)

The law states that limiting molar conductivity of an electrolyte can be

Limiting molar conductivity for sodium chloride is

chloride ions respectively.

Application of Kohlrausch’s Law:

1.Calculation of Molar Conductance at Infinite Dilution for Weak Electrolytes

Electrolytic Cells and Electrolysis:

Daniel cell : Zn (s) | Zn 2+ (aq) || Cu 2+ (aq) | Cu (s) E0cell = 1.10 V

S H E (standard hydrogen electrode):

Nernst equation: It shows the relationship between the electrode potential

For cell, E cell at 298 K = E0 cell - 0.059 log [products]

E.g. for cell reaction Cu (s) + 2 Ag + aq 2e- Cu2+ (aq) + 2 Ag (s)

E cell = E0 cell - 0.059 log [Cu2+] [Ag (s)] 2

2 [Cu (s)] [Ag +] 2

Relationship between E cell and Gibbs energy (∆rG)

Relationship between ∆rG and equilibrium constant KC

Products of electrolysis depend on

Application of electrochemical series

(1.) Anode- Zn container.

Cell potential: nearly 1.5V.

Anode – Zn-Hg amalgam

Lead Storage Battery