CHAPTER 2 - 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.
Galvanic cell or Voltaic cell (ELECTROCHEMICAL CELL)
Device used for the production of electricity from energy released during spontaneous chemical
reaction is called Galvanic cell or voltaic cell or Electrochemical cell.
Eg: - Daniell cell
Electrolytic cell
A cell that uses electrical energy to carry non-spontaneous chemical reactions is called
Electrolytic cell
Eg: - Daniell cell acts as electrolytic cell (reaction gets reversed) when an
opposite voltage which is greater than 1.1 V is applied.
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When external potential and standard electrode potential are equal:
Half cells or redox couples
In a galvanic cell, oxidation and reduction reactions take place at different electrodes. These two
portions of the cell are called half-cell or redox couples.
Eg: - The half reactions occur in Daniell cell are:
Cu2+ + 2e- → Cu(s) (Reduction half reaction - CATHODE)
2+ -
Zn(s) → Zn + 2e (Oxidation half reaction - ANODE)
Cu electrode is called the reduction half-cell and zinc electrode is called the oxidation half-cell.
Standard electrode potential
Potential difference between electrode and electrolyte is called electrode potential (E).
When concentrations of all the species involved in a half cell is unity, then the electrode
potential is known as standard electrode potential (Eθ).
Cell potential and emf (Ecell)
The potential difference between the two electrodes of a galvanic cell is called cell potential.
OR
The difference between electrode potentials of cathode and anode is called cell potential.
Cell potential is called cell emf when no current is drawn through the cell.
Ecell = Eright – Eleft or Ecell = Ecathode – Eanode
Function of Salt Bridge
i) It allows flow of ions and the circuit is completed.
ii) It maintains electrical neutrality.
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Cell representation
Cell reaction of Daniell cell is Zn(s) + Cu2+(aq) → Zn2+ (aq) + Cu(s).
Half-cell reactions are:
Cu2+ + 2e- → Cu(s) Cathode (Reduction half reaction)
Zn(s) → Zn2+ + 2e- Anode (Oxidation half reaction)
The cell can be represented as
Zn(s) │ Zn2+ (aq) ║ Cu2+(aq) │Cu(s)
Standard Hydrogen electrode (SHE)
Standard hydrogen electrode is used to determine the potential of individual half cells.
The potential of SHE is zero at all temperatures.
SHE consists of a platinum electrode coated with platinum black. The electrode is dipped in an
acidic solution and pure hydrogen gas is bubbled through it.
SHE is represented as Pt(s) │H2(g) │H+(aq)
SHE is always taken as the anode.
Electrode potential of a single electrode
Eg: - Zinc
Nernst Equation
0.059 [OXIDATION ]
Ecell = { Eɵcell } – { log }
n [ REDUCTION ]
Equilibrium Constant from Nernst Equation
0.059
Eɵcell = log Kc
n
Electrochemical Cell and Gibbs Energy of the Reaction
Under standard conditions,
Maximum work = – rGɵ = nFEɵcell
Conductivity
The conductivity of a solution at any given concentration 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.
Resistance, R = ρ l , ρ(rho) is called resistivity.
A
The inverse of resistivity is called conductivity, κ (kappa)
SI unit of conductivity is S m-1 (S = Siemens)
Cell constant, G*, is then given by the equation
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Molar conductivity
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.
(S cm2 mol-1) =
where, κ is the conductivity and c is the concentration in molL-1
Limiting molar conductivity (˄m0)
Molar conductivity at zero concentration or at infinite dilution is known as limiting molar
conductivity.
Variation of Conductivity and Molar Conductivity with Concentration
Conductivity always decreases with decrease in concentration, both for strong and weak
electrolytes.
This can be explained by the fact that the number of ions per unit volume that carry the
current in a solution decreases when concentration decreases (on dilution).
Molar conductivity increases with decrease in concentration.
This is because on dilution the interionic interactions are overcome and ions are free to move.
For strong electrolytes, ˄m = ˄m0 – A c½, where –A is the slope of the plot when ˄m is drawn
against c½ and ˄m0 is its point of interception.
For weak electrolytes, molar conductivity increases steeply on dilution, especially near lower
concentrations. Therefore, limiting molar conductivity cannot be measured by extrapolation of
˄m to zero concentration.
˄m0 for weak electrolytes is obtained by using Kohlrausch law of independent migration of ions.
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Kohlrausch law of independent migration of ions
The law states that “limiting molar conductivity of an electrolyte can be represented as the
sum of the individual contributions of anion and cation of the electrolyte”.
Eg: - ˄m0(NaCl) = λ0 Na+ + λ0 Cl-
Applications
1) It is used to calculate the limiting molar conductivity for weak electrolytes.
2) It is used to calculate α and Kc
Degree of dissociation,
Dissociation constant,
Faraday’s Laws of Electrolysis
o First Law: The amount of substance deposited or liberated at an electrode is directly
proportional to the quantity of electricity passed through the electrolyte.
Q = It, where Q is the quantity of electricity passed in coloumbs, I is
the current strength in ampere and t is the time in seconds.
o Second Law: When same quantity of electricity is passed through different
electrolytes the amount of substance deposited is directly proportional
to its equivalent masses.
Primary Batteries
In primary batteries, the reaction occurs only once and after a long period of use it becomes
dead and cannot be used again.
Eg:- Dry cell, used in clocks and transistors.
Dry cell consists of Zinc anode and graphite cathode surrounded by powdered MnO2 and
carbon. The space between electrodes is filled by a moist paste of NH4Cl and ZnCl2
Electrode reactions are:
Anode: Zn(s) → Zn2+ + 2e-
Cathode: MnO2 + NH4+ + e- → MnO(OH) + NH3
Mercury cell consists of Zn-Hg amalgam as anode and a paste of HgO and carbon as the
cathode. The electrolyte is a paste of KOH and ZnO.
Electrode reactions of Mercury cell are:
Anode: Zn(Hg) + 2OH- → ZnO(s) + H2O + 2e-
Cathode: HgO + H2O + 2e- → Hg(l) + 2OH-
The overall reaction is: Zn(Hg) + HgO ⎯→ ZnO + Hg
The cell potential is 1.35 V and remains constant during its life as the overall reaction does not
involve any ion in solution. So, the concentration doesn’t change during its life time.
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Secondary Batteries
It can be recharged by passing current through it in the opposite direction.
Eg:- Lead storage battery, used in automobiles and invertors.
In lead storage battery, lead is taken as the anode, PbO2 as cathode and 38% solution of H2SO4
as electrolyte.
Electrode reactions are:
Anode: Pb + SO42- → PbSO4 + 2e-
Cathode: PbO2(s) + SO42- + 4H+ +2e- → PbSO4 + 2H2O
Overall cell reaction is: Pb(s) + PbO2 + 2H2SO4 → 2PbSO4 + 2H2O
Nickel-Cadmium cell is another secondary battery, has longer life than the lead storage cell but
more expensive. The overall reaction is: Cd + 2Ni(OH)3 → CdO + 2Ni(OH)2 + H2O
Fuel cells
Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen,
methane, methanol etc directly into electrical energy are called fuel cells.
Eg:- Hydrogen fuel cell.
In hydrogen fuel cell, hydrogen and oxygen are bubbled through porous carbon electrodes into
concentrated aqueous NaOH solution Finely divided Pt or palladium is used as a catalyst.
Electrode reactions are:
Anode: O2 + 2H2O + 4e- → 4OH-
Cathode: 2H2 + 4OH- → 4H2O + 4e-
Overall reaction is: 2H2 + O2 → 2H2O
Advantages of fuel cells
(i) Pollution free (ii) High efficiency.
Corrosion
In corrosion, a metal is oxidised by loss of electrons to oxygen and forms oxides.
Corrosion of iron occurs in presence of water and air.
At a particular spot, oxidation takes place and that spot behaves as anode.
Anode: 2Fe(s) → 2Fe2+ + 4e-
Electron released at anodic spot move through the metal and go to another spot on the metal and
reduce oxygen in presence of H+. This spot behaves as cathode.
Cathode: O2(g) + 4H+ + 4e- → 2H2O
Overall reaction is: 2Fe(s) + O2(g) + 4H+ → 2Fe2+ + 2H2O
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Products of Electrolysis
Products of electrolysis depend on the nature of material being electrolysed and 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.
1) Electrolysis of molten NaCl
At cathode
Na+ + e- → Na (Reduction)
At anode
2Cl- → Cl2 + 2e- (Oxidation)
2) Electrolysis of aqueous NaCl
It contains Na+, H+, Cl- and OH- ions.
The two possible reactions at cathode are:
The reaction with higher positive value of Eθ is preferred at cathode.
At cathode
but H+ is produced by the dissociation of H2O.
Therefore, the net reaction at the cathode is the sum of the above equations.
At anode
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The following oxidation reactions are possible:
At anode, the reaction with lower value (more -ve / less +ve) of Eθ is preferred. However, on account
of overpotential of oxygen (slow kinetically at lower voltages), the first reaction is preferred.
3) Electrolysis of dilute sulphuric acid
At cathode
At anode
4) Electrolysis of concentrated sulphuric acid
At cathode
At anode
QUESTION
i. Ag+/Ag has higher positive Eθ than H+/H2
At cathode
Ag+ + e- → Ag
At anode
Silver electrode is attacked by NO3- ions. Therefore, silver undergoes oxidation and
dissolves in the solution.
Ag → Ag+ + e-
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ii. Ag+/Ag has higher positive Eθ than H+/H2
At cathode
Ag+ + e- → Ag
At anode
Compared to NO3- ions, OH- ions have more -ve Eθ
iii. At cathode
At anode
iv. Cu2+/Cu has higher positive Eθ than H+/H2
At cathode
Cu2+ + 2e- → Cu
At anode
Electrochemistry - Equations
1. Ecell = Ecathode – Eanode
2. Nernst Equation for Daniel cell
3.
4. 0.059
Eɵcell = n
log Kc
5.
The inverse of resistance, R, is called conductance, G,
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The SI unit of conductance is siemens, represented by the symbol ‘S’ and is equal to
ohm–1
6. Molar conductivity
(S cm2 mol-1) =
7. For strong electrolytes, ˄m = ˄m0 – A c½
8.
9.
10.
TERM SYMBOL / UNIT EQUATION
R
Resistance Ohm
Resistivity Ohm metre
The inverse of resistance, G
Conductance Si unit is siemens, ‘S’ and is ohm–1
Κ 1
Conductivity The inverse of resistivity ❑
Sm–1
Cell constant G*
(S cm2 mol-1) =
Molar conductivity
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CONDUCTIVITY AND MOLAR CONDUCTIVITY
1. Define Conductivity.
The conductivity of a solution at any given concentration 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.
2. Define Molar conductivity.
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.
=
where, κ is the conductivity and c is the concentration in molcm-3
3. Define Limiting molar conductivity (˄m0)
Molar conductivity at zero concentration or at infinite dilution is known as limiting
molar conductivity.
4. Why does conductivity increase with increase in concentration?
OR
Why does conductivity decrease on dilution?
The number of ions per unit volume that carry the current in a solution decreases
when concentration decreases (on dilution).
5. Why does Molar conductivity decrease with increase in concentration?
OR
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Why does Molar conductivity increase on dilution?
On dilution the interionic interactions are overcome and ions are free to move.
6. Explain the difference between variation in Molar conductivity for strong and weak
electrolytes?
For strong electrolytes, Molar conductivity increases slowly with dilution as strong
electrolytes are completely ionized.
For weak electrolytes, molar conductivity increases steeply on dilution, especially
near lower concentrations as weak electrolytes are partially ionized and more ionization
takes place during dilution.
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