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.
ELECTROCHEMICAL CHANGE: Chemical changes involving production or consumption of electrical energy are
called as electrochemical changes.
Electrochemical changes are performed using cells.
The 3 main Aspects of Electrochemistry
1. Electrochemical cells/voltaic cells/Galvanic cells.
2. Conductance of Electrolytic Solution
3. Electrolysis
GALVANIC CELLS
A galvanic cell is an electrochemical cell that converts the chemical energy of a spontaneous redox reaction into
electrical energy. In this device the Gibbs energy of the spontaneous redox reaction is converted into electrical
work which may be used for running a motor or other electrical gadget like heater, fan, geyser, etc.
Daniel cell: Daniel cell is the one such cell in which the following redox
reaction occurs.
In Daniel cell, electrodes of zinc and copper are dipped in the solutions of their
respective salts. These two portions of the cell are also called half-cells or
redox couples.
Reduction half-cell reaction: Cu2+ + 2e ---> Cu(s) (At cathode)
Oxidation half-cell reaction: Zn(s) ---> Zn2+ + 2e (At anode)
Overall reaction: Zn(s) + Cu2+ (aq) ----> Zn2+ (aq) + Cu(s)
Cell Representation:
Salt bridge connects solutions and separates two half-cell.
Electrode potential (Ecell): A potential difference develops between the electrode and the electrolyte which is
called electrode potential.
Standard electrode potential (Eocell): When the concentrations of all the species involved in a half-cell is unity
then the electrode potential is known as standard electrode potential.
In a galvanic cell, the half-cell in which oxidation takes place is called anode and it has a negative potential with
respect to the solution. The other half-cell in which reduction takes place is called cathode and it has a positive
potential with respect to the solution. Thus, there exists a potential difference between the two electrodes and
as soon as the switch is in the on position the electrons flow from negative electrode to positive electrode. The
direction of current flow is opposite to that of electron flow. The potential difference between the two
electrodes of a galvanic cell is called the cell potential and is measured in volts.
Cell potential or electromotive force (e.m.f) of the cell is the potential difference between the two electrodes
when no current is drawn through the cell.
The EMF of the cell is positive and is given by:
Ecell = Eright - Eleft OR Ecell = E cathode - E anode
Standard hydrogen electrode (SHE):
It is a reference electrode and consists of a platinized platinum electrode in contact with H 2 gas (1 bar) and
aqueous H+ ions (1 M).
The standard electrode potential of SHE is assigned as 0.0 V
It may behave as anodic or cathodic half-cell.
It is represented as:
Pt(s) / H2(g)(p= 1bar) / H+(aq)(1M)
When SHE is coupled with another half-cell then cell potential measured gives the value of the electrode
potential of half-cell.
Nernst equation and its application to chemical cells:
The Cell Potential under Non-standard Conditions is determined using Nernst Equation when concentrations of
electrolytes are not equal to 1M.
For the Daniel cell, Zn(s) IZn2+ (aq) II Cu2+(aq) I Cu (S)
Cell reaction: Cu2+ (aq) + Zn(s) → Zn2+ (aq) + Cu(s)
For a general electrochemical reaction of the type:
Equilibrium Constant from Nernst Equation:
Relation between ∆G˚ and K
The value of Equilibrium constant, K is related to ∆G˚ by:
∆G˚ = – 2.303 R T log K
Electrochemical Cell and Gibbs Energy of the Reaction:
Relation between ∆G˚ and E˚ cell
The value of E˚ cell is related to Gibbs free energy, ∆G˚ by:
∆G˚ = – n F E˚ cell
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CONDUCTANCE OF ELECTROLYTIC SOLUTIONS
Terms involved in Conductance:
1. Resistance, R
2. Conductance, G = 1/R
3. Resistivity or Specific resistance, ρ: The electrical resistance of any object is directly proportional to its length, l,
and inversely proportional to its area of cross section, A. That is, R = ρ l / A.
ρ=RA/l
When l = 1 cm and A = 1 cm2, ρ = R
Hence, Resistivity can be defined as the resistance offered by conductor of 1cm length and area of cross section
1cm2.
4. Conductivity or Specific conductance, k: The conductivity of a solution at any given temperature is the
conductance of ions per unit volume of solution kept between two electrodes having area 1 cm2 and distance
of separation as 1 cm.
It is the inverse of resistivity.
k = 1/ ρ Unit: S cm-1
Conductivity of a solution decreases with dilution for both 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
decrease on dilution.
5. Molar conductivity (λm): Molar conductivity is defined as the conductivity of all the ions produced when 1 mole
of an electrolyte is dissolved in V mL of solution.
Molar conductivity = λm = k V
Molar conductivity = λm = k / c
Or λm = k x 1000 / M
Unit of λm is S cm2 mol-1
Molar conductivity increases with dilution. This is because the total volume, V, of solution containing one mole of
electrolyte also increases on dilution. At a given concentration, λm can be defined as the conductance of the
electrolytic solution kept between the electrodes of a conductivity cell at unit distance but having area of cross
section large enough to accommodate sufficient volume of solution that contains one mole of the electrolyte.
When concentration approaches zero, the molar conductivity is known as limiting molar conductivity and is
represented by the symbol λmo.
The variation in λm with concentration is different for strong and weak electrolytes can be explained graphically.
Strong Electrolytes: For strong electrolytes, λm increases slowly with dilution and can be represented by the
equation:
λm = λ°m - A c1/2
(Debye-Huckel Onsager Equation)
Value of A depends on the type of electrolyte i.e., the charges on the
cation and anion produced on the dissociation of the
electrolyte in the solution. Thus, 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 A.
Kohlrausch Law of Independent migration of ions:
▪ It states that limiting molar conductivity of an electrolyte is the
sum of the individual contributions of the anion and cation of
the electrolyte.
▪ Thus, if λ°Na+ and λ°Cl- are limiting molar conductivity of the
sodium and chloride ions , then the limiting molar conductivity
for sodium chloride is given by the equation:
▪ λ °m(NaCl) = λ°Na+ + λ°Cl -
Weak Electrolytes
Weak electrolytes like acetic acid have lower degree of dissociation at higher concentrations, for such
electrolytes, the change in λm with dilution is due to increase in the degree of dissociation.
At any concentration c, if is the degree of dissociation, then
Dissociation constant ‘Ka’ of a weak electrolyte.
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ELECTROLYSIS
It is a process of decomposition of an electrolyte by the passage of electricity through its aqueous solution or
molten (fused) state of electric current.
Quantitative Aspects of Electrolysis
Faraday’s Law of Electrolysis:
(i) Faraday first law of electrolysis: The amount (MASS) of substance deposited or liberated at the electrode
during a chemical reaction is proportional to the quantity of electricity passed through the electrolyte (solution
or melt).
mαQ Q = It Unit of Charge, Q = Coulomb(C)
Coulomb is the charge transferred when 1 A current flows through the cell for 1 sec.
mass, m = Z Q
(Z = electrochemical equivalent)
Mass, m = Z I t [z = molar mass/nF]
(ii) Faraday Second Law of electrolysis: The amounts of different substances deposited or liberated by the same
quantity of electricity passing through the electrolytic solution are proportional to their chemical equivalent
weights.
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), it does not participate in the chemical reaction and acts only as source
or sink for electrons, but if the electrode is reactive, it participates in the electrode reaction.
▪ The products of electrolysis depend on the different oxidizing and reducing species present in the electrolytic
cell and their standard electrode potentials.
▪ some of the electrochemical processes although feasible, are so slow kinetically that at lower voltages these do
not seem to take place and extra potential (called over potential or bubble voltage) has to be applied, which
makes such process more difficult to occur.
INERT ELECTRODES: Platinum, gold, graphite
REACTIVE ELECTRODES: Copper, Zinc, silver
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BATTERIES
PRIMARY BATTERIES
1. Dry Cell/ Leclanche cell: A dry cell consists of:
• Zinc container whose base acts as a negative electrode (anode)
• carbon road acts as a positive electrode (cathode).
• Electrolyte: manganese dioxide and low moisture electrolyte like ammonium
chloride paste.
Cell potential = 1.5V
2. Mercury cell: It consists of:
• Zinc mercury Amalgam as anode
• paste of HgO and carbon as the cathode
• Electrolyte is a paste of KOH and ZnO.
The cell potential is approximately 1.35 V and remains constant during its life as no
ions are involved in the redox reaction. It is suitable for low current devices like
hearing aids, watches, etc.
SECONDARY BATTERIES
1. Lead storage battery: It consists of
• Lead anode and a grid of lead packed with lead dioxide (PbO2) as cathode.
• A 38% solution of sulphuric acid is used as an electrolyte.
• Commonly used in automobiles and invertors.
2. Nickel-cadmium cell which has longer life than the lead storage cell but more expensive to manufacture.The
overall reaction during discharge is:
FUEL CELLS
To convert the energy of combustion of fuels like hydrogen, methane,
methanol, etc. directly into electrical energy are called fuel cells. Fuel cells
use the reaction of hydrogen with oxygen to form water. The cell was used
for providing electrical power in the Apollo space Programme. Fuel cells are
pollution free. Fuel cell using H2 and O2 produces electricity.
CORROSION
In corrosion, a metal is oxidised by loss of electrons to oxygen and formation of oxides.
Corrosion of iron (commonly known as rusting) occurs in presence of water and air. The
chemistry of corrosion is an electrochemical phenomenon.
We can write the reaction
Anode: 2 Fe (s) → 2Fe2+ + 4 e E0 (Fe2+/Fe) = 0.44 V
Cathode: O2 (g) + 4 H+ (aq) + 4 e → 2 H2O (l)
E0 (H+/O2/H2O) = 1.23 V
The overall reaction being:
2Fe(s) + O2 (g) + 4H+ (aq) → 2Fe2+ (aq) + 2 H2O (l)
EO cell =1.67 V
The ferrous ions are oxidised by atmospheric oxygen to ferric
ions which come out as rust in the form of hydrated ferric oxide
(Fe2O3. x H2O) and with further production of hydrogen ions.
Prevention of corrosion can be done by covering the surface
with paint or by some chemicals (e.g. bisphenol), Barrier protection, Sacrificial Protection, Cathodic Protection,
Anti rust solution.
