Electrochemistry
is the branch of chemistry which
deals with the relationship between electrical energy
and chemical energy and inter-conversion of one form
into another.
2. An electrochemical cell consists of two metallic
electrodes dipped in electrolytic solutions. The cells are
of two types:
(a) Electrolytic cells (b) Galvanic cells
3. A galvanic cell consists of two half cells. Each half
cell contains an electrolytic solution and a metallic
electrode.The electrode at which- oxidation takes place
is called an anode and the electrode at which reduction
takes place is called the cathode. The half-cells are
separated from each other by means of a porous pot or
a salt bridge.
4. The passage of current from one electrode to the
other indicates the existence of potential difference
between them. This difference of potential which
causes current to flow from the electrode of higher
negative potential is called the electromotive force
(emf).
5. Electrical energy = Emf (volts) x Quantity of
electricity (coulombs)
6. The potential of SHE is assigned an arbitrary value
of zero. E° = 0 V. It is used as a reference electrode for
measuring the standard electrode potentials. .
7. When the elements are arranged in order of their
standard electrode potentials, a series known as
electrochemical series is obtained.
8. Standard emf of a cell,
E0cell =E0cathode – E0node = E0Riglit – E0Left
9. ΔG° = -nFE0cell
If E0cell is positive, ΔG° would be negative and reaction
would be spontaneous. If E0cell is
negative, ΔG° would be positive and the reaction would
be non-spontaneous.
10. A species with higher standard reduction
potential has greater tendency to accept electrons to
undergo reduction or vice versa.
11. The potential of an electrode in contact with its
ions in solution varies with the concentration of the ion.
Thus, for a redox reaction,
12. For an electrochemical cell for which the overall
reaction is
13. The equilibrium constant, Aofcell can be relate to
standard emf of cell
14. Resistance is the measure of obstruction to the
flow of current.
where S = specific resistance or resistivity. Unit of R is
ohm.
15. Resistivity is defined as the resistance of a
conductor of 1cm length and having an area of cross-
section equal to 1cm2.
unit of resistivity is ohm-cm
16. Conductance is reciprocal of resistance, i. e.,
Unit of conductance is ohm-1 or mho or Siemen(S).
17. Specific conductance Λsp is reciprocal of specific
resistance.
Specific conductance is thus defined as the
conductance of a solution taken in a cell whose
electrodes are at unit distance apart from each other
and each having an area equal to 1 cm2. Unit of specific
conductance is ohm-1 cm-1 or S cm-1.
18. Molar conductance (Λm) is defined as the
conductance of the volume of solution which contains
one mole of the solute and is placed between two
parallel electrodes which are one centimetre apart and
having sufficient area to hold the whole of the solution.
Unit of molar conductance is Ω-1 cm2 mol-1 or S cm2 mol-1
19.
where C = concentration of solution in moles per litre
(or Molarity).
20. The electrical conductance through metals
decreases with increase in temperature.
21. The electrolytic conductance increases with
increase of temperature.
22. Effect of Dilution on
(а) Equivalent conductance: The value of equivalent
conductance increase with dilution and attains a
maximum value at infinite dilution.
(b) Specific conductance: The value of specific
conductance decreases with dilution as the number of
current carrying particles i.e., ions present per cm3 of
solution decreases on dilution.
(c) Molar conductance: The value of molar
conductance increases with dilution and finally attains a
maximum value at infinite dilution.
23. Variation of molar conductance with
concentration:
(a) Strong electrolytes:
(b) Weak electrolytes:
24. According to Kohlrausch law of independent
migration of ions, the limiting molar conductivity of an
electrolyte can be expressed as the sum of the
contributions of the cation and the anion of the
electrolyte.
where v+, v– are the number of cat ions and anions per
unit formula of the electrolyte respectively; λ0+,
and λ0– are the limiting molar conductivities of the cation
and anion respectively.
25. Faraday’s laws of electrolysis:
(a) First law: The amount of a substance deposited or
liberated at an electrode is directly proportional to the
quantity of electricity passed through the electrolyte.
Mathematically,
where m = mass of substance deposited or liberated.
Mass of substance A deposited or liberated Mass of
substance B deposited or liberated current in amperes t
= time in seconds, and Z = constant called
electrochemical equivalent.
(b) Second law: When the same quantity of electricity
is passed through solutions of different electrolytes, the
weight of different substances deposited or liberated at
the respective electrodes are proportional to their
chemical equivalent weights.
26.
27. The charge on one mole of electrons is
approximately equal to 96500 coulombs. This quantity
of electricity is called Faraday constant (F).
28. A battery consists of two or more galvanic cells
connected in series. There are two kinds of batteries:
(a) Primary batteries: In primary batteries, when the
reactants have been converted into
products, no more electricity is produced. The cell
reaction cannot be reversed and the battery becomes
dead.
(b) Secondary batteries: In secondary batteries (or
cells), the cell reaction can be reversed by passing
electricity through the battery (charging). It means that
the battery can be used again and again through a
large number of discharging and charging cycles.
29. The most common example of secondary battery is
the lead storage battery.
30. Electrical cells that are discharged to convert the
energy from the combustion of fuels (hydrogen, carbon
monoxide, methane, etc.) directly into the electrical
energy are called fuel cells.
31. The corrosion of metals is an electrochemical
process. It occurs in presence of water and oxygen
