UNIT-I Types of electrolytic conductors
ELECTROCHEMISTRY Strong electrolytes: Completely dissociate into ions in solution
Examples: HCl, NaOH, NaCl, KCl
Weak electrolytes: Which dissociate only to some extent in
Electrochemistry deals with Chemical applications of electricity
solution
i.e., Chemical reactions produced by passing electric current
Non – electrolytes: Do not ionise in solution
through an electrolyte or production of electric curerent through a
chemical reaction
Cell Terminology
Conductors: Material which allows free flow of electricity
i. Current : Flow of electrons through a conductor
Examples: All metals, graphite, fused salts, solution of electrolytes,
ii. Electrode : Electrode is a material (rod, bar, strip)
Non-conductors (Insulators): Materials which cannot conduct
which conducts electrons
electrical current
iii. Anode : Electrode at which oxidation occurs
Examples: wood, plastics, most of non metals
iv. Cathode : Electrode at which reduction occurs
Types of conductors
v. Electrolyte : Water soluble substance forming ions in
(i) Metallic conductors : All solid material, which
solution and conducts electric current
conduct electric current due to the movement of
vi. Anode compartment: Compartment of the cell in
electron from one end to the other end
which the oxidation half reaction occurs. Contains the
(ii) Electrolytic conductors : Conduct electric current due
anode
to the movement of ions
vii. Cathode compartment: Compartment of the cell in
which the reduction half reaction occurs. Contains the
Differences between metallic conduction and electrolytic
cathode
conduction
viii. Half – cell: Part of the cell, which contains an
Metallic conduction Electrolytic conduction
electrolyte dipped in an electrolyte. If oxidation occurs
Involves flow of electrons Involves movement of ions in
in this half, then it is called the oxidation half cell. If
a solution
reduction occurs at the cell, it is called the reduction
Does not involve any transfer Involves transfer of electrolyte
half cell
of matter in the form of ions
ix. Cell: Device consisting of two half cell. The two half
Conduction decreases with Conduction increases with cells are connected by a conductor
increase in T increase in T
No change in the chemical Chemical changes occur aat
properties of the conductor the two electrodes
Electrode Potential Standard electrode potential (E0): Tendency of a metallic
electrode to lose or gain electrons when it is in contact with a
When a metal (M) is placed in a solution of its own salt (Mn+) one solution of its own ions of 1M Concentration.
of the two processes are possible. Nernst Equation for Electrode Potential
(i) +ve metal ions may pass into solution Consider the redox reaction : M Mn+ + ne-
M Mn+ + ne- (Oxidation) For such redox reversible reactions, the free energy change (∆G)
(ii) +ve metal ions from solution may deposit on the metal and its equilibrium constant (K) are related by
Mn+ + ne- M (reduction)
G RT ln K RT ln
Pr oduct
Re ac tan t
+
Zn electtrode Cu electtrode G 0 RT ln
Pr oduct (1)
+ Re ac tan t
+ + +
+ + ∆G0 = Standard free energy change
+ +
+ ZnSO4
Cu2+
CuSO4 The above equation is Van’t Hoff Isotherm
solution solution
(i) In the cell, if the reaction involves the transfer of ‘n’ electrons, ‘n’
When Zn electrode is dipped in ZnSO4 solution, Zn goes into faraday of electricity will flow.
solution as Zn2+ ions. If E is the emf of the cell, the total electrical energy produced will
(iii) When Cu electrode is dipped in CuSO4 solution, Cu2+ be
ions from solution deposit on the metal. G nEF (or) G 0 nE 0 F (2)
A layer of + or – ve ions if formed on the metal, Helmholtz
electrical double layer due to which a difference of potential is Comparing (1) & (2) - nEF - nEF0 RT ln
M (3)
M n
setup between the metal ions and the solution.
At equilibrium, the potential difference becomes a constant value Dividing (3) by – nF and knowing that [M] = 1
(Electrode potential of the metal). RT 1 RT
E=E 0 ln (or) E=E 0 ln M n
The tendency of the electrode to lose electrons is Oxidation nF M n
nF
potential.
Tendency of an electrode to gain electrons is reduction potential.
2.303RT
E=E 0 log M n (4)
nF
Single electrode potential (E): Tendency of a metallic electrode
When, R = 8.314 J/K/mole; F = 96,500 coloumbs, T = 298 K the
to lose or gain electrons when it is in contact with a solution of its
above equation becomes
own ions.
It is represented as
0.0591 In the cell, when SHE acts as anode, the electrode reaction is
E=E 0 log C (Nernst equation for single H2(g) 2H+ + 2e-
n
electrode potential) When it acts as cathode, the electrode reaction is
2H+ + 2e- H2(g)
Applications of Nernst equation Limitations
i. To calculate unknown electrode potentials i. requires hydrogen gas and is difficult to set up and
ii. Prediction of corrosion tendency of metals transport
iii. To construct emf series ii. requires large volume of test solution
iii. The solution may poison the surface of Pt electrode
Measurement of single electrode potential iv. Potential of the electrode is dependent on atmospheric
It is not possible to evaluate the absolute value of a single electrode pressure.
potential. Potential difference between two electrodes can be
measured. For this purpose a reference electrode is used. Secondary reference electrode: Saturated calomel electrode
Saturated hydrogen electrode (SHE) is a common reference (SCE)
electrode whose potential is fixed as zero (Primary reference
electrode) Pt wire Construction: Calomel electrode
The emf of the cell with SHE and the electrode under test as consists of a glass tube containing Hg at
the bottom over which mercurous
electrodes will be equal to the potential of the electrode chloride paste is placed. The tube is
Setting up of SHE is difficult filled with a saturated solution of KCl. A
Pt electrode is dipped in. The side tube
Saturated calomel electrode is used as a secondary reference is for making contact via a salt bridge.
electrode The electrode potential of this electrode
is +0.2422 V. It is represented as:
Hg, Hg2Cl2(s), KCl (sat. solution)
Primary reference electrode: Saturated hydrogen electrode
(SHE)
In the cell, when SCE acts as anode, the electrode reaction is
Construction: Hydrogen electrode
consists of a Pt foil that is connected to a Pt 2Hg(l) Hg22+ +2 e -
H2 gas wire sealed in a glass tube. Hydrogen gas When it acts as cathode, the electrode reaction is
is passed through the arm of the
HCl surrounding gas tube. The electrode Hg22+ +2 e - 2Hg(l)
solution dipped in 1N HCl and hydrogen is passed
Pt foil at 1 atm.is SHE
Pt , H2 (1atm) / H+n(1M) ; E0 = 0V
The electrode potential (cathode) is given by Electrochemical series
RT
E( calomel ) E (0calomel ) ln aCl
2F Electrode Electrode E0 Nature
The electrode potential depends on the activity of Cl – and reaction (V)
+
Temperature. Li /Li Li+ + e Li -3.01 Anodic
Mg2+/Mg Mg2+ +2 e Mg -2.37
a Kcl emf a Kcl emf (V) a Kcl emf (V) 2+
Pb /Pb Pb2+ +2 e Pb -1.12
0.1 0.3338 1.0 0.2800 Saturated 0.2422 2+
Zn /Zn Zn 2+
+2 e Zn -0.76
Values at 298 K
Fe2+/Fe Fe2+ +2 e Fe -0.44
2+
Measurement of single electrode potential of Zn using SCE Sn /Sn Sn2+ +2 e Sn -0.136 Pt-
Pt wire H+/H2 2H+ + 2e H2 0.00 Reference:
V Zn electrode is coupled with calomel
2+
Zn electrode. Since, the reduction potential of Cu /Cu Cu2+ +2 e Cu +0.34
electrode Zn electrode is less than E0Cal ; calomel +
electrode will act as cathode and the reaction Ag /Ag +
Ag + e Ag +0.80
Hg2Cl2(s) 2Hg(l) + 2C l- Au+/Au Au+ + e Au +1.50
Cathodic
Ecell Eright
0
Eleft
0
; Ecell Ecal EZn
0 0
½ F2/F- ½ F2 + e F- +2.87
0
EZn Ecal
0
Ecell 0.2422 1.0025 0.7603V
1 M Zn2+ Significance of emf series (or) Application of electrochemical
series (or) Applications of Nernst equation
Electrode potentials of metals with respect to SHE
(Electrochemical series (or) EMF series) i. Calculation of standard emf of the cell
E0can be calculated if the standard electrode potential values are
Definition: known
When the various metals are arranged in the order of their Ecell Eright
0
Eleft
0
increasing values of standard reduction potential on the hydrogen
scale, the arrangement is called the electrochemical series
ii. Relative ease of oxidation or reduction
Higher (+ve) value of standard reduction potential, greater is the
tendency for reduction.
Metals on the top (- value) are more easily oxidized.
Fluorine has higher +ve value of standard reduction potential Galvanic series
(+2.87V) and shows higher tendency for reduction. Magnesium Oxidation potential of various
Lithium has highest – ve value (-3.02V) and shows higher Magnesium alloys metals alloys are measured by
immersing them in sea water.
tendency towards reduction. Zinc SCE is used as the reference
Alluminium electrode. The values are
iii. Displacement of one element by the other arranged in decreasing order of
Alluminium alloys activity and the series is Galvanic
Metals which lie higher in the series can displace those which lie Copper series
below them in the series. Copper – nickel
Copper will displace silver from its solution. alloys
Iron will displace copper from its solution. Gold
iv. Determination of equilibrium constant (K) for a reaction Platinum
G 0 RT ln K 2.303RT log K This series provide more practical information on the
G 0
nFE 0
relative corrosion tendencies of different metals and alloys. The
log K G 0 nFE 0
2.303RT 2.303RT speed of corrosion depends on the difference in potential between
From the value of E0, the equilibrium constant for the reaction can the anodic and cathodic metals in contact.
be obtained
Electrolytic cells
v. Hydrogen displacement behaviour Chemical changes are brought about by using electrical energy in
Metals with – ve reduction potential (metals placed above H2) in electrolytic cells
emf series will displace hydrogen from acid solutions. Electrolysis
Zn will displace H2 from dilute acids whereas, silver cannot. Process of chemical decomposition of an electrolyte by passage of
electricity
vi. Predicting the spontaneity of redox reactions Example: Electrolysis of HCl
If E0 of a cell is +ve the reaction is spontaneous Mechanism
If E0 of a cell is -- ve the reaction is not possible HCl will dissociate into H+ and Cl – in water
On passing electric current the following reactions
1N HCl occur at the electrodes
-
At anode: 2Cl Cl2 + 2 e (oxidation)
At cathode:
2H+ + 2 e - H2 (reduction)
Bright
Pt electrodes
Electrochemical cells (Galvanic cells) Representation of a galvanic cell (Cell diagram)
Chemical energy is converted to electrical energy in i. Galvanic cell consists of two electrodes, anode and
electrochemical cells cathode
Example: Daniel Cell through the voltmeter. ii. Anode is written on the LHS and cathode on RHS
iii. The anode is written with the metal first and then the
V electrolyte which are separated by a vertical line
Salt bridge
Example: Zn/Zn2+ (or) Zn/ZnSO4
Zn Cu
electrode electrode iv. The cathode is written with the electrolyte first and then
the metal Example : Cu2+/Cu (or) CuSO4/Cu
v. The two half cells are separated by a salt bridge, which
ZnSO4 CuSO4
solution is indicated by two vertical lines.
solution
Using the above representation, the galvanic cell is represented as
Cell device (construction) Zn/ZnSO4 (1M) //) CuSO4 (1M) /Cu
Consists of Zn electrode dipped in 1M ZnSO4 solution and a Cu electrode
dipped in 1M CuSO4 solution. Each electrode is a half cell. The solutions
are inter connected by salt bridge and the two electrodes are connected by Differences between electrolytic cells and electrochemical cells
wire Electrolytic cell Electrochemical cell
Electrical energy converted to Chemical energy converted to
Reactions occuring in the cell At anode: oxidation takes place chemical energy electrical energy
Zn Zn2+ + 2e (at anode) with the liberation of e-.
At cathode: Reduction takes place Anode carries +ve charge Anode carries – ve charge
Cu2+ + 2e Cu (at cathode)
by the acceptence of e - .
The electrons liberated in oxidation Cathode carries – ve charge Cathode carries + ve charge
Cu2+ + Zn Zn2+ +Cu (nett cell reaction flow through external wire
reaction) and are consumed by the copper Electrons are supplied to the Electrons are drawn from the
ions at the cathode. cell from an external source cell
Amount of electricity is Emf produced is measured by
Salt bridge: It consists of a U-tube containing a saturated solution measured by coulometer potentiometer
of KCl or (NH4)2NO3 in agar – agar gel. It connects the two half Extent of chemical change is The e.m.f of the cell depends
cells. governed by Faraday’s laws on the concentration of the
Functions electrolyte and chemical
i. Eliminates liquid junction potential nature of the electrode
ii. Provides a path for the flow of electrons between two
half cells
Standard cell Cu(s) | CuNO3(C1M)(dilute) || CuNO3(C2 M)(concentrated) |
A standard cell is the one which
gives constant emf. It is a souce Cu(s)+; C1<C2
Cathode: Cu2+( C2 M) + 2e– → Cu(s)
of constant potential.
Weston cadmium cell consists of
a H – shaped glass vessel. The
Saturated soloution
CdSO4
bottom of the glass tubes are Anode: Cu(s) → Cu2+( C1M) + 2e–
sealed with Pt wires.
CdSO4.8/3H20 +ve electrode (left arm) contains Net: Cu2+(C2 M) → Cu2+(C1 M)
Crystals Hg over which a paste of Hg2SO4
is placed
Hg+Hg2SO4 The transport of cupric ion from a region of higher oncentration to
paste
Hg one of lower concentration.
Cd - Hg + _ ● E° for a concentration cell is always zero, since this would be
amalgam
the potential of a cell in which the electro active species are at
unit activity in both compartment.
The – ve electrode (right arm) contains Hg – Cd amalgam over
which crystals or CdSO4.8/3H2O is placed. 0.0592V logC2/C1
Remaining part of the cell is filled with a saturated solution of Ecell = -------------------------------------------
CdSO4. The upper ends of the tubes are closed with corks. n
The emf of the cell is 1.0807 V. Ex: Oxygen concentration Cell (differential aeration
Representation corrosion).
Cd in Hg/3CdSO4.8H2O // CdSO4.Hg2SO4 / Hg
Ion-Selective Electrodes (ISE)
Concentration Cells ● Electrodes possess certain selectivity towards certain ions.
● Ion Selective Electrodes (ISE) are membrane electrodes that
●The transport of ions due to concentration gradient of the respond selectively to ions in the presence of others
electrolyte at both half-cells is accompanied by a fall in ● The potential developed at the membrane surface is related to
free energy. the concentration of the species of interest.
The loss in free energy produces electrical energy ● The sensing part of the electrode is an ion-specific membrane
● electrolyte (concentrated) → electrolyte (dilute) which is permeable to specific ion and also known as a specific
● No net chemical reaction. ion electrode (SIE).
● Concentration cell is made up of two half-cells having
identical electrodes, identical electrolyte, except that the
concentrations of reactive ions at two electrodes are
different.
