Chapter–3

1 1
Units: k = t =
= ohm –1 cm –1 (S cm –1)
ohm cm

Electrochemistry
The SI unit of conductivity is S m–1.
6. Factors Affecting Metallic Conductance
Electrical conductance through metal is called metallic or electronic conductance and is due to the
movement of electrons. It depends on:
(a) The nature and structure of metal.
(b) The number of valence electrons per atom.
(c) Temperature (it decreases with increase in temperature).
7. Factors Affecting Electrolytic Conductance
Electrolyte: An electrolyte is a substance that dissociates in solution to produce ions and hence conduct
electricity in dissolved or molten state.
Examples: HCl, NaOH, KCl (Strong electrolytes).

1. Electrochemistry: Electrochemistry is the study of production of electricity from the energy released    
CH3COOH, NH4OH (Weak electrolytes).
during a spontaneous chemical reaction and the use of electrical energy to bring about non-spontaneous The conductance of electricity by ions present in the solution is called electrolytic or ionic conductance.
chemical transformations. The following factors govern the flow of electricity through a solution of electrolyte.
2. Ohm’s Law: It states that the potential difference (V) across the conductor is directly proportional to the
(a) Nature of electrolyte or interionic attractions: Lesser the solute–solute interactions, greater will be
current (I) flowing through it. Mathematically, the freedom of movement of ions and higher will be the conductance.
V ? I or V = IR

(b) Solvation of Ions: Larger the magnitude of solute–solvent interactions, greater is the extent of
where R is a constant called resistance of the conductor. Ohm’s law is obeyed by both the metallic, as well solvation and lower will be the electrical conductance.
as electrolytic conductors.

(c) The nature of solvent and its viscosity: Larger the solvent–solvent interactions, larger will be the
3. Resistance (R): It is the property of a substance by which it obstructs the flow of electric current through it.
viscosity and more will be the resistance offered by the solvent to flow of ions and hence lesser will
The electrical resistance (R) of any object is directly proportional to its length (l) and inversely proportional
be the electrical conductance.
to its area of cross-section (A).
l l (d) Temperature: As the temperature of electrolytic solution rises solute–solute, solute–solvent and
Thus, R? or R = t
A A solvent–solvent interactions decrease, which results in the increase of electrolytic conductance.
where r (rho) is a constant of proportionality called specific resistance or resistivity. 8. Difference between Metallic and Electrolytic Conductance
A
t=R S.No. Metallic Conductance Electrolytic Conductance
l
If l =1 cm and A =1 cm2 then R = r. (i) Movement of electrons is responsible for conduction. Movement of ions is responsible for conduction.
Thus, resistivity may be defined as the resistance offered by a conductor of 1 cm length with area of (ii) Does not involve transfer of matter. Matter moves in the form of ions.
cross-section equal to 1 cm2, i.e., it is the resistance of 1 cm3 of the conductor. (iii) Decreases with increase in temperature as kernels Increases with increase in temperature due to decrease
A cm 2 start vibrating which produce hindrance in the flow in interionic attraction or increase in dissociation.
Units: t = R = ohm cm = ohm cm of electrons.
l
Its SI unit is ohm metre (W m). 1 l
9. Measurement of Conductance: As we know, k = #
4. Conductance (G): It is the reciprocal of resistance and may be defined as the ease with which the electric R A
current flows through a conductor. The value of k could be known, if we measure l, A and R. The
1 value of the resistance of the solution between two parallel Conductivity R2 R1
Detector
G= electrodes is determined by using ‘Wheatstone’ bridge method
cell
           R P
(Fig. 3.1).
Its SI unit is Siemen (S).
1 S = ohm–1 (mho) It consists of two fixed resistance R3 and R4, a variable resistance R4 R3
R1 and the conductivity cell having the unknown resistance
5. Conductivity (k): It is the reciprocal of resistivity (r).
R2. The bridge is balanced when no current passes through the
1 1 l l detector. Under these conditions,
k = t = # = G # Fig. 3.1: Wheatstone Bridge
R A A R1 R3 R1 R4
2
If l = 1 cm and A = 1 cm , then k = G. = or R2 =
R2 R4 R3
Hence, conductivity of an electrolytic solution may be defined as the conductance of a solution of 1 cm
length with area of cross-section equal to 1 cm2. Knowing the values of R1, R3 and R4 the resistance of the solution, R2 is determined. The reciprocal of R2
Alternatively, it may be defined as the conductance of 1 cm3 of the solution of an electrolyte. gives the conductance of the solution.

Electrochemistry 97 98 Xam idea Chemistry–XII

 10. Molar Conductivity (Lm): It may be defined as the conducting power of all the ions produced by 12. Kohlrausch’s Law: It states that the limiting molar conductivity of an electrolyte can be represented as the
dissolving one gram mole of an electrolyte placed between two large electrodes at one centimetre apart. sum of the individual contributions of the anion and cation of the electrolyte.
Mathematically, In general, if an electrolyte on dissociation gives n+ cations and n– anions then its limiting molar
k # 1000 conductivity is given by
   K m = k # V, Km =
c K om = v+ m o+ + v– m o–
where, V is the volume of solution in cm3 containing 1 gram mole of electrolyte and c is the molar Here, m o+ and m o– are the limiting molar conductivities of cations and anions, respectively.
concentration. Applications of Kohlrausch’s Law:
k # 1000 S cm –1 (a) Calculation of molar conductivities of weak electrolyte at infinite dilution: For example, molar
Units: K m =
c = conductivity of acetic acid (weak acid) at infinite dilution can be obtained from the knowledge of
mol cm –3
molar conductivities at infinite dilution of strong electrolytes like HCl, CH3COONa and NaCl as
= ohm–1 cm2 mol–1 or S cm2 mol–1 illustrated below:
11. Variation of Conductivity and Molar Conductivity with Concentration:     Kom(CH o
= mCH – + moH+
3 COOH) 3 COO

Conductivity decreases with the decrease in concentration, this is because the number of ions per unit o
= [mCH – + moNa+] + [moH+ + mCl
o
– ] – [m
o
+ o
Na + m Cl –]
3 COO
volume that carry the current in the solution decreases on dilution.
i.e., K om (CH = K om (CH + K om (HCl) – K om (NaCl)
3 COOH) 3 COONa)
Molar conductivity (Lm = k × V) increases with the decrease in concentration or increase in dilution. This
is because the total volume V of solution containing one mole of electrolyte increases with increase in (b) Determination of degree of dissociation of weak electrolytes:
K cm
dilution. It has been found that the decrease in k on dilution of a solution is more than compensated by Degree of dissociation (a) = o
increase in its volume. Km
(c) Determination of dissociation constant (K) of weak electrolytes:
Graphical representation of the variation of Λ m vs
c
ca 2
K=
400 1– a
CH3COOH (Weak electrolyte) K cm
Also, a = o
Km
Λm (S cm2 mol )
–1

c (K cm /K om) 2 c (K cm) 2
` K= =
200 1– K cm /K om K om (K om – K cm)
(d) Determination of solubility of sparingly soluble salts:
KCl (Strong electrolyte)
k # 1000 k # 1000 k # 1000
K om = = or, Solubility =
Molarity Solubility K om
13. Electrochemical Cells: An electrochemical cell is a device in which chemical energy of the redox reaction
0 0.2 0.4 is converted into electrical energy. The redox reaction is carried out in an indirect manner and the decrease
c1/2/(mol/L) 1/2 in free energy during chemical reaction appears as electrical energy.
Fig. 3.2: Λ m vs c for weak and strong electrolytes The simplest electrochemical cell is Voltmeter
Daniel cell or Galvanic cell in which
a zinc rod is placed in a solution
Limiting Molar Conductivity (Lom ): The limiting value of molar conductivity when the concentration

of Zn2+ ions (say, ZnSO4) in the e– e–
approaches zero is known as limiting molar conductivity or molar conductivity at infinite dilution. left container and a bar of copper Salt bridge
Anode Cathode
+
It is possible to determine the molar conductivity at infinite dilution (Lom ) in case of strong electrolyte metal is immersed in a solution of –ve K +ve
2+
by extrapolation of curve of Lm vs c (Fig. 3.2). On contrary, the value of molar conductivity of weak Cu ions (say, CuSO4) in the right Cl –
electrolyte at infinite dilution cannot be determined by extrapolation of the curve as the curve becomes container. The two metals which
act as electrodes are connected by a
almost parallel to y-axis when concentration approaches to zero.
metallic wire through a voltmeter. ZnSO 4 CuSO 4
The mathematical relationship between Lm and K om for strong electrolyte was developed by Debye, The two solutions are joined by an (1M)
(1M) Zn Zn 2+ Cu 2+ Cu
Huckel and Onsager. In simplified form, the equation can be given as inverted U-tube containing semi-
2–
solid paste of either KCl, KNO3 or SO
K m = K om – bc1/2 4
–
NH4Cl in gelatin or agar-agar jelly. Cl
K+
where K om is the molar conductivity at infinite dilution and b is a constant which depends on the nature of SO42–
This arrangement of U-tube is called Zn 2+
the solvent and temperature. salt bridge (Fig. 3.3). 2+ – 2+ –
Zn Zn +2 e Cu +2 e Cu
Fig. 3.3: A simple voltaic cell

Electrochemistry 99 100 Xam idea Chemistry–XII

 The overall cell reaction, 15. Reversibility of Daniel Cell:
Zn(s) + Cu2+ (aq) Zn2+ (aq) + Cu(s) (a) When external voltage is less than 1.10 V, electrons flow from Zn to Cu but current flows from Cu to
can be split into two half cells. The deflection in the voltmeter indicates the flow of current through the Zn, i.e., in opposite direction. Zinc dissolves at anode and copper deposits at cathode [see Fig. 3.4(a)]
external circuit. The conventional current flows through the outer circuit from copper metal to zinc metal, (b) When external voltage applied is less than 1.10 V and is increased slowly, it is observed that the
which implies flow of electrons from zinc to copper bar. reaction continues to take place till the external voltage attains the value 1.10 V. When this is so,
(a) At zinc electrode, the metal undergoes oxidation and releases two electrons. reaction stops altogether and no current flows [see Fig. 3.4(b)].
Zn(s) Zn2+ (aq) + 2e– (oxidation) (c) If the value of external voltage exceeds the voltage of Daniel cell (1.10 V), the reaction takes place in
Because oxidation is taking place, the electrode behaves as anode. These electrons travel through wire opposite direction, i.e., the cell functions like an electrolytic cell [see Fig. 3.4(c)].
and reach the copper metal. E ext < 1.1 V E ext = 1.1 V E ext > 1.1 V
(b) Cu2+ (aq) + 2e– Cu(s) (reduction)
The above reaction occurs at the copper electrode. Electronation takes place which is a reduction e– e–
process and that is why it acts as cathode. Anode Cathode Cathode Anode
Current +ve Current –ve
As a result of the two half cell reactions, zinc metal dissolves in anode solution to form Zn2+ ions, I=0
while the Cu2+ ions are discharged at the cathode by accepting two electrons and are deposited at Zn
Salt
Cu Zn
Salt
Cu Zn Cu
–ve +ve Salt
cathode. The electrical neutrality is maintained in two half cells using a salt bridge. The anions of the bridge bridge bridge
inert electrolyte in the salt bridge migrate to the anodic chamber and cations to the cathodic chamber.
As a result, as the reaction progresses, copper bar gains weight whereas zinc rod loses weight. As
a consequence, the cell continues to function till either zinc metal or copper ions in solution are
consumed fully.
Since electrons are released at anode, it acquires negative polarity and cathode becomes positive ZnSO4 CuSO4 ZnSO 4 CuSO4 ZnSO 4 CuSO4
because it needs electrons for the reduction of +ve ions. This observation is against the usual
(a) (b) (c)
electrolytic cell where anode is +ve and cathode is –ve.
Fig. 3.4: Functioning of Daniel cell when external voltage Eext opposing the cell potential is applied
Salt Bridge and Its Functions
16. Electrode Potential: It may be defined as the tendency of a metal, when it is placed in contact with its own
A commonly used form of salt bridge consists of a glass U-tube containing semi-solid paste of either
ions to either lose or gain electrons and in turn become positively or negatively charged.
KCl, KNO3 or NH4Cl in gelatin or agar-agar jelly.
The electrode potential will be named as oxidation or reduction potential depending upon whether oxidation
The electrolytes that are often used in salt bridge are called inert electrolytes which are supposed:
or reduction has taken place.
(a) not to interact chemically with either of the solutions present in anodic or cathodic chamber.
M n+ (aq) + ne –
oxidation
M (s )
(b) not to interfere with overall cell reaction. reduction

(c) only those electrolytes can be used in a salt bridge in which mobility of ions is almost the same. Or
  Example, KCl, K2SO4 , etc. + reduction
M n (aq) + ne – M (s )
A salt bridge carries out two important functions: oxidation

(a) It allows only flow of ions through it. Thus, the circuit is completed. Characteristics:
(b) It also maintains the electrical neutrality. (a) Both oxidation and reduction potentials are equal in magnitude but opposite in sign.
14. Cell Diagram or Representation of an Electrochemical Cell: The following conventions or notations (b) The reduction potential shows an increase with increasing concentration and decrease with decreasing
are applied for writing the cell diagram in accordance with IUPAC recommendations: The Daniel cell is concentration of ions in a solution.
represented as follows: (c) It is not a thermodynamic property, so values of E are not additive.
Zn (s) | Zn 2+ (c1) || Cu 2+ (c2) | Cu (s) 17. Standard Hydrogen Electrode (SHE): It is a reference electrode and its
(a) Anode half cell is written on the left hand side while cathode half cell on right hand side. reduction potential is arbitrarily assigned as zero volt at all temperature.
(b) A single vertical line separates the metal from aqueous solution of its own ions. The standard hydrogen electrode consists of a platinum electrode coated H 2 at 298 K
Zn(s) | Zn2+ (aq); Cu2+ (aq) | Cu(s) with platinum black. The electrode is dipped in an acidic solution having 1 bar
Anodic chamber Cathodic chamber 1M concentration of H+ ions. Pure hydrogen gas at 1 bar pressure is
(c) A double vertical line represents salt bridge which allows the passage of ions through it but prevents continuously bubbled through the solution at a temperature of 298 K
the mixing of two solutions. (Fig. 3.5).
(d) The molar concentration (c) is placed in brackets after the formula of the corresponding ion. The hydrogen electrode can act both ways—as an anode or as a cathode.
(e) The value of EMF of the cell is written on the extreme right of the cell. For example, Acting as anode — oxidation takes place, 1M HCl
Zn(s) | Zn2 + (1M) || Cu2 + (1M) | Cu (s) EMF = + 1.1 V H2 (g) 2H+ (aq) + 2e–
Pt foil
(f) If an inert electrode like platinum is involved in the construction of the cell, it may be written along with the Acting as cathode — reduction takes place,
working electrode in bracket, say for example, when a zinc anode is connected to a hydrogen electrode. 2H+ (aq) + 2e– H2(g)
Fig. 3.5: Standard or
Zn(s) | Zn2+ (c1) || H+ (c2) | H2 (Pt) Normal Hydrogen Electrode

Electrochemistry 101 102 Xam idea Chemistry–XII

 Representation of SHE Substituting the values of R and F we get
Pt(s) | H2 (g) | H+ (aq) (c = 1 M) [C] c [D] d
0.0591
18. Standard Electrode Potential (Eo): It may be defined as the electrode potential of an electrode determined Ecell = Ecell
o
– n log [A] a [B] b , at 298 K
relative to standard hydrogen electrode under standard conditions. The standard conditions taken are:
(a) 1 M concentration of each ion in the solution. 21. Equilibrium Constant from Nernst Equation: For a Daniel cell, at equilibrium

(b) A temperature of 298 K. 2.303RT [Zn 2+]

Ecell = 0 = Ecell
o
– log
(c) 1 bar pressure for each gas. 2F [Cu 2+]
19. Cell Potential or EMF of a Cell: The difference between the electrode potentials of two half cells is called 2.303RT [Zn 2+]
cell potential. It is known as electromotive force (EMF) of the cell if no current is drawn from the cell. or Ecell
o
= log
2F [Cu 2+]

Ecell = Ereduction – Eoxidation = Ecathode – Eanode [Zn 2+]
But at equilibrium,
= Kc
Since anode is put on left and cathode on right, therefore it follows [Cu 2+]
Ecell = ER – EL ` Ecell
o 2.303RT
= log Kc
For a Daniel cell, 2F
o o 2.303 # 8.314 # 298
Ecell
o
= ECu 2+
/Cu – E Zn 2+ /Zn Ecell =
o
log Kc =
0.0591
log Kc
2 # 96500 2
= 0.34V – (– 0.76V)
0. 0591 n
= 1.10V In general, Ecell
o
= n log Kc or, log Kc = 0.0591 Ecell
o

20. Nernst Equation: It relates electrode potential with the concentration of ions.
For an electrode reaction, Mn+ (aq) + ne– M(s) 22. EMF and Gibbs Free Energy: The work done by a reversible galvanic cell is equal to decrease in its free
Nernst equation can be written as energy.
Mathematically, DrG = –nFEcell
o RT [M]
EMn+ /M = E M n+
/M – nF ln If concentration of all the reacting species is unity, then,
[M n+]
o 2.303RT 1 Ecell = Ecell
o
and we get, D r G o = – nFEcell
o
EMn+ /M = E M n+
/M – log n+
nF [M ] From D r G o, we can calculate the equilibrium constant of a reaction,
where, EM n+
/M
= Electrode potential
D r G o = – RT ln Kc or D r G o = – 2.303 RT log Kc
o
EM n+
/M
= Standard electrode potential
23. Electrochemical Series: The arrangement of various standard half-cells in the order of their decreasing
   R = 8.314 JK–1 mol–1 standard reduction potential values is known as electrochemical series.
   T = Temperature in kelvin OO A negative value of Eo means that the redox couple is stronger reducing agent than H+/H2. e.g., Mg (– 2.36).
   n = No. of electrons gained OO A positive value of Eo means that the redox couple is weaker reducing agent than H+/H2. e.g., Br2 (1.09).
   F = Faraday constant (96500 C mol–1) 24. Concentration Cells: If two electrodes of the same metal are dipped separately into two solutions of the
Substituting the value of R and F, we get same electrolyte having different concentrations and the solutions are connected through salt bridge, such
cells are known as concentration cells. In these cells, oxidation takes place on the electrode with lower
o 0.0591 1
EMn+ /M = E M n+
/M – n log [M n+] , at 298 K concentration (c1) while reduction takes place on the electrode with higher concentration (c2). For example,

H2 | H+(c1) || H+(c2) | H2; Cu | Cu2+(c1) || Cu2+(c2) | Cu
o 0.0591 n+
EMn+ /M = E M n+ + n log [M ], at 298 K Zn | Zn2+ (c1) || Zn2+ (c2) | Zn
or /M

Thus, the reduction potential increases with the increase in the concentration of ions. The EMF of concentration cell at 298 K is given by
0.0591 c2
For a general electrochemical reaction of the type: Ecell = n log c1 , where c2 > c1
ne –
aA + bB cC + dD
25. Electrolysis: The process of decomposition of an electrolyte when electric current is passed through its
Nernst equation can be given as
aqueous solution or fused state is called electrolysis.
c d
RT [C] [D] The process of electrolysis of a substance is governed by Faraday’s laws of electrolysis.
Ecell = Ecell
o
– ln
nF [A] a [B] b (a) Faraday’s first law of electrolysis

2.303 [C] c [D] d “The amount of any substance deposited or liberated at the electrode is directly proportional to the quantity
Ecell = Ecell
o
– RT log
nF [A] a [B] b of electricity passing through the electrolyte.”

Electrochemistry 103 104 Xam idea Chemistry–XII

 If w grams of the substance deposited on passing Q coulombs of electricity, then
Another type of primary cell is the mercury cell, consisting of zinc–mercury amalgam as anode and a
w ? Q or w ? I # t [a Q = I # t] paste of HgO and carbon as the cathode. The electrolyte is a paste of KOH and ZnO. The electrode
reactions are:
or w = Z × I × t
Anode: Zn(Hg) + 2OH– ZnO(s) + H2O + 2e–
where, Z is a constant of proportionality known as electrochemical equivalent of the substance deposited. –
Cathode: HgO(s) + H2O + 2e Hg (l) + 2OH–
OO Electrochemical equivalent (Z): If I = 1 ampere and t = 1 second, then
The cell potential is approximately 1.35 V and remains constant as the ionic concentration of the
w = Z
solution is not changed during its life.
Thus, the electrochemical equivalence may be defined as the amount of the substance deposited by passing Cathode Anode
(b) Secondary cells (Batteries)
one ampere of current for one second or by passing one coulomb of charge through the electrolyte. –
A secondary battery is rechargeable and can be
OO 1 Faraday = Quantity of electricity carried by 1 mole of electrons. used again and again. It is recharged by passing +

(6.023 × 1023 mol–1 × 1.6 × 10–19 C = 96472 C mol–1 - 96500 C mol–1) current through it from an external source. Most
OO If n mol of electrons are involved in an electrode reaction, then familiar example of secondary cell is the lead
n × 96500 C of charge will deposit = M g of the element storage battery commonly used in automobiles
M and invertors. It consists of a lead anode and a
1 C of charge will deposit = g of element grid of lead packed with lead dioxide (PbO2) as
n # 96500
But 1 C of charge deposit mass of element = Z g cathode.
M E A 38% solution of H2SO4 is used as an electrolyte
` Z= g= g
n # 96500 96500 (Fig. 3.7).
Atomic mass Positive plates:
where E is the equivalent mass of the element and is equal to of the element. The cell reactions when the battery is in use, are: Sulphuric lead grids filled
Valency acid solution with PbO2
or E = 96500 × Z At anode:   
Equivalent mass: The mass of an element deposited by passing 96500 C of charge. Fig. 3.7: The lead storage battery
OO Pb (s) SO 4 (aq)
+ 2–
PbSO 4 (s) 2e
+ –

(b) Faraday’s second law of electrolysis At cathode:  
“When same quantity of electricity is passed through different electrolytes, the amount of different PbO 2 (s) + SO 4 (aq) + 4H + (aq) + 2e –
2–
PbSO 4 (s) + 2H 2 O (l)
substances deposited at the electrodes is directly proportional to their equivalent masses.” The overall reaction is:
W1 E1    Pb(s) + PbO2(s) + 2H2SO4 (aq) 2PbSO4 (s) + 2H2O(l)
Mathematically, =
W2 E2 On recharging the cell, operated like an electrolytic cell; the reaction is reversed and PbSO4(s) on
anode and cathode is converted into Pb and PbO2, respectively.
26. Commercial Cells (Batteries): Batteries are the electrochemical
Carbon rod At anode: PbSO4(s) + 2H2O(l) PbO2(s) + SO42– (aq) + 4H+ + 2e–
cells used commercially to generate electricity. “Any battery (cathode) At cathode: PbSO4 (s) + 2e– Pb(s) + SO42– (aq)
consists of two or more than two galvanic cells connected in
series where the chemical energy of the redox reactions is Another important secondary cell is the nickel–cadmium cell which has longer life than the lead
converted into electrical energy.” There are mainly two types storage cell but is costly. Here, the overall reaction during discharge of the battery is
of batteries: Cd(s) + 2Ni(OH)3 (s) CdO(s) + 2Ni(OH)2 (s) + H2O(l)
Water
(a) Primary cells (Batteries): These cells are not chargeable 27. Fuel Cells: Fuel cells are those cells which produce
because the electrode reaction occurs only once and after electrical energy directly from the combustion of
the use over a period of time the cells become dead and fuels such as hydrogen, carbon monoxide or methane.
cannot be reused. The most successful fuel cell, H2–O2 cell utilises the
reaction between hydrogen and oxygen to produce

KOH (aq) or NaOH(aq)

The most familiar example of this type of cell is the dry
water. Hydrogen and oxygen are bubbled through a
cell (known as Leclanche cell after its discoverer) which porous carbon electrode in the cell into concentrated
is used commonly in watches, radios, calculators, etc. H2 gas O2 gas
Zinc cup MnO 2 + Carbon black aqueous sodium hydroxide. Catalysts are incorporated
It consists of a zinc container that also acts as anode (anode) + NH 4 Cl paste into the electrode (Fig. 3.8). The electrode reactions
and the cathode is a carbon (graphite) rod surrounded Fig. 3.6: The dry cell are
by powdered manganese dioxide and carbon. The space
Anodic reaction:  2H2 (g ) + 4OH– (aq) 4H2O(l) + 4e–
between the electrodes is filled by a moist paste of NH4Cl and ZnCl2 (Fig. 3.6).
Cathodic reaction: O2 (g) + 2H2O(l) + 4e– 4OH– (aq)
The electrode reactions are: Fig. 3.8: A simple H2–O2 fuel cell
Overall reaction 2H2 (g) + O2 (g) 2H2O(l)
Anode: Zn(s) Zn2+ + 2e– Advantages of Fuel Cells:
Cathode:   MnO 2 + NH 4 + e
+ –
MnO (OH) + NH3 (a) It is a pollution-free device since no harmful products are formed.
The cell has a potential of nearly 1.5 V. (b) Its efficiency is about 75% which is considerably higher than conventional cells.

Electrochemistry 105 106 Xam idea Chemistry–XII

 (c) These cells are light in weight as compared to electrical generators to produce corresponding quantity
of power.
(d) It is a continuous source of energy if the supply of gases is maintained.
ipe
28. Corrosion: The process of slow eating up of metals by gases and water vapours present in atmosphere due np
Iro
to the formation of certain compounds like oxides, sulphides, carbonates, etc. is called corrosion. Corrosion
of iron is known as rusting. Chemically, rust is hydrated ferric oxide, Fe2O3 . xH2O. Corrosion may be Anode Cathode
considered as an electrochemical phenomenon. According to electrochemical theory of rusting, the impure Mg Mg2++ 2e – O2 + 4H+ + 4e – 2H2O
iron surface behaves like a small electrochemical cell in the presence of moisture containing oxygen or
carbon dioxide. Such a cell is called corrosion cell or corrosion couple. In these miniature corrosion cells, Fig. 3.10: Electric Protection
pure iron acts as anode, impure surface area acts as cathode and moisture having dissolved carbon dioxide 30. Products of Electrolysis: Under the influence of electric current through molten electrolytes or their
or oxygen acts as electrolyte. aqueous solutions, ions move towards oppositely charged electrodes. Many times the electrode products
At anode, oxidation of iron takes place. Thus, Fe enters into the solution as Fe2+ ions leaving behind differ. For example, the electrolysis of molten sodium chloride yields sodium metal at the cathode and
electrons which are pushed into cathodic area. chlorine gas is liberated at the anode.
o
    Fe Fe2+ + 2e–; E Fe 2+ = –0.44 V ...(i) NaCl (s) Na + + Cl –
^molten stateh
/Fe
At cathode, the electrons are picked up by the H+ ions which are produced from H2CO3 (formed due to
dissolution of CO2 in moisture) or from H2O. At anode, Cl – Cl + e – Oxidation
+ Cl + Cl Cl 2 (g)
H2CO3 2H + CO32–
At cathode, Na + + e – Na (s) Reduction
H+ ions, thus formed, reduces the dissolved oxygen as the net reaction at the cathodic area is
1 However, when a concentrated aqueous solution of sodium chloride is electrolysed, H2 gas at cathode
2H + + O 2 + 2e – H 2 O; E Ho + /O /H O = 1.23 V …(ii) and Cl2 gas at anode are obtained. This is because water is preferably reduced at cathode.
2 2 2

The overall reaction of the corrosion cell can be obtained by adding equations (i) and (ii) At cathode, 2H2O(l) + 2e– H2(g) + 2OH – (aq)
1 o This happens because the standard reduction potential of water is greater than the standard reduction
Fe + 2H + + O 2 Fe 2+ + H 2 O; Ecell = 1.67 V
2 potential of Na+ ion.
The ferrous ions so formed move through water and come at the surface where these are further oxidised Na+ (aq) + e– Na(s) Eocell = – 2.71 V
by atmospheric oxygen to ferric ions and form rust which is hydrated ferric oxide (Fig. 3.9). 2H2O(l) + 2e– H2 (g) + 2OH – (aq) Eocell = – 0.83 V
1 At anode, however, Cl2 gas is liberated because of over potential of oxygen. In fact, the remaining solution
2Fe 2+ + O 2 + 2H 2 O Fe 2 O3 + 4H +
2
after electrolysis yields solid NaOH on evaporating. Thus,
Fe 2 O3 + xH 2 O Fe 2 O3 . xH 2 O
Hydrated ferric oxide (Rust)
At anode 2Cl – (aq) Cl 2 (g) + 2e –

29. Prevention of Corrosion: The metal surface can be +

At cathode: 2H 2 O (l ) + 2e –
H 2 (g) + 2OH – (aq)
O2+ Fe
2+ 4H (aq) + O2
protected against corrosion by the following methods: 2H2O 2H 2 O (l ) + 2Cl – (aq) + 2Na + (aq) H 2 (g) + Cl 2 (g) + 2OH – (aq) + 2Na + (aq)
2+ 2+
(a) Barrier protection: A thin film is introduced Fe Fe
between iron and atmospheric oxygen, carbon Fe2O3 (a) Electrolysis of dilute H2SO4
dioxide and moisture. The following methods are Fe Fe –
4e During electrolysis of dilute H2SO4, the products are H2(g) at cathode and O2(g) at anode:
adopted for depositing thin film on metal surface: – –
2e 2e H 2 SO 4 2H + (aq) + SO 24– (aq)
(i) By covering the surface with paint or a thin film
Fig. 3.9: Corrosion
of grease. At anode, H 2 O ( l)
1
O (g) + 2H + (aq) + 2e – Ecell
o
= + 1.23 V
(ii) By electroplating iron with some non-corrosive metals such as nickel, chromium, copper, etc. 2 2
(b) Sacrificial protection: In this method, iron surface is covered with a more electropositive metal than At cathode, 2H + (aq) + 2e – H 2 (g)
iron which gets oxidised in preference to iron. In such a situation the more electropositive metal loses If H2SO4 is concentrated then the following reaction occurs at anode
electrons instead of iron and thus this metal is sacrificed at the cost of iron, hence the name sacrificial o
       2SO 24– (aq) S 2 O82– (aq) + 2e – Ecell = + 1.96 V
protection. Iron is generally coated with zinc and this process is called galvanization.
(c) Electrical protection: This is also a case of sacrificial protection. This method is used for the protection (b) Electrolysis of aqueous copper sulphate using inert electrodes (Pt)
of underground water pipes or iron tanks. In this method, the exposed surface of iron is protected by In this, copper is deposited at cathode and oxygen is liberated at anode.
connecting it to a block of some active metal such as magnesium, aluminium or zinc (Fig. 3.10). This      CuSO (aq) 
more electropositive metal acts as anode and lose electrons in preference to iron. The iron surface acts 4  Cu 2  (aq)  SO24  (aq)
1
as cathode. This method, therefore, is also called cathodic protection. The electrons released at the At anode H 2 O (l) O (g) + 2H + (aq) + 2e – Ecell
o
= + 1.23 V
2 2
anode are accepted by H+ ions of water at the surface of iron. More electropositive metal is consumed 2 2 o
gradually in the process and needs periodical replacement. 2SO 4 (aq) S2 O8 (aq) 2e Ecell 1.96 V
   

Electrochemistry 107 108 Xam idea Chemistry–XII

 Water, having low Eo, would be preferably oxidised at anode instead of SO 2–
ions. Ecell
o
= Ecathode
o
– Eanode
o
4
Cu2+ ions have greater reduction potential, copper metal is deposited at the cathode.
= E right – Eleft
o o

At cathode,   Cu 2+ (aq) + 2e – Cu (s), Ecell
o
=+ 0.34 V
7. Nernst equations for a general electrode reaction:
2H 2 O (l ) + 2e – H 2 (g) + 2OH – (aq), Ecell
o
= – 0.83 V M n+ + ne – M
(c) If CuSO4 is electrolysed between two copper electrodes (active electrodes), the Cu2+ ions discharge at RT [ M]
the cathode (negatively charged) and the following reaction occurs EMn+ /M = E Mn+ /M –
o
ln
nF [M n+]

       Cu 2+ (aq) + 2e – Cu (s) 2.303 RT 1
EMn+ /M = E M
o
n+
/M – log n+
nF
Thus, copper metal is deposited at cathode. At the anode, copper is converted into Cu2+ ions with the
[M ]
0.059 1
following change: EMn+ /M = E M
o
n+
/M – n log [M n+] at 298 K
       Cu (s) Cu 2+ (aq) + 2e –
8. Nernst equation for a general electrochemical reaction:
Thus, copper is dissolved (oxidised) at anode and deposited (reduced) at cathode. This forms the basis
of an industrial process in which impure copper is converted into copper of high purity. The impure ne –
aA + bB cC + d D
copper is made as anode that dissolves on passing current and pure copper is deposited at cathode.
RT [C] c [D] d
Ecell = Ecell
o
– ln
(d) Electrolysis of aqueous sodium bromide: Like aqueous NaCl, the electrode products are Br2 (l) at
nF [A] a [B] b
anode and H2 (g) at cathode. [C] c [D] d
2.303RT
Conclusions: 1. Cathodic reaction will be one which has higher E reduction
o
value. Ecell = E cell
o
– log
nF [A] a [B] b
       2. Anodic reaction will be one which has higher Eoxidation
o
value or lower E reduction
o
value. [C] c [D] d
0.059
Ecell = E cell
o
– n log [A] a [B] b at 298 K
Important Formulae n
9. log Kc = Eo
l
R = tc
m = t # Cell constant
0.0591 cell
1.
A
where, Kc = Equilibrium constant
where, R = Resistance
10. D r Go = – nFEcell
o
A = Area of cross-section of the electrodes
r = Resistivity D r G° = –2.303RT log Kc

1 where, DrG° = Standard Gibbs energy of the reaction
2. k =
× cell constant
R
where, k = Conductivity or specific conductance 11. Q = I × t
k×1000 where Q = Quantity of charge in coulombs
3. K m =
M I = Current in amperes
where, K m = Molar conductivity t = Time in seconds
M = Molarity of the solution. 12. m = Z × I × t
4. K om (Ax B y) = xK om (A y+ ) + yK om (B x– ) where m = Mass of the substance deposited at the electrodes
where, Kom = M  olar conductivity at infinite dilution, x and y are the number of cations and anions produced Z = Electrochemical equivalent
by one formula unit of the electrolyte on complete dissociation.
K cm
5. a = o
Km NCERT Textbook Questions
where, a = Degree of dissociation
K cm = Molar conductivity at a given concentration NCERT Intext Questions
6. For a weak binary electrolyte AB
Q. 1. How would you determine the standard electrode potential of the system Mg2+ | Mg?
ca 2 c (K cm) 2
K= = Ans. Set up an electrochemical cell consisting of Mg | MgSO4 (1 M) as one electrode by dipping a magnesium
1 – a K om (K om – K cm) rod in 1 M MgSO4 solution and standard hydrogen electrode Pt, H2 (1 atm) | H+ (1 M) as the second

electrode as shown in given figure.
where, K = Dissociation constant

Electrochemistry 109 110 Xam idea Chemistry–XII