Electrochemistry

CHAPTER

4 ELECTROCHEMISTRY

LEARNING OBJECTIVES
(i) Describe an electrochemical cell and differentiate between galvanic and electrolytic cells.
(ii) Apply Nernst equation for calculating the emf of galvanic cell and define standard potential of the cell.
(iii) Derive relation between standard potential of the cell, Gibbs energy of cell reaction and its equilibrium constant.
(iv) Define resistivity , conductivity and molar conductivity of ionic solutions.
(v) Justify the variation of conductivity and molar conductivity of solutions with change in their concentration and define 0m
(molar conductivity at zero concentration or infinite dilution).
(vii) Enunciate Kohlrausch law and learn its applications.

INTRODUCTION
Electrochemistry deals with the chemical changes produced by electric current and with the production of electricity by chemical
reactions. Many metals are purified or are plated onto jewelry by electrochemical methods. Digital watches, automobile starters,
calculators, and pacemakers are just a few devices that depend on electrochemically produced power. Corrosion of metals is an
electrochemical process.
We learn much about chemical reactions from the study of electrochemistry. The amount of electrical energy consumed or
produced can be measured quite accurately. All electrochemical reactions involve the transfer of electrons and are therefore,
oxidation-reduction reactions. The sites of oxidation and reduction are separated physically so that oxidation occurs at one
location while reduction occurs at the other. Electrochemical processes required some method of introducing a stream of
electrons into a reacting chemical system and some means of withdrawing electrons. In most applications the reacting system is
contained in a cell, and an electric current enters or exists by electrodes.
Electrodes are surfaces upon which oxidation or reduction half-reactions occur.
The cathode is defined as the electrode at which reduction occurs as electrons are gained by some species. The anode is the
electrode at which oxidation occurs as electrons are lost by some species.

ELECTROCHEMICAL CELLS :
Cell is a system or arrangement in which two electrodes are fitted in the same electrolyte or in two different electrolytes which are
joined by a salt bridge. Cells are of two types.
(a) Electrolytic cell (b) Galvanic or voltaic cell
(a) Electrolytic cell : It is a device in which electrolysis (chemical reaction involving oxidation and reduction) is carried out by using
electricity or in which conversion of electrical energy into chemical energy is done.
(b) Galvanic or voltaic cell : It is a device in which a redox
reaction is used to convert chemical energy into G e
Key
electrical energy, i.e., electricity can be obtained with
the help of oxidation and reduction reaction. The Current
chemical reaction responsible for production of Cl Salt bridge K+ Copper rod
electricity takes place in two separate compartments. Zinc rod (Cathode)
Each compartment consists of a suitable electrolyte (Anode)
KCl in
solution and a metallic conductor. The metallic Agar-agar
conductor acts as an electrode. The compartments
containing the electrode and the solution of the Zinc
electrolyte are called half-cells. When the two Dissolves Cotton Copper is
compartments are connected by a salt bridge and plugs deposited
electrodes are joined by a wire through galvanometer
the electricity begins to flow. This is the simple form of 1 M ZnSO4 1 M CuSO4
voltaic cell.
Anode : Zn Zn2+ + 2e Cathode : Cu+2 + 2e Cu
(Ist half cell reaction) (IInd half cell reaction)
Total cell reaction : Zn(s) + Cu+2(aq) Zn+2(aq.) + Cu(s)
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 Electrochemistry
Salt bridge : It is U-shaped glass tube filled with a gelly like substance, agar-agar, mixed with an electrolyte like KCl, KNO3,
NH4NO3, etc. It performs following functions.
(i) It prevents voltage drops, i.e. prevents junction potential.
(ii) It allows flow of current by completing the circuit, i.e., migration of anion from anode to cathode half cell.
(iii) It prevents accumulation of charges and maintains the electrical neutrality of solutions.
(iv) Nature of junction potential is opposite to EMF of cell.
(v) Salt bridge form a electrolyte which have almost same movability of cation and anion.
Representation of Galvanic cell : Galvanic cell is a combination of two half cells, namely, oxidation half cell and reduction half cell.
If M represents the symbol of the element and Mn+ represents its cation (i.e., its oxidised state) in solution, then
Oxidation half cell is represented as M/Mn+(C)
Reduction half cell is represented as Mn+(C)/M Conventional Current
e
In both the notations C refers to the molar Electron Flow
concentration of the ions in solution.
Conventionally, a cell is represented by writing
the cathode on the right hand side and anode on
the left hand side. The two vertical lines are put
between the two half cells which indicate salt
2+ Saturated 2+
bridge. Sometimes the formula of the electrolyte Zn / Zn (1M) Cu (1M)/ Cu
KCl
used in the salt bridge is also written below the
vertical lines. For example, zinc-copper sulphate
cell is represented as follows : ANODE () CATHODE (+)
2 2
Zn (s) | Zn (aq) || Cu (aq) | Cu (s)
anode salt bridge Cathode OXIDATION HALF SALT BRIDGE REDUCTION HALF

ELECTRODE POTENTIAL :
The potential difference between the two electrodes of a
galvanic cell is called the cell potential and is measured
H2 gas under
in volts. The cell potential is the difference between the
electrode potentials (reduction potentials) of the cathode 1 atm pressure
and anode. It is called the cell electromotive force (emf)
of the cell when no current is drawn through the cell. It is
now an accepted convention that we keep the anode on Electrode
the left and the cathode on the right while representing
the galvanic cell. 1MHCl
EMF = Eright(cathode) Eleft(Anode) solution
or simply as EMF = Ecation Eanion Platinum coated
The potential of individual half-cell cannot be measured. with platinum black
Fig. Standard hydrogen electrode (SHE)
We can measure only the difference between the two half-cell potentials that gives the emf of the cell. If we arbitrarily choose the
potential of one electrode (half-cell) then that of the other can be determined with respect to this. According to convention, a half-
cell called standard hydrogen electrode represented by Pt (s) | H2(g) | H+(aq), is assigned a zero potential at all temperatures
corresponding to the reaction
1
H+ (aq) + e H (g)
2 2
The standard hydrogen electrode 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. The concentration of both the reduced and oxidised forms of
hydrogen is maintained at unity. This implies that the pressure of hydrogen gas is one atm. and the concentration of hydrogen
ion in the solution is one molar.
Thus, we can define standard electrode potential as the potential of an electrode relative to a standard hydrogen electrode at
298K, 1 atm pressure when the concentration of the ion taking part in the electrode reaction is 1 mol L1.
If we consider left half cell as SHE than the measured emf of the cell equals the standard electrode potential of the right half cell.
The measured emf of the cell :
Pt (s) | H2(g , 1 atm) | H+ (aq, 1 M) || Cu2+ (aq, 1 M) | Cu
is 0.34 V and it is also the value for the standard electrode potential of the half-cell corresponding to the reaction :
Cu2+ (aq, 1M) + 2e Cu(s)
2 Gyaan Sankalp
 Electrochemistry
Similarly, the measured emf of the cell :
Pt(s) | H2(g , 1 atm) | H+ (aq, 1 M) || Zn2+ (aq, 1M) | Zn
is -0.76 V corresponding to the standard electrode potential of the half-cell reaction:
Zn2+ (aq, 1 M) + 2e Zn(s)
The positive value of the standard electrode potential in the first case indicates that Cu2+ ions get reduced more easily than H+
ions. The reverse process cannot occur, that is, hydrogen ions cannot oxidise Cu (or alternatively we can say that hydrogen gas
can reduce copper ion) under the standard conditions described above. Thus, Cu does not dissolve in HCl. In nitric acid it is
oxidised by nitrate ion and not by hydrogen ion. The negative value of the standard electrode potential in the second case
indicates that hydrogen ions can oxidise zinc (or zinc can reduce hydrogen ions).
Following above convention, the half reaction for the zinc-copper cell can be written
Zn(s) Zn2+ (aq, 1M) + 2e (oxidation, anode) left
Cu2+ + 2e Cu(s) (reduction, cathode) right
(aq. 1M)

Cu2+ + Zn (s) Zn2+ (aq) + Cu (s) (overall reaction)
emf of the cell = Ecell ER E L 0.34 (0.76) 1.10V

ELECTRO CHEMICAL SERIES :

The arrangement of various elements in order of increasing values of standard reduction potential is called electro chemical
series. Standard reduction potentials at 298 K (Electrochemical Series)

Element Electrode Reduction Reaction Standard Reduction Potential E (in Volt)

Li Li+ + e Li 3.05
K K+ + e K 2.93
Ba Ba2+ + 2e Ba 2.90
Increasing strength as oxidizing agent

Ca Ca2+ + 2e Ca 2.87
Na Na+ + e Na 2.71
Mg Mg2+ + 2e Mg 2.37
Al Al3+ + 3e Al 1.66
Increasing strength as reducing agent

Mn Mn2+ + 2e Mn 1.18
Zn Zn2+ + 2e Zn 0.76
Cr Cr3+ + 3e Cr 0.74
Fe Fe2+ + 2e Fe 0.44
Cd Cd2+ + 2e Cd 0.40
Ni Ni2+ + 2e Ni 0.25
Sn Sn2+ + 2e Sn 0.14
Pb Pb2+ + 2e Pb 0.13
H2 2H+ + 2e H2 0.00
Cu Cu2+ + 2e Cu 0.34
I2 I2 + 2e 2I 0.53
Hg Hg2+2 + 2e 2Hg 0.79
Ag Ag+ + e Ag 0.80
Hg Hg+2 + 2e Hg 0.85
Br2 Br2 + 2e 2 Br 1.08
Cl2 Cl2 + 2e 2 Cl 1.36
Au Au3+ + 3e Au 1.50
F2 F2 + 2e 2F 2.87

Strength of oxidising and reducing agents : Standard electrode potentials are useful in determining the strengths of oxidizing
and reducing agents under standard-state conditions. Because electrode potentials are reduction potentials those reduction
half-reactions in the table with the larger (that is more positive) electrode potentials have the greater tendency to go left to right
as written. A reduction half-reaction has the general form.
Oxidised species + ne reduced species.
The oxidized species acts as an oxidizing agent. Consequently, the strongest oxidizing agents in a table of standard electrode
potentials are the oxidized species corresponding to half-reactions with the largest (most positive) E values.
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 Electrochemistry
Those reduction half-reactions with lower (that is, more negative) electrode potentials have a greater tendency to go right to left.
That is, Reduced species oxidized species + ne
The reduced species acts as a reducing agent. Consequently, the strongest reducing agents in a table of standard electrode
potentials are the reduced species corresponding to half-reactions with the smallest (most negative) E values.
It can be seen that the standard electrode potential for fluorine is the highest in the Table indicating that fluorine gas (F2) has the
maximum tendency to get reduced to fluoride ions (F) and therefore fluorine gas is the strongest oxidising agent and fluoride ion
is the weakest reducing agent. Lithium has the lowest electrode potential indicating that lithium ion is the weakest oxidising agent
while lithium metal is the most powerful reducing agent in an aqueous solution.

Applications of Electrochemical Series :

(a) Reactivity of metals :
(i) Alkali metals and alkaline earth metals having high ve values of SRP which are chemically active. These react with cold water
and evolve hydrogen and readily dissolve in acids.
(ii) Metals like Fe, Pb, Sn, Ni, Co, etc. do not react with cold water but react with steam to evolve hydrogen.
(iii) Metals Li, Be, Cu, Ag, and Au which lie below hydrogen are less reactive and do not evolve hydrogen from water.
(b) Electropositive character of metals : Electropositive character of metals decreases from top to bottom.
(c) Displacement reactions : To predict whether a given metal will displace another, from its salt solution. The metal having low SRP
will displace the metal from its salts solution which has higher value of SRP.
(d) Reducing power of metals : Reducing nature decreases from top to bottom in the electrochemical series.
(e) Oxidizing nature of non-metals : Oxidizing nature increases from top to bottom in the electrochemical series.
(f) Thermal stability of metallic oxides : The thermal stability of the metal oxide decreases from top to bottom.
(g) Products of electrolysis : The ion which is stronger oxidizing agent is discharged first at cathode.
(h) Corrosion of metals : Corrosion is defined as the deterioration of a substance because of its reaction with its environment. The
corrosion tendency increases from top to bottom.
(i) For a reaction that is spontaneous at standard conditions, E must be positive.
Example 1 :
Electrode potential of the metals in their respective solution are provided. Arrange the metals in their increasing order of reducing
power. K+/K = 2.93V, Ag+/Ag = + 0.80V, Hg+/Hg = +0.79V, Mg2+/Mg = 2.37V, Cr3+/Cr = 0.74V
Sol. We know that the reducing power of a metal depends upon its tendency to lose electrons. Thus lower the reduction potential,
more the tendency to get oxidized and thus more will be the reducing power. Hence increasing order of reducing power is:
Ag < Hg < Cr < Mg < K
Example 2 :
Using the standard electrode potentials predict the reaction, if any, that occurs between the following :
(a) Fe3+(aq) and I(aq) (b) Ag+(aq) and Cu(s) (c) Ag(s) and Fe3+(aq) (d) Br2(aq) and Fe2+(aq)

Given : EFe3 /Fe2 0.77V, E I 0.54V ; E 0.80V, E 2+ 0.34V ; E 1.08V
2/I Ag / Ag Cu /Cu Br 2 / Br
Sol. (a) Here I(aq) loses electrons and Fe3+ (aq) gains electrons. Thus

Oxidation half cell reaction 2I I2 + 2e, E = 0.54V

Reduction half cell reaction [Fe3++e Fe2+] 2 ; E = +0.77V

Overall reaction 2I+2Fe3+ I2 + 2Fe2+, E0cell=0.23V
Since Ecell is +ve, the reaction is spontaneous i.e., the reaction does take place.

(b) Here Cu(s) loses electrons and Ag+(aq) gains electrons. Thus

Oxidation half cell reaction: Cu Cu2+ + 2e, E = 0.34V

Reduction half cell reaction [Ag+ + e Ag] 2, E = +0.80V

Overall reaction Cu + 2Ag+ Cu2+ + 2Ag, Ecell= 0.46V
Since Ecell is +ve, the reaction is spontaneous

4 Gyaan Sankalp
 Electrochemistry
(c) Here Ag loses electrons and Fe3+ (aq) gains electrons. Thus

Oxidation half cell reaction Ag Ag+ + e, E = 0.80V

Reduction half cell reaction Fe3+ +e Fe2+, E = +0.77V

Overall reaction Ag + Fe3+ Ag+ + Fe2+, Ecell = 0.03V
Since Ecellisve,thereactionisnon-spontaneous,i.e.,reactiondoesnottakeplace.

(d) Here Fe2+(aq) loses electrons and Br2(aq) gains electrons. Thus

Oxidation half cell reaction 2Fe2+ 2Fe3+ + 2e, E=0.77

Reduction half cell reaction Br2 + 2e 2Br, E = +1.08V

Overall reaction 2Fe2+ + Br2 2Fe3+ + 2Br, Ecell = +0.31V
Since Ecell is +ve, the reaction is spontaneous, i.e., the reaction does not take place.

TRY IT YOURSELF
Q.1 Calculate e.m.f. of the half cell given below :
(a) Fe | FeSO4 ; E = 0.44 V (b) Zn | ZnSO4 E = 0.76 V (c) Cu | Cu(NO3)2 ; E = 0.34 V
0.1M 0.2 M
Q.2 A galvanic cell is constructed with 2 metals P and Q . Electrolysis used in the galvanic cell are sulphates of the metals.
If EP+n | P = a and EQ+n | Q = b and a > b then find out :
(a) Anode of the cell (B) Cathode of the cell (C) Reaction at anode (d) Reaction at cathode
Q.3 Which one of the following is different from others
(A) Daniel cell (B) Voltaic cell (C) Galvanic cell (D) Electrolytic cell
Q.4 The standard reduction potentials of 4 elements are given below. Which of the following will be the most suitable reducing
agent
I = 3.04 V II = 1.90 V III = 0 V IV = 1.90 V
(A) III (B) II (C) I (D) IV
Q.5 The reaction Zn2+ + 2e Zn has a standard potential of 0.76 V. This means
(A) Zn can't replace hydrogen from acids (B) Zn is reducing agent
(C) Zn is an oxidising agent (D) Zn2+ is a reducing agent
Q.6 Choose the correct statement from the following which is related to the electrochemical series-
(A) Electrochemical series is not the arrangement of metals and ions according to their reactivity.
(B) The metal ions at the top of the electrochemical series are highly electronegative
(C) Strongly electropositive metals can displace weakly electropositive metals from their salt solution
(D) All metals above hydrogen in the series do not displace hydrogen from dilute acids.
Q.7 Which one of the following reaction occurs at the cathode
(A) 2OH H2O + O + 2e (B) Ag Ag+ + e (C) Fe2+ Fe3+ + e (D) Cu2+ + 2e Cu

ANSWERS
(1) (a) 0.47 V (b) 0.78 V (c) 0.33 V (2) (a) Q (b) P (c) Q Q+n + ne (d) P+m + me P
(3) (D) (4) (C) (5) (B) (6) (C) (7) (D)

NERNST EQUATION :
The electrode potential and the emf of the cell depend upon the nature of the electrode, temperature and the activities
(concentrations) of the ions in solution. The variation of electrode and cell potentials with concentration of ions in solution. The
variation of electrode and cell potentials with concentration of ions in solution can be obtained from thermodynamic considerations.
For a general reaction such as
m1A + m2B +.................. n1X + n2Y + ........... .............. (1)
occurring in the cell, the Gibbs free energy change is given by the equation

a nx1 a ny 2
G = G + 2.303 RT log10 m m .............. (2)
a A1 a B 2
Gyaan Sankalp 5
Electrochemistry
where a represents the activities of reactants and products under a given set of conditions and G refers to free energy change
for the reaction when the various reactants and products are present at standard conditions. The free energy change of a cell
reaction when the various reactants and products are present at standard conditions. The free energy change of a cell reaction
it related to the electrical work that can be obtained from the cell, i.e.,
G = nFEcell and G = FE. (F is Faraday constant 96500C)
On substituting these values in Eq. (2), we get

a nx1 a ny 2 ...
nFEcell = nF E 0cell + 2.303RT log10 .............. (3)
m m
a A1 a B 2 ...

2.303RT a nx1 a ny 2 ...

or Ecell = E 0cell log10 .............. (4)
nF m m
a A1 a B 2 ...

2.303RT [Products]
E = E0 log10 .............. (5)
nF [Reactants]
This equation is known as Nernst equation.
Putting the values of R = 8.314 JK1 mol1,T = 298 K and F = 96500 C, Eq.(5) reduces to

0.0591 [Products]
E = E log10 .............. (6)
n [Reactants]
0.0591 [P]
E = E log10
n [R]
Potential of single electrode (Anode) : Consider the general oxidation reaction,
M Mn+ + ne

0.0591 [M n ]
Applying Nernst equation, Eox = E 0ox log10
n [M]

where Eox is the oxidation potential of the electrode (anode), E 0ox is the standard oxidation potential of the electrode.
The concentration of pure solids and liquids are taken as unity.
0.0591
Eox = E 0ox log10 [Mn+]
n
Potential of single electrode (Cathode) : Consider the general reduction reaction.
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Mn+ + ne M
Applied Nernst equation,
0.0591 [M] 0.0591
EReduction= E0Reduction log10 n
= E0Reduction + log10 [M n ]
n [M ] n
Emf of the cell : Cell potential depend upon potential of cathode and anode.
Ecell = Eanode + Ecathode
Ecell = Eox + Ered

0.0591 concentration of Anode

= (E 0ox E 0red ) log10
n concentration of Cathode
Let us consider an example, in which the values of n for the two ions in the two half-cells are not same.
For example, in the cell Cu | Cu2+ || Ag+ | Ag
The cell reaction is Cu(s) + 2Ag+ Cu2+ + 2Ag
The two half-cell reactions are: Cu Cu2+ + 2e
Ag+ + e Ag
The second equation is multiplied by 2 to balance the number of electrons.
2Ag+ + 2e 2Ag
0.0591
Eox = E 0ox log10[Cu2+]
2
6 Gyaan Sankalp
 Electrochemistry
0.0591
Ered = E 0red log10[Ag+]2
2

0.0591 [Cu 2 ] 0 0.0591 [Cu 2 ]

Ecell = Eox + Ered = E 0ox + E 0red log10 = E cell log
2 [Ag ]2 2 10 [Ag ]2

Example 3 :
The standard electrode potentials of the electrode Cu2+|Cu and Ag+|Ag are 0.34V and 0.7991V respectively. What would be the
concentration of Ag+ in a solution containing 0.06M of Cu2+ ion such that both the metals can be deposited together. Assume
that activity coefficients are unity and both silver and copper do not dissolve among themselves.
Sol. The individual reactions are :
Cu2+ + 2e Cu(s) ; Ag+ + e Ag(s)
The electrode potentials given by Nernst equation
0.0591 1 (0.0591) 1
E(Cu 2 | Cu) E 0 log 2
= 0.037 log = 0.037 0.036 = 0.301
2 [Cu ] 2 0.06

0.0591 1
E(Ag | Ag) 0.7991 log
1 [Ag ]
Two metals will be deposited together when the electrode potentials are equal i.e.
1 1 0.7991 0.301
0.301 0.7991 0.0591log
i.e. log
8.428
[Ag ] [Ag ] 0.0591

1

108.428 or [Ag+] = 108.428 = 0.37 108 mol dm3
[Ag ]

THERMODYNAMICS OF THE CELLS :

The e.m.f. of the cell is related to free energy by equation
G = nFE ...(1)
G
Now, T S
P

G E E
So nF S or S nF ...(2)
T P T P T P
The enthalpy of the cell reaction will be
E
H = G + TS = nFE TnF ...(3)
T P
The thermodynamic quantities of the cell reaction can be calculated by equations (1), (2) and (3) provided one knows the emf
of cell and its dependence on temperature.
The heat effects in the system can be calculated as follows. If the process is irreversible (i.e. by mixing the reactants together),
heat flow to the system can be given by the reaction ,
H = QP. If the process is reversible the heat flow to system is given by QP = TS.

CONDITION OF EQUILIBRIUM :
When Ecell = 0.0 V, i.e., no potential difference is obtained between the terminals of cell (battery), the cell reaction in such a state
is said to be in equilibrium. So in such cases ,
When, Q = Keq=equilibriumconstant.
0 0.059 0.059
E cell E cell log Q ; 0.0 E 0cell log K eq
n n
0.059
E 0cell log K eq
n

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 Electrochemistry
SOLUBILITY PRODUCT :
The solubility product of sparingly soluble salt MX can be discussed in terms of the equilibrium of the kind

MX(s)
M(aq) X (aq)
Since the activity of the pure solid is always unity, the equilibrium constant of the solubility product can be written.
K sp a a ...(1)
M x

RT a M a X
E E ln
nF a MX
Under equilibrium conditions the emf of the cell will be zero i.e. , E = 0 and also the activity of pure solid is unity. Further
Ksp a a , the above equation at 25C can be written as :
M X

E n
log K sp ....(2)
0.0591
The solubility product thus can be calculated from the standard emf of one cell, formed in such a way that the final reaction is
the type given above.
Example 4 :
(a) Calculate the electrode potential at a copper electrode dipped in a 0.1 M solution of copper sulphate at 298 K ; assuming
CuSO4 to be completely dissociated. The standard electrode potential of Cu2+ | Cu system is + 0.34 volts at 298 K.
(b) At what concentration of copper ions will this electrode have a potential of zero volt?
Sol. (a) The reduction electrode reaction is
Cu2+(aq.) + 2e Cu(s)
Thus here, n = 2 ; E = + 0.34 volts, [Products] = 1 , [Cu2+] = 0.1 M
Substituting these values in the Nernst equation,
0.059 [Products] 0.059 1
E = E log = 0.34 log = 0.34 0.0295 log 10 = 0.3105 volt
2 [Reactants] 2 0.1
(b) Here, E = 0 Volt, [Cu2+] = ?
Applying again Nernst equation
0.059 [Cu] 0.059 1 0.34
E = E log 2 ; 0 = 0.34 log ; log [Cu2+] =
n [Cu ] 2 [Cu 2 ] 0.0295
On solving, we get [Cu2+] = 2.95 1012 M
Example 5 :
Calculate the equilibrium constant for the reaction ,
Zn2+ + 4NH3 [Zn(NH3)4]2+
E (Zn2+/Zn) = 0.763 and E [Zn(NH3)4]2+/Zn + NH3) = 1.03V
Sol. The electrode reactions for the given electrodes, can be written as
Zn2+ + 2e Zn E1 = 0.763V ............ (1)

[Zn(NH3)4]2+ + 2e Zn + 4NH3 E1 = 1.03V ............ (2)

Reaction (1) (2)
Zn2+ + 4NH3 [Zn(NH3)4]2+
The standard emf of this reaction = E1 E2 = 0.763V (1.03) = 0.267V

a
RT [Zn(NH3 )4 ]2
According to Nernst equation E E ln
2F a 2 a NH3
Zn

0.0591
If the process is equilibrium, E = 0 at 25C, log K 0.267
2
(0.267)(2)
log K 9.036 ; K 100.36109 1.09 109
(0.059)
8 Gyaan Sankalp
 Electrochemistry
Example 6 :
Calculate the Ksp of AgI by forming proper cell.

Given E 0.151V and E 0.7991V

I / Ag(s) / Ag Ag + / Ag

Sol. The cell can be written as : Ag | Ag+ || I | AgI | Ag

At left electrode Ag(s) Ag+ + e E = 0.7991V
At right electrode AgI(s) + e Ag(s)+I E=0.151V
AgI(s) Ag++I
The standard emf of the cell is E ER EL 0.151 0.7991 = 0.9501V

(0.9501)(1)
log K sp 16.1 ; Ksp 1016.1 7.94 1017
0.059
TRY IT YOURSELF
Q.1 The standard electrode potentials of the two half cells are given below :
Ni2+ + 2e = Ni ; E = 0.25 Volt Zn2+ + 2e = Zn ; E = 0.77 Volt
The voltage of cell formed by combining the two half cells would be -
(A) 1.02 volt (B) + 0.52 volt (C) + 1.02 volt (D) 0.52 volt
Q.2 Calculate the standard free energy change for the reaction 2Ag + 2H+ H2 + 2Ag+ ,
E for Ag+ + e Ag is 0.80 V -
(A) + 154.4 kJ (B) + 308.8 kJ (C) 154.4 kJ (D) 308.8 kJ
Q.3 The correct representation of Nernst's equation is
0.0591 0.0591
(A) E M n / M = E log (Mn+) (B) E M n / M = E log (Mn+)
Mn / M n Mn / M n
n
(C) E M n / M = E log (Mn+) (D) None of these
Mn / M 0.0591
RT
Q.4 The nernst equation, E = E ln Q indicates that the equilibrium constant Kc will be equal to Q when -
nF
RT
(A) E = E (B) =1 (C) E = 0 (D) E = 1
nF
Q.5 The cell Pt(H2) (1atm) | H+ (pH= X) | | Normal calomel electrode has e.m.f. of 0.67 V at 25C. Calculate pH of solution. The oxidation
potential of calomel electrode on H scale is 0.28 V .
Q.6 The e.m.f. of the cell obtained by combining Zn and Cu electrodes of a Daniel cell with N calomel electrodes are 1.083 V and
0.018V respectively at 25C. If the potential of N calomel electrode is 0.28 V , find e.m.f. of Daniel cell.
Q.7 What is the e.m.f. of a cell containing two H electrodes, the negative one in contact with 108 molar OH and the positive one in
contact with 103 molar H+ ?
Q.8 Calculate the potential of a cell in which H electrodes are immersed in a solution with a pH of 3.5 and in a solution with a pH of
10.7 at 30 C .

ANSWERS
(1) (B) (2) (C) (3) (A) (4) (C)
(5) 6.6 (6) 1.1 V (7) 0.295 V (8) 0.425 V

CONDUCTANCE OFELECTROLYTIC SOLUTIONS :

Conductance (C) : The amount of electric current can be passed through the solution is called conductance. Conductance is
inverse to resistance.
1 1
Conductances = or C = ; Unit of Conductance is inverse to ohm it represent as mho.
Resistance R
Factors affecting electrolytic conduction :
(i) Nature of the electrolyte : The conductance of solution is depend on nature of electrolyte. Generally strong electrolytes ionize
almost completely in the solution and hence conduct electricity to a large extent whereas weak electrolytes ionize to a small
extent.

Gyaan Sankalp 9
 Electrochemistry
(ii) Concentration of the solution : The conductance of solution increase with increase the dilution. (because rate of dissocation
increase with increase the dilution for weak electrolyte so no. of ions in solution increases and movability of ion also increase).
(iii) Temperature : Conductances increase with increase the temperature because the all attraction force will be decrease.
(iv) Degree of ionization : Conductance of solution increase with increase the degree of ionization.
(v) Interionic attractions : Movability of ion decrease with increase the interionic attractions so conductance of electrolyte decrease.
(vi) Viscosity : Movability of ion decreases with increase the viscosity so conductance of electrolyte decrease.
(viii) Solvation of ions : Movability of ion decrease with increase the solvation so conductance of electrolyte decreases.
Specific Conductivity (or simply called conductivity) : Ohms law is valid for electrolytic solution so that resistance of electrolyte
R is directly proportional to its length () and inversely proportional to its area of cross section (a).

i.e., R or R =
a a
where = distance between two electrode and a= area of cross-section of electrode
where is a constant of proportionality, called specific resistance or resistivity. Its value depends upon the material of the
conductor. Inverse of resistance is called conductance or observed conductivity while inverse of specific resistance is called
specific conductivity or conductivity , we can write
1 1

Observed conductivity Specific conductivity a

or Specific conductivity = conductivity
a
or Specific conductivity = conductivity cell constant

ratio for a cell is constant and it known as cell constant it denoted by x
a
Now if = 1 cm and a = 1 sq. cm, then
Specific conductivity = Observed conductivity
If the volume of the solution is V cm3, the specific conductivity of such a solution at this dilution V is written as .
Units :
a (cm 2 )
(i) Resistivity () = R = ohm = ohm cm or cm
cm
1 1
(ii) Specific conductivity (v) = = = ohm1 cm1 or 1 cm1 or S cm1
ohm cm

1 1
Cell constant : We know that R = =
a Ra

1 1
v = ( = cell constant cm1) G, conductance
Ra a R
The conductivity of the solution is measured in a cell known as conductivity cell. Since in such cells the electrodes may be
exactly 1 cm apart or may not have an area of 1 cm. Therefore we calculate a factor called constant. (/a) for these cells.
Also, Specific conductivity = cell constant observed conductivity
conductivity
or cell constant =
conductance
Equivalent conductivity : Equivalent conductivity is the conducting power of all the ions produced by one g-equivalent i.e. one
equivalent of an electrolyte in a given solution. The equivalent conductivity may, therefore, be defined as the conductivity which
is observed when two sufficiently large electrodes are dipped into solution at such a distance so as to enclose in between them
the entire volume of solution containing one equivalent of the electrolyte.
It is denoted by the symbol .
Let one equivalent of an electrolyte is dissolved in V mL solution. Then all the ions produced by 1 equivalent of the electrolyte
will be present in this V mL solution. So, the conductance of this V c.c. solution will be the equivalent conductance of the
electrolyte i.e.
eq = Conductivity of V c.c. solution containing one equivalent of the dissolved electrolyte.
= Conductivity of 1 c.c solution V = V
10 Gyaan Sankalp
 Electrochemistry
Where V = volume of solution in c.c containing 1 equivalent of the electrolyte
If C be the normality of solution i.e. concentration of electrolytic solution in equivalent/L, then
1000 1000
V= =
C C
Unit of : Ohm1 cm1 cm3 i.e. Ohm1 cm2 or 1cm2
Molar Conductivity : The recent trend is to describe electrolytic conductivity in terms of molar conductivity which is defined as
the conductivity of solution due to all the ions produced by one mole of the dissolved electrolyte in a given solution.
It is denoted by the symbol m
m and are inter-related as
1000
m = V m =
C
Where V = Volume of solution in c.c. containing one mole of the electrolyte and
C = Concentration of solution in mole L1 i.e. molarity
The above inter-relationship may also be expressed as
Unit of m : 1cm2mol1
In SI system it is S m2mol1
Relation between eq and m :
m=nfactoreq
M
Where n = n-factor of the electrolyte = total charge carried by either ion =
E
Determination of Conductance (, eq and m)

= Observed conductivity
a

For a given conductivity cell in a given experiment , = constant called cell constant (x).
a
1
Thus, = conductance x = x
Observed resistance
The resistance of a solution is determined by Wheatstone bridge method using a meter bridge the conductivity cell remains
dipped in the test solution. The current used is AC.
Variation of molar conductivity with concentration : Molar conductivity increases with decrease in concentration. This is
because the total volume, V, of solution containing one mole of electrolyte also increases. It has been found that decrease in on
dilution of a solution is more than compensated by increase in its volume. When concentration approaches zero, the molar
conductivity is known as limiting molar conductivity and is represented by the symbol 0m . The variation in m with concentra-
tion is different for strong and weak electrolytes.
The m vs C plot of strong electrolyte being linear it can be m0

extrapolated to zero concentration. Thus, m values of the so- Stron g el ectrol yte

lution of the test electrolyte are determined at various concen-

trations the concentrations should be as low as good. m val- m
ues are then plotted against C when a straight line is Weak e lectro lyt e

obtained.
This is the extrapolated to zero concentration. The point where
C
the straight line intersects m axis is 0m of the strong electrolyte.
However, the plot in the case of weak electrolyte being non linear, shooting up suddenly at some low concentration and
assuming the shape of a straight line parallel to m axis. Hence extrapolation in this case is not possible. Thus , of a weak
electrolyte cannot be determined experimentally. It can , however , be done with the help of Kohlrauschs law.

KOHLRAUSCH LAW OF INDEPENDENT MIGRATION OF IONS :

Kohlrausch determined values of pairs of some strong electrolytes containing same cation say KF and KCl , NaF and NaCl
etc., and found that the difference in values in each case remains the same .
0m (KCl) 0m (KF) 0m (NaCl) 0m (NaF)
Gyaan Sankalp 11
 Electrochemistry
He also determined values of pairs of strong electrolytes containing same anion say KF and NaF , KCl and NaCl etc. and
found that the difference in values in each case remains the same .
0m (KF) 0m (NaF) 0m (KCl) 0m (NaCl)
This experimental data led him to formulate the following law called Kohlrauschs law of independent migration of ions.
At infinite dilution when dissociation is complete , every ion makes some definite contribution towards molar conductance of the
electrolyte irrespective of the nature of the other ion which with it is associated and that the molar conductance at infinite dilution
for any electrolyte is given by the sum of the contributions of the two ions . Thus
0m 0 0

Where 0 is the contribution of the cation and 0 is the contribution of the anion towards the molar conductance at infinite

dilution. These contributions are called molar ionic conductances at infinite dilution. Thus, 0 is the molar ionic conductance of

cation and 0 is the molar ionic conductance of anion, at infinite dilution. The above equation is, however, correct only for
binary electrolyte like NaCl, MgSO4 etc.
For an electrolyte of the type of AxBy, we have :
0m x 0 y 0
Application of Kohlrauschs Law :
(i) Determination of 0m of a weak electrolyte :

In order to calculate 0m of a weak electrolyte say CH3COOH , we determine experimentally 0m values of the following three
strong electrolytes :
(a) A strong electrolyte containing same cation as in the test electrolyte , say HCl
(b) A strong electrolyte containing same anion as in the test electrolyte , say CH3COONa
(c) A strong electrolyte containing same anion of (a) and cation of (b) i.e. NaCl.
0m of CH3COOH is then given as :

0m (CH3COOH) = 0m (HCl) + 0m (CH3COONa) 0m (NaCl)

Proof :
0
0m (HCl) = H Cl I

0 0
0m (CH3COONa) = CH3COO Na II

0 0
0m (NaCl) = Na Cl III
Adding equation (I) and equation (II) and subtracting (III) from them :
0(HCl) 0(CH3COONa) 0(NaCl) 0 0 0(CH 3COOH)
(H ) (CH3COO0 )

(ii) Determination of degree of dissociation () :

No. of molecules ionised
m
total number of molecules dissolved 0m
(iii) Determination of solubility of sparingly soluble salt :
The specific conductivity of a saturated solution of the test electrolyte (sparingly soluble) made in conductivity water is
determined. From this the specific conductivity of conductivity water is deducted. The molar conductance of the saturated
solution is taken to be equal to 0m as the saturated solution of a sparingly soluble salt is extremely dilute. Hence from equation.

1000
0m = , Where C is the molarity of solution and hence the solubility..
C
(iv) Determination of ionic product of water : From Kohlrauschs law , we determine 0m of H2O where 0m is the molar conductance
of water at infinite dilution when one mole of water is completely ionised to give one mole of H+andonemoleofOH ions i.e.
12 Gyaan Sankalp
 Electrochemistry

0m (H2O) = 0H + 0OH
Again using the following
1000
m , where C = molar concentration i.e. mol L1 or mol dm3
C

m , where C = concentration in mol m3
C
Assuming that m differs very little from 0m

0m = C= 0
C m
Specific conductance () of pure water is determined experimentally. Thereafter, molar concentration of dissociated water is
determined using the above equation . Kw is then calculated as : Kw = C2
Example 7 :
The specific conductivity of 0.02 M KCl solution at 25 C is 2.768 103 ohm1 cm1. The resistance of this solution at 25 C when
measured with a particular cell was 250.2 ohms. The resistance of 0.01 M CuSO4 solution at 25 C measured with the same cell was
8331 ohms. Calculate the molar conductivity of the copper sulphate solution.

Sp. cond. of KCl 2.768 103

Sol. Cell constant = = = 2.768 103 250.2
Conductance of KCl 1/ 250.2
For 0.01 M CuSO4 solution
1
Sp. conductivity = Cell constant conductance = 2.768 103 250.2
8331
1000 2.768 103 250.2 1000
Molar conductance = Sp. cond. = = 8.312 ohm1 cm2 mole1
C 8331 1/100
Example 8 :
The specific conductivity of a saturated solution of silver chloride is 2.30 106 mho cm1 at 25 C . Calculate the solubility
of silver chloride at 25 C if Ag = 61.9 mho cm2 mol1 and = 76.3 mho cm2 mol1.
Cl
Sol. Let the solubility of AgCl be s gram mole per litre
1000
Dilution =
S

0AgCl = 61.9 + 76.3 = 138.2 mho cm2 mol1

Ag Cl

Sp. conductivity dilution = 0 AgCl = 138.2

1000
2.30 106 = 138.2
S

2.30 103
S= = 1.66 105 mole per litre = 1.66 105 143.5 gL1 = 2.382 103 gL1
138.2
Example 9 :
The equivalent conductances of sodium chloride , hydrochloric acid and sodium acetate at infinite dilution are 126.45 , 426.16
and 91.0 ohm1 cm2 equiv1, respectively at 25 C. Calculate the equivalent conductance of acetic acid at infinite dilution.
Sol. According to Kohlrauschs law,
0CH3COONa = CH3COO Na = 91.0 .......(i)

0HCl Cl = 426.16 ......(ii)

H

0 NaCl Cl = 126.45 .......(iii)

Na

Gyaan Sankalp 13
 Electrochemistry
Adding equations (i) and (ii) and substracting (iii),
+ H Cl Na Cl = 91.0 + 426.16 126.45
CH3COO Na

0

CH3COO + = CH3COOH = 390.7 ohm1 cm2 equiv1
H

TRY IT YOURSELF
Q.1 The specific conductance of a salt of 0.01M concentration is 1.061 10-4. Molar conductance of the same solution will be :
(A) 1.061 10-4 (B) 1.061 (C) 10.61 (D) 106.1
Q.2 The specific conductances of a 0.1 N KCl solution at 23C is 0.0112 ohm-1 cm-1. The resistance of the cell containing solution
at the same temperature was found to be 55 ohm. The cell constant will be :
(A) 0.142 cm-1 (B) 0.918 cm-1 (C) 1.12 cm-1 (D) 0.616 cm-1
Q.3 The conductivity of 0.25 M solution of univalent weak electrolyte XY is 0.0125 cm . The value of 0m of XY is 500 -1 cm2
-1 -1

mol-1. the value of Ostwald dilution constant of AB is :

(A) 2.5 10-3 (B) 2.5 10-4 (C) 2.8 10-3 (D) 2.8 10-4
Q.4 CH3COOH = 20 ohm-1 cm2 eq-1 and CH3COOH = 400 ohm-1 cm2 equiv-1 , then pH of 1 M CH3COOH solution is :
(A) 1.3 (B) 0 (C) 1.7 (D) 4
Q.5 If molar conductance at infinite dilution of (NH4)2SO4, NaOH and Na2SO4 solutions are x1, x2 and x3 respectively, then molar
conductance of NH4OH solution is -
x1 2x 2 x 3 x1 x 2 x3
(A) (B) x1 2x 2 x 3 (C) (D) x1 x 2 x 3
2 2
Q.6 The resistance of 1 N solution of acetic acid is 250 ohm, when measured in a cell of cell constant 1.15 cm-1. The equivalent
conductance (in ohm-1 cm2 equiv-1) of 1 N acetic acid is :
(A) 4.6 (B) 9.2 (C) 18.4 (D) 0.023
Q.7 Which of the following solutions of KCl has the lowest value of specific conductance ?
(A) 1M (B) 0.1 M (C) 0.01 M (D) 0.001 M
ANSWERS
(1) (C) (2) (D) (3) (A) (4) (A)
(5) (A) (6) (A) (7) (D)

FARADAYS LAW OF ELECTROLYSIS :

On passing an electric current through electrolyte chemical change take place is called electrolysis.
Faraday's First Law : When an electric current is passed through an electrolyte, the amount of substance deposited is proportional
to the quantity of electric charge passed through the electrolyte.
If W be the mass of the substance deposited by passing Q coulomb of charge, then according to the law, we have the relation.
WQ
A coulomb is the quantity of charge when a current of one ampere is passed for one second. Thus, amount of charge in coulombs.
Q = current in amperes time in seconds = t
Wt
W=Zt
where Z is a constant, known as electro-chemical equivalent, and is characteristic of the substance deposited.
When a current of one ampere is passing for one second, i.e., one coulomb (Q = 1), then
W=Z
Thus, electrochemical equivalent can be defined as the mass of the substance deposited by one coulomb of charge or by one
ampere of current passed for one second.
equivalent wt.of element
Electro-chemical equivalent (Z) =
96500
(the electrochemical equivalent (Z) of an element is directly proportional to its equivalent weight (E), i.e. E Z or E = FZ
Where F is again a proportionality constant and has been found to be 96500 coulombs. It is called Faraday. Thus E = 96500 Z
Therefore, when 96500 coulombs of electricity is passed through an electrolyte, one gram equivalent of its ions is deposited at
the respective electrode. This quantity of electricity which liberates one gram equivalent of each element is called one Faraday
and is denoted by F.
1 Faraday = 96500 coulombs)

14 Gyaan Sankalp
 Electrochemistry
Faraday's second Law : G
It states that when same quantity of electricity is
passed through different electrolytes then the
quantity of deposit is directly proportional to its
equivalent weight. (Equivalent wt. of electrolytes).
WE
WA WB WC

EA EB EC
Example 10 : A B C
Exactly 0.4 faraday electric charge is passed through three electrolytic cells in series, first containing AgNO3, second CuSO4
and third FeCl3 solution. How many gram of each metal will be deposited assuming only cathodic reaction in each cell.
Sol. The cathodic reaction in the cell are respectively,
Ag+ + e Ag Cu2+ + 2 e Cu Fe3+ + 3 e Fe
1 mole 1 mole 1 mole 1 mole 1 mole 1 mole
108 g 1F 63.5 g 2F 56 g 3F
Hence, Ag deposited = 108 0.4 = 43.2 g
63.5 56
Cu deposited = 0.4 = 12.7 g and Fe deposited = 0.4 = 7.47 g
2 3
Example 11 :
Copper sulphate solution (250 mL) was electrolysed using a platinum anode and a copper cathode. A constant current of 2 mA
was passed for 16 minute. It was found that after electrolysis, the absorbance of the solution was reduced to 50% of its original
value. Calculate the concentration of copper sulphate in the solution to begin with.
Sol. Equivalent of Cu2+ lost during electrolys is
it 2 10 3 16 60
= = 1.989 105
96500 96500

1.989 10 5
or mole of Cu2+ lost during electrolysis =
2
This value is 50% of the initial concentration of solution
2 1.989 10 5
Thus, initial mole of CuSO4 = = 1.989 105
2

1.989 105 1000

Thus, initial concentration of CuSO4=
250
[CuSO4] = 7.95 105 M

Example 12 :
A current of 2.68 ampere is passed for one hour through an aqueous solution of copper sulphate using copper electrodes.
Calculate the change in mass of cathode and that of the anode. (at. mass of copper = 63.5).
Sol. The electrode reactions are :
Cu2+ + 2 e Cu (cathode)
1 mole 2 96500 C
Cu Cu2+ + 2 e (Anode)
Thus, cathode increases in mass as copper is deposited on it and the anode decreases in mass as copper from it dissolved.
Charge passed through cell = 2.68 60 60 coulomb
63.5
Copper deposited or dissolved = = 2.68 60 60 = 3.174 g
2 96500
Increase in mass of cathode = Decrease in mass of anode = 3.174 g

Gyaan Sankalp 15
 Electrochemistry
FUELCELL :
It is an electrochemical device for continuous conversion of the portion of free energy change into electrical energy. Such cell
converts 74% of chemical energy into electrical energy. The fuel used is in the gaseous state, H2 O2 fuel cell is a common
example.
In the cell hydrogen and oxygen are bubbled through a porous carbon electrode into concentrated aqueous sodium hydroxide.
Catalysts are incorporated in the electrode. The electrode reactions are:
Anode : 2[H2(g) + 2OH (aq) 2H2O() + 2e]
Cathode : O2(g) + 2H2O() + 4e 4OH (aq)
Overall reaction : 2H2(g) + O2(g) 2H2O ()
Nickel-cadmium storage cell.
It consists of cadmium anode and a metal grid containing NiO2 acting as cathode. The electrolyte in this cell is is KOH. Following
reactions take place during discharging.
Cd(s) + 2OH (aq) Cd(OH)2(s) + 2e
NiO2(s) + 2H2O() + 2e Ni(OH)2(s) + 2OH (aq)
Cd(s) + NiO2(s) + 2H2O() Cd(OH)2 (s) + Ni(OH)2(s)
As after discharging products formed are solid. Hence, the reaction can be reversed during charging. Further, as no gases are
produced during charging or discharging the cell can be sealed. It produces a potential of 1.4 V. The cell has a longer life than
lead storage cell and is used in cordless appliances (Phones, pagers, mobile phones, electric shavers etc.)
Advantages of fuel cells over ordinary batteries : The fuel cells convert the energy of the fuel directly into electricity, while the
conventional method of generating electricity by burning hydrogen, carbon fuels first convert fuels in to thermal energy and
then in to electrical energy although theoretically, fuel cells are expected to have an efficiency of 100% practically only 6070%
efficiency has been attained, efficiency of the conventional method is only about 40%.

CORROSION :
If any household item of iron is left outside, then it gets rusted and it becomes Water
rough and porous. Almost all useful metals except gold, platinum, aluminium, O2(g)
Rust Dropled
etc., are destroyed slowly. Decay process of the metals is called corrosion of
metals. Corrosion takes place rapidly at bends, seratches, nicks and cuts in Fe2 O 3 .xH 2 O
the metal. Cathode Anode
Electrochemical Theory of rusting : According to this theory follow of electric 2+
current between separate anode and cathode bar as reason because of this e Fe Fe +2e
corrosion is held. In the anodic reason metal is destroyed by the formation of +
their ion or combined state (ex. oxide) in the oxidation reaction. So corrosion is O2+4H +4e +
2H2O
always held in the anodic part. O 2 +2H 2O +4e 4OH
Overall reaction of corrosion cell : IRON
+ 1 2+
Fe + 2H + O2 Fe + H2O ; Ecell = 1.67V
2
The ferrous ions so formed move through water and come at the surface of iron object where these are further oxidised to ferric
state by atmospheric oxygen and constitute rust which is hydrated iron (III) oxide.
2+ 1 +
2Fe + O + 2H2O Fe2O3 + 4H
2 2
Fe2O3 + xH2O Fe2O3.xH2O
To prevent corrosion the metal surface is coated with paint which keeps it out of contact with air, moisture etc. till the paint layer
develops cracks.

TRY IT YOURSELF
Q.1 How long will it take for a current of 3 amperes to decompose 36 g of water. (Eq. wt. of hydrogen is 1 and that of oxygen 8)
(A) 36 hours (B) 18 hours (C) 9 hours (D) 4.5 hours
Q.2 If m represents mass of a substance (equivalent weight E) consumed or produced when quantity Q of electricity is passed then,
(A) m Q (B) m (1/Q) (C) m (I/E) (D) m Q.E.
Q.3 A current of 0.5 ampere when passed through AgNO3 solution for 193 sec deposited 0.108g of Ag. The equivalent weight of silver
is
(A) 108 (B) 54 (C) 5.4 (D) 10.8
Q.4 A current of 9.65 ampere flowing for 10 minutes deposits 3.0 g of the metal which is monovalent the atomic mass of the metal is
(A) 10 (BB) 50 (C) 30 (D) 96.5
16 Gyaan Sankalp
 Electrochemistry
Q.5 On passing electric current into a solution of a salt of metal, M, the reaction at the cathode takes place as : M2+ + 2e M. Atomic
weight of M is 65. The equivalent weight of metal is
(A) 65 (B) 32.5 (C) 130 (D) 200
Q.6 The electrolytic cell, one containing acidified ferrous chloride and another acidified ferric chloride are connected in series. The
ratio of iron deposited at cathodes in the two cells when electricity is passed through the cells will be-
(A) 3 : 1 (B) 2 : 1 (C) 1 : 1 (D) 3 : 2
Q.7 10800 C of electricity through the electrolyte deposited 2.977 g of metal with atomic mass 106.4 g mol1. The charge on the metal
cation is
(A) + 4 (B) + 3 (C) + 2 (D) + 1

ANSWERS
(1) (A) (2) (A) (3) (A) (4) (B)
(5) (B) (6) (D) (7) (A)

USEFUL TIPS
1. m = Z.I.t
eq Equivalent conductance at given concentration
2. Degree of dissociation : = =
0eq equivalent conductance at infinite dilution

3. Kholrauschs law : 0m x 0A y 0B

0.0591 [Products] nE
4. Nernst Equation E = E log10 & Ecell = Eright + Eleft & Keq. = antilog
n [Re ac tants] 0.0591

G
G = nFEcell & G = nFE cell & Wmax= +nFE & G = H + T T
P
E cell 0.2415
5. Calculation of pH of an electrolyte by using a calomel electrode : pH
0.0591

MISCELLANEOUS SOLVED EXAMPLES

Example 1 :
Would H2O2 behave as oxidant or reductant with respect to the following couples at standard concentrations ?
(a) I2 / I : E = 0.533 V (b) S2O82/SO42; E = 2.0 V (c) Fe3+ / Fe2+; E = 0.771 V
Given : H2O2 O2 + 2H + 2e + E = 0.69 V .......... (P)
H2O2 + 2H+ + 2e 2H2O E = 1.77 V .......... (Q)
Sol. (a) Given 2e + I2 2I E = 0.533 V on adding with eq. (P)
I2 + H2O2 O2 + 2H+ + 2I E = 0.157 V
On reversing direction
2I I2 + 2e E = 0.535 V on adding with eq. (Q)
+
H2O2 + 2H + 2I 2H2O + I2 E = 1.235 V
So H2O2 acts as an oxidizing agent in the reaction for which its E value is positive.
(b) Given S2O82 + 2e 2SO42 E = 2.0 V on adding with eq. (P)
H2O2 + S2O8 2 2SO42 + O2 + 2H+ E = 1.31 V
On reversing direction 2SO42 S2O82 + 2e E = 2.0 V on adding with eq. (Q)
2SO42 + H2O2 + 2H+ S2O82 + 2H2O E = 0.23 V
So H2O2 is the reducting agent in the reaction with a positive E value.
(c) Given Fe3+ + e Fe2+ E = 0.771 V on adding with (P)
3+
2Fe + H2O2 2Fe2+ + O2 + 2H+ E = 0.081 V
On reversing direction Fe2+ e + Fe3+ E = 0.771 V on adding with (Q)
2Fe 2 H 2 O2 2H 2 2Fe3 2H 2 O E 0.999V
Since both potentials are positive, H2O2 will act as an oxidizing agent and a reducing agent. In fact, iron (II) or ion (III) salts
catalyze the self-oxidation-reduction of H2O2.

Gyaan Sankalp 17
 Electrochemistry
Example 2 :
A T+ / T couple was prepared by saturating 0.1 M KBr with TBr and allowing the T+ from the relatively insoluble bromide to
equilibrate. This couple was observed to have a potential of 0.443 V with respect to Pb2+ / Pb couple in which Pb2+ was 0.1 M.
o
What is Ksp of TBr. (Report answer in multiplication of 108) ( E o = 0.126, ET / T = 0.336 V)
Pb 2 / Pb

2.303 RT
(Take antilog (0.5509) = 3.55, = 0.059)
F
Sol. Pb2+ + 2e
Pb

0.0591 1
E0 = E0 log 0.1 = 0.1555 volt
Pb 2 / Pb Pb 2 / Pb 2
Ecell = E E ; 0.443 = 0.1555 E
Pb 2 / Pb T / T T / T

E = 0.5985V ; T+ + e T
T / T

1
E = E0 0.059 log
T / T T / T
(T )
0.5985 = 0.336 + 0.059 log (Tl+) ; T+ = 3.55 105 M
Ksp = (T+) (Br) = 3.55 105 0.1 = 3.55 106 = 355 108
Example 3 :
Calculate the volume of gas liberated at anode at NTP from the electrolysis of CuSO4 solution by a current of 2 ampere passed
for 10 minutes.
Sol. At cathode : Cu+2 + 2e Cu At anode : 2H2O 4H+ + 4e + O2
32
EO2 = = 8.
4
E.i.t. 32 2 10 60
w O2 = 96500 = 4 96500 = 0.0995 g

0.0995 22.4
At NTP : Volume of O2 = 32
= 0.0696 litre.

Example 4 :
Formulate a cell in which the following reaction
2Cu+(aq) Cu++ (aq) + Cu
can occur. Given that the standard electrode reduction potential of Cu|Cu+ and Cu|Cu++ electrodes are 0.52 and 0.34 volts
respectively at 25C, calculate the standard EMF of the cell constructed and also find out the equilibrium constant of the reaction.
Sol. Cell : Cu|Cu++ (C = 1.0m) || Cu++ (C = 1.0 m) | Cu
Ecell = ER EL = 0.52 0.34 = 0.18 V
RT 0.18 2
E = ln K Using n = 2, loge K = = 6.1 ; K = 106.1
nF 0.0591
Example 5 :

Fe2
Determine potential for the cell Pt Cr2 O72 , Cr 3 , H Pt; in which [Fe+2] and [Fe+3] are 0.5 M and 0.75 M respectively
Fe 3
and [Cr2O72], [Cr+3] and [H+] are 2M, 4M and 1M respectively.
Given : Fe+3 + e Fe+2; E = 0.770 V and 14H+ + 6e + Cr2O72 2Cr+3 + 7H2O; E = 1.35 V
o
Sol. E Fe2 / Fe3 > E o Redox changes will be
Cr 3 /Cr26
Anode : Fe+2 Fe+3 + e Cathode : 14H+ + 6e + Cr2O72 2Cr+3 + 7H2O
o
Ecell = E Fe2 / Fe3 E o = 0.770 + 1.35 = 0.58 V
Cr 3 /Cr26

18 Gyaan Sankalp
 Electrochemistry

0.059 [Fe 3 ]6 [Cr 3 ]2 0.059 (0.75)6 (4) 2

Ecell = Ecell log 2 6 2 14 = 0.58 log
6 [Fe ] [Cr2O7 ] [H ] 6 (2) (1)14 (0.5)6

0.059
= 0.58 log (91.125) = 0.58 0.0192 = 0.56 V..
6
Example 6 :
On the basis of the following Evalues, predict whether ferricyanide ion is stronger or weaker oxidising agent than ferric ions.
[Fe(CN)6]4 [Fe(CN)6]3 + e; E = 0.36 V
Fe2+ Fe3+ + e ; E = 0.77 V
Sol. The given reactions are oxidation reactions. On writing them as reduction reactions we get :
Oxidising agent Reducing agent
[Fe(CN)6]3 + e [Fe(CN)6]4; Ered = + 0.36 V
Fe3+ + e Fe2+ ; Ered = + 0.77 V
Now since the value of SRP for Fe3+/Fe2+ couple is greater than the value of SRP for
[Fe(CN)6]3 / [Fe(CN)6]4 couple. Fe3+ is stronger oxidising agent than [Fe(CN)6]3.
Example 7 :
Write the electrode reactions and the net cell reactions for the following cells. Which electrode would be the positive terminal in
each cell ?
(a) Zn | Zn2+ || Br, Br2 | Pt (b) Cr | Cr3+ || I, I2 | Pt
(c) Pt | H2, H+ || Cu2+ | Cu (d) Cd | Cd2+ || Cl, AgCl | Ag
Sol. (a) Oxidation half cell reaction, Zn Zn2+ + 2e
Reduction half cell reaction, Br2 + 2e 2Br
Net cell reaction Zn + Br2 Zn2+ + 2Br Positive terminal : Cathode Pt

(b) Oxidation half reaction, [Cr Cr3+ + 3e] 2

Reduction half reaction, [I2 + 2e 2I] 3
Net cell reaction 2Cr + 3I2 2Cr3+ + 6I Positive terminal : Cathode Pt

(c) Oxidation half reaction, H2 2H+ + 2e

Reduction half reaction, Cu2+ + 2e Cu
Net cell reaction, H2 + Cu2+ Cu + 2H+ Positive terminal : Cathode Cu

(d) Oxidation half reaction, Cd Cd2+ + 2e

Reduction half reaction, [AgCl + e Ag + Cl] 2
Net cell reaction Cd + 2AgCl Cd2+ + 2Ag + 2Cl Positive terminal : Cathode Ag
Example 8 :
Pt (H ) HA HB Pt (H 2 )
Calculate emf of the following cell 1atm2 pK 5 pK a 3 1atm
a

0.0591
Sol. Left half cell E = Eoxid log [H]
H/ H 1
E = E ooxid 0.0591 pH (HA)
H/ H

1
Right half cell E (H /H) = E oRe d 0.0591 log
[H ]HB

E = E oRe d 0.0591 pH (HB)

(H /H)

1 1
For HA (H+) = CK a or log [H+] = log C log Ka
2 2
1 1
(pH)HA = (pKa)HA log C
2 2

Gyaan Sankalp 19
 Electrochemistry
Similarly for HB
1 1
(pH)HB = (pKa)HB log C
2 2
1 1 0.0591
Ecell = Eright Eleft = 0.0591 pKa (HA) pKa (HB) = [5 3] = 0.0591.
2 2 2
Example 9 :
Write a cell diagram for each of the following reactions and calculate E for each cell :
(a) 2Fe3+ + Sn2+ 2Fe2+ + Sn4+ (b) AgBr(s) + H2(g) Ag(s) + H+ + Br
Given than E o = + 0.77 volt; Eo = 0.15 volt
Fe3 / Fe 2 Sn 4 /Sn 2

E oAgBr /Ag(s), Br = 0.10 volt; Eo = 0.00 volt

H /H 2
Sol. (a) From the given reaction Sn2+ is oxidised to Sn4+ is oxidised to Sn4+ and Fe3+ is reduced to Fe2+. Hence the cell diagram is :
(Pt) Sn2+ | Sn+4 || Fe3+ | Fe2+ (Pt) Ecell = Eright Eleft= (0.77 0.15) volt = 0.62 volt.
(Platinum inert electrode was used to make electrical contact).
(b) From the reaction we see that H2 is oxidised to H+ and AgBr is reduced to Ag(s)
The cell diagram is : Pt|H2(g) | H+ || Br | AgBr(s), Ag(s)
Ecell = Eright Eleft = (0.10 0.0) volt = 0.10 volt.
Example 10 :
Small spherical ball of silver metal used in jewellery having diameter 0.1 cm, which is obtained by the electrolytic deposition. If
total number of balls in jewellery is 10,000, then calculate the applied amount of electricity in coulombs, which is used on the
deposition on electrodes having entire surface area 0.12 m2. [Density of Ag = 10.47]. Also determine the thickness of deposited
metal. It is assumed that 10% electricity consumed as wastage during electrolysis and 60% of electrode body immersed in
electrolyte.
0.1
Sol. Here, radius of ball = = 0.05 cm ; Total number of balls = 10,000
2
Surface area of electrodes = 0.12 m2 = 1200 cm2 of 60% = 2000 cm2
Density of Ag metal = 10.47
4 3 4
Weight of jewellery = r 10,000 density = 3.14 (0.05)3 10,000 10.47 = 5.23 10.47 g
3 3
Therefore, Surface area thickness density = Total weight of Ag
2000 thickness 10.47 = (5.23 10.47) g
5.23
Thickness = = 2.615 103 cm
2000
Amount of electricity in Faraday = Number of equivalent
Weight of Ag 5.23 10.47
= = g
Equivalent weight of Ag 108

48250 100
= 0.50 F = 48250 coulomb; then applied electricity amount = = 53611.11 coulomb
90
Example 11 :
The standard oxidation potential of Ni/Ni+2 electrode is 0.236 V. If this is combined with a hydrogen electrode in acid solution, at
what pH of the solution will the measured emf be zero at 25C. Assume [Ni+2] = 1M.
Sol. Ni Ni+2 + 2e; E = 0.236 V 2H+ + 2e H2; E = 0.0 V
Ecell = 0.236

0.059 [H ]2 0.059
Ecell = Ecell + log or 0 = 0.236 + log [H+]2
2 [Ni 2 ] 2
or log H+ = 1 104 pH = 4.

20 Gyaan Sankalp
 Electrochemistry
Example 12 :
Write the Nernst equation and e.m.f. of the following cells at 298 K.
(i) Mg(S) | Mg2+ (0.001 M) || Cu2+ (0.0001 M) | Cu(s)
(ii) Fe(s) | Fe2+ (0.001 M) || H+(1M) | H2(g) (1 bar) | Pt(s)
(iii)Sn(s) | Sn2+ (0.050 M) || H+ (0.020 M) | H2(g) (1 bar), Pt(s)
(iv) Pt(s) | Br2(), Br (0.010 M)|| H+(0.030 M) | H2(g) (1 bar), Pt(s)
Sol. (i) The cell reaction is
At anode : Mg(s) Mg2+(0.001 M) + 2e
At cathode : +
Cu (0.0001 M) + 2e Cu(s)

Net cell reaction : Mg(s) + Cu2+ (0.0001 M) Mg2+(0.001 M) + Cu(s)

The Nernst equation is,

2.303 RT [Mg 2 ]
Ecell = Ecell log
nF [Cu 2 ]

o o 2.303 8.314 298 0.001

Ecell = (E Cu 2 /Cu E Mg 2 / Mg )

log = {0.34 ( 2.37) 0.0295 log 10} V
2 96500 0.0001
So,Ecell = (2.71 0.0295) V = 2.68 V
(ii) The cell reaction is
At anode : Fe(s) Fe2+(0.001 M) + 2e
At cathode : 2H+(1 M) + 2e H2 (1 bar)

Net cell reaction : Fe(s) + 2H+ (1M) Fe2+ (0.001 M) + H2 (1 bar)

The Nernst equation for the cell emf is,

2.303 RT [Fe2 ] pH 2
Ecell = Ecell log
2F [H ]2

o o 2.303 8.314 298 0.001 1

= E H /H E Fe2 /Fe log = {0.0 ( 0.44 ) 0.0295 log 0.001}V
2 2 96500 12
Ecell = 0.44 V + 0.09 V = 0.53 V
(iii)The cell reaction is
At anode : Sn(s) Sn2+ (0.05 M) + 2e
At cathode : 2H+ (0.02 M) + 2e H2 (1 bar)

Net cell reaction : Sn(s) + 2H+(0.02 M) Sn2+ (0.05 M) + H2(1 bar)

The Nernst equation for this cell at 298 K is

0.0591 [Sn 2 ] pH 2 0.05 1

Ecell = Ecell log = (Ecathode Eanode) 0.0295 log
2 [H ] 2 (0.02) 2

0.05
Ecell = {0.0 ( 0.14 ) 0.0295 log }V
(0.02) 2
or Ecell = 0.14 V 0.062 V = 0.078 V
(iv) For the given cell, the cell reaction can be written as follows :
At anode : 2Br (aq) (0.01 M) Br2(l) + 2e
At cathode : 2H+ (0.03 M) + 2e H2 (1 bar)

Net cell reaction : 2Br (0.01 M) + 2H+ (0.03 M) Br2(l) + H2 (1 bar)

Gyaan Sankalp 21
 Electrochemistry
The corresponding Nernst equation at 298 K is

0.0591 pH2 1
Eo Eo
Ecell = Ecell log 2 = H / H 0.0295 log 2
2

[Br ] [H ] 2 Br2 / Br (0.01) (0.03) 2
This gives,
1
Ecell = {(0 1.09 ) 0.0295 log }V
9 108
Ecell = 1.09 V 0.21 V = 1.30 V
Example 13 :
Chromium metal can be plated out from an acidic solution containing CrO3 according to the following equation
CrO3(aq) + 6H+ + 6e+ Cr(s) + 3H2O
Calculate, (i) How many grams of chromium will be plated out by 24000 coulombs ?
(ii) How long will it take to plate out 1.5 gm of Cr using 12.5 ampere current ?
Atomic weight 52
Sol. (i) Eq. wt. of Cr = =
Change in oxidation number per mole 6

52
96500 coulomb deposit = 6 gm (Cr)

52 24000
24000 coulomb will deposit = gm = 2.1554 gm of Cr
6 96500
(ii) WCr = 1.5 gm, i = 12.5 ampere
52 Eit 52 12.5 t
ECr = ,t=? ; W= 1.5 = t = 1336.15 sec.
6 96500 6 96500
Example 14 :
Calculate the potential of an indicator electrode, versus the standard hydrogen electrode, which originally contained 0.1 M
MnO4 and 0.8 M H+ and which has been treated with 90% of the Fe2+ necessary to reduce all the MnO4 to Mn2+.
Sol. MnO4 + 8H+ + 5e Mn2+ + 4H2O E = 1.51 V
5Fe2+ 5Fe3+ + 5e
MnO4 + 8H+ + 5Fe2+ 5Fe3+ + Mn2+ + 4H2O
[MnO4] = 0.10 [Fe3+] = 0.450 [H+] = 0.080 [Mn2+] = 0.0900
Since the Mn7+/Mn2+ and Fe3+/Fe2+ systems are both in the same vessel, they must both experience the same half-cell potential.

0.0591 [Mn 2 ] 0.0591 (0.09)

E = 1.51 log
8 = 1.51 log = 1.39 V
5

[MnO4 ] [H ] 5 (0.01) (0.08)8
Example 15 :
Estimate the cell potential of a Daniel cell having 1M Zn 2+ and originally having 1M Cu2+ after sufficient NH3 has been added
to the cathode compartment to make NH3 concentration 2M, Kf for [Cu(NH3)4]2+ = 1 1012, E for the reaction
Zn + Cn2+ Cu + Zn2+ is 1.1 V.
Sol. Cu + 4NH3 [Cu(NH3)4]2+, Kf = 1 1012
2+
x 2 1 At equilibrium
[Cu(NH3 )42 ]
Kf = = 1 1012
[x] [NH3 ]4
x = 6 1014
Zn + Cu2+ Cu + Zn2+

0.059 [Zn 2 ]
E = E log
2 [Cu 2 ]
Substituting the values we get, E = 0.71 V

22 Gyaan Sankalp
 Electrochemistry
Example 16 :
Calculate the reduction potential for the following half cells at 25C.
(i) Mg | Mg2+ (1.5 105 M) ; Eo = + 2.36 V
Mg, Mg 2

(ii) Cl2 | Cl (2 105 M); Eo = + 1.36 V

Cl 2 , Cl

(iii)Pt | Fe2+ (0.1 M), Fe3+ (0.01 M) Eo = 0.77 V

Fe3 , Fe2
Sol. (i) Mg2+ + 2e Mg (reduction)
0.0591
Eo = Eo + log (1.5 105)
Mg 2 , Mg Mg 2 , Mg 2

4 0.0591
= 2.36 = 2.4782 V..
2
(ii) Cl2 + e Cl (reduction)

o 0.0591
E = E log [Cl]
Cl2 , Cl Cl2 , Cl 1
0.0591
= 1.36 log (2 105) = 1.6377 V
1
(iii)Fe3+ + e Fe2+ (reduction)

0.0591 [Fe 2 ]
Eo o
= E Fe3 , Fe2 log
Fe3 , Fe 2 n [Fe3 ]

0.0591 0.1
= 0.77 log = 0.7109 V.
1 0.01
Example 17 :
A fuel cell uses CH4(g) and forms CO32 at the anode. It is used to power a car with 80 Amp. for 0.96 hr. How many litres of CH4(g)
(STP) would be required ? (Vm = 22.4 L/mol) (F = 96500). Assume 100% efficiency.
Sol. CH4 + 10OH
CO32 + 7H2O + 8e
80 3600 0.96
No. of Fradays required =
96500
1 80 3600 0.96
Hence mol. of CH4 required =
8 96500
1 80 3600 0.96
VCH4 = 22.4 L = 8.356 0.96 = 8.02 L
8 96500
Example 18 :
The redox reaction involved in the rusting of iron is believed to be
2Fe(s) + O2(g) + 4H+ (aq) 2Fe (aq) + 2H2O ()
++

Calculate the standard EMF of the cell in which this reaction occurs and what is the equilibrium constant of this reaction ?
EFe|Fe++ = 0.44 V, E for O2 + 4H+ + 4e = 2H2O () = 1.23 V
Sol. 2Fe(s) + O2(g) + 4H+ (aq) 2Fe (aq) + 2H2O ()
++
++ +
Cell : Fe|Fe (C = 1.0 m) || H (C = 1.0 m), H2O|H2(g), Pt.
E = 1.23 (0.44) = 1.67 V
RT E 1.67
E = ln K; ln K = = = 56.42
nF 0.0591 / 2 0.0296
K = 2.63 1056

Gyaan Sankalp 23
 Electrochemistry
Example 19 :
The following two cells with initial concentration as given are connected in parallel with each other.
(1) Fe(s) | Fe(NO3)2(aq.) (1M)||SnCl2(aq.) (1M)|Sn(s)
(2) Zn(s)|ZnSO4(aq.)(1M)||Fe(NO3)2(aq.)(1M)|Fe(s)
After sufficient time equilibrium is established in the circuit. What will be the concentrations (in mmoles/L) of Fe2+ ions in first
and second cells respectively.
0 0 0
[Take ESn 2 / Sn = 0.14V, E Zn 2 / Zn = 0.76V,, E Fe 2 / Fe = 0.44 V, 2.3 RT = 6433, log 2 = 0.3]

Sol. Fe(s) + Sn2+ (aq.) Fe2+(aq) + Sn(s) ; E 0cell = 0.30 V

Zn(s) + Fe2+ (aq.) Zn2+ (aq.) + Fe(s) ; E 0cell = 0.32 V

If above cells are connected in parallel then first cell will get charged up and second cell will get discharged so net cell reaction
will be.
Fe22+(aq.) + Fe12+ (aq.) Zn2+ (aq.) + Sn2+ (aq.) ; E 0net = 0.02
t=0 1M 1M 1M 1M
t(aq.) (1 x) (1 x) (1 + x) (1 + x)
G 0net = nF E 0net
= 2 96500 0.02 J/mole
So, 2.30 RT log K. = 2 96500 0.02
2 96500 0.02
log K = = 0.6 ; K= 4
6433

(1 x) 2 (1 x) 1
2 = 4 (1 x) = 2 x =
(1 x) 3
So, concentration of Fe2+ ions in the first cell
2
= concentration of Fe2+ ions in the second cell = M = 667 mmoles/L
3
Example 20 :
An acidic solution of Cu+2 salt containing 0.4 g of Cu+2 is electrolysed until all the Cu is deposited. The electrolysis is continued
for seven more minutes with the volume of solution kept at 100 ml and the current at 1.2 ampere. Calculate volume of gases
evolved at N.T.P. during entire electrolysis At. wt. of Cu = 63.6.
Sol. For I part of electrolysis
Anode : 2H2O 4H+ + O2 + 4e Cathode : Cu+2 + 2e Cu
Eq. of O 2 formed = Eq. of Cu
0.4 2
= = 12.58 103
63.6
For II part of electrolysis : Since Cu+ ions are discharged completely and thus further passage of current through solution will
lead the following changes.
Anode : 2H2O 4H+ + O2 + 4e Cathode : 2H2O + 2e H2 + 2OH
i.t 1.2 7 60
Eq. of H2 = Eq. of O2 = = = 5.22 103
96500 96500
Total eq. of O2 = 5.22 103 + 12.58 103 = 17.8 103
2 Eq. of H2 at NTP = 22.4 litre or 4 eq. O2 at NTP = 22.4 litre
22.4 5.22 103
5.22 103 eq. at NTP = L = 58.46 ml (Hydrogen)
2

22.4 17.8 103

and 17.8 103 eq. at NTP = L = 99.68 ml (Oxygen)
4

24 Gyaan Sankalp
 Electrochemistry
Example 21 :
The conductivity of sodium chloride at 298 K has been determined at different concentrations and the results are given below:
Concentration/M 0.001 0.010 0.020 0.050 0.100
102 /S m1 1.237 11.85 23.15 55.53 106.74
Calculate for all concentrations and draw a plot between and C1/2. Find the value of .
Sol. The data are rewritten as follows :
C(mol L1) 0.001 0.01 0.02 0.05 0.1
C 0.032 0.1 0.14 0.22 0.32
102 (S m1) 1.237 11.85 23.15 55.53 106.74
10 (S cm1)
4 1.237 11.85 23.15 55.53 106.74
123.7 118.5 115.7 111.1 106.7

1000 (S cm1 )
130
= C (mol / L) 125.5

The C plot is shown in the figure.

1
120

/S cm2 mol
From the plot (by graphical extrapolation), = 125.5 S cm2 mol1

Plot of against 110

C for sodium chloride solution at 298 K

100
01 02 03
Example 22: C
o
The Ecell for Ag(s) | AgI (satd) || Ag+ (0.10M) | Ag(s) is + 0.417 V. Calculate Ksp for AgI. E = 0.80 V..
Ag / Ag
Sol. The cell reaction occuring in this concentration cell is
Oxidation : Ag(s) Ag+ (satd AgI) + e E = 0.80 V
Reduction : Ag+ (0.10 M) + e Ag(s) E = + 0.80 V
Cell reaction : Ag+ (0.10 M) Ag+ (satd) AgI) Ecell = 0.0 V

0.059 [Ag from AgI]

Now Ecell = Ecell log
n 0.10 M

0.059 [Ag ] [Ag ] 0.417

0.417 = 0 log ; log = = 0.07
1 0.10 0.10 0.059
[Ag+] = 8.5 108 0.10 = 8.5 109M
In a saturated AgI solution, [Ag+] [I] = Ksp
Ksp = [Ag+] [I] = (8.5 109)2 = 7.2 1017.
Example 23 :
Conductivity of 0.00241 M acetic acid is 7.896 105 S cm1. Calculate its molar conductivity and if for acetic acid is 390.5 S
cm2 mol1, what is its dissociation constant ?
Sol. Given : = 7.896 105 S cm1
Conc. of acetic acid solution,
C = 0.00241 mol L1
1000 1000 7.896 105
So, = = S cm2 mol1
C 0.00241
= 32.76 S cm2 mol1 We have = 390.5 S cm2 mol1

32.76S cm 2 mol1
Then = = 2
2 1 = 8.39 10 = 0.0839
390.5 S cm mol

Gyaan Sankalp 25
 Electrochemistry
Acetic acid ionises as follows :
CH3COOH CH3COO + H+
C(1 ) C C
C.C C 2
Ka = C (1 ) = C2
1
So, Ka = 0.00241 (0.0839)2 = 1.7 105.

Example 24 :
The standard EMF of the cell
Pt | H2 (g) | H+ (aq) || OH (aq) | O2 (g) | Pt is
0.3900 V at 27C and 0.4000 V at 7C.
If entropy change during formation of H2O() from H2(g) and O2(g) is 193 J/K, then find the S (magnitude only, in mJ/K) for
H2O ().
H+ (aq) + OH (aq)
1
Sol. anode : H+ + 1e
H
2 2
1 1
cathode : H2O + O2 + 1e
OH
2 4

1 1 1 1e
net : H2 + O2 + H2O H+ + OH
2 4 2
1 96500 (0.3900 0.4000) J
S = = 48.25
20 K

1 1 1 193
Now, H2 + O2
H2O ; S = J/K = 96.5 J/K
2 4 2 2
1 1 1
H+ + OH
H2 + O2 + H2 ; S = + 48.25 J/K
2 4 2

H2O () ; S = 48.25 J/K = 48250 mJ/K

add : H+ (aq) + OH (aq)

Example 25 :
The conductivity of a solution may be taken to be directly proportional to the total concentration of the charge carries (ions)
present in it in many cases. Find the percent decreases in conductivity (k) of a solution of a weak monoacidic base BOH when its
0.1 M solution is diluted to double its original volume.
(Kb = 105 for BOH) (take 50 = 7.07)

Sol. Initially [OH] = 10 5 0.1 = 103

[ions]total = 2 103 M

5 1
later [OH] = 10 = 4
50 10 M
20
[ions]total = 2 50 104 M

2 50 20
% change on [ions]total = 100 = 29.29%
20

26 Gyaan Sankalp
 Electrochemistry
Example 26:
Calculate the standard cell potentials of the galvanic cells in which the following reactions take place :
(i) 2Cr(s) + 3Cd2+ (aq) 2Cr3+(aq) + 3Cd(s)
(ii) Fe2+(aq) + Ag+(aq) Fe3+(aq) + Ag(s)
Calculate the G and equilibrium constant of the reactions.
2Cr(s) + 3Cd2+(aq) 3Cd(s) + 2Cr 3+(aq)
Sol. (i) Reduction
Oxidation
Thus, Cr(s) | Cr3+(aq) is anode, and Cd2+(aq) | Cd(s) is cathode.

Then, Ecell = Ecathode Eanode = Eo Eo

(Cd 2 |Cd) Cr|Cr3
Taking the values of the standard electrode potentials
Ecell = 0.40 V ( 0.74V) = + 0.34 V
and G = nF Ecell = 6 96500 0.34 J mol1 = 196860 J mol1
G = 196.86 kJ mol1
The equilibrium constant of the cell reaction is obtained from the equation,
G = 2.303 RT log K
196860 J mol1 = 2.303 8.314 J K1 mol1 298 K log K
196860 J mol1
So,log K = = 34.5
2.303 8.314 J K 1mol1 298K
K = 3.17 1034
Reduction
2+ + 3+
(ii) Fe (aq) + Ag (aq) Fe (aq) + Ag(s)
Oxidation
Thus, Pt | Fe2+, Fe3+ electrode is anode and Ag+(aq) | Ag is cathode in this cell.
o o
Then, Ecell = Ecathode Eanode = EAg / Ag EFe3 , Fe2
Substituting the E values, one gets
Ecell = 0.80 V 0.77 V = 0.03 V
and G = nFEcell = 1 96500 0.03 J mol1 = 2895 J mol1 = 2.895 kJ mol1
G ocell 2895 J mol 1
and log K = = = 0.507 or K = 3.2
2.303 RT 2.303 8.314 J K 1 mol 1 298K
Example 27 :
At 0.04 M concentration the molar conductivity of a solution of electrolyte is 5000 1 cm2 mol1 while at 0.01 M concentration
the value is 5100 W1 cm2 mol1. Making necessary assumption (Taking it as strong electrolyte) find the molar conductivity at
infinite dilution and also determine the degree of dissociation of strong electrolyte at 0.04 M.
Sol. For strong electrolyte graph between m and C is a straight line . Plot st. line from given data.
From the graph we can see the 0m value of 5200 1 cm2 mol1. Hence
0
5000 m
= = 0.9615 0.96
5200

Gyaan Sankalp 27