Electrochemistry

Electrochemistry
Introduction
Batteries are everywhere in modern societies. They provide the electric current to start our autombiles
and to power a host of products such as pocket caculators, digital watches, heart pacemaker, radio,
and tape recorders.
Electrochemistry is the area of chemistry concerned with the interconversion of chemical and
electrical.A battery is a an electrochemical cell, a device for interconverting chemical and electrical
energy. A battery takes the energy relased by a spontaneous chemical reaction and uses it to produce
electricity.
Electrochemical cell :
It is device for converting chemical energy in to electrical energy.

Electrochemical cell are of two types

Galvanic cells or Voltaic cell Electrolytic cell.

  A spontaneous chemical reaction  An electric current drives a
generates an electric current. nonspontaneous reaction.

The two types of cells are therefore reverse of each other

Construction/ Working principle
When ever an metal strip is put in an electrolyte the process of oxidation and reduction takes place
simultaneously within the system. Due to this there is a potential difference between the metal phase
and the liquid phase.
On joining the metal strips through a wire (of negligible resistence) the current flows as long as the
potential difference exists between the metal phase and the liquid phase.
 Anode :
Some metals (which are reactive) are found to have tendency to go into the solution phase when these
are placed in contact with their ions or their salt solutions.
For example : Zn rod is placed in ZnSO 4solution .

Figure : 1 Figure : 2 Figure : 3

Electrochemistry

The Zn atom or metal atoms will move in the solution to form Zn +2. After some time following
equilibrium will be established. Zn(s) Zn2+ +2e–
There will be accumulation of sufficient negative charge on the rod which will not allow extra zinc ions to
move in the solution. i.e. solution will be saturated with Zn +2 ions.
The positive charge will be more concentrated nearly the rod.
The extra positive charge of the solution will be more concentrated around the negatively charged rod.
An electrical double layer is developed in the system and hence a potential difference is created
between the rod and the solution which is known as electrode potential
This particular electrode is known as anode :
 On anode oxidation will take place. (release of electron).  To act as source of electrons.
 It is of negative polarity.  The electrode potential is represented by EZn(s) / Zn2+ (aq)

  Cathode :

Figure : 1 Figure : 2 Figure : 3

Some metals(Cu, Ag, Au etc.,) are found to have the opposite tendency i.e. when placed in contact with
their aqueous ions, the ions from the solution will get deposited on the metal rod.
The following equilibrium will be established : Cu2+ +2e– Cu(s).
So rod will have deficiency of electron (positive charge).Extra negative charge will surround this
positively charged rod and form double layer. An electrical double layer is developed in the system and
hence a potential difference is created between the rod and the solution which is known as electrode
potential. This will be known as cathode.
 At cathode reduction will take place.(gain of e – will take place)
 To act as sink of electron.
 Positive polarity will be developed.
 Their electrode potential can be represented by : E Cu2+(aq)/Cu(s)

Is where oxidation occurs Is where reduction occurs

 
Anode : Is where electrons are produced Cathode : Is where electrons are consumed
Has a negative sign Has a positive sign
 
Construction of Cell :
 It has two half–cells,each having a beaker containing a metal strip that dips in its aqueous solution.
 The metal strips are called electrodes and are connected by an conducting wire.
 Two solutions are connected by a salt bridge.
 The oxidation and reduction half reactions occur at a separate electrodes and electric current flows
through the wire.

Selection of electrolyte for Salt Bridge :

Electrochemistry

 The electrolyte in salt bridge should be such that speed of it's cation equals speed of it's anion
in electrical field.
 For that charge and sign of the ions should be almost equal.
Transport number of cation = Transport number of anion
or
Mobility of cation = Mobility of anion
KCl is generally preffered but KNO3 or NH4NO3 can also be used.

 If Ag+, Hg2+, Pb2+, Tl+ ions are present in a cell then in salt bridge KCl is not used because
there can be formation of precipitate of AgCl, Hg 2Cl2, PbCl2 or TlCl at mouth of tube which will
prevent the migration of ions and its functioning will stop.
Functions of Salt Bridge :
 A salt bridge is a U–shaped inverted tube that contains a gel permeated with an inert
electrolyte.
 It connects the solution of two half cell to complete the circuit.
 It minimise the liquid junction potential. The potential difference between the junction of two
liquids.
 It maintains the electhical neutrality of the solution in order to give continious flow or generation
of current.
" The simultaneous electrical neutrality of the anodic oxidation chamber and cathodic reduction
chamber is due to same mobility or velocity of K+ and NO3– ions taken into salt bridge.
 If the salt bridge is removed then voltage drops to zero.
 The ions of the inert electrolyte do not react with other ion in the solution and the ions are not
oxidised or reduced at the electrodes.
 Generally tube is filled with a paste of agar-agar powder with a natural electrolyte/generally not
common to anionic/cathodic compartment with porous plugs at each mouth of tube.
 It prevents mechanical mixing of two electrolytic solution.
Electrode Potential :
 The driving force that pushes the negative charge electrons away from the anode and pulls
them towards the cathode is an electrical potential called electromotive force also known as
cell potential or the cell voltage. Its unit is volt
 The potential difference devepoled between metal electrode and its ions in solution in known as
electrode potential.
 Electrode potential depends upon :
   Concentration of the solution.   Nature of the metal.
 Nature of the electrolyte.  Pressure temperature coditions.
 The potential difference developed between metal electrodes and the solution of its ions at 1 M
concentration at 1 bar pressure and 298 K is known as standard electrode potential.

Oxidation Potential (O.P.) : Reduction Potential (R.P.)

The electrode potential for The electrode potential for
oxidation half reaction reduction half reaction
Tendency to get oxidised. Tendency to get reduced.
 Greater the O.P. than greater  Greater the R.P. greater will
will be tendency to get oxidised. be tendency to get reduced.

Type of Electrode Electrode reaction in standard condition Representation

1. Metal electrode Reduction : Zn2+ + 2e–  Zn(s) E0Zn2 / Zn(s) ( SRP)
Electrochemistry

(Zn electrode, Oxidation : Zn(s) Zn2+ + 2e– E0Zn(s) / Zn2 (SOP)

Cu electrode etc.)
2. Hydrogen peroxide Reduction : 2e– + 2H+ + H2O2 2H2O EH0 2O2 / H2O
electrode Oxidation : H2O2 O2 + 2H+ + 2e– EH0 2O2 / O2
3. Redox electrode Reduction : MnO4– + 8H+ + 5e–  Mn2+ + 4H2O 0
EMnO
/ Mn2
4

4. Metal Metal Reduction : AgCl(s) + e–  Ag(s) + Cl– E0AgCl(s) / Ag(s) / Cl

salt insoluable Oxidation : Ag(s) +Cl– AgCl(s) + e– E0Ag(s) / AgCl(s) / Cl

electrode

Reference electrode :
 The potential of a singal electode cannot be determined what were the potential difference
between two electrodes can be accurately measured using a reference electrode.
 An electrode is chosen as a reference with respect to which all other electrodes are valued.
 Standard Hydrogen Electrode (SHE) is taken as standard reference electrode. Its electrode potential
is arbitrarily assumed to be 0.00 volt.
 Standard Hydrogen Electrode (SHE) consists of a platinum electrode in contact with H2 gas and
aqueous H+ ions at standard state conditions (1 atm H2 gas, 1 M H+ (aq), 25°C).
2H+ (aq, 1M) + 2e–  H2 (g, 1 atm) E° = 0V
H2(g, 1atm)  2H+ (aq, 1M) + 2e– E° = 0V

Cell potential :
 The difference in electrode potentials of the two half cell reactions (oxidation half cell and
reduction half cell) is known as emf of the cell or cell potential.
The emf of the cell or cell potential can be calculated from the values of electrode potential of
the two half cell constituning the cell. The following three methode are in use :
 When oxidation potential of anode and reduction potential of cathode are taken into account :
E°cell = oxidation potential of anode + reduction potential of cathode
E°ox (anode) + E°red(cathode)

 When reduction potential of both electrodes are taken into account :
E°cell = Reduction potential of cathode – Reduction potential of anode
= E°cathode – E°anode C both are reduction potential.

 When oxidation potential of both electrodes are taken into account :
E°cell = oxidation potential of anode – Oxidation potential of cathode
= E°ox (anode) – E°ox (cathode)
  The standard cell potential E° is the cell potential when both reactants and products are in their
standard states – solutes at 1 M concentration, gases at a potential pressure of 1 atm, solids
and liquids in pure from, with all at a specified temperature, usually 25° C.
 E°cell is intensive property so on multiplying/Dividing cell reaction reaction by any number, the
E°cell value would not change.

Free energy changes for cell reaction :

 The free energy change G (a thermochemical quantity) and the cell potential E(an
electrochemical quantity) both measure the driving force of a chemical reaction.
 The values of G and E are directly proportional and are related by the equation.
G = –nFE
Electrochemistry

where n = Number of moles of electron transfered in the reaction.

F = Faraday constant = 96485 C/mole e – 96500 C/mole e–
Shorthand Notation for Galvanic Cells
 We require two half cells to produce an electrochemical cell, which can be represented by follwing few rules;
 The anode half-cell is always written on the left followed on the right by cathode half cell.
 The separation of two phases (state of matter) is shown by a vertical line. 
  The various materials present in the same phase are shown together using commas.
 The salt bridge is represented by a double slash (||).
 The significant features of the substance viz. pressure of a gas, concentration of ions etc. are
indicated in brackets immediately after writing the substance.
  For a gas electrode, the gas is indicated after the electrode for anode and before the electrode
in case of cathode. (i.e Pt H2 / H+ or H+ /H2 Pt)

Ex.1 Write short hand notation for the following reaction, Sn 2+ (aq) + 2Ag+ (aq)  Sn4+ (aq) + 2Ag(s).
Sol. The cell consists of a platinum wire anode dipping into an Sn+2 solution and a silver cathode dipping
into an Ag+ solution therefore Pt(s) | Sn2+(aq), Sn4+ (aq) || Ag+ (aq) | Ag(s).

Ex.2 Write the electrode reaction and the net cell reaction 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–] x 2
reduction half reaction, [I2 + 2e– 2I–] x 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–] x 2
Net cell reaction Cd + 2AgCl  Cd2+ + 2Ag + 2Cl– (Positive terminal : cathode Ag)

Calculation of electrode potential :

At Anode At Cathode
H2(g) 2H+ + 2e– 2H+ + 2e– H2(g)
Electrochemistry

Oxidation potential O.P. = EH (g) / H (aq.) Reduction Potential (R.P.) EH / H = RP

2 2 (g)

under standard state  under standard state.

0 0
 E H2 (g) / H (aq.) = SOP  EH / H = SRP
2 (g)

  For SHE reference potential is taken to be zero at all temperature.

SOP = – SRP = 0 for SHE.
To calculate standard potential of any other electrode a cell is coupled with standard hydrogen
electrode (SHE) and it's potential is measured that gives the value of electrode potential of that
electrode.

Anode : Zinc electrode

Cathode : SHE
Cell : Zinc electrode || SHE
Cell potential :
Ecell = EH / H (g) – E°Zn2+/Zn
2

= 0.76 V (at 298 K experimentaly)

So, E0Zn2+/Zn = – 0.76 V (SRP)
E0 Zn/Zn 2+
(aq) = 0.76 V(SOP)

 So, w.r.t. H2, Zn has greater tendency to get

oxidised.
In similar manner reduction potentials (SRP) at
298 K for many other electrodes are calculated
and are arranged in a series increasing order
known as electro chemical series.

Electrochemical Series :

Electrode Reaction SRP (at 298 K)

* Li Li+ + e–  Li(s) – 3.05 V
K K+ + e–  K (s) – 2.93 V
Ba
Ca Ca+2 + 2e–  Ca(s) – 2.87 V
Na Na+ + e–  Na(s) – 2.71 V
Electrochemistry

Mg Mg+2 + 2e–  Mg(s) – 2.37 V

Al
* Zn Zn+2 + 2e–  Zn(s) – 0.76 V
Cr Cr+3 + 3e–  Cr(s) – 0.74 V
* Fe Fe2+ + 2e-  Fe – 0.44 V
* Electrolytes (H2O) H2O(l) + e–  1
2
H2 + OH– – 0.41 V
Cd Cd+2 +2e–  Cd(s) – 0.40 V
Co
Ni Ni+2 + 2e–  Ni(s) – 0.24 V
Sn Sn+2 + 2e–  Sn(s) – 0.14 V
Pb Pb+2 + 2e–  Pb(s) – 0.13 V

* H2 2H+ + 2e–  H2(g) 0.00 V

Cu Cu2+ + 2e–  Cu(s) 0.34 V

2
Fe Fe3+ + e–  Fe2+ 0.77 V
Hg Hg22+ + 2e-  Hg(l) 0.79 V
Ag Ag+ + e–  Ag 0.80 V
Hg Hg2+  Hg(l) 0.85 V
Br2 Br2 + 2e–  2Br– 1.06 V
* Electrolytes 1
2
O2 + 2H+ + 2e–  H2O() 1.23 V
* Cr2O72– + 14H+ + 6e–  2Cr+3 + 7H2O 1.33 V

* Cl2  Cl2 +2e–  2 Cl– 1.36 V

* MnO4– + 8H+ + 5e–  Mn2+ + 4H2O 1.51 V

* F2 + 2e–  2F– 2.87 V

Ex.3 Calculate E0cell of (at 298 K),

Zn(s) / ZnSO4(aq) || CuSO4(aq) / Cu(s)
given that E0Zn/Zn2+
(aq) = 0.76 V ; E0Cu(s) / Cu 2+
(aq) = – 0.34 V

Sol. E0cell = (S.R.P)cathode – (S.R.P)anode

= 0.34 – (– 0.76) = 1.1 V

Ex.4 Given the cell Ag AgCl(s) | NaCl (0.05 M) || Ag NO3 (0.30) | Ag

(a) Write half reaction occurring at the anode. (b) Write half reaction occurring at the cathode.
(c) Write the net ionic equation of the reaction. (d) calculate E°cell at 25°C.
(e) Does the cell reaction go spontaneous as written ?
(Given E°AgCl,Cl = + 0.22 volt) ; E0Ag / Ag = + 0.80 volt)

Sol. (a) LHS electrode is anode and half reaction is oxidation.

Ag+ + Cl– 
 AgCl(s) + e– ... (i)
Electrochemistry

(b) RHS electrode is cathode and half reaction is reduction.

Ag + e 
 Ag(s) ... (ii)
(c) From equation (i) and (ii) cell reaction is : Cl – (0.05 M) + Ag+ (0.30 M) 
 AgCl(s)
(d) E°cell = E°right – E°left = (0.80 – 0.22 volt = 0.58 volt
(e) Yes, the e.m.f. value is positive, the reaction will be spontaneous as written in the cell reaction.

Ex.5 An aqueous solution containing Na+ , Sn2+, Cl– & SO42– ions, all at unit concentration, is electrolysed
between a silver anode and a platium cathode. What changes occcur at the electrodes when curent is
passed through the cell? Given : E0Ag |Ag = 0.799 V,

E0Sn2 |Sn = – 0.14 V, E0Cl | Cr 

= 1.36 V , E0S O2 |SO2 = 2 V, E0Sn4 |Sn2 = 0.13 V
2 2 8 4

(A) Sn2+ is reduced and Cl– is oxidized (B) Ag is oxidized and Sn2+ is reduced
(C) Sn2+ is reduced and Sn2+ is oxidized (D) H+ is reduced and Sn2+ is oxidised
Sol. At anode either Ag can oxidised to Ag + or Sn2+ to Sn4+ or Cl– to Cl2 or SO24 to S2O82 Their respective
oxidation poential values are –0.799 V, 0.13 V, –1.36 V and –2 V. From these values, it is evident that
Sn2+ would be oxidised first, followed by Ag at anode. At cathode, either Na + can get reduced to Na. or
Sn2+ to Sn or H+ to H2. The reduction potential value for Na + is highly negative while for Sn2+ | Sn is –

 1 
0.14 V and for H+ + e–  1/2 H2  EH |H  0.059log 7  is –0.413 V. Thus Sn2+ will get reduced
 2
10 
at cathode followed by H+  (C)

 Calculation of Electrode Potential of unknown electrode with the help of given (two) electrode.
Obtain the reaction of the 3rd electrode with the help of some algebraic operations on reactions of
the given electrodes.
Then calculate G of the 3rd reaction with the help of some algebaric operations of G0 of 1st and
2nd reactions.
Use G0 = –nF E0elec. to calculate unknown E.P.
0 0
 Ecell is intensive property so if we multiply/Devide electrode reaction by any number the Ecell value

would not changed

i.e. Zn2+ + 2e–  Zn(s) E° = – 0.76 V
Multiply by 2
2Zn2+ + 4e–  2Zn(s) E° = – 0.76 V (remain same)

Ex.6 Given that E0Cu 2+

/Cu = 0.337 V and E0Cu +
/Cu
2+ = – 0.153 V. Then calculate E0 Cu /Cu.
+

Sol. (i) Cu2+ + 2e–  Cu G1

(ii) Cu+  Cu2+ + e– G2

after adding Cu++ e–  Cu

G1 + G2 = G3
–2F E10 – F E02 = – F E03
Electrochemistry

E3 = 2 E10 + E02
= 2 x 0.337 – 0.153 = 0.674 – 0.153 = 0.521 V

Nernst Equation :
Cell potentials depend on temperature and on the composition of the reaction mixtures.
It depends upon the concentration of the solute and the partial pressure of the gas, if any.
The dependence upon the concentration can be derived from thermodynamics.
From thermodynamics
G = G° + RT ln Q
– nFE = – nFE° + 2.303 R T log Q
2.303RT
E = E° – log Q
nF
Take T = 298 K , R = 8.314 J/mol K , F = 96500 C
0.059
Now we get, E = E° – log Q
n
Where n = number of transfered electron , Q = reaction quotient
 Nernst equation can be used to calculate cell potentials for non standard conditions also.
Nernst equations can be applied to half cell reactions also.

Applications of Nerst equation



 Nernst Equation for Electrode Potential

Mn+(aq) + ne– M(s)

RT  M(s) 
0
ERedn = Ered – n  n  
nF M 
2.303 RT  M(s) 
0
ERedn = Ered – log  n  
nF M 
at 298K ,
0.059  1 
0
ERedn = ERe dn
– log  n  
n M 

Hydrogen Electrode
H2(g) 2H+(aq) + 2e–

0.0591  (H )2 
E = E0 – log  
2  PH2 

 Metal–metal soluble salt electrode.

Zn2+ + 2e–  Zn(s)
2.303 RT  1 
0
ERedn = ERe dn
 log  2  at 298K
nF  Zn 
0.059  1 
0
ERedn= Ered  log  2 
2  Zn 
 Gas – electrode Hydrogen electrode.

2H+ + 2e–  H2(g)

0.059  PH 
0
ERedn= ERe dn
 log   2 2 
2  [H ] 
Electrochemistry

 Redox electrode
4H2O + Mn2+  Mn O 4 + 8H+ + 5e–
0.059 [MnO4 ][H ]8
EOX = E0ox  log
5 [Mn2 ]

Ex.7 Calculate R.P. of hydrogen electrode at 298K which is prepared with the help of aq. solution of acetic
acid with 0.1 M conc at 1 atm pressure Ka = 1.8 x 10 –5.
Sol. [H+] = Ka  c = 1.8  105  101 = 1.8  106
2H+ + 2e–  H2
0.059 PH
0
ERedn= Ered  log  2 2 (E0Redn = 0)
2 [H ]
0.059  1  0.059
ERedn=  log  6 
=  [6 – log (1.8)]
2  1.8  10  2
0.059
ERedn =  x 5.74 = –0.169 V
2

 Nernst Equation for cell Potential :

aA + bB CC + dD
RT
Ecell = E0cell – lnQ
nF
n – no. of electrons which gets cancelled out while making cell reaction.
Equilibrium in electrochemical cell
G0 = – nF Eºcell
G = – nF Ecell
From thermo dynamics
G = G0 + RTnQ
at chemical eqlibrium G = 0
Ecell = 0 cell will be of no use
so, G0 = – RTn Keq
at eqlibrium – nF Eºcell = –2.303 RT log (Keq)
nF
log Keq = Eºcell
2.303 RT
at 298 K and R = 8.314 J/mol K
n
log Keq = Eºcell
0.059

Ex.8 The E°cell for the reaction Fe + Zn2+ Zn + Fe2+ , is – 0.32 volt at 25°C. What will be the equilibrium
concentration of Fe , when a piece of iron is placed in a 1 M Zn2+ solution ?
2+

Sol. We have the Nernst equation at equilibrium at 25°C

0.0591
E° = log K ... (i)
n
Since E°Cell for the given reaction is negative, therefore, the reverse reaction is feasible for which E°cell
will be + 0.32 V, Thus for Zn + Fe2+ Fe + Zn2+ ; E°Cell + 0.32 V
Electrochemistry

0.0591 [Zn2  ] 0.0591 1

Now , E° = log 2
or 0.32 = log
n [Fe ] 2 [Fe2  ]
log [Fe2+] = – 10.829 Taking antilog,
[Fe2+] = 1.483 x 10–11 M

Concentration cells :
 A concentration cell consists of two electrodes of the same material, each electrode dipping in a
solution of its own ions and the solution being at different concentrations.
 The two solutions are separated by a salt bridge.
e.g. Ag(s) | Ag+ (a1) || Ag+ (a2) | Ag(s) (a1 < a2) a1 , a2 are concentrations of each half cell
At LHS electrode Anode : Ag (s) 
 Ag+(a1) + e–
At RHS electrode Cathode : Ag+(a2) + e– 
 Ag(s)
The net cell reaction is : Ag+ (a2) 
 Ag+ (a1)
The nernst eq. is
0.059 a
Ecell = – log 1 (Here n = 1, Temp, 298 K)
n a2
Likewise, the e.m.f. of the cell consisting of two hydrogen electrodes operating at different pressure
P1 and P2 (P1 > P2 ) and dipping into a solution HCl is :
0.059 P
Ecell = log 1 (at 298 K)
2 P2
Solubility product and EMF (Metal Metal Insoluble Salt Electrode) :
  A half cell containing metal M and its sparingly soluble salt MA in a saturated solution.
i.e M(s) | MA (satd) or a metal, its sparingly soluble salt in contact with a solution of a soluble
salt NaA of the same anion, i.e. M(s) | MA(s) | NaA is set up.
 The solubility product of a sparingly doubles salt is a kind of equilibrium constant.
MX (s) M+(aq) + X– (aq) Ksp = [M+] [X–]

At Anode At Cathode
M (s) M+ (aq) + e– e– + MX(s) M(s) + X– (aq)

Overall reaction : MX (s) M+ (aq) + X– (aq)

Cell representation : + –
M | M M (satd. sol.) || MX (s) | M (s)
Eºcell = E°red – E°ox

From thermodyanmics G° = – nFE°

G° = –2.303 RT log Ksp
combining both equations – 2.303 RT log Ksp = – nFE°
2.303 RT
or E° = log Ksp
nF
0.0591
E° = log Ksp at 25°C
n
Work done by a cell :
(i) Let 'n' faraday charge be taken out of a cell of EMF 'E' ; then work done by the cell will be
calculated as : work = Charge × Potential = nFE
Electrochemistry

(ii) Work done by cell = Decrease in free energy

so – G = nFE
or Wmax = + nFEº where Eº is standard EMF of the cell

Ex.9 Calculate the maximum work that can be obtained from the Daniell cell given below -
Zn(s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s). Given that Eº Zn2 / Zn = – 0.76 V and EºCu2 / Cu = + 0.34 V.
Sol. Cell reaction is : Zn(s) + Cu2+ (aq)   Cu(s) + Zn2+ (aq) Here n = 2
Eºcell = Eºcathode – Eºanode (On the basis of reduction potenital)
= + 0.34 – (0.76) = 1.10 V
We know that : Wmax = Gº = – nFEº
= – (2 mol) × (96500 C mol) × (1.10 V) = – 212300 C.V. = – 212300 J
or Wmax = – 212300 J

Electrolysis & Electrolytic cell :

Electrolysis :
  Electrolyte is a combination of cations and anions which in fused state can conduct electricity.
 This is possible due to the movement of ions from which it is made of and electrolyte.
 The process of using an electric current to bring about chemical change is called electrolysis.
 Electrolysis is a process of oxidation and readuction due to current in the electrolyte.
 The product obtained during electrolysis depends on following factors.
   The nature of the electrolyte 
   The concentration of electrolyte
   The charge density flowing during electrolysis.
   The nature of the electrode
Active vs Inactive electrodes :
 The electrodes in the cell that are active because the metals themselves are components of the
half reactions.
 As the cell operates, the mass of the zinc electrode gradually decreases, and the [Zn2+] in the
anode half – cell increases. At the same time, the mass of the copper electrode increases and
the [Cu2+] in the cathode half – cell decreases; we say that the Cu2+ "plates out" on the
electrode.
 For many redox reactions, however, there are no reactants or products capable of serving as
electrodes. Inactive electrodes are used, most commonly rods of graphite or platinum, materials that
conduct electrons into or out of the cell but cannot take part in the half -reactions.
 In a voltaic cell based on the following half reactions, for instance, the species cannot act as electrodes
2I–(aq)   I2(s) +2e– [anode ; oxidation]
MnO4– (aq) + 8H+ (aq) + 5e– 
 Mn2+ (aq) + 4H2O() [cathode ; reduction]
Therefore, each half – cell consists of inactive electrodes immersed in an electrolyte solution that
contains all the species involved in that half -reaction. In the anode half-cell, I– ions are oxidized to solid
I2. The electrons released flow into the graphite anode, through the wire, and into the graphite cathode.
From there, the electrons are consumed by MnO 4– ions as they are reduced to Mn2+ ions.
Examples of Electrolysis
 Using inert (pt/graphite) electrodes.
Cathode (red) : Pb2+ + 2e–  Pb(s) E0 = 0.126V
Anode : 2Br-  Br2 + 2e- E0 = – 1.08 V
Ecell = – 0.126 – (0.108) x 10 = – 1.206 V
Eext > 1.206 V
Electrochemistry

 Electrolysis of CuSO4 molten

Cathode : Cu2+ + 2e–  Cu E0 = +0.34 V

Anode : 2 SO24 S2 O82  + 2e– E0 = – 2.05 V
H2S2O8 – marchall's acid peroxy disulphuric acid.
Ecell = 0.34 – (2.05) = – 1.71 V (negative  not feasible)
O O
H O S O O S O H
O O
 Electrolysis of aq CuSO4

Cathode : Cu2+ + 2e–  Cu(s) E0 = 0.34 V

2e + 2H2O() H2(g) + 2OH–(aq) E0 = –0.83V
Anode : 2 SO24  S2 O82  + 2e– E0 = –2.05 V
2H2O()  O2 + 4H+ + 4e– E0 = –1.23 V

 Electrolysis of aq NaBr solution (initially PH = 7)

Cathode : Na+(aq) + e–  Na(s) E0 = – 2 V
2e– + 2H2O()  H2 + 2OH– E0 = – 0.83 V
Anode : 2Br-  Br2 + 2e– E0OX = – 1.08 V
2H2O () O2 + 4H+ + 4e– E0OX = – 1.23 V

 Electrolysis of aq NaCl
Cathode : Na+ + e–  Na E0 = – 2V
2e– + 2H2O()  H2(g) + 2OH- E0 = –0.83 V
Anode : 2Cl–  Cl2 + 2e– E0OX = –1.30 V
2H2O()  O2 + 4H+ + 4e– E0OX = –1.23 V
Rate of production of Cl 2 is more than rate of production of O2 gas.

Note : According to thermodynamics, oxidation of H2O to produce O2 should take place on anode but
experimentally (experiment from chemical kinetics) the rate of oxidation of water is found to be very
slow. To increase it's rate, the greater potential difference is applied called over voltage or over
potential but because of this oxidation of Cl – ions also become feasible and this takes place on anode.

Electrolysis using attackable (reactive) electrodes.

 Electrolysis of aq. CuSO4 using Cu electrode.
Cathode (reduction) : Cu2+ + 2e–  Cu E0 = + 0.34 V
2H2O() + 2e–  H2(g) + 2OH– E0 = –0.83 V
Anode (oxidation) : SO24  S2 O82  + 2e– E0OX = – 2.05 V
2H2O()  O2 + 2H+ + 4e– E0 = 1.23 V
Cu(s)  Cu2+ + 2e– E0 = –0.34 V
electrolytic refining
 AgNO3(aq) using Cu cathode & Ag anode.
Cathode : Ag+ + e–  Ag(s) E0 = 0.8 V
2H2O () + 2e–  H2(g) + 2OH– E0 = – 0.083 V
Anode : NO3–  X (No reaction)
2H2O()  O2 + 4H+ + 4e– E0 = – 1.23 V
Electrochemistry

Ag(s)  Ag+(aq) + e– E0 = – 0.80 V

 Faraday's Law of Electrolysis :

  1st Law : The mass deposited/released/produced of any substance during electrolysis is
proportional to the amount of charge passed into the electrolyte.
WQ
W = ZQ
Z – electrochemical equivalent of the substance.
mass
Unit of Z = = Kg/C or g/C
coulomb
Z = Mass deposited when 1 C of charge is passsed into the solution.


Equivalent mass (E) : mass of any substance produced when 1 mole of e – are passed through the
solution during electrolysis.
Molar mass
E=
no. of e involved in oxidation / reduction
e.g.
M M
Ag+ + e–  Ag E= Cu2+ + 2e-  Cu(s) E=
1 2
M
Al3+ + 3e–  Al(s) E=
3
1 mole of e– = 1 Faraday of charge.
 96500 C – Charge deposite E gram metal charge
 E  E
 1C    g Z=
 96500  96500
EQ Molar mass Q
W= = x
96500 (no. of e involved) 96500
i x t Molar mass
 dQ =I  dt Q = it W=
96500
x
(no. of e  involved)


  2nd Law : When equal charge is passed through 2 electrolytic cells and this cells are connected in
series then mass deposited at electrode will be in the ratio of their electrochemical equivalents or in the
ratio of their equivalent masses.
EQ
W = ZQ =
96500
W1 z E
= 1 = 1 ( Q = same)
W2 z2 E2
Current Efficiency :
charge actually used in electricity
current efficiency = x 100
charge passed
mass actually produced
current efficiency = x 100
mass that should have been produced

Ex.10 Calculate volume of the gases liberated at STP if 1 L of 0.2 molar solution of CuSO 4 is electrolysed by
5.79 A current for 10000 seconds.
5.79  10000 579
Sol. No. of moles of e– = = = 0.6
96500 965
Cathode : Cu2+ + 2e-  Cu(s)
0.2 mole 0.4 mole
2H2O() + 2e–  H2 + 2OH–
0.2 mole of e–  0.1 mole of H2 at S.T.P.
Electrochemistry

Anode : 2H2O()  O2 + 4H+ + 4e–

4 mole of e–  1 mole of O2
0.6 mole of e–  0.15 mole of O2
so, total moles = 0.25 mole
Total volume = 5.6 Ltr.

Ex.11 How many cc of chlorine will be deposited by 100 amp. current flowing for 5 hours through melted
NaCl.
Sol. Q = It = 100  5  60  60 = 18  105
E 18 18  35.5
W = ZQ =  18  155 =  103 =  103 = 662.2 gm
96500 96500 965
 Volume of 71 gm Cl2 at NTP = 22.4 litre
22.4
 volume of 662.2 gm Cl 2 at NTP = ´ 662.2 = 208.9 litre
71
Ex.12 The time required to coat a metal surface of 80 cm2 with 0.005 mm thick layer of silver (density = 10.5
gm cm–3) with the passage of 3A current through silver nitrate solution is :
Sol.  Volume of layer of silver = 0.005  10–1  80 = 0.04 cm3
 mass = Density  volume = 10.5  0.04 = 0.42 gm
E 108
So w =  It 0.42 = 3t
96500 96500
0.42  96500
t= = 125.09 seconds.
108  3

Electrolytic Conductance :
Conductors

Metallic Conductors Electrolytic Conductors

–
1. Charge carries are e 1. Charge carries ions (cations/ anions)
2. No chemical changes 2. Decomposition of electrolyte takes place.
3. No transfer of mass 3. Transfer of mass
4. Resistance is because of 4. Resistance is because of collision
–
collision of e s with fixed of ions with solvent molecules & because
n
metal atoms. of interionic force of attraction
5. Temp  R  5. Temp  R 
6. Low resistance generally 6. High resistance generally
good conductor.

Factors Affecting Conductance & Resistance :

1. Solute – Solute interactions (Inter – Ionic force of attraction) Greater the force of attraction,
greater will be the resistance.
Force  Charge
2. Solute – Solvent Interaction (Hydration/Solvation of Ions)
Greater the solvation
1
Solvation  Charge  greater will be resistance
size
Li+ (Hydrated largest) Cs+ (Hydrated smallest)
Electrochemistry

resistance of LiCl > resistance of CsCl

3. Solvent solvent interaction (Viscosity) : greater the viscosity greater will be resistance
4. Temperature
T  R 

5. Nature of electrolyte
Weak electrolyte – high resistance strong electrolyte – Low resistance
Resistance :
V
R= (Ohm's law (  ))


R=
A
 – resistivity/specific resistance
– resistance of unit length wire of unit area of cross section = constant = (  m)
RA
 =

Resistivity of a solution is defined as the resistance of the solution between two electrodes of 1 cm 2
area of cross section and 1 cm apart.
or
Resistance of 1 cm3 of solution will be it's resistivity.

Conductance :
1
= = mho =  –1
R
= S (Siemens)
Conductivity/specific conductance
1  
K= = = 
 RA A
unit –1 cm–1
= conductivity of 1 cm3 of solution
 concentration of ions
1 1
K= G=
 R
K  ( no. of ions) no. of charge carries
 Since conductivity or resistivity of the solution is dependent on it's concentration, so two more
type of conductivities are defined for the solution.

 Molar conductivity/molar conductance (m) :

Conductance of a solution containing 1 mole of an electrolyte between 2 electrodes which are 1cm
apart.
Let the molarity of the solution 'C'
C moles of electrolyte are present in 1 Lt. of solution.
so molar conductance = K
K  1000 K  1000
 m = KV m =  m =
C molarity
 Its units are Ohm–1 cm2 mol–1
 Electrochemistry


 Equivalent conductance : Conductivity of a solution containing 1 g equivalent of the electrolyte. 

 eq – equivalent conductivity/conduction.
K  1000
eq =
Normality
  Its units are Ohm–1 cm2 eq–1


Ex.13 If resistivity of 0.8 M KCl solution is 2.5 x 103 cm calculate m of the solution.
Sol.  = 2.5 x 10–3  cm
103
K= = 4 x 102
2.5
4  102  1000  10
m = = 5 x 105  –1 cm2 mole–1
0.8
Ex.14 The resistance of a 1 N solution of salt is 50  . Calculate the equivalent conductance of the solution, if
the two platinum electrodes in solution are 2.1 cm apart and each having an narea of 4.2 cm 2.
1 1 L 1 2.1 1
Sol. k= =   =  =
 R A 50 4.2 100
k  1000 1000
and eq. = = = 10
N 0.08

Ex.15 Which of the following have maximum molar conductivity.

(i) 0.08 M solution and its specific conductivity is 2  10–2  –1.
(ii) 0.1 M solution and its resistivity is 50  cm.
k  1000 1000
Sol. (i) M = = 2  10–2  = 250  –1 cm2 mol–1
M 0.08
k  1000
(ii) M =
M
1
k=

1 1000
 lM =  = 200  –1 cm2 mol–1
50 0.1
So, the molar conductivity of 0.08 M solution will be greater than 01 M solution.

Variation of conductivity and molar conductivity with concentration

  Conductivity always decreases with the decrease in concentration both for weak and strong
electrolytes.
  The number of ions per unit volume that carry the current in a solution decreases on dilution.
  Molar conductivity increases with decreases in concentration. This is because the total volume,
V of solution containing one mole of electrolyte also increases.
  Molar conductivity is the conductance of solution.
  When concentration approaches zero, the molar conductivity is known as limiting molar
conductivity and is represented by the symbol  .
Strong Electrolytes :
  For strong electrolytes.  increses slowly with dilution and can be represented by the equation
Electrochemistry

 =  – A C1/2
 The value of the constant 'A' for a given slovent and temperature depends on the type of
electrolyte i.e. the charges on the cations and anion produced on the dissociation of the
electrolyte in the solution.
Example : Thus NaCl, CaCl2, MgSO4 are known as 1-1 , 2-1 and 2-2 electrolyte respectively.

 All electrolytes of a particular type have the same value for 'A'.

Weak electrolytes
 Weak electrolytes like acetic acid have lower degree of dissociation at higher concentration and hence
for such electrolytes, the change in  with dilution is due to increases in the number of ions in total
volume of solution that contains 1 mol of electrolyte.
 At infinite dilution (i.e. concentration c  zero) electrolyte dissociates completely ( = 1),but at such low
concentration the conductivity of the solution is so low that it connot be measured accurately.

 Molar conductivity versus c1/2 for acetic acid (weak electrolyte) and potassium chloride
(strong electrolyte in aqueous solutions.

Kohlarausch's Law :
"At infinite dilution, when dissociation is complete, each ion makes a definite contribution towards
equivalent conductance of the electrolyte irrespective of the nature of the ion with which it is associated
and the value of equivalent conductance at infinite dilution for any electrolyte is the sum of contribution
of its constituent ions."
i.e.,  = + + –
 At infinite dilution or near zero concentration when dissociation is 100%, each ion makes a definite
contribution towards molar conductivity of electrolyte irrespective of the nature of the other ion.
(because interionic forces of attraction are zero)
0m electrolyte = 0
m    m0 +   m
0
Electrochemistry

  = no. of cation in one formula unit of electrolyte, = no. of anions in one formula unit of electrolyte
For NaCl = 1   = 1
For Al2(SO4)3 = 2   = 3
 0eq electrolyte =  eq +  eq

m0 m0 Al3 

 0eq =  0eq .Al3+ =
charge on the cation 3
m0 m0 electrolyte
 0eq =  0eq , electrolyte =
charge on the anion total  ve charge on cation
or
total ve charge on anion
m0 Al3  m0 SO24
 0eq Al2(SO4)3 =  0eq Al3+ +  0eq SO24 = +
3 2
2
2mAl
0
3  3SO4
 0eq Al2(SO4)3 =
6

Ex.16  m0 Na+ =  150–1 cm2 mole–1 ;  0eq Ba2+ = 100 –1 cm2 eq–1
 0eq SO24 =  125-1 cm2 eq–1 ;  m0 Al3+ = 300 –1 cm2 mole–1
 m0 NH4 = 200–1 cm2 mole–1 ;  m0 Cl– = 150  –1 cm2 mole–1
Then calculate
(a)  0eq , Al3+ (b)  0eq Al2(SO4)3 (c)  m0 (NH4)2SO4
(d)  m0 NaCl, BaCl2. 6H2O (e)  m0 , (NH4)2 SO4 Al2(SO4)3 . 24H2O (f)  0eq NaCl
300
Sol. (a)  0eq Al3+ = = 100 (b)  0eq Al2(SO4)3 = 100 + 125 = 225
3
(c)  m0 (NH4)2SO4 = 2 x 200 + 2 x 125 = 650
(d)  m0 NaCl.BaCl2.6H2O = 150 + 200 + 3 x 150 = 800 r–1
(e)  m0  0eq , (NH4)2 SO4 Al2(SO4)3 . 24H2O  m0 (NH4)2 = 400 + 600 + 4 x 250 = 2000
(f) NaCl = 300–1 cm2 eq–1

Ex.17 To calculate  m0 or  0eq of weak electrolyte

mCH
0
3 COOH
= mCH
0
COO
+  m0 H+
3

= ( 0
mCH3 COO
+  0
mNa
) – mNa
0
 + 
0
mH
+ mCl
0
 – 
0
mCl

0CH3COOH = mCH
0
3 COONa
+ mHCl
0
– mNaCl
0

Ex.18 Calculate  m0 of oxalic acid, given that

 0eq Na2C2O4 = 400 –1 cm2 eq–1
H2SO4 = 700 –1 cm2 mole–1
Na2SO4 = 450 –1 cm2 eq–1
Sol.  m0 H2C2O4 = 700 + 800 – 900 = 600 –1 cm2 mole
700
 0eq = 400 + – 450
2
Electrochemistry

m
= 350 – 50 = 300
2
m = 600

Applications of Kohlaraushch's law

 Calculate  for any electrolyte from the  of individual ions.
 Determine the value of its dissociation constant once we known the  and  at a given
concentration c.
 Degree of dissociation : At greater dilution the ionization become 100%, therefore called infinite
dilution.
At lower dilution the ionization (dissociation into ions) is less than 100% and equivalent conductance
become lower,
i.e., eq < °eq
degree of dissociation
 eq equivalent conduc tance at a given concentrati on
 = 0 =
 eq equivalent conduc tance at at inf inite dilution

 Dissociation constant of weak electrolyte :

C 2
KC = ;  = degree of dissociation
1 
C = concentration
 The degree of dissociation then it can be approximated to the ratio of molar conductivity  c at the
concentration c to limiting molar conductivity,  , Thus we have :
 =  / 
But we known that for a weak electrolyte like acetic acid.
C 2 c 2 c 2
Ka = = =
(1   )  1   /      

 Solubility(s) and KSP of any sparingly soluble salt.

Sparingly soluble salt = Very small solubility
Solubility = molarity = 0
so, solution can be considered to be of zero conc or infinite dilution.
K  1000 K  1000
m, saturated = M = S = KSP = S2
Solubility M0

Ex. 19 If conductivity of water used to make saturated solution of AgCl is found to be 3.1 x 10 –5 –1 cm–1 and
conductance of the solution of AgCl = 4.5 x 10 –5 –1 cm–1
If M0 AgNO3 = 200 –1 cm2 mole–1 , M0 NaNO3 = 310 –1 cm2 mole–1
calculate KSP of AgCl.
Sol. M0 AgCl = 140
Total conductance = 10–5
140  4  105  1000 1.4  10 4
S= =
140 14
S = 5.4 x 10–4
S2 = 1 x 10–8

Ex.20 At infinite dilution the equivalent conductance of Al +3 and SO4–2 ion are 189 and 160 –1 cm–2 eq–1
respectively. calculate the equivalent and molar conductivity at infinite dilute of Al 2(SO4)3.
Electrochemistry

1  1 
Sol. eq[Al2 (SO4 )3 ] =  Al3 +  2
3 2 SO4
1 1
 189 +  160 = 143 –1 cm2 eq–1
3 2
Molar conductivity =  eq  V.F. = 143  6 = 858 –1 cm2 mol–1

Variation of K, m &eq of solutions with Dilution

Kconc. of ions in the solution. In case of both strong and weak electrolytes on dilution the concentration
of ions will decrease hence K will decrease.
m or eq (K  C) strong electrolyte
1000  K
m = (K  K a c ) weak electrol.
normality
1000  K
eq =
normality
K C
For strong electrolyte : m   = constant
C C
K K ac 1
For weak electrolyte : m   
C C C
Battery :
A battery is a an electrochemical cell, a device for interconverting chemical and electrical energy. A
battery takes the energy relased by a spontaneous chemical reaction and uses it to produce electricity.
Primary Batteries : In the primary batteries, the reaction occurs only once and after use over a period
of time battery becomes dead and cannot be reused again. The most familiar example of this type is
the dry cell (known as Leclanche cell after its discoverer) which is used commonly in our transistors and
clocks. All substances used are either pure solids or pure liquids.

T ypes of primary batteries :

(i) Dry cell
Anode : Zn(s)
Cathode : MnO2(s)
Electrolyte : Paste of NH4Cl + ZnCl2 in starch
+ Seal
Graphite (cathode)

MnO2 +C (Depolariser)

Paste of NH4Cl+ZnCl2

–
Zinc anode
Fig. 12.4
Cathode :
MnO2 + NH4+ + e–   MnO(OH) + NH3
(Oxidation state of Mn changes from +4 to +3)
Anode :
Zn   Zn2+ + 2e–

(ii) Mercury cell :

Anode : HgO(s)
Cathode : Zn(Hg)
Electrolyte : Paste of KOH + ZnO
Electrochemistry

Cathode :
Zn(Hg) + 2OH– 
 ZnO(s) + H2O(l) + 2e–
(amalgam)
Anode :
HgO(s) + H2O(l) + 2e– 
 Hg(l) + 2OH–

Secondary Batteries : A secondary cell afer use can be recharged by passing current through it in the
opposite direction so that it can be used again. A good secondary cell can udnergo a large number of
discharing and charging cycles. The most important secondary cell is the lead storage battery
commonly used in automobiles and inverters.
Anode : Pb(s)
Cathode : PbO2(s)
Electrolyte : 38 % Conc. H2SO4 solution Ecell = 2.05 V.
+ –
Glass vessel

PbO2

Pb
dil. H2SO4

Anode : Pb(s)  Pb2+ (aq) + 2e–

Pb2+(aq) + SO42  (aq)  PbSO4(s)
Pb(s) + SO42  (aq) PbSO4 + 2e–
most of the PbSO4(s) ppt sticks to the lead rod.
Cathode :
2e– + 4H+ + PbO2(s)  Pb2+(aq) + 2H2O()
2
Pb2+ SO4 (aq)+(aq)+4H++2e–  PbSO4(s) + 2H2O()
PbSO4(s) sticks to cathode rod.
Overall cell reaction Pb(s) + PbO2(s) + 2H2SO4(aq)  2PbSO4(s) + 2H2O()
During the working of the cell discharge H2SO4 will be consumed so it's concentration in the solution
hence density of the solution will decrease during charging of the cell PbSO 4 will get converted into
Pb(s) and, PbO2(s) and H2SO4 will be produced.
Nickel – cadmium battery.
Ecell = constant as cell reaction has pure solide/liquids only.
Anode : Cd(s)
Cathode : NiO2(s)
Electrolyte : KOH
Cd + 2OH–  Cd(OH)2 + 2e–
2e– + NiO2 + 2H2O  Ni(OH)2(s) + 2OH–
Cd(s) + NiO2(s) + 2H2O()  Cd(OH)2(s) + Ni(OH)2(s)
Electrochemistry

Fuel cells (H2 – O2 cell) : Galvanic cells those are designed to convert the energy of combustion of
fuels like hydrogen, methane, methanol etc. directly into electrical energy are called fuel cells.
H2O
Anode – + Cathode

Porous carbon electrode

OH–
H2 O2
Electrolyte
Fig. 12.6

Anode : H2  2H+ + 2e– x 2

Cathod : 4e– + 4H+ + O2  2H2O
–––––––––––––––––––––––
2H2 + O2  2H2O()
–––––––––––––––––––––––
Fuel cells (CH4 – O2) :

Anode : 2H2O + CH4  CO2 + 8H+ +8 e–

Cathod : 4e– + 4H+ + O2  2H2O
–––––––––––––––––––––––
CH4 + 2O2  CO2 + 2H2O()
Corrosion :
It is a process of deterioration of a metal as a result of its reaction with air or water (environment)
surrounding it.
In case of iron, corrosion is called rusting. Chemically, rust is hydrated form of ferric oxide, Fe2O3 .xH2O
Rusting of iron is generally caused by moisture, carbon dioxide and oxygen present in air.

Mechanism of corrosion :

Oxidation : Fe(s)  Fe2+ (aq) + 2e–

Reduction :
2O2–(g) + 4H+ (aq)  2H2O(I)
Atomospheric oxidation :
2Fe2+(aq) + 2H2O(l) + 1/2O2  Fe2O3(s) + 4H+(aq)

Factors which affect corrosion : The main factors which affect corrosion are
Rate of corrosion  Rectivity of metal
 Presence of impurities.
 Presence of electrolytes.
 temperature (with in a reason able limit)

Corrosion protection : Corrosion of metals can be prevented in many ways. Some commonly used
methods are
 Electrochemistry

(i) By surface coating

(a) By applying, oil, grease, paint or varnish on the surface.
(b) By sacrifical protection; coating/depositing a thin layer of any other metal which does not corrode.
For example, iron surface can be protected from corrosion by depositing a thin layer of zinc, nickel or
chromium on it.
(c) By Galvanization : Prevention of corrosion of iron by Zn coating.
(ii) cathodic protection : (By connecting metal to a more electropositive metal) In presence of the more
electropositive metal, the given metal does not get corroded. For example, iron can be protected from
corrosion by connecting it to a block/plate of zinc or magnesium.
(iii) By forming insoluble phosphate or chromate coating : Metal surfaces are treated with phosphoric
acid to form an insoluble phosphate. Formation of a thin chromate layer also prevents the corrosion of
metals.
(iv) Using anti – rust solutions : Solutions of alkaline phosphates and alkaline chromates are generally
used as anti – rust solutions.

MISCELLANEOUS SOLVED PROBLEMS (MSPs)

1. Calculate the EMF of the cell Mg (s)/Mg2+ (0.2M) || Ag+ (1  10–3 M)/ Ag ; EMg2 /Mg = –2.37 V,

EAg / Ag = +0.80V. What will be the effect on EMF if concentration of Mg 2+ ion is decreased to 0.1 M ?
Sol. The net cell reaction is
Mg(s) + 2Ag+(aq)   2Ag(s) + Mg2+ (aq)
According to Nernst equation,
0.059 [Mg2  ]
Ecell = Ecell + log
n [Ag ]2
0.059 (0.2)
= 0.80 – (–2.37) + log
2 (1  103 )2
= 3.17 + 0.0295  5.3010 = 3.32 V
When, conc of Mg2+ is decreased to 0.1, the new emf is
0.1
Ecell = 3.17 + 0.0295  log = 3.34
(1 103 )2
2. Explain the following.
(i) Rusting of iron becomes rapid in saline water than ordinaryy water.
(ii) Mobility of H+ ions is high through the ice than the liquid water.
(iii) Why does a cell stops working after some time.
Sol. (i) The concenration of electrolyte in saline water is much higher than that in ordinary water. The ions
present in saline water help in rapid flow of current in miniature electrochemical cells set up on the
surface of iron which makes rusting process rapid.
(ii) In ice the water molecules are highely associated giving rise to rigid tetrahedral structure, whereas in
liquid water the H2O molecules are randomly associated and they donot adopt so rigid structure. Due to
proper orientations of water molecules in ice, the movement of H + ions becomes faster as compared to
that in randomly distributed aggregates of H2O molecules in water.
(iii) We know that Ecell = Ecathode – Eanode with the passage of time the concentration of metal ions around
cathode decrease, thereby decreasing the value of E cathode. Similarly, at a anode, the concentration of
metal ions increases causing increases in the value of E anode. As a result the difference Ecathode – Eanode
goes on decreasing and gradually becomes zero. At this stage the flow of current stops and cell
becomes dead.
Electrochemistry

3. Zinc electrode is constituted at 298 K by placing zinc rod in 0.1 M aqueous solution of zinc sulphate
which is 95% dissociated at this concentration. What will be the electrode potential ( EZn2 / Zn ) of the
electrode given that EZn2 / Zn = – 0.76 V
Sol. [ZnSO4] = 0.1 M
% Dissociation = 95%
0.1 95
 [Zn2+] = = 0.095 M
100
The electrode reaction is Zn2+ + 2e–   2n
According to Nernst equation,
0.059 [Zn2  ]
EZn2 / Zn = EZn2 / Zn + log
2 [Zn]
0.059
= – 0.76(V) + log (0.095)  [Zn] = 1
2
= – 0.79 V.

4. The emf of the cell,

Ag/AgCl (saturated sol.) || 0.01 M AgNO3 |Ag at 298 K is 0.169 V. Calculate solubility and solubility
product of AgCl at 298 K.
Sol. The given cell is a concentration cell and can be represented as
Ag/Ag+(C) || Ag+ (0.01 M) /Ag.
The Ecell is given by
0.059 [Ag ]cathode
Ecell = log
1 [Ag ]anode
0.059 0.01
0.169 = log
1 C
0.169
log 0.01 = = 2.864
C 0.059
0.01 = antilog 2.864 = 731.13
C
C = 1.36  10–5 M
or
Thus solubility of AgCl = 1.36  10–5 mol L–1
or 1.36  10–5  142.5 = 1.94  10–3 gL–1
Ksp of AgCl = [Ag+] [Cl–1] = (solubility)2
= (1.36  10–5) = 1.84  10–10 mol2 L–2

5. Consider the reaction given below

Hg2+ + Ag   Ag+ + Hg . Comment on the feasibility of reaction under different concentration of ions
given below.
(i) [Hg2+] = 10–4 M ; [Ag+] = 10–1 M
(ii) [Ag+] = 10–4 M ; [Hg2+] = 10–1 M
Given EAg / Ag = 0.80 V ;

EHg2
/ Hg
= 0.79 V
Sol. The cell reaction is :
Hg2+ + 2 Ag   2Ag2+ + Hg
  
Ecell = Ecathode – Eanode = 0.79 0.80
Case – I
Electrochemistry

 0.059 [Hg2  ]
Ecell = Ecell + log
2 [Ag ]2
 [Ag] and [Hg] = 1

= – 0.01 + 0.0295 log

10 
4

10 
2
1

= – 0.01 – 0.059 = – 0.069 V

since Ecell is –ve, the reaction is no feasible

Case – II

Ecell = – 0.01 + 0.0295 log

10  1

10 
2
4

= – 0.01 + 0.0295  7 = 0.1965 V

Since Ecell is +ve, the reaction is feasible.

 
6. Given that EMn3
/ Mn2
= + 1.51 V; EMn2
/ Mn
= – 1.18 V
 
ECr 3
/ Cr 2
= – 0.41 V ; ECr 2
/ Cr
= – 0.91 V
Which oxidation state (+2 or +3) will be more stable for manganese and chromium as per the data.
Sol. (i) Conversion of Mn3+ to Mn2+ is represented by +ve value of E (1.51 V) but conversion of Mn2+ to Mn
has – ve value of E (–1.18 V). This means that for manganese Mn 2+ is more stable.
(ii) Conversion of Cr3+ to Cr2+ or Cr2+ to Cr both have negative values of E . This means that for
chromium Cr3+ state is more stable.
7. Na-amalgam is prepared by electrolysis of NaCl solution using liquid Hg as cathode. How long should
the current of 10 amp. is passed to produce 10% Na – Hg on a cathode of 10 gm Hg. (atomic mass of
Na = 23).
(A) 7.77 min (B) 9.44 min. (C) 5.24 min. (D) 11.39 min.
Sol. (A)
90 gm Hg has 10 gm Na
10 10
 10 gm Hg = x10 = gm Na
90 9
M ixt
 weight of Na = x
n 96500
10 23 10 x t
= x [ Na+ + e  Na]
9 1 96500
10 x 96500
t= = 7.77 min
9 x10 x 23

8. Calculate the cell EMF in mV for

Pt  H2 (1atm)  HCl (0.01 M)  AgCl(s)  Ag(s) at 298 K
if Gf° values are at 25°C
kJ
– 109.56 for AgCl(s) and
mol
kJ
– 130.79 for (H+ + Cl– ) (aq)
mol
(A) 456 mV (B) 654 mV (C) 546 mV (D) None of these
Sol. (A)
G0cell reaction = 2 (– 130.79) – 2 (– 109.56)
= – 42.46 kJ/mole
Electrochemistry

(for H2 + 2AgCl 
 2Ag + 2H+ + 2Cl–)
42460
 E0cell = = + 0.220 V
2  96500
0.059 1
Now Ecell = + 0.220 + log = 0.456 V = 456 mV.
2 (0.01)4