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C-03:- Redox Reactions & Electrochemistry

Redox Reactions are those in which both oxidation and reduction go hand in hand. There are different concepts of oxidation and
reduction.
1. OXIDATION AND REDUCTION CLASSICAL CONCEPT
1.1 Oxidation is a process, which involves
i) Addition of oxygen

2 Mg +O2 2 MgO

(Oxidation of magnesium)

S +O 2 SO 2

(Oxidation of sulphur)

2CO +O2 2 CO 2

(Oxidation of carbon monoxide)

ii) Removal of hydrogen

H 2 S+Cl 2 2 HCl+S

(Oxidation of hydrogen sulphide)

4 Hl +O2 2 H 2 O+2l 2

(Oxidation of hydrogen iodide)

iii) Addition of an electronegative element

Fe+ S FeS

(Oxidation of iron)

SnCl 2 +Cl2 SnCl 4

(Oxidation of stannous chloride)

iv) Removal o an electronegative element

2 Kl + H 2 O2 2 KOH + I 2

(Oxidation of potassium iodide)

2 K 2 MnO4 + Cl2 2 KCl+2 KMnO 4

(Oxidation of potassium manganate)

A substance, which brings oxidation is known as oxidising agent.


Reduction is just the reverse of oxidation.
1.2 Reduction is a process which involves
i) Removal of oxygen

CuO+C Cu++CO

(Reduction of cupric oxide)

H 2 O+C CO + H 2

(Reduction of water)

ii) Addition of hydrogen

Cl2 + H 2 H 2 S

(Reduction of sulphur)

iii) Removal of an electronegative element

2 HgCl2 + SnCl2 Hg2 Cl2 =SnCl 4

2 FeCl 3+ H 2 FeCl 2+ 2 HCl

(Reduction of mercuric chloride)


(Reduction of ferric chloride)

iv) Addition of an electropositive element

HgCl2+ Hg Hg 2 Cl 2

(Reduction of mercuric chloride)

CuCl2 +Cu Cu 2 Cl 2

(Reduction of cupric chloride)

The substance, which brings reduction is known as reducing agent. A substance, which undergoes oxidaton, acts as a reducing agent
while a substance, which undergoes reduction, acts as an oxidising agent.
1.3 Modern Concept of oxidation and Reduction
According to the modern concept, loss of electrons is oxidation whereas gain of electrons is reduction.

++ e
Na Na

Zn Zn+2 +2 e

Sn+2 Sn+4 +2 e

++2 e

H 2 O2 O2 +2 H

2 S 2 O 32 S 4 O62 +2 e

CN 6 +e
Fe
4
[Fe ( CN )6 ]

+e
MnO42 MnO 4
Example of reduction reactions are

Cl2 +2 e 2Cl

S +2 e S2

++5 e Mn+2 +4 H 2 O
+8 H

MnO4

++2 e 2 H 2 O
H 2 O 2+ 2 H

2. OXIDATION NUMBER (OXIDATION STATE):It is defined as the charge (real or imaginary) which an atom appears to have when it is in combination. In the case of electrovalent
compounds, the oxidation number of an element of radical is the same as the charge on the ion. This is the real charge and is devloped
by the loss and gain of electron or electrons. For example, in the electrovalent compound, sodium choride (NaCl), the charge on
sodium and chlorine is +1 and 1, respectively.
i) The oxidation number (Ox.no) of an atom in free elements is zero, no matter how complicated the molecule is, hydrogen in H 2,
sulphur is S8, phosphorus in P4, oxygen in O2 or O3, al have zero value of oxidation numbers.
ii) Th fluorine, which is the most electronegative element, has oxidation number 1 in all of the its compounds.

iii) Oxidation number of oxygen is 2 in all compounds except in peroxides, superoxides and oxygen fluorides. In peroxides

oxygen has oxidation number 1; in superoxides (O2), oxygen has oxidation number

1 /2 ; and in OF2, the oxygen has an

oxidation number +2.


iv) The oxidation number of hydrogen is +1 in all of its compounds except in metallic hydrides like NaH, BaH 2, etc, hydrogen is in
1oxidation state in these hydrides.
v) The oxidation number of an ion is equal to the electrical charge present on it.
vi) The oxidation number of IA elements (Li, Na, K, Rb, Cs and Fr) is +1 and the oxidation number of IIA elements (Be, Mg, Ca, Sr, Ba
and Ra) is +2
vii) For complex ions, the algebric sum of oxidation numbers of all the atoms is equal to the net charge on the ion.
viii) in the case of neutral molecules, the algebric sum of the oxidation numbers of all the atoms present in the molecule is zero.
What is the oxidation number of Mn in KmnO4 and of S in Na2S2O3?
We know that

Ox . no . of K =+1

Ox . no . of O=2
So

( Ox . no .O ) =0
Ox . no . K +Ox . no . Mn+ 4

Or

+1

+x

+4 (2 )=0

Or

+1

+x

8=0

Or

x=+81=+7

Hence

Ox . no . of MnKMnO 4 is+7.

Similarly for S in

Na 2 S2 O3 , 2 (Ox . no . K ) +2 ( Ox .no . S ) +3 ( Ox . no .O ) =0
2 ( +1 )+ 2+3 (2 )=0 ; =+2

Hence, Ox.no. of S in

Na 2 S2 O3=+2

2.1 Special Examples of Oxidation State Determination


i) Oxidation state of sulphurin Na2S4O6.
From the structure, it is clear that the sulphur atoms acting as donor atoms have +5 oxidation
number (each). On the othr hand, the sulphur atom involved in pure covalent bond information
has zero oxidation number.

CH

Oxidation number of sulphur in

ii)

SO (dimethyl sulphoxide): Here, oxidation

number O = 2, oxidation number of each CH3 group is +1.

+2+ x2=0

Or

x=0

Thus, sulphur lies in zero oxidation state.


iii) Oxidation number of sulphur in perdisulphuric acid H 2S2O8: It may be done only when the structure is drawn.

Oxidation numbr of S = x
Oxidation numbr of H = +1
Oxidation number of oxygen in peroxo linkage = 1
Oxidation number of other six oxygen atoms = 2 each.

+2+ (12 ) +2 x2=0

x=+ 6 ( oxidation number of sulphur )


iv) Oxidation number of sulphur in hypo, Na2S2O3: Let the average oxidation number of sulphur be x.

+2+2 x6=0

Structure of

x=+2

hypo may be drawn as

Here, the
two sulphur atoms have different oxidation states:
i) Oxidation number of donor sulphur atom is +5. It gives up four electrons in co-ordination and one electron in covalent bond formation
with oxygen.
ii) Sulphur, bonded with Na lies in 1 states since one electron of Na lies towards the sulphur. Electrons of SS bond are equally shared
between two sulphur atoms.
Thus +5 and 1 are two oxidation states of the two sulphur atoms.
v) Oxidation number of sulphur in peroxo monosulphuric acid (H2SO4: Let us draw its structure.

Here,
we have to consider ox. no. of H = +1
ox. no. of oxygn in peroxo linkage = 1
ox.no. of rest of oxygen = 2

+2+ x62=0

Or

x=+6

Thus, sulphur in H2SO5 lies in +6 oxidation state.


vi) Fe in its oxides, FeO, Fe2O3 and Fe3O4 :

FeO x 2=0,

x=+2

Fe2 O3 2 x6=0,

x=+3

Fe3 O 4 3 x8=0,

x=+8/3 ( fractional )

vii) Oxidation state of chromium in CrO5: CrO5 has butterfly structure having two peroxo bonds.

Let oxidation state of chromium be x.

x+ 4 (1 ) + (2 )=0, x=+6
viii) Oxidation state of chlorine in bleaching powder
Bleaching powder has two chlorine atoms having different oxidation state.

Ca+2(OCl)

Cl

( hypochloride ion )

(chlorine ion)

Chlorine in
Chlorine in
+1 state
1 state
ix) Fractional values of oxidation numbers are possible as in Na 2S4O6, Fe3O4, N3H, etc.
Na2S4O6
Fe3O4

2 1+4 +6 (2 )=0

3 X + 4 (2 )=0

2+4 x 12=0

3 x8=0

4 x =+ 10
x=

3 x=8

+10
=+ 2.5
4

x=

Oxidation numbr of S is +2.5

Oxidation number of iron is +

N3 H ,

2
3

+2

2
3

3 +1=0

3 x=1,

x=1/3

Oxidation number of S is +2.5

Oxidation number of iron is

N3 H ,

3 x+1=0

3 x=1,
Oxidation number of nitrogen is

+8
1
+2
3
3

x=1/3
1 /3

CN

+
x)
Fe in iron complex NO lies in NO state; thus oxidation statae of Fe may be determined as;
Na 2
+2+ x5+1=0 ; x =+2
xi)

NoClClN =O:Oxidation statae of chlorine=1

Oxidation state of oxygen = 2


Thus, oxidation state of nitrogen = +3
3. BALANCING OF REDOX REACTIONS
3.1 By oxidation number method
In a balanced redox reaction, total increase in oxidation number must be equal to the decrease in oxidation number. This equivalence
provided the basis for balancing redox reactions. This method is applicable to both molecular and ionic equations. The general
procedure involves the following steps.
i) Write the skeleton equation (if not given, frame it) representing the chemical change.
ii) Assign oxidation numbers to the atoms in the equation and find out which atoms are undergoing oxidation and reduction. Write
separate equations for the atoms undegoing oxidation and reduction.
iii) Find the change in oxidation number in each equation. Make the change equal n both the equations by multiplying with suitable
intergers. add both the equation.
iv) Complete the balancing by inspection. First balance those substances which have undergoing change in oxidation number and then
other atoms except hydrogen number and then other atoms except oxygen by putting H2O molecules wherever needed. The final
balanced equation should be checked to ensure that there are as many atoms of each element on the right as there as on the left.
v) in ionic equations the net charges in both sides of the equation must be exacty the same. Use H+ ion/ions in acidic reactions and OH
ion/ions in basic reactions to balance the carge and number of hydrogen and oxygen atoms.
Example
i) Balance the following equation by oxidation number method.

NO

Cu
Cu+ HNO3

Writing the oxidation numbers of a the atoms

0
+2+52
NO

Cu+ +1+52 Cu
HNO3

Change in ox. no. has occurred in copper and nitrogen.

Increase in ox. no. of copper = 2 units per molecules Cu


Decreases in ox. no. of nitrogen = 1unit per molecules

HNO3

To make increase and decrease equa, eq. (ii) is multiplied by 2.

NO

Cu
Cu+ 2 NHO 3

Balancing nitrate ions, hydrogen and oxygen, the following equation is obtained.

Cu+ 4 HNO3 Cu NO3 2 +2 NO 2 +2 H 2 O

This is balanced equaion.


ii) Balance the following equation by oxidation number method.

SO

SO

K 2 Cr 2 O7 + FeSO 4 + H 2 SO 4=Cr 2
Writing oxidation numbers of all the atoms.
Change in ox no. has occurred in chromium and iron.

Decrease in ox.no. of Cr per molecule

( 2 62 3 )=6 units

Increase in ox. no. of Fe per molecule = 1 unit


Hence, eq. (i) should be multipied by 6.

SO

SO

K 2 Cr 2 O7 + 6 FeSO 4 Cr2

To balance sulphate ions and potassium ions, 7 molecules of

H 2 SO 4 are needed.

SO

SO

K 2 Cr 2 O7 + 6 FeSO 4 +7 H 2 SO 4 Cr 2
To balance hydrogen and oxygen,

7 H 2 O should be added on R.H.S. Hence, balanced equation is,

SO

SO

K 2 Cr 2 O7 + 6 FeSO 4 7 H 2 SO 4 Cr 2
3.2 By Ion-electron method
3.2.1 Write down the redox reaction in ionic from.
3.2.2 Split the redox reaction into two half reactions, one for oxidation and the other for reduction.
3.2.3 Balance each half reaction for the number of atoms of each element. For the purpose.
i) Balance the atoms other than H and O for each half reaction using simple multiples.
ii) Add water molecules to the side deficient in oxygenand H+ to the side dificient in hydrogen. This is done in acidic or neutral soutions.
iii) In alkaline solution, for each excess of oxygen, add one water molecule to the same side and two OH ions to the other side. If
hydrogen is still unbalanced, add one OH ion for each excess hydrogen on the same side and one water molecule to the other side.
3.2.4 Add electrons to the side deficient in electrons as to equalise the charge on both sides.
3.2.5 Multiply one or both the half reactions by a suitable number so that the number of electrons become equal in both the equations.
3.2.6 Add the two balanced half reactions and cancel any term common to both sides.

2++CO 2+ H 2 O
+ Mn
2+ H
+C 2 O4
MnO4
Splitting into two half reactions.

2 2 CO 2
2++ H 2 O; C 2 O4
+ Mn
+ H
MnO4

Balanced as in question(a),

2 2 CO 2+2 e
2++4 H 2 O ; C2 O4
++5 e Mn
+8 H
MnO 4

Balanced electrons in both half reactions.

MnO

2++ 4 H 2 O
C

2 2CO 2 +2 e
5
++5 e Mn ;
2

Adding both the half reactions,

2++10 CO2 +8 H 2 O
2 2 Mn
++5 C2 O4
+ 16 H
2 MnO4
+ H 2 O
+l
lO3
l 2+ OH

First step. Splitting into two half reactions.

+ H 2 O ; l 2 l

l O3

l 2 +OH

(Oxidation half reaction)


Second step. Adding

(Reductionhalf reaction)

OH ions,

+6 H 2 O

2l O 3
l 2 +12 OH
Third step. Adding electrons to the sides deficient in electrons.

+ 6 H 2 O+10 e ; l 2 +2 e 2l

2 l O 3

l 2 +12OH

Fourth step. Balancing electrons in both the half reactions.

2l
5
+ 6 H 2 O+10 e ;
2l O3
l 2 + 12OH

Fifth step. Adding both the half reactions.

+6 H 2 O
+10 l
2l O 3
6 l 2+ 12OH

+ 3 H 2 O
+5 l
Dividing by 2. lO 3
3 l 2+ 6 OH
3.3 Disproportion and Oxidation-Reduction
One and the same substance may act simultaneously as an oxidising agnt and as a reducing agnt with the result that a part of it gets
oxidised to a higher state and rest of it is reduced to lower statae of oxidation. Such a reaction, in which a substance undergos
simultaneous oxidation and reduction and reduction is called disproportionation and the substance is said to diproportionate.

4. ELECTRICAL CONDUCTORS
Substances which allow the passag of electric currnt through them are called electrical conductors. Those which do not allow the
flow of electric current through them ar termed insulators. Electric conductors are of two types:
i) Metallic or electronic conductors: Conductors which transfr electric current by transfer of electrons, without transfer of any matter,
are known as metallic or electronic conductors. Metals such as copper, silver, aluminium, etc., non-metals like carbon (graphit) and
various alloys belong to this class.
ii) Electrolytic conductors: Conductors like aqueous solutions of acids, bases and salts in which the flow of electric current is
assompanied by chemical decomposition are known as electrolytic conductors. The substances whose aqueous solutions allow the
passage of electric current and are chemically decomposed, are termed electrolytes.

The substances whose aqueous do not conduct electric current are called non-electrolytes. Solutions of cane sugar, glycerine, alcohol,
etc. are examples of non-electrolytes.
5. ELECTROLYSIS
The process of chemical decomposition of an electrolyte by passage of electric current through its solution is called electrolysis. The
device in which electrolysis is carried out by using electricity or in which conversion of electric energy into chemical change is done is
known as electrolytic cell. An electrolytic cell consists of a vessel for the electrolytic solution or fused electrolyte and two metallic
electrodes immersed in the reaction material which are connected to a source of electric current. The metallic electrodes, which do not
react with ions or final products are called inert electrodes.
6. FARADAYS LAWS OF ELECTROLYSIS
6.1 Faradays First Law: The amount of substance depositd is proportional to the quality 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
relatoion:

W Q

A coulomb is the quality of charge when a current of one ampere is passed for one second. Thus, amount of charge in coulombs.

Q=current ampere timesecond=l t

So

W l t

Or

W =Z l t

Where Z is a constant, known as electro-chemica equivalent, and is a characteristic of the substance deposited. When =1 ampere, t
= 1 sec then W =Z
Thus, electrochemical equivalent can be defined as the mass of the substance deposited by one coulombs of charge or by one ampere
of current for one second.
6.2 Faradays Second Law: When the same quantity of charge is passed through different electrolytes, then the masses of different
substances deposited at the respective electrodes will be in the ratio of their equivalent masses.
The law can be illustrated by passing same quantity of electric current through three voltameters contianing solutions of

H 2 SO 4 , CuSO4 and AgNO 3 respectively.


Mass of hydrogen Equivalent mass of hydrogen
=
Mass of copper
Equivalent mass of copper
Or

Mass of copper Equivalent mass of copper


=
Mass of silver
Equivalent mass of silver

Or

Mass of silver
Equivalent mass of silver
=
Mass of hydrogen Equivalnt mass of hydrogen

96500 colomb of electric charge will deposit one g equivalent of any subtance, 96500 coulomb is termed as one Faraday and is denoted
by F.
Again according to first law,

W =Z Q

When

Q=96500 coulomb ,W becomes gram equivalent mass ( E ) .

Thus,

E=Z 96500

Or

Z=

Z E
E
; 1= 1
96500 Z 2 E2

6.3 Faradays law for gaseous electrolytic product


For the gases, we use

V=
Where,

ItV e
96500

V =volume of gas evolved at S .T . P . at an electrode

V e =Equivalent volume
volume of gas evolved at an electrode at STP by 1 Faraday charge
6.4 Applications of Electrolysis
i) Determination of equivalent masses of elements:

W A Equivalent mass of A
=
W B Equivalent mass of B

ii) Electrometallurgy: The metals like sodium, potassium, magnesium, calcium, aluminium, etc, are obtained by electrolysis of fused
electrolysis.
Fused electrolyte

Metal isolated

NaCl+CaCl2 + KF

Na

CaCl2 +CaF 2

Ca

Al 2 O3+ cryolite

Al

MgCl 2 ( 35 )+ NaCl ( 50 )+ CaCl2 (15 )

Mg

NaOH

Na

KCl+CaCl2

iii) Manufacture of non-metals: Non-metals like hydrogen, fluorine, chlorine are obtained by electrolysis.
iv) Electro-refining of metals : The metals like copper, silver, gold, aluminium, tin, etc, are refined by electrolysis.
v) Manufacture of compounds : Compounds like NaOH, KOH, Na2Co3,

KClO3 , white lead, KMnO 4 , etc, ar manufactured

by electrolysis.
vi) Electroplating: The process of coating an inferior metal with a superior metal by electrolysis is known as electroplating.
The aims of electroplating are:
i) To prevent th inferior metal from corrosion.
ii) To mak it more attractive in appearance.
6.5 Thickness of coatd layer
Let the dimesnsions of metal sheet to be coat by

( a cm b cm ) .

Thickness of coated layer = c cm

( a b c )cm3

Volume of coate layer

Mass of the deposited substance

( a b c ) d =

Volume density =(a b c) d

l t E
96500

Using abov relation we may calculate the thickness of coated layr. If radius of atom of depositd metal is given instead of density, e.g.,
Radius of silver atom
Atomic mass of Ag

108 cm
108

Mass of single silver atom

108
g
23
6.023 10

8 3

10 cm
4
Volume of single atom R3= 4 3.14
3
3
108 3

4
3.14
3
Mass of single atom
108/6.023 10 23
Density of Ag=
=

VOlume of single atom


6.6 Current efficiency: % current efficiency

i)
ii)

Actual current
100
Ammeter current

7. ARRHENIUS THEORY OF ELECTROLYTIC DISSOCIATION


The main points of the theory are:
An electrolyte, when dissolved in water, breaks up into two types of charged particles, one carrying a positive charg and the othr a
negative charge. Positively chargd ions are termed cations and negatively charged as anions.
The process of splitting of the molecules into ions of an electrolyte is called ionisation. The fraction of the total number of molecules
present in solution as ions is known as degree of ionisation or degree of dissociation. It is denoted by a

a=

Number of molecules dissociated into ions


Total number of molecules

iii) Ions present in solution constantly re-unite to form neutral moecules and, thus, there is a state of dynamic equilibrium betweeen the
ionised and non-ionised molecules, i.e.,

++ B
AB A

Applying the law of mass action to above equilibrium

+
A

K is known as ionisation constant. The electrolytes having high value of K are termed strong electrolytes and those haivng low value
of K as weak electrolytes.
iv) When an electric current is passed through the electrolytic solution, the positive ions (cations) move towards cathode and the
negative ions (anions) move towards anode and get discharged, i.e., electroysis occurs. The ions are discharged always in equivalnt
amounts, no mattr what their relative speeds are.
v) The electrolytic solution is always neutra in nature as the total charge on one set of ions is always equal to the total charge on the
other set of ions.
vi) The properties of electrolysis in solution are the properties of ions present in solution.
vii) The ions act like molecules towards depressing the freezing point, elevating the boiling point, lowering the vapour pressure and
establishing the osmotic pressure.
viii) The conductivity of the electrolytic solution depends on the nature and number of ions as the current is carried through solution by
movement of ions.
8. ELECTROLYTIC CONDUCTANCE
8.1 Conductance: The conductanc is the property of the conductor (metallic as well as electrrolytic) which facilitates the flow of
electricity through it. It is equal to the reciprocal of resistance, i.e.,

Conductance=

1
1
=
Resistance R

ohm
(1mho)
It is expressed in the unit called reciprocal ohm
or siemens.

8.2 Specific conductance or conductivity: The resistance of any conductor varies directly as its length (l) and inversely as its crosssectional area (a), i.e.,

l
l
R R= p
a
a

Where
If

is called the specific resistnce.

l=1 cma=1 cm 2 , then R=

The specific resistance is, thus, defined as the resistance of one centimetre cube of a conductance of one centimetre cube of a
conductor.
It is denoted by the symbol k. Thus,

1
k = , k=kappathe specific conductance

Specific conductance is also called conductivity.


From equation (ii), we have

a
p= . R
l

or

1 l 1
= .
a R

or

l
k = C
a

( al =ce ll cons tan t )


or specific conductance = Conductance

Cell constant

In the case of electrolytic solutions, the specific


conductance is defined as the conductance of a
solution of definite dilution enclosed in a cell
having two electrodes of unit area separated by
one centimetre apart.
The unit of specific conductance if

ohm1 cm1

8.3 Equivalent conductance:- One of the factors on which the conductance of an electrolytic solution depends is the concentration of
the solution. In order to obtain comparable results for different electrolytes, it is necessary to take equivalent conductances.
Equivalent conductance is defined as the conductance of al the ions produced by one gram equivalent of an electroyte in a given
solution. It is denoted by

=k V
Where V is the volume in mL containing 1 g equivalent of the electrolyte.
In case, if the concentration of the solution is given e.g. equivalent per litre, then the volume containing 1 g equivalent of the
electrolyte will be 1000/c.
So equivalent conductance.

=k

1000
N

Where N = normality

The unit of equivalent conductance is

2 1

ohm cm

8.4 Molar conductance: The molar conductance is defined as the conductance of all the ions produced by ionisation of 1 g mole of an
electrolyte when present in V mL of solution. It is denoted by
Molar conductance

=k V

Where V is the volume in mL containing 1 g mole of the electrolyte. If c is the concentration of the solution in g mole per litre, then

=k

1000
where M is molarity .
M

Its units are

ohm1 cm2 mol1

Equivalent conductance=
where n=

Molar conductance
n

Molecular mass
Equivalent mass

8.5 Measurement of conductance: When the solution of an electrolyte is taken between two parallel electrodes of cross-sectional area
a and l cm apart, then the specific conductance, k, should be.

l 1
k= .
a R

Thus, knowing the values of R, l and a, th specific conductance can be measured. The resistance of the solution between two parallel
electrodes is determined by using Wheatstone bridge method. The diagram of the apparatus is shown in figure. AB is a uniform wire
and X is a sliding contact, which moves over it. C is the conductivity cell containing the solution of the electrolyte and S represents the
source o alternating current. R is the resistance box and T is a headphone to defect the flow of current. A suitable resistanc is taken out
from the resistance box and the sliding contact X is moved on the wire to search a point of minimum sound in the headphone. At this
point the bridge is balanced.

Resistance
Resistance of solution
Resistance XB Length XB
resistance box =
=

Resistance XA Length XA
The solution whose conductance is to be measured is taken in a special type of cell known as conductivity cell. The electrodes consist
of platinum discs coated with finely divided patinum black and welded to platinum wires fused in two glass tubes. The glass tubes
contain mercury and are firmly fixed in the cover of cells.
Contact with the platinum is made by dipping the copper wires of the circuit in the mercury contained in the tubes. As the conductivity
cahnges with temperature, the cell is usually placed in a constant temperature bath during the experiment. Cells with long paths are
used for concentrated solutions and cells with short paths and large electrodes are used for dilute solutions.

8.6 CELL CONSTANT: The resistance of cell, i.e., conductance is measured when filed with a standard solution (say N/10 KCl
solution) at a given temperature. The standard values of specific conductance of KCl solutions of various concentration at different
temperatures are known. Thus, the cell constant is calculated by using the above equation. The sam cel constant applies to a
measurement with any other solution.
The determination of specific conductance of an electrolytic solution, thus, consists of two steps:
i) Determination of cell constant by using a standard KCl solution of known concentration in the conductivity cell.
ii) Determination of resistance of the given solution using the same cell. The reciprocal this gives the value of conductance.
Multiplication of conductance and cell constant gives the value of specific conductance of the solution.
9. EFFECT OF DILUTION ON EQUIVALENT CONDUCTANCE
The value of equivalent conductance increase with diution. This is due to the fact that degree of ionisation increases with dilution
thereby increasing the total number of ions in solution. Solution which contains large number of ions compared to another solution of
the same concentration at the same temperature has more conductance and is aid to be stronger electrolyte. The one which has
relatively small number of ions is called a weak electrolyte. The number of ions from an electrolyte depends on the degree of
dissociation. The curve shows the variation of the equivalent conductance of some electrolytes with dilution. It shows that electrolytes
behave in two ways on dilution.
i) Electrolytes like KCl have high value of conductance even at low concentration and there is no rapid increase in their equivalent
conductance on dilution. Such electrolytes are termed strong electrolyte. In the case of strong electrolytes, there is a tendency for
equivalent conductance to approach a limiting value when the concentration approaches zero. When the whole of the electrolyte has
ionised, further addition of the water does not bring any change in the value of equivalent conductance. This stage is caleld infinite
diution. The equivalent conductance has a limiting value at infinite dilution and is represent by

,.

ii) Electrolytes like acetic acid have a low value at high concentraion and there is a rapid increase in the value of equivalent conductance
with dilution. Such electroytes are termed weak electrolyts. There is no indication that a limiting value of equivalent conductance can
be attained even when the concentration approaches zero. Thus, graphicay,

, of weak electrolytes cannot be obtained.

It is thus concluded that equivalent conductance of electrolytes whether strong or weak increases with dilution and reaches to a
maximum or limiting value which is termed

, (equivalent conductance at infinite diution).

, in the case of strong

electrolytes can be obtained by extrapolation of the graph of equivalent conductance to zero concentration but in the case o weak
electrolytes it connot be obtained accurately. An indirect method for obtaining

, or weak electrolytes has been given by

Kohlrausch.
10. KOHLRAUSCHS LAW
An 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, anions and cations. Thus,

'

=x c + y a

c and a are called the ionic conductances of cation and anion at infinite dilution respectively. The ionic conductances

The

are proportional to their ionic mobilities. Thus, at infinite dilution.

c =kuc

a =ku a

and

i) Degree of dissociation

a=

Equivalent conductance at a given concentration


=

Equivalent conductance at infinite diution

ii) Calculation of absolute ionic mobilities: It has been experimentally found that ionic conductance is directly proportional to ionic
mobilities.

+
u

Where

and

+u.
are ionic mobilities of cations and anions.
u

+ where F =Faraday ,
+ =Fu

Fu=96500 coulomb

iii) Relation between equivalent and molar conductance at infinite dilution

iv) Molar conductance at infinite dilution

11. PREFERENTIAL DISCHARGE THEORY


If an electrolytic solution consists of more than two ions and the electolysis is done, it is observed that all the ions are not discharged
at the electrodes simultaneously but certain ions are liberated at the electrodes in preference to others. This is explained by preferential
discgarge theory. It states that if more than one type of ions are attracted towards a particular electrode, then the one discharged is the
ion which requires least energy. The potential at which the ion is discharged or deposited on the appropriate electrode is termed the
discharge or deposition potential. The values of discharge potential are different for different ions. For example, the discharge
potential H+ ions is lower than Na+ ions when platinum or most of the other metals are used as cathodes. Simiary, discharge potential
of Cl ions is lower than the of OHions.
11.1 Products of electrolysis: In case two or more types of positive and negative ions are present in solution, during electrolysis certain
ions are discharged or liberates at the electrodes in preference to others. In general, in such competition the ion, which is stronger
oxidising agent (high value of standard reduction potential) is discharged first at the cathode. The increasing order of deposition of few
cations is:

3+

+ ,

Au
Increasing order of deposition
2+ , Ag
+ , Cu
2+ , H

2+ , Fe

3+ , Zn
2+ , Al
2+ , Mg
+ , Ca

+ , Na

Similary, the anion, which is stronger reducing agent (low value of standard reduction potential) is liberates first at the anode.
The increasing order of discharge of few anions in

l
Increasingorder of discharge
, Br
, Cl
,OH
2 , NO 3

SO 4

+
, H

+
+ ,Cl
Thus, when an aqueous soution of NaCl containing
and OH
ions is electroysed, H
ions are discharged at

+ , Ca
Na
cathode and

H 2 is liberated at cathode and chlorine at anode.


Cl ions at the anode, i.e.,

When an aqueous soution of

cathode and

OH

CuSO 4

+
2 , H
2

containing 2+ , SO 4
and Ohions is electrolysed, Cu ions are discharged at

Cu

ions at the anode.

Cu ( Cathodic reaction )
2++ 2e
Cu
( Anodic reaction )

O2+2 H 2 O+ 4 e

4 OH
Cu is deposited on cathode while

O2 is liberated at anode.

This can be expained by some examples given below

i) Electrolysis of sodium chloride soution: The solution of sodium chloride besides Na+ and Cl ions possesses H+ and OH ions due to
ionisation of water. However, the number is smal as water is a weak electrolyte. When potential difference is established across the
two electrodes, Na+ and H+ ions move towards cathode and Cl and OH ions move towards anode. At cathode H+ ions are discharged
in preference to Na+ ions as the discharge potential of H+ ions are discharged in preference to Na+ ions as the discharge potential of

H ions is lower than Na+ ions. Similarly at anode, Cl ions are discharged in preference to OH ions.

++Cl
NaCl Na

++OH
H2O H
At cathode

At anode

+ +e
H

Cl+ e
Cl
2Cl Cl 2

2 H H2

Thus, Na+ and OH ions remain in solution and the solution when evaporated yields crystals of sodium hydroxide.
ii) Electrolysis of copper sulphate solution using platinum electrodes:

CuSO 4 Cu+2+ SO 42

++OH
H2O H
At cathode

At anode

H 2 O+O+2 e
2OH

Cu
Cu +2+2 e

O+O O2
Copper is discharged at cathode as Cu+2 ions have lower discharge potential than H+ ions. OH ions are discharged at anode as these
have lower discharge potential than

SO 4

ions. Thus, copper is deposited at cathode and oxygen gas is evolved at anode.

iii) Electrolysis of sodium suphat solution using inert electrodes

Na2 SO 4 Cu+2+ SO 4+2


++ OH

H2O H
At cathode

+ +e
H

2 H H2

At anode

H 2 O
+O+2e
2OH
O+O O2

Hydrogen is discharg at cathode as

H ions have lower discharge potential than Na+ ions. OH ions are discharged at anode

as these have lower discharge potential than

SO 4

ions. Thus, hydrogen is evolved at cathode and oxygen is evolvd at anode,

i.e., the net reaction describes the elecroysis of water. The ions of

Na 2 SO 4 conduct the current through the solution and take no

part in the overall chemical reaction.


The decreasing order of discharge potential or the increasing order of deposition of some of the ions is given below

+
+ , Cu , Hg +2 , Ag
+2
+2
+3
+2

For cations : + , Ca , Mg , AL , Zn , H
+ , Na
K
+2

,
, Br
, Cl
For anions :
, OH
SO 42 , NO3
iv) Electrolysis of copper sulphate solution using copper electrodes

CuSO 4 Cu+2 + SO 42
At cathode, copper is deposited.

Cu
Cu +2+2 e

At anode, the copper of the electrode is oxidised to

Cu

+2

ions or

SO 42 ions dissolve equivalent amount of copper of the

anode.

+2

or
Cu+
SO
CuSO
Cu Cu 2 e
4
4 +2 e

Thus, duing electrolysis, copper is transferred from anode to cathode.


v) Electrolysis of silver nitrate solution using silver electrodes

++ NO 3

AgNO 3 Ag

At cathode, silver is deposited.

Ag

++ e
Ag

At anode, the silver of the electrode is oxidised to


amount of silver of the electrode.

++ e
Ag Ag


+
Ag ions which go into the solution or NO3 ions dissolve equivalent


AgNO 3 +e
Ag+ NO3
Some more example of electrolysis

Electrolyte

CuCl2
Aqueous acidified
solution

Electrode
Pt
Pt

Cathodic reaction

Hg

Pb
Pb+2+2 e

PbBr2
Molten

Cu
Cu +2+2 e

Pt
Sodium chloride solution
Siver nitrate solution
Sodium nitrate solution

Pt

2 Na

++ 2 e

2 Na

Ag
++ e
Ag

H 2
++2 e
2 H

Anodic reaction

Cl2 +2 e
2Cl

Br 2 +2 e
2 Br

Cl2 +2 e

2Cl

1
O2+ H 2 O+2 e
2
2 OH

O2+ H 2 O2 e
2
2OH

11.2 Theory of weak Electrolytes


i) Weak electrolytes are not completely ionized when dissolved in polar medium like water. There exists equilibrium between ions and
unionised molecules.


++ B
AB A

ii) Concept of chemical equilibrium and law of mass action can be appled to ionic equilibrium also.

++ B
AB A

t=0 C 0 0
t eq CC a C a C a
+
A

K=

For weak electrolytes,

a1

(1 ) 1
Thus equation (i) can be written as

K=C 2 =

K
C

12. ELECTROCHEMICAL CELL


Electrochemica cell is a device in which tow electrodes are fitted in the same electrolyte or in two different electrolytes, which are
joined by a salt bridge and is used to convert chemical energy to electrical energy.
Electricity can be obtained with the help of oxidation and reduction reaction. The chemical reaction responsible for production of
electricity takes place in two separate components. Each compartment consists of a suitable electrolyte solution and a metallic
conductor. The metallic conductor acts as an electrode. The compartments containing the electrode and the soution of the electrolytes
are called half-cells. When the two compartments are connected by a salt bridge and electrodes are joined by a wire through
galvanometr the electricity begins to flow. This is the simple form of voltaic cell.
It is designed to make use of the spontaneous redox reaction between zinc and cupric ions to produce an electric current (fig.).

It consists of two
The half-cel on
electrode dipped in

half-cells. The half cells.


the left contains a zinc metal

ZnSO 4 solution. The half-cell on the right consists of copper metal electrode in a soution of CuSO 4 . The

half-cells are joined by a salt bridge that prevents the mechanical mixing of the soution.
When the zinc and copper electrodes are hoined by a wire, the following observations are made.
i) There is a flow of electric current through the external circuit.
ii) The zinc rod loses its mass while the copper rod gains in mass
iii) The concentration of

ZnSO 4 solution increases while the concentration of copper sulphate solution decreases.

iv) The solutions in both the compartments remain electrically neutral. During the passage of electric current through external, electrons
flow form the zinc electrode to the copper electrode. At the zinc electrode, the zinc metal is oxidised to zinc ions which go into the
solution. The electrons released at the electrode travl through the external circuit to the copper electrode where they are used in the
reduction of Cu2+ metallic copper which is deposited on the electrode. Thus, the overall redox reaction is:

2+ ( aq )

2+ ( aq ) Cu ( s ) + Zn
Zn ( s ) +Cu
Thus, indirect redox reaction leads to the production of electrical energy. At the zinc rod, oxidation occurs. It is the anode of the cell
and is negatively charged while at copper electrode, reduction takes place; it is the cathode of the cell and is positively charged. Thus,
the above points can be summed up as:
i) Voltaic or Galvanic cell consists of two half-cells. The reactions occuring in half-cell reactions. The half-cell in which oxidation occurs
is called oxidation half-cel and the reaction taking place in it is called oxidation half-cell reaction. Similarly, the half-cell and the
reaction taking place in it is called reducation half cell reaction.
ii) The electrode where oxidation occurs is caleld anode and the electrode where reduction occurs is termed cathode
iii) Electrons flow from anode to cathode in the external circuit
iv) Chemical energy is converted into electrical energy
v) The net reaction is the sum of two half-cell reactions. The reaction in Daniel cell can be represented as

Oxidation half reaction


Net reaction
2+ ( aq ) +Cu ( s )
2+ ( aq ) +2 e Zn ( S ) Zn Reductionhalf reaction Cu2 + ( aq)+2 e Cu(S)
2+ ( aq ) Zn Electrode signs Zn ( S ) +Cu

The signs of the anoe and cathode in the voltaic or galvanic cels are oposite to those in the electrolytic cells.

12.1 Difference in electroytic cell and galvanic cell

Galvanic cell
Chemical energy is converted into
electrical energy
ii
Anode positive electrode, cathode negative electrode
Anode negative electrode, cathode positive
electrode.
iii
Ions are discharged on both the electrodes
Ions are discharged only on the cathode
i
If the electrodes are inert concentration of the electrolyte decreases when the Concentration of the anodic half-cell
electric current is circulated
increases while that of cathodic half-cell
decreases when these two electrodes are
joined by a wire.
v
Both the electrodes can be fitted in the same compartment
The electrodes are fitted in different
compartments.
12.2 Salt bridge and its significance: Salt bridge is usually an inverted U-tube filled with concentrated solution of inert electrolytes. An
inert electrolyte is one whose ions are neither involved in any electrochemical change nor do they react chemically with the
electrolytes in the two half-cells. Generally salts lke KCl, KNO3, NH4NO3, etc., are used. For the preparation of salts bridge, gelatine
or agar-agar is dissolved in a hot concentrated aqueous solution of an inert electrolyte and the solution thus formed is filled in the Utube. On cooling the solution sets in the form of a gel in the U-tube. The ends of the U-tube are plugged with cotton wool as to
minimise diffusion effects.
12.3 Significance of salt bridge: The following are the functions of the salt bridge.
i) It connects the of two half-cells and completes the cell circuit.
ii) If prevents transference of diffusion of the solutions from one half-cel to the other.
iii) It keeps the solutions in two half-cells electrically neutral.
iv) It prevents liquid-liquid junction-potential. i.e the potential differnece which arises between two solutions when in contance with
each other.
i

Electrolytic cell
Electrical energy is converted into chemical energy

12.4 Representation of an electrochemical cell


i) The anode (negative electrode) is written on the left hand side and cathode (positive electrode) on the right hand side.
ii) A vertical line or semicolon (;) indicates a contact between two phases. The anode of the cell is represented by writing metal first and
then the metal ion present in the electrolytic solution. Both are separated by a vertical line or a semicolon. For example,

2+

2+Zn ; Zn

ZnZn

The molar concentration or activity of the solution is written in brackets after the formula of the ion. For example,

2+ ( 1 M )Zn

Zn

2+ (0.1 M)
Zn

iii) The cathode of the cell is represented by writing the cation of the electrolyte first and then metal. Both are separated by a vertical line
or semicolon. For example,

2+(1 M )Cu
2+ ; CuCu
2+ CuCu
Cu
iv) The salt bridge which separates the two half-cells is indicated by two parallel vertical lines.
The Daniel cell can be represented as

Zn /ZnSO 4 (aq ) CuSO 4 (aq) lCu


Anode Salt bridge Cathode
Oxidation half-cell Reduction half-cell

2+ Cu
2+ Cu
ZnZn

2+ (1 M )Cu
2+(1 M )Cu
ZnZn
13. ELECTRODE POTENTIAL
When a metal is placed in a soution o fits ions, the metal acquires either a positive or negative charge with respect to the solution. On
account of this, a definite potential difference is developed between the metal and the solution. This potential difference is called
electrode potential.

n++ ne

MM

Depending upon one the nature of the metal electrode to lose or gain electrons, the electrodes potential may be of two types:
i) Oxidation potential: When electrode is negatively charged with respect to solution. i.e it acats as anode, oxidation occurs

n+ ne
M M

ii)Reduction potential: When electrode is positively cahrged with respect to soution i.e., it acts as cathode reduction occurs.

n++ ne

iii) It is not possible to measure the absolute value of the single electrode potential directly. Only the difference in potential between two
electrode can be measured experimentally. It is, therefore, necessary to couple the elctrode with another electrode whose potential is
known. this electrode is termed as reference electrode. The em o the resulting cell is measured experimentally. The emf of the cell is
equal to the sum of potentials on the two electrodes.

Em of the cell=E Anode + Ecathode

= oxidation potential of anode + Reduction potential of cathode


Knowning the value of reference electrode, the value of other electrode can be determined.
13.1 Standard electrode potential. : The potential diffrence developed between metal electrode and the solution of its ions of unit
molarity (1M) at

250 C (298 K) is called standard electrode potential.

Standard reduction potential = (Standard oxidation potential)


or Standard oxidation potential = (Standard reduction potential)
13.2 Reference electrode (Standard hydrogen electrode, SHE or NHE): Hydrogen electrode is the primary standard electrode. It
consists of a small platinum strip coated with platinum as to adsorb hydrogen gas. A platinum wire is welded to the platinum strip and
sealed in a glass tube as to make contact with the outer circuit through mercury. The palatinum and glass tube is surrounded by an
outer glass tube which has an inlet for hydrogen gas at the top and a number of holes at the base for the escape of excess of hydrogen
gas. The platinum strip is placed in an acid solution which ahs H+ ions concentration I M. Pure hydrogen gas is circulated at one

atmospheric pressure. A part of the gas is adsorbed and the rest escapes through holes. This gives an equilibrium between the adsorbed
hydrogen and hydrogen ions in the solution.


++2 e
H2 2 H

The temperature of the cell is maintained at


assigned a potential of xactly
electrode.
SHE half reaction

++2 e
H2 2 H

H 2
++2 e
2 H

250 C . By international agreemnt the standard hydrogen electrode is arbitrarily

0.000 volt . The hydrogen can act as cathode or anode with respect to other
Electrode potential
0.0 V (anode)

0.0 V (Cathode)

13.3 Measurement of Electrode Potentia: The measurement of electrode potential of a given electrode is made by constituting a
voltaic cell by conncecting it with standard hydrogen electrode (SHE) through a salt bridge. I M soution is used in hydrogen half-cell
and the temperature is maintained at 250C.
The emf of the cell is measured either by a
calibrated potentiometer or by a high resistance
voltmeter, i.e. a value voltmeter. The reading of
the voltmeter gives the electrode potential of the
electrode in question with respect to the
hydrogen electrode.
The standard electrode potential of a metal may
be determined as it is the potentia difference in
volt developed in a cell consisting of two
electrodes; the pure metal is contace with a
molar solution of one of its ions and the standard hydrogen electrode.
For this electrode the emf of the cell is 0.76 volt

cell E0Anode + E0Cathode


0.76=E0Anode+ 0.76 V
E0Anode is the standard oxidation potential of zinc. This potential is given the positive sign.
2+
Zn /Zn =0.76+ volt
E oox

Zn

2+/
Zn
So standard reduction potential of Zn, i.e.

E0
13.4 EMF of a Galvanic Cell: Every galvanic or voltaic cell is made up of two hal-cells the oxidation

half cell cathode. The

potentials of these half-cells are always different. On account of this difference in electrode potentials, the electric current moves from
the electrode at higher potential to the electrode at lower potential, i.e, from cathode to anode. The direction of the flow of electrons is
from anode to cathode.
The difference in potentials of the two half-cells is known as the electromotive force (emf) of the cell or cell potential.

i) When oxidation potential of anode and reduction potential of cathode are taken into account:

Ecello =oxidation potential of anode+ Reduction potential of cathode=Eox o ( anode ) + E o ( cathode )


ii) When reduction potentials of both electrodes are taken into account

Ecell

=Reduction potentials of cathodeReduction potential of anode=E ocathode E0 Anode =E onght Eo

iii) When oxidation potentials of both electrodes are take into account :

Eocell =Oxidation potntial of anodeOxidation potential of cathode=Eoox ( anode )E oox ( cathode )


13.5 Difference between emf and potential difference

2.

EMF
It is the potential difference beteen two electrodes when
no current is flowing in the circuit.
It is the maximum voltage that the cell can deliver.

3.

It is resonsible for the steady flow of currrent in the cell.

1.

POTENTIAL DIFFERENCE
It is the difference of the electrode potentials of the two
electrodes when the cell is under operation
It is always less than the maximum value of voltage which the
cell can deliver.
It is not responsibel for the steady flow of current in the cell.

13.6 Some other reference Electrodes: Since standard hydrogen electrodes is difficult to prepare and maintain, it is usually replaced by
other reference electrodes. Which are known as secondary reference electrodes. These are convenient to handle and are prepared
easily. Two important secondary reference electrodes are described here.
i) Calomel electrode: It consists of mercury at the bottom over which a paste of mercury-mercurous chloride is placed. A solution of
potassium chloride is then placed over the paste. A platinum wire sealed in a glass tube helps in making the electrical contact. The
electrode is connected with the help of the side tube on the left through a salt bridge with the other electrode to make a compete cell.
The potential of the calomel electrode depends upon the concentration of the potassium chloride solution. If potassium chloride
solution is saturated, the electrode is known as saturated calomel electrode (SCE) and if the potassium chloride solution is 1 N, the
electrode is known as normal calomel elctrode(NCE) while for 0.1 N potassium chloride solution the electrode is referred to as
decinormal calomel electrode (DNCE). The electrode reaction when the electrodes acts as cathode is

Hg+ Cl

1/ 2 Hg 2 Cl 2 +e

The reduction potentials of the calomel electrodes on hydrogen scale at 298 K are as follows
Saturated KCl
0.2415 V
1.0 N KCl
0.2800 V
0.1 N KCl
0.3338 V
The electrodes potential of any other electrode on hydrogen scale can be measured when it is combined with calomel electrode. The
emf of such a cell is measured. From the value of electrode potential of calomel electrodes, the electrode potential of the other
electrode can be evaluated.
ii) Silver-silver chloride electrode: This is another widely used reference electrode. It is reversible and stable and can be combined with
cells containing chlorides without inserting liqid junctions.
Silver chloride is deposited electrolyticaly on a silver or platinum wire are and it is then immersed in a solution containing chloride
ions. Its standard electrode potential with respect to the standard hydrogen electrode is 0.224 V at 298 K. The electrode is represented
as

Ag+ Cl
Ag AgClCl and the electrode reaction is
AgCl+e

13.7 Prediction for occurrence of a redox reaction: Any redox reaction would occur spontaneously if the free energy cahnge (G) is
negative. The free energy is related to cel emf in the following manner:

G0=nFE 0
When

G can be negative if E0 is positive.

E0 is positive, the cell reaction is spontaneous and serves as a source of electrical energy.

14. ELECTRODE AND CELL POTENTIALS. NERNST EQUATION


The electrode potential and the emf of the cel depend upon the nature of the electrode, temperature and the acativities (concentrations)
of the ions in solution. The variation of electrode and cell potential with concentration of ions in solution can be obtained from
thermodynamic considerations. For a general reaction such as

m1 A+ m2 B+ .. n1 X +n2 Y + ..
Occuring in the cellm the Gibbs free energy change is given by the equation

a nX X a ny .
1

G= G +2.303 RT log 1 0

a mA X a nB ..
1

Where a represents the activities of reactants and products under a given set of conditions and

refers to free energy change

for the reaction when the various reactants and products are present at standard conditions. The free energy change of the electric
cahnge of the elctrical work that can be obtained from the cell, i.e.,

G=nFE cell Go =nFE o . On subsituting these values in Eq. (ii). we get


nFE cell =nFE

anX X any ..
1

cell +2.303 RT log 10

amA X anB
1

2 .

anX X any ..
2.303 RT
E cell=E cell
log 10 m
nF
a A X anB .
o

Nernst equation.

R=8.314 JK 1 mol1 , T =298 K F=96500 C , above eq . reduces

Putting the values of


0

E=E

an X any
[ Products ]
0.0591
0.0591
o
log 10 mX
=E
log10
n
n
n
[
Reactants]
a A X aB ...
1

14.1 Potntial of single electrod (Anode): Consider the general oxidation reaction..

n++ ne
M M

n+
M

Applying Nernst equation , Eox =E oox

0.0591
log 10
n

The oxidation potential of the electrode (anode).

Eox =E oox

Eoox is the standard oxidation potential of the electrode.

0.0591
log 10 [ M +n ]
n

14.2 Emf of the cell

Ecell =Eox + E

( o ox+ E )

0.0591
log 10
n

+2
+2
Zn
0.0591
Zn
0
=
E

log
cell
10
+2
+2
n
Cu
Cu

[ ]

[ ]

14.3 Concentration cells: If two plates of the same metal are dipped separately into two solutions of the same electrolyte and are
connected with a salt bridge, the whole arrangement is found to act as a galvanic cell. In general, there are two types of concentration
cells.
i) Electrode concentration cells: In these cells, the potential difference is developed between two like electrodes at different
concentrations dipped in the same solution of the electrolyte. For example, two hydrogen electrodes at different gas pressure in the
same solution of hydrogen ions constitute a cell of this type.

+
H

Pt , H 2 ( Pressure p1 )

Anode
If

p1> p 2 , oxidation occurs at L.H.S. electrodes and reduction occurs at R.H.S. electrode.
Ecell =

(p )
0.0591
log 1 at 250 C
2
(p 2)

ii) Electrolyte concentration cells: In these cells, electrodes are identical but these are immersed in solutions of the same electrolyte of
different concentrations. The source of electrical energy in the cell is the tendency of the electrolyte to diffuse from a solution of
higher concentration to that of ower concentration. With the expiry of time, the two concentrations tend to become equal. Thus, at the
start the emf of the cell is maximum and it gradually falls to zero. Such a cell is represented in the following manner:

C
( 2 is greater thanC 1).

n+
M

C
( 2) M
n+
M

+2
Zn| Zn+2 (C1 ) Zn (C 2)| Zn
Anode
Cathode

Or

The emf of the cell is given by the following expression:

Ecell =

C ( R . H . S)
0.0591
log 2
at 250 C
n
C 1(L . H .S .)

The concentration cells are used to determine the solubiity of sparingly solute salts, valency of the cation of the electrolyte and
transition point of the two allotropic forms of a mtal used as electrods, etc.
16. APPLICATIONS OF ELECTROCHEMICA SERIES

16.1 Reactivity of metals: The activity of th metal depends on its tendency to lost electron or elctrons, i.e., tendency to form cation

M
( +n) . This tendency depends on the magnitude of standard reduction potential. The metal which has high negative value (or

smaller positive value) of standard reduction potential readily loses the electron or electrons and is converted into cation. Such a metal
is said to be chemically active.
The chemcial reactivity of metals decreases from top to bottom in the series. The metal higher in the series is more acative than the
metal lowr in the series. For example,
i) Alkali metals and alkaline earth metals haiving high negative values of standard reduction potentials are chemically active. These react
with cold water and evolve hydrogen. These react with cold water and evolve hydrogen. These readily dissolve in acids forming
corresponding salts and combine with those substances which accept electrons.
ii) Metals like Fe, Pb, Sn, Ni, Co., etc, which lie a little down in the series do not react with cold water but react with steam to evolve
hydrogen.
iii) Metals like Cu, Ag and Au which lie below hydrogen are less reacative and do not evolve hydrogen from water.
16.2 Electropositive character of metals: The elctropositive character also depends on the tendency to lose electron or electrons. Like
reactivity, the electropositive character of metals decreases from top to bottom in the electrochemical series. On the basis of standard
reduction potential values, metals are divided into three groups.
i) Strongly electropositive metals: Metals having standard reduction potential near about -2.0 volt or more negative like alkali metals,
alkaline earth metals are strongly electropositive in nature.
ii) Moderately electropositive metals: Metals having values of reduction potentials between 0.0 and about 2.0 volt are moderately
electropositive. Al, Z, Fe, Ni, Co, etc., belong to this group.
iii) Weakly electropositive metals. The metals which are below hydrogen and possess positive values of reduction potentials are weakly
electropositive metals. Cu, Hg, Ag etc., belong to this group.
16.3 Displacement reactions:

i) To predict wheather a given metal wil displace another, from its salt solution. A metal higher in the series will displace the metal
from its solution which is lower in the series, i.e., the metal having low standard reduction potential wi displace the metal from
its salts solution which ha shighr value of standard reduction potential. A meta high in the series has greater tendency to provide
electrons to the cations of the metal to be precipiated.
ii) Displacement of one non-metal from its salt solution by another non-metal: A non-metal higher in the series (towards bottom
side), i.e., having high value of reduction potential wil displace another non-metal with lower reducton potential i.e. occupying
position above in the series. The non-metals which possess high positive reduction potentials have the tendency to accept electrons
readily. These electrons are provided by the ions of the nonmetal having ow value of reduction potential. Thus,

Cl2 can displace

bromine and iodine from bromides and iodides.

Cl2 +2 Kl 2 KCl+ I 2

I 2 +2 e
2I

(oxidation)


2Cl
Cl 2+2 e

(Reduction)

[The activity or electronegative characater or oxidising nature of the nonmetal increases as the value of reduction potential increases.]
iii) Displacement of hydrogen from dilute acids by metals: The metal which can provide electrons to H+ ions present in diute acids for
reduction, evolve hydrogen from dilute acids.

Mn Mn +n+ ne

(Oxidation)

H 2
++2 e
2 H

(Reduction)

The metal having negative values of reduction potential possess the property of losing electron or electrons. Thus, the metals
occupying top positions in the electrochemical series readily liberate hydrogen from dilute acids and on descending in the series
tendency to liberate hydrogen gas from diute acids decreases. The metals which are below hydrogen in electrochemical series like Cu,
Hg, Au, Pt, etc, do not evolve hydrogen from dilute acids.
iv) Displacement of hydrogen from water: Iron and the metals above iron are capable of liberating hydrogen from water. The tendency
decreases from top to bottom in electrochemical series.
Alkali and alkaline earth metals liberate hydrogen from cold water but Mg, Zn and Fe liberate hydrogen from hot water or steam.
16.4 Reducing power of metals: Reducing nature depends on the tendency of losing electrons or electrons. More the negative reduction
potential, more is the tendency to accept electron or electrons or electrons. Thus, oxidising nature increases from top of bottom in the
electrochemical series. The strength of an oxidising agent increases as the value of reduction potential becomes more and positive.
F2(Fluorine) is a stronger oxidant than Cl2, Br2 and 2. Cl2 (Chlorine) is a stronger oxidant than Br2 and 2.
stronger oxidant than

C I 2 (Chlorine) is a

Br 2 and I 2 . C I 2 (Chlorine) is a stronger oxidant than Br 2 and I 2 .

Reduction potential

Na Zn Fe
2.71 0.76 0.44

ducing nature decreases

Re

Alkali and alkaline earth metals are strong reducing agents.


16.5 Oxidising nature of non-metals: Oxidising nature depends on the tendency to accept electron or electrons. More the value of
reduction potential, highr is the tendency to accept electron or electrons or electrons. Thus, oxidising nature increases from top of
bottom in the electrochemical series. The strength of an oxidising agent increases as the value of reduction potential becomes more
and positive.

F2

(Fluorine) is a stronger oxiant than

Cl2 , Br 2I 2 . C I 2 ( Chlorine )
is a

stronger oxidant than

Br 2 and

I2 .

16.6 Thermal stability of metallic oxides: The thermal stability of the metal oxide depends on its electropositive nature. As the
elecropositivity decreases from top to bottom, the thermal stability of the oxide also decrease from top to bottom. The oxides of metals
having high positive reduction potential are not stable towards heat. The metals which come below copper form unstable oxides, i.e.,
these are decomposed on heating.

16.7
Corrosion of metals: Corrosion is defined as the deterioration of a substance
because
of its reaction with its environment. This is also defined as the process by
which metals have the tendency of go back to their combined state i.e., reverse of extraction of metals.
Ordinary corrosion is a redox reaction by which metals an oxidised by oxygen in presence of moisture. Oxidation of metal occurs
more rapidly at points of strain. Thus, a steel nail first corrodes at the tip and head. The end of a steel nail acts as an anode where ion is
oxidised to

2+

Fe ions.

2++2 e
Fe Fe

(Anode reaction)

The electrons flow along the nail to areas containing impurities which act as cathodes where oxygen is reduced to hydroxyl ions.

The overall reaction is

2 Fe+ O2+2 H 2 O=2 Fe (OH )2

Fe(OH )2 may be dehydrated to iron oxide, FeO, or further oxidised to Fe(OH )3 and then dehydrated to iron rust,
Fe2 O3 .
Several methods for protection of metals against corrosion have been deveoped. The most widely used are (i) plating the metal with a
thin layer of a less easily oxidised metal (ii) allowing a protective film such as metal oxide (iii) galvanising steel is coated with zinc
(a more active metal).
16.8 Extraction of metals: A more electropositive metal can displace a less electropositive metal from its salts solution. This principe
is applied for the extraction of Ag and Au by cyanide process. Silver from the solution containing sodium argento cyanide,

NaAg(CN )2 can be obtained by addition of zinc as it is more electro-positive then Ag.


CN

2 NaAg
17. CONCEPT OF EQUILIBRIUM IN ELECTROCHEMICAL CELL
In an electrochemical cell a reversible redox process taks place, e.g., in Daniel cell

2+ ( aq ) +Cu( s)
+2

Zn ( s ) +Cu ( aq ) Zn

Re

i) At equilibrium mass acation ratio becomes equa to equillibrium constant, Q =

ii) Oxidation potential of anode = Reduction potential of cathode


i.e., emf = Oxidation potential of anode + Reduction potential of cathode = 0 Cell is fully discharged.
According to Nernst equation: E = E0

0.0591
nE
K ; K = Antilog
n
0.0591

18. WORK DONE BY THE CELL


Let n faraday charge be taken put of a cell of emf E then work done by the cell will be calculated as

Work=Charge Potentia=n FE

Work done by the cell is equal to decrease in free energy

G=nFE

Simiary, maximum obtainable work from the cell will be

W max =nFE

Where

E = standard emf of standard cel potential.


o

G =nFE

The relationship among

k , G E cell

19. HEAT OF REACTION IN AN ELECTROCHEMICAL CELL


Left n faraday charge flows out o a cell of emf E,
Then

G=nFE

Gibbs Helmholtz equation from thermodynamics may be given as

G= H +T

( )

From above equations we get

[ ]

nFE=H +T = H nFT ; H=nFE+ nFT


p
p

Here

=
(
)

Case I: When
Case II: When
Case III: When

( )

( )

Temperature coefficient of cell

=0,then H =nFE
(
)

>0,
(
)
<0,
(
)

then

nFE > H , i. e . , process inside the cell is endothermic.

then nFE

H ,i . e . , process inside the cell is exothermic.

20. TYPES OF CELLS OR BATTERIES


20.1 Primary voltaic cell : In this cell, once the
chemicals have been consumed, further
reaction is not possible. It cannot be
regenerated by reversing the current flow
through the cell using an external direct
current source of electrical energy.
The container of the dry cell is made of
zinc which also serves as one of the
electrodes. The other electrode is a
carbon rod in the centre of the cell. The
zinc container is lined with a porous
paper. A most mixture of ammonium
chloride, manganese dioxide, zinc
chloride and a porous inert filler occupy
the space between the paper lined zinc container
and the carbon rod. The cell is sealed with a material like wax.

Electrolyte NH 4 Cl + MnO2 +ZnCl 2 : Anode zinc container :Cathode carbon rod

2+ ( aq ) +2 e
At anode :Zn ( s ) Zn
Mn2 O3 ( s ) +2 NH 3 ( g ) + H 2 O
+ ( aq ) +2 e
At cathode :2 MnO 2 ( s ) +2 NH 4

2+ ( aq ) + Mn 2 O3 ( s ) +2 NH 3 ( g )+ H 2 O

+ ( aq ) Zn
Zn ( s )+ 2 MnO2 ( s ) +2 NH 4
20.2 Secondary voltaic cell (Lead storage battery) : The cell in which original reactants are regenerated by passing direct current from
external source, i.e., it is re-charged, is called secondary cell. Lead storage battery is the example of this type.
It consists of a group of lead plates bearing compressed spongy lead, alternating with a group of lead plates bearing lead 30%

H 2 SO 4 . When the cell discharges, it operates as a voltaic cell. In this cel no salt bridge is needed . The spongy lead is oxidised to
Pb+2 ions and lead plates acquire a negative charge.

Pb Pb+2+ 2e
Pb

+2

(Anode reaction)

ions combin with sulphate ions to form insoluble lead sulphate,

PbSO 4 , which begins to coat lead electrode.

Pb+2+ 2 H 2 O ( Cathode reaction )


++ 2e
PbO2 +4 H
Pb+2+ SO 42 PbSO 4 ( Precipitation )
Overall cell reaction is

++2 SO 42 2 PbSO 4 +2 H 2 O
Pb+ PbO2 + 4 H
Ecell is 2.041 volt.
When a potential slightly greater than the potential of battery is applied, the battery can be re-charged.

2 PbSO 4 +2 H 2 O Pb+ PbO 2 +2 H 2 SO 4

After many repeated charge-discharge cycles, some of the lead sulphate falls to the bottom o the container, the sulphuric acid
concentration remains low and the battery cannot be recharged fully.

20.3 Fuel Cell: Fuel


cells are another means by which
chemical energy
may be converted into electrical energy.
The main disadvantage of a primary cell is that it can deliver current for a short period only. This is due to the fact that the quantity of
oxidising agent and reducing agent is limited. But the energy can be obtained indefinitely from a fuel cell as long as the outside supply
of fuel is maintained. One of the examples is the hydrogen-oxygen fuel cell. The cell consists of three compartments separate by a
porous electrode. Hydrogen gas is introduced into one compartment and oxygen gas is fed into another compartemnt. These gases then
diffuse slowly through the electrodes and react with an electrolyte that is in the central compartment. The electrodes are made of
porous carbon and the electrolyte is a resin containing concentrated aqueous sodium hydroxide solution. Hydorgen is oxidised at
anode and oxygen is reduced at cathode. The overall cell reaction produces water. The overall ce reaction produces water. The
reactions which occur are:

Anode

( aq ) 2 H 2 O ( l )+2e 2

Cathode

(aq)
4 OH
O2 ( g ) +2 H 2 O ( i )+ 4 e

Overall

2 H 2 ( g ) +O2 ( g) 2 H 2 O(l)

This type o cells are used in space-crafts. Fuel cells are efficient and pollution free.
21. COMMERCIAL PRODUCTION OF CHEMICALS
The process of electrolysis forms the basis of the commercia production of large number of chemical substances. The electrode
reactions involved in the manufacture of some important chemicals are being discussed here.
21.1 Manufacture of Caustic soda (NaOH): This manufacture is based on the electrolysis of aqueous solution of sodium chloride. The
products of electrolysis are sodium hydroxide, chlorine gas and dihydrogen gas. The chemical reactions involved are as follows:

( aq )
(
+ aq ) +Cl 2
NaCl ( aq ) Na

At anode

At cathode

Net reaction

Cl2 ( g ) +2 e
2 Cl
( aq )
H 2+ 2OH
2 H 2 O+ 2e
2 NaCl+ 2 H 2 O Electricity 2 NaOH ( aq ) +Cl2 ( g ) + H 2 (g)

The electrolytic cell is designed in such a way so that products of electrolysis

Cl2 (at anode), NaOH (at cathode) are kept separate

so that they may not undergo chemical reaction to produce sodium hypochlorite. There are different types of electrolytic cells. The two
important cells are Nelsons cel and Castner Kellner cell.
21.2 Manufacture of Sodium Metal : Sodium metal is extracted by electrolysis of molten sodium chloride. Calculated amount of
calcium chlride is added to sodium chloride to lower its melting point. The chemical reactions taking place are

++ Cl
NaCl (l ) Na

At anode

Oxidation of

Cl ions occurs to liberate chlorine

Cl2 ( g ) +2 e
2 Cl
At cathode

Reduction of

+
Na ions occurs to form sodium in liquid state

2 Na(l)
++2 e
2 Na
Net Reaction

2 NaCl (l) Electricity 2 Na (l ) +Cl 2 (g)

The electrolysis is carried out in specially designed cell called Downs Electrolytic cell.

Al
21.3 Manufacture of Aluminum: Aluminum is extracted by the electrolysis of molten alumina ( 2 O 3) containing cryolite

AlF
( 3 .3 NaF) . Cryolite is added to alumina to lower its melting point and to improve its conductivity. The temperature of

electrolyte is maintained between

12001300 K . The reactions taking place are


3++ 3 F
AlF 3 ( l ) Al
At anode:

Al 2 O 3 to form AlF 3 and dioxygen gas


F ions are oxidized and nascent fluorine so produced reacts with

F+ e
F
2 Al 2 O3 +12 F 4 AlF3 +3 O 2

At cathode: Aluminum ions get reduced to give aluminium metal

Al

3++3 e
Al

The electrolysis is carried out in special type of electrolytic cel using carbon electrodes. The dioxygen gas liberated at carbon anode
reacts with carbon to form CO gas either escapes out or is brunt to produce

CO2 .

21.4 Manufacture of Fluorine : Fluorine is manufacture by the electrolysis of 90% soluton (by mass) of potassium hydrogen fluoride
(KHF2) in anhydrous hydrogen fluoride (HF). The electrolysis is carried out strictly in anhydrous conditions. The reactions occuring at
the electrodes are

KHF 2 KF+ HF

++ F
KF K

At cathode : Reduction of

+
K ions occurs as the potassium so produced reacts with HF to liberate H2 gas.

At anode : Oxidation of F ions occurs as

F2 ( g ) +2 e
2 F

EXAMPLES :EXAMPLE:1 Find the oxidation no. of underlined elements

A.

E.

K 2 Cr 2 O7
(CO) 4

P2 O

I.

B.

O3

C.

Co Cl 2
F.

4
7

J.

MnO4

D.

H. Ba

G.

KCrO3 Cl

C3 O

K.

Fe0.94 O

NH

L.
FeSO 4

EXAMPLE:2 Balance the following equations by oxidation number method.


A.

P+ HNO3 HPO3 + NO+ H 2 O

B.

NO 3 2+ H 2 O
MnO+ PbO 2+ HNO3 HMnO 4 + Pb

C.

H 2 S+ KMnO 4 K 2 SO 4 + MnSO 4 +S + H 2 O

D.

KMnO 4 + H 3 AsO 3 + HCl KCl+ MnCl 2 + H 3 AsO 4 + H 2 O

EXAMPL:3 Balance the following quations


A.

( Basic medium )

P PH 3+ H 2 PO 2

+ MnO2+ H 2 O ( Basic medium )


C2 H 3 O
B.
C 2 H 5 OH + MnO 4
EXAMPLE:4 Chromium metal can be plated out from an acidic solution containing

CrO 3 according to the following

equation,

Cr ( s ) +3 H 2 O
++ 6 e
CrO 3 ( aq ) +6 H
Calculate:
A. how many grams of chromium wil be platd out by 24000 coulomb?
B. how ong wil it take to plate out 1.5 g of Cr by using 12.2 ampere current?
EXAMPLE:5 Electrolysis of a solution of

MnSO4 in aqueous sulphuric acid is a method for the preparation of

MnO2

as per reaction,

+ ( aq ) + H 2 (g)
Mn ( aq ) +2 H 2 O MnO 2 ( s ) +2 H
+2

Passing a current of 27 A for 24 hours gives one kg of

MnO2 . What is the value of current efficiency. Write th reactions

taking place at the cathode and at the anode.


EXAMPLE:6 Calculate the quantity of electricity required to reduce 6.15 g of nitrobenzene to aniline if the current efficiency is
68%. If potential drop across the cell is 7.0 volts, calculate the energy consumed in the process.
EXAMPLE:7 The standard reduction potential for
above couple. Ksp of Cu(OH)2 is

1.0 1019 .

+2

Cu /Cu is 0.34 V. Calculate the reduction potential at pH = 14 for the

EXAMPLE:8

H 2 O2 can be prepared by the successive reactions:

NH

2 NH 4 HSO 4 H 2 +
NH

The first reaction is an electrolytic reaction and second a steam distilation. What current would have to be used in first
reaction to produce enough intermediate to yield 100 g pure

H 2 O2 per hour? Assume 50% anode current efficiency.

EXAMPLE :9 After electrolysis of a sodium chloride solution with inert electrodes for a certain period of time, 200 mL of the
solution was left with 0.2 N NaOH. During the same time 10.8 g of Ag was deposited in a siver voltmeter in series with the
electrolytic cell. Calculate % of the theoretical yield of NaOH obtained.
EXAMPLE:10 The electrolsynthesis of MnO2 is carried out in a soution of MnSO4 in H2SO4 (aq). A current of 25.5 A is used. If
current efficiency is 85% how long would it take to produce 1.0 kg of MnO2?
EXAMPLE:11 Copper is purified by electrolysis, a method called electro-refining. After passage of 140 A for 182.5 s, the mass
of the anode decreased by 22.260 g and the cathode increased in mass by 22.011 g. Estimate the % of iron and copper
originally present. Assume Fe, Cu, Au and Ag are present in impure Cu anode.
EXAMPLE:12 In the reaction;

Al + Fe3 O4 Al 2 O3 + Fe

A. Which element is oxidized and which is reduced?


B. Total no. electrons transferred during the change.
EXAMPLE:13 Identify the oxidants and reductants in the following reactions:

14. The composition of a sample wustite is

Fe0.93 O 1.00 . What percentage of iron is present in the form of Fe ()?

EXAMPLE:15 Arrange the following in ordr of:


A. Increasing oxidation no:

MnCl 2 , MnO2 , Mn (OH )3 , KMnO 4

B. Decreasing oxidation no:

HXO4 , HXO3 , HXO3 , HXO2 , HXO

C. Increasing oxidation no:

l 2, Hl , HlO 4 , lCl

EXAMPLE:16 Calculate the quantity of electricity that wil be required t liberate 710 g of Cl 2 gas by electrolysing a conc.
Solution o NaCl. What weight of NaOH and what volume of H2 at 270C and 1 atm pressure is obtained during this process?
EXAMPLE:17 Calculate the volume of Cl2 at NTP produced during electrolysis of MgCl2 which produces 6.50 g Mg. At. Wt. of
Mg = 24.3
EXAMPLE:18 How long would it take to deposit 100 g of Al from an electrolytic cell containing Al 2O3 using a current of 125
ampere?
EXAMPLE:19 A metal wire carries a current of 1 ampere. How many electrons pass a point in the wire in one second?
EXAMPLE:20 Calculate the number of electrons lost or gained during electrolysis of:
A.

ions ,

2 g Cl

B.

2+ ions

1 g zn

EXAMPLE:21 Calculate the volume of gas iberated at anode NTP from the electrolysis of
ampre passed for 10 minutes.

CuSO 4 solution by a current of 2

EXAMPLE:22 A current o 3.7 ampere is passed for 6 hrs. beteen Ni electrodes in 0.5 litre of 2 M solution of

NO

What wil be

the molarity of solution at the end o electrolysis?


II. MULTIPE CHOICE QUESTIONS (with only one correct choice)

2+ ( aq )
Zn

EXAMPLE:23 Calculate Eo or the ce


if the equilibrium constant for the reaction
2+ (aq)|Cu at 250 C
Zn|
2+ ( aq ) +Cu is1.94 1037

2+ ( aq ) Zn
Zn+Cu
A. 2.10 V
B. 1.10 V
C. 1.40 V
D. 2.40 V
EXAMPLE:24. An electrochemical cell is set up as follows.
Pt,

H 2 (1 atm)

|0.1 M HCl 0.1 MCH 3 COOH| H 2 ( 1 atm ) , Pt

The E.M.F. of this cell is expected to be


A. zero
C. negative
EXAMPLE:25. The E.M.F. o the half cell

B. positive
D. infinity.

0.02 M

1
+ H 2 ( g ) ( 2 atm ) , Pt is
2
H

A. 1.09 V
B. 1.09 V
C. 0.109 V
D. 0.109 V
EXAMPLE:26. During the electrolysis of acidulated water, using inert electrodes, the total volume of the gases collected at NTP
is 1.68 L. The amount of electicity passed through water is
A. 1 F
B. 0.5 F
C. 0.2 F
D. 0.1 F
EXAMPLE:27. The E.M.F. of the cell

+
H

Pt, +( pH =3.5)
H 2 ( 1 atm ) ,

|H 2 (1 atm ) , Pt at 250 C would be


A. 0 V
B. 0.425 kJ
C. 0.212 V
D. 0.212 V.
EXAMPLE:28. The cell reaction occuring in the cell

+ ( 1 M )

Pt , H 2 ( p 1 atm ) H+ ( 1 M )

A.

p1= p2

B.

p1> p 2

C.

p1< p 2

D.

p1= p2=1 atm

EXAMPLE:29. During electrolysis of acidulated water, H2 gas is collectd at the cathode. In order to obtain H2 gas at rate of 4.48
c.c. per second at STP, the current passed should be
A. 3.86 amp
B. 7.72 amp
C. 38.6
D. 19.3 amp

+
M

EXAMPLE:30. For the electrochemical cell


Form this data, one can deduce that
+ /M

X / X =0.33 V .
M =0.44 V E o
M |
is the spontaneous reaction
++ X
A.
M + X M
M + X isthe spontaneous reaction

++ X
B.

M
C.

Ecell =0.77 V

D.

Ecell =0.77V

( aq)
( aq )+2Cl
31. The reaction ( aq ) CIO isan example of
3
3 CIO
A. Oxidation reaction
B. reduction reaction
C. disroportionation
D. decomposition reaction
32. The oxidation potential of hydrogen electrode at pH = 10 and pH2 =1 atm is:
A. 0.51 V
B. 0.00 V
C. + 0.59 V
D. 0.059 V
33. The emf of the following concentration cell at 250C is

Ag ( s )| AgNO 3 ( 0.01 M ) AgNO 3 ( 0.05 M )| Ag( s)


A.

0.414 V

B.

0.828 V

C. 0.414 V
D. 0.0414 V
34. The pH of the following half-cell solution is:

H
( 2 SO 4 ); E=0.3 volt
+
PtH 2 (1 atm)| H

A. 5.076
C. 4.302

B. 9.824
D. 3.021

35. The solubility product of a saturated solution of

Ag 2 CrO 4 in water at 298 K if the emf of the cell

+ (satd . Ag2 CrO 4 soln.) Ag+(0.1 M )| Agis 0.164 V at 298 K will be


Ag| Ag
A.

2.287 1010 mol3 L3

B.

2.287 1011 mol 3 L3

C.

2.287 1012 mol3 L3

D.

2.287 109 mol3 L3

36. What is the standard potential of the

3+ /Tl electrode ?

TI

+ ; Eo =1.26 volt
Tl
3++2 e
Ti
Tl; E o=0.336 volt
++ e
Tl
A. 0.0728 V
C. 0.364 V

B. 0.728 V
D. 0.0364 V

37. The variation of Ecell with temperature i.e,

A.

S
nF

C.

B.

H
/T
nF

(
)

is equal to:

HG
nFT

D. All of these.

MULTIPLE CHOICE QUESTIONS (with more than one correct choice)


EXAMPLE:38

H 2 C 2 O 4 and KHC 2 O4 behave both as acids and reuctance. Amongst the following, the true statement

(s) is/are
A. Equal volumes of 1 M solution of each is oxidised by equal volumes of 1 M KmnO 4
B. Their equivalent masses are equal to respective molecular masses when behaving as reducing agents.
C. V ml of 1 M solution of each is neutralized by equal volumes of 1 M NaOH
D. V ml of 1 N solution of each (as an acid) is neutralized by equa volumes o 1 M Ca(OH)2.
EXAMPLE:39. If equal volumes of 0.1 M HBr and 0.1 M KOH are mixed, then which of the following is/are correct about the
resulting solution?
A.

+
H 3 O

+
K
C.

OH
B.

Br
D.

EXAMPLE:40. For preparing standard solution of Fe(II), Mohrs salt, FeSO 4 (NH4)2.SO4. 6H2O, is usd instead of any other
ferrous salt like FeSO4 .7H2O. This is due to the reason that
A. FeSO4.7H2O undergoes atmospheric oxidation to form basic ferric sulphate
B. The Mohrs salt is not oxidised by atmospheric oxygen
C. FeSO4.7H2O is deliquscent but the Mohrs salt is not

D. FeSO4.7H2O efforesces but the Mohrs sat does not


EXAMPLE:41. For the reaction:

OH 2 CaHPO 3 +2 H 2 O
the true statement (s) is/are
H 3 PO 3 +Ca

A. The resulting mixture requires 1 mol of NaOH for complete neutralization


B. CaHPO3 is an acid salt
C. CaHPO3 is a normal salt
D. The equivalent mass o H3PO3 is 4l.
EXAMPLE:42. When NH4NO2 is heated
A. there is oxidation o nitrogen
B. there is reducton of nitrogen
C. net reaction is disproportionation
D. net reaction is double decomposition
EXAMPLE:43. At the equivalence point of a titration, the titrant and titrand will always have
A. equal millimoles
B. equal moles
C. equal miliequivalents
D. equal equivalents
EXAMPLE:44. A gas X at 1 atm is bubbled through a solution containing a mixture o 1 M Y and 1 M Z at 250C. If the reduction
potential of Z>Y>X then
A. Y will oxidise X and not Z
B. Y will oxidise Z and not X
C. Y will oxidise both X and Z
D. Y will reduce both X and Z
EXAMPLE:45. Given that

; E 0=0.54 V
2 I
I 2 +2 e
; E o=1.09 V
2 Br
Br 2 +2 e
Predict which of the following statement is true.
A. I ions will be able to reduce bromine
B. Br ions wil be able to reduce iodine
C. Iodine will be able to reduce bromine
D. Bromine wil be able to reduce iodide ions
EXAMPLE:46 Which one is not correct for e.m.f of a galvanic cell
A.

Ecell =E P + E RP

B.

Ecell =higher reduction potentiallower reduction potential

C.

Ecell =higher oxidation potentiallower oxidation potential

D.

Ecell =lower reduction potentialhigher reduction potential

anode

cathode

COLUMN MATCHING
EXAMPLE:47 Match the following:
Column I

Na(s)
+ ( aq )+ e
A)
Na
B) The concentration of CuSO4 solution does not
change on electroysis

2+ ( aq ) +2 e
C)
Cu ( s ) Cu

2 H 2 O+O2+ 4 e
D)
4 OH

Column-II
P) Reaction taking place at anod during electrolysis of very dilute
Solution of NaCl using Pt electrodes.
Q) Reaction taking plate at anode during electrolysis of CuSO4 using
Cu electrode.
R) Electroysis of aq CuSO4 using Cu electrodes

S) Reaction taking place at cathode when electroysis of aq NaCl


is done using Hg electrode

EXAMPLE:48. Match the following


Column I
A) K Specific conductance
B)

m Molar conductance

Column II
P) Increases with dilution
Q) Increases with increasing the distance between parallel plates

C)

degree of dissociation

R) Decreases with dilution

D) Resistance

S) Decreases with increase in concentration o electrolyte

T)

EXAMPLE:49. Match the following, given that

I 2 / I =0.54 V
Br 2 / Br =1.08 V , E o

0
Cl2 /Cl =1.36 V , E
2 +/Cu
o
Cu
=0.34 V , E
E o
Column I

Column II

Cu+ Cl2
2+ +2Cl
A)
Cu

P) Can produce electricity in a galvanic cell


2+ +2 Cl
B)
Cl2 +Cu Cu

Q) Can be made to occur in electroysis cell

C)

+ Strach solution+Chlorine water


2I

R) Appearance of brown colour

D)

+ CCl4 +Chlorine water


2 Br

S) Appearance of violet colour

EXAMPE:50. Consider the reduction reactions:

Sn ; E o=0.14 V
2++2 e
i)
Sn

2+ ; Eo=0.13V
Sn
ii)
4++2 e
Sn

Column I

Column II

4+ /Sn

A)

Sn
Eo

P)

0.005V

B) Standard oxidation potential of Sn to Sn (+ IV)

Q) +0.005 V

C) Disproportionation of

R) Spontaneous

2+

Sn

D) Oxidation of Sn to Sn4+
S) Non-spontaneous
FILL IN THE BLANKS
EXAMPLE:51. Molten NaCl conducts current due to the presence of..
EXAMPLE:52. On Electrolysis..of ions takes place at electrodes.
EXAMPLE:53. Zn is abe to displace Ag from AgNO3 solution because its standard oxidation electrode potential ispositive
than that of Ag.
EXAMPLE:54. Dilute H2SO4 on electrolysis liberates.at the anode.
EXAMPE:55. In a Daniel cell, current flows fromtooutside the cell.

EXAMPLE:56.

Ecell =EOP + .....................if two electrodes are connected.

EXAMPLE:57. Coating of iron with zinc to prevent corrosion is called.


EXAMPLE:58. In a galvanic cellenergy is generated at the expense of ..energy.
EXAMPLE:59. During recharging of lead storage cell it acts as..cell.
EXAMPLE:60. Presence of CO2 in natural water..rusting of iron.