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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
H 2 S+Cl 2 2 HCl+S
4 Hl +O2 2 H 2 O+2l 2
Fe+ S FeS
(Oxidation of iron)
2 Kl + H 2 O2 2 KOH + I 2
CuO+C Cu++CO
H 2 O+C CO + H 2
(Reduction of water)
Cl2 + H 2 H 2 S
(Reduction of sulphur)
HgCl2+ Hg Hg 2 Cl 2
CuCl2 +Cu Cu 2 Cl 2
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
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
CH
ii)
+2+ x2=0
Or
x=0
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+2 x6=0
Structure of
x=+2
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
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.
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=
N3 H ,
2
3
+2
2
3
3 +1=0
3 x=1,
x=1/3
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)
NO
Cu
Cu+ HNO3
0
+2+52
NO
Cu+ +1+52 Cu
HNO3
HNO3
NO
Cu
Cu+ 2 NHO 3
Balancing nitrate ions, hydrogen and oxygen, the following equation is obtained.
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.
( 2 62 3 )=6 units
SO
SO
K 2 Cr 2 O7 + 6 FeSO 4 Cr2
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,
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
MnO
2++ 4 H 2 O
C
2 2CO 2 +2 e
5
++5 e Mn ;
2
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
+ H 2 O ; l 2 l
l O3
l 2 +OH
(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
2l
5
+ 6 H 2 O+10 e ;
2l O3
l 2 + 12OH
+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.
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
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
Thus,
E=Z 96500
Or
Z=
Z E
E
; 1= 1
96500 Z 2 E2
V=
Where,
ItV e
96500
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
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,
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 ) .
( a b c )cm3
( 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
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=
=
i)
ii)
Actual current
100
Ammeter current
a=
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
+
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
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
a
p= . R
l
or
1 l 1
= .
a R
or
l
k = C
a
Cell constant
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
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
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,
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
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
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
c =kuc
a =ku a
and
i) Degree of dissociation
a=
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
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
cathode and
OH
CuSO 4
+
2 , H
2
containing 2+ , SO 4
and Ohions is electrolysed, Cu ions are discharged at
Cu
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.
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.
H2O H
At cathode
+ +e
H
2 H H2
At anode
H 2 O
+O+2e
2OH
O+O O2
H ions have lower discharge potential than Na+ ions. OH ions are discharged at anode
SO 4
i.e., the net reaction describes the elecroysis of water. The ions of
+
+ , 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
Cu
+2
ions or
anode.
+2
or
Cu+
SO
CuSO
Cu Cu 2 e
4
4 +2 e
++ NO 3
AgNO 3 Ag
Ag
++ e
Ag
++ 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
++ 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=
a1
(1 ) 1
Thus equation (i) can be written as
K=C 2 =
K
C
It consists of two
The half-cel on
electrode dipped in
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
The signs of the anoe and cathode in the voltaic or galvanic cels are oposite to those in the electrolytic cells.
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
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
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.
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
++2 e
H2 2 H
H 2
++2 e
2 H
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
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
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:
Ecell
iii) When oxidation potentials of both electrodes are take into account :
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.
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
E0 is positive, the cell reaction is spontaneous and serves as a source of electrical energy.
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
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.,
anX X any ..
1
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.
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
0.0591
log 10
n
Eox =E oox
0.0591
log 10 [ M +n ]
n
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
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 +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
Reduction potential
Na Zn Fe
2.71 0.76 0.44
Re
F2
Cl2 , Br 2I 2 . C I 2 ( Chlorine )
is a
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.
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,
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
0.0591
nE
K ; K = Antilog
n
0.0591
Work=Charge Potentia=n FE
G=nFE
W max =nFE
Where
G =nFE
k , G E cell
G=nFE
G= H +T
( )
[ ]
Here
=
(
)
Case I: When
Case II: When
Case III: When
( )
( )
=0,then H =nFE
(
)
>0,
(
)
<0,
(
)
then
then nFE
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)
++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.
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.
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)
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
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
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
3++ 3 F
AlF 3 ( l ) Al
At anode:
F+ e
F
2 Al 2 O3 +12 F 4 AlF3 +3 O 2
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.
F2 ( g ) +2 e
2 F
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
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.
( Basic medium )
P PH 3+ H 2 PO 2
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
MnO2
as per reaction,
+ ( aq ) + H 2 (g)
Mn ( aq ) +2 H 2 O MnO 2 ( s ) +2 H
+2
1.0 1019 .
+2
EXAMPLE:8
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
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
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.
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
2+ ( aq )
Zn
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)
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 ) ,
+ ( 1 M )
Pt , H 2 ( p 1 atm ) H+ ( 1 M )
A.
p1= p2
B.
p1> p 2
C.
p1< p 2
D.
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
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
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
B.
C.
D.
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
A.
S
nF
C.
B.
H
/T
nF
(
)
is equal to:
HG
nFT
D. All of these.
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
OH 2 CaHPO 3 +2 H 2 O
the true statement (s) is/are
H 3 PO 3 +Ca
; 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.
C.
D.
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
m Molar conductance
Column II
P) Increases with dilution
Q) Increases with increasing the distance between parallel plates
C)
degree of dissociation
D) Resistance
T)
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
2+ +2 Cl
B)
Cl2 +Cu Cu
C)
D)
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
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.