ELECTROCHEMISTRY

The branch of chemistry which deals

with the relationship between chemical
reaction & electrical energy is known
as electrochemistry. It has two
aspects, the study of chemical reaction
which occurs due to the passage of an
electric current & the generation of
electricity by chemical reaction.


Arrhenius theory of electrolytic dissociation(1887)
(i) An electrolyte on dissolving in suitable solvent gives equal no.
of +ve charge & -ve charge ions.
(ii) Since the no. of cations & anions are equal in given solution ,
the solution as whole is electrically neutral in nature.
(iii) Cations are obtained from metallic atoms or radicals by loss of
electrons, while anions are obtained from non-metallic atoms or
radicals by gain of electrons.
(iv) The process of electrolytic dissociation is a reversible process.
(v) The ions are free to move & under the influence of electricity , they are
directed towards oppositely charged electrodes.
(vi) The properties of the electrolytes in solution are the properties of the ions
produced.
(vii) No. of molecules dissociated into ions
Degree of ionization= --------------------------------------------------
Total of molecules taken
(viii) Strong & weak electrolytes.
(ix) The conduction of an electrolytic solution ,generally increases with
increase in temp
Electrolysis
The process in which by conversion of electrical energy into
chemical energy or decomposition of an electrolyte takes place is
known as electrolysis . This process is carried out in electrolytic
cell
Electrolytic cell:
A suitable device of glass or steel in convenient shape & size in
which electrical energy converted into chemical energy known as
electrolytic cell .
Mechanism of electrolysis:
BA=B
+
+ A

At cathode : B
+
+e
-
B(Reduction)
At anode:A

A + e
-
( Oxidation)



Specific conductivity(K):
The resistance of a conductor is directly proportional to its length
& inversely proportional to its cross-sectional area.(Ohms law)
l
R= Where R= resistance in ohms ; = specific
A resistance or resistivity; l= length in cm; A= area of
cross- section in cm
2
Thus, if l=1 cm; A=1 cm
2
; then R=
Sp resistance of a conductor is the resistance between two
opposite faces of a cm cube of that substance. Sp cond is the
reciprocal of sp resistance of an electrolytic solution.
K=1/ = l/AR ohm
-1
cm
-1

If l=1cm; A=1 cm
2
;
then K= 1/R= conductance
Sp cond (K) is the cond of 1 cm
3

of solution of an electrolyte.

B. Equivalent conductivity(A
eq
):
Eq cond of an electrolytic solution is defined as the conductance
of all the ions present in 1 eq of the electrolyte in the solution at
given dilution. If I eq of electrolyte is contained in v mL, then:
A
eq
= v xSp cond of 1 cm
3
of solution= vx K
If normality of electrolytic solution is N, then;
v= (1/N)L=(1000/N)mL(or cm
3
)
A
eq
=1000K/N ohm
-1
cm
2
eq
-1


MOLAR CONDUCTIVITY((m)
Molar cond of a solution is defined as the conductance of all the
ions present in 1 mole of the electrolyte in the solution at given
dilution. If M is the molar conc. In mol/L, then
m =1000K/M ohm
-1
cm
2
mol
-1

Cond=
K
Eq
cond
=9xK
Variation of conduction with dilution :
Specific conductance: Sp cond of a solution depends on
i) the no. of ions ii) the amt of water present in the
solution. Sp cond decreases with dilution.
Equivalent conductance: Eq cond increases with
dilution.
Eq
cond
C
o.o5 o.1 0.15
140
120
100



NaCl
BaCl
2
CH
3
COOH
CH
3
COONa
Conductometric titration:
1. Titration of strong acid with strong base:





2.Titration of weak acid with strong base:
Cond
Vol of alkali added
Cond
Vol of alkali added
End point
Faradays first law of electrolysis(1834)
During the electrolysis , the amount of substance liberated or
deposited at an electrode is directly proportional to the quantity of
electricity passed through an electrolyte.
WQ Where W= wt of sub
Q= qty of electricity in coulomb
But Q=it i= current in amp
t= time in sec
W it
W= Zit When i=1 & t=1sec i e Q=1Coulomb
W=Z Z= Electrochemical equivalent( ECE) of sub
ECE is the amount of sub deposited or liberated at an electrode
when 1Q of electricity passed through its solution i e current of 1
amp passed for 1 sec through the solution

Faradays second law of electrolysis:
When different electrolytes are arranged in series & same amount
of electricity passed through them , the amount of different sub
deposited or liberated at the respective electrode are directly
proportional to their chemical equivalent
W
1
E
1
Where W
1
& W
2
are the wt of sub
W
2
E
2
deposited or liberated & E
1
& E
2
are the
chemical equivalent of sub
W
1
E
1

----- = -----
W
2
E
2



CuSO
4
AgNO
3
B
RELATION BETWEEN ECE & CE:
ACCORDING TO FARADAYS FIRST LAW
W
A
= Z
A
i t
W
B
= Z
B
i t
W
A
Z
A
---------- = --------

W
B
Z
B
ACCORDING TO FARADAYS SECOND LAW

W
A
E
A
---------- = --------

W
B
E
B


E
A
Z
A
-------= --------

E
B
Z
B

E

Z

; E/Z= CONST; E/Z= 96500C( 1F=96500C)
E/Z of Cu=31.75/3.29x10
-4
=96504
coulombs
[1F=96500 coulombs]
E/Z of Ag=107.9/1.110x10
-3
= 96469
coulombs
E/Z of I= 127/1.31x10
-3
=96500 coulomb
E/Z of Zn=32.7/3.39x10
-4
=96500 coulomb
Kohlrauschs law of independent migration of ions:
At infinite dilution, when dissociation is complete & all
interionic effects vanish , each ion contributes to the
total molar cond. of an electrolyte at a definite share.
Thus molar cond at infinite dilution[A
m

] of any
electrolyte is equal to the sum of the molar cond of its
cation & anion.
A
m

=v
+

+ v
-

Where v
+
&v
-
the no. of cations & anion per formula of
electrolyte &
+

&
-

are molar cond at infinite dilution
of cation & anion respectively.
e.g. (MgCl
2
), v
+
= 1& v
-
=2;
A
m

(MgCl
2
)=

( Mg
2+
) + 2

(Cl
-
)

Applications of Kohlrauschs law:
A.Determination of molar cond of a weak
electrolyte (Acetic acid):
= A
m

(HCl)+ A
m

(CH
3
COONa)- A
m

(NaCl)
=[

( H
+
)+

(Cl
-
)]+[

(CH
3
COO
-
) +

( Na
+
)]-
[

( Na
+
)+

(Cl
-
)]
=[

( H
+
)+

(CH
3
COO
-
)= A
m

(CH
3
COOH)



B.Determination of degree of dissociation:
No of molecules dissociated into ions
o
c
= -------------------------------------------------
Total of molecules taken
A
m
c
, the molar cond at a particular dilution No of molecules
dissociated into ions at this dilution (i)
A
m

Total of molecules taken .(ii)
Dividing (i) by (ii) we get;
A
m
c
No of molecules dissociated into ions at this dilution
------= -------------------------------------------------------------------
A
m

Total of molecules taken
The value ofA
m
c
can be obtained by direct measurement; while
A
m

can be obtained with the help of Kohlrauschs law
Determine of solubility of sparingly soluble salt:
AgCl, BaSO
4
,CaCO
3
,PbS, etc
For very sparingly soluble salts: A
eq

c
=A
eq

= Kv
v= A
eq

/K=

v
+

+ v
-

/K


But v cm
3
of saturated solution contains= I eq
1000 cm
3
or 1 L sat. sol contains=(1000/v)eq
Hence , solubility of salt, S= 1000/v eq/L
=1000E/v g/L
=1000xE(eq wt) xK/ [v
+

+ v
-

] g/L

~
Ostwalds dilution law:
Binary electrolyte BA, dissociates as:
BA B
+
+A
-

Suppose 1 mole BA is dissolved in V L of water & at equilibrium a
fraction o of it is dissociated into ions
BA B
+
+ A
-

Amt at equilibriumm (1-o) mol o mol o mol
Equi concentrtion (1-o/V) mol /Lit o/V mol /Lit o/V mol /Lit
On applying law of mass action, we get:
[B
+
] [A
-
] o/V.o/V o
2
o
2
o
2
C
--------- = ----------- = ------- = K, K=-------- = --------
[BA] 1-o/V (1-o)V (1-o)V (1-o)
Where C is the conc in mol/Lit
For a wk electrolyte
K=

o
2
/V (Where o is very small)
pH & pOH
pH value of a solution is defined as negative of logarithm
of the hydrogen-ion conc, expressed in mole/litre
pH= -log
10
[H
+
] = log
10
1/[H
+
]
At 25 C , the ionic product of water,
Kw= [H
+
][OH
-
] = 10
-14
.
Also in pure water:
[H
+
]=[OH
-
]
In neutral solution,
[H
+
]=[OH
-
] = \1x 10
-14
= 1x10
-7

or pH of neutral solution = -log
10
1x10
-7
= 7
pOH= = -log
10
[OH
-
]
pH + pOH=14
pH=7 neutral solution
pH< 7 acidic solution
pH> 7 basic solution

Buffer solutions :
A buffer solutions is one which maintains a fairly
constant pH, even when small amt of acid or alkali is
added to it
(i) Acidic Buffer : Acidic buffer can be made from acetic
acid & sodium acetate
CH
3
COOH H
+
+ CH
3
COO
-
(feebly ionized)
CH
3
COONa Na
+
+ CH
3
COO
-
(highly ionized)


When a few drops of acid are added to it
HCl H
+
+ Cl
-

CH
3
COONa

+ H

Cl

CH
3
COOH + NaCl
(from buffer) (from added acid)
When a few drops of base are added to it,
NaOH Na
+
+ OH
-

CH
3
COOH + NaOH H
2
O + CH
3
COONa
(from buffer) (from added base)

(ii) Basic buffer: A basic buffer can be made from
mixture of ammonium hydroxide & ammonium chloride
NH
4
OH NH
4
+
+ OH
-
(feebly ionized)
NH
4
Cl NH
4
+
+ Cl
-
(highly ionized)


When a few drops of base are added to it,
NaOH Na
+
+ OH
-

NH
4
Cl + NaOH NH
4
OH + NaCl
(from buffer) (from added base)
When a few drops of acid are added to it ,
HCl H
+
+ Cl
-


NH
4
OH

+ H

Cl

NH
4
Cl + H
2
O
(from buffer) (from added acid)
pH of acidic buffer: The dissociation of a wk acid HA is expressed as:
HA H
+
+ A
-

[H
+
] [A
-
] [HA]
K
a
= ------------ or [H
+
]= K
a
----------- ---------(i)
[HA] [A
-
]
Where K
a
is dissociation const of acid
For preparing a buffer , a highly ionized salt of acid, BA is added to it
BA B
+
+ A
-

It can be assumed that all the ions have come from the salt itself i. e.,
[A
-
] =[ BA] -------- (ii)
From (i) & (ii) , we get:
[HA] [ Acid]
[H
+
]= K
a
-------- = K
a
-------- ;
[BA] [salt]
Taking log & reversing the sign, we get:
[Acid] [Salt]
-log [H
+
]= -log K
a
log--------;pH = p K
a
+log --------
[Salt] [Acid]

Henderson- Hasselbatch equation
[base] [Salt]
-log [OH
-
]= -log K
b
log--------;pOH =p K
b
+ log ---------
[Salt] [Base]
Henderson- Hasselbatch equation



Solubility product:
In a saturated solution of any sparingly soluble electrolyte, the
product of the conc of the ions, raised to a power equal to the
no of times the ion appears in the equation representing the
ionization of the electrolyte , is a const at a given temp.
A saturated solution is a solution in which the dissolved &
undissolved solute are in equilibrium.
The solubility of a substance in a solvent is the conc in the
saturated solution.
Exa AgCl Ag
+
+ Cl
-
Applying the law of mass action:
K=[Ag
+
] [Cl
-
] /[ AgCl] K
sp
= [Ag
+
] [Cl
-
] where K
sp
solubility
product, [Ag
+
] & [Cl
-
] are expressed in mole/lit
K
sp
= [ Ag
+
] [Cl
-
]
solubility product S mol / L S mol /L
=S
2
mol
2
/L
2
=S
2
The product [Ag
+
] [Cl
-
] in the K
sp
expression above is called Ionic
product or ion product.
Electrochemical cell:
An electrochemical cell is a device in which a redox reaction is
utilized to get electrical energy. The electrode where oxidation
occurs , is called anode; while the electrode where reduction
occurs , is called cathode.

At anode (-ve electrode): Zn Zn
++
+ 2e
-
( Oxidation)
At cathode(+ ve electrode): Cu
++
+2e
-
Cu ( Reduction)
____________________________________________
Cell reaction: Zn + Cu
++
Zn
++
+ Cu

Representation of galvanic cell:
Zn; Zn
++
(1M) II Cu
++
(1M);Cu

ZnSO
4
Zn anode -
Electron flow
Voltmeter
Cu
cathode+
CuSO
4
Salt-bridge
EMF of electrochemical cell:
Zn
-
I Zn(aq) II Cu(aq);Cu
+
E
cell
=E
right
- E
left

E
cell
= e.m.f. of cell
E
right
= reduction pot of right hand side electrode
E
left
= reduction pot of left hand side electrode
Nernsts equation for a cell reaction:
Cell reaction: Zn
(s)
+ Cu
++
(aq)
Zn
++
(aq)
+ Cu
(s)

2.303RT V [Zn
++
]
E
cell
= E
0
cell
- --------------- log ---------
nF [Cu
++
]
At 298 K, the Nernsts equation can be written as:
0.0592 V [Zn
++
]
E
cell
= (E
0
cathode
- E
0
anode
) - ---------------log ---------
n [Cu
++
]


Concentration cell:
A conc cell is made up of two half-cells having identical electrodes, identical
electrolytes, but conc of the reactive ions at the two electrodes are different.
The two half-cells may be joined by a salt bridge .

-
Ag|AgNO
3
(C
1
M) Dil || AgNO
3
(C
2
M) conc|Ag
+


2 .303RT C
2
0.0592 V C
2

E
cell
= ------------log-------- = --------- log ------
nF C
1
1

C
1

At left electrode(anode) :Ag Ag
+
(C
1
) + 1e
-
( Oxidation)
At right electrode(cathode):Ag
+
(C
2
)+1e
-
Ag( Reduction)



AgNO
3
Ag-
Ag+
AgNO
3
Electron flow
Voltmeter
Salt bridge
Std electrode potentials(reduction)at 25
0
C
Metal ion Potential in volts
Li
+
+e
-
Li
K
+
+e
-
K
Zn
++
+2e
-
Zn
Fe
++
+2e
-
Fe
Sn
++
+2e
-
Sn
H
+
+e
-
H
Cu
++
+2e
-
Cu
Ag
+
+e
-
Ag
Pt
4+
+4e
-
Pt
Au
+
+e
-
Au
F
2
+e
-
F
-

-3.05 (anode)
-2.93
-0.76
-0.44
-0.14
0.00 ( Reference)
+0.34
+0.80
+0.86
+1.69
+2.87 (Cathode)