ELECTROCHEMISTRY Potential

generated
Oxidation
b/w electrode and

potential Reduction
electrolyte solution

potential
.

voltmetey
e er
↑ >
-

cathode
Anode Cathode Spontaneous process
Anode
-
t
& Reduction (
Functions of salt Bridge Ezn/In
+2
Ecu/cut2 Eint/In Ecut/CU
(oxidation) AGCO Ecell > O
Salt
Bridge

-
& &
· &

Neutralise the solution

EAglAgt EFet/Fe EAgt/Aq
----
+3

Non-spontaneous process
- - - - -
----

----

Completes the circuit

- - - - -

O
- - -
- - -
O

D aniel Cell
.

- - - - ---
- - - -
- -
- - - -
--

Ecell <O
---

AG 30
-

↑
InSO4 CUSO4

y
Properties of inest
electrolyte /KC KNO3 ,
KISOG / 7
into electrical
.

converts chemical energy

energy
should not participate in reaction
.

e-moves

current
from anode to cathode

moves from C to A .
.
↑
( - mobility of cation and anion should be same .

Standard Electrode Potential (E)

Potential measured at 298K and IM conce

Electrochemical cell
Electro de potential :
(E) Standard Oxidation potential (SOP)
Anode (oxidation)

f &> Ezn/In + AglAgt

:
2
E
In t (ap) electron move from anode to cathode
ins(s)
-
: + ze- .

> Standard Reduction (SRP)

Cathode (Reduction ( current move from cathode to anode
. potential
*
Current in outer circuit is due to electrons
. E
:
In 2/ In
+
Ecell Eoxi + ERed
cu
(ag) culs)
-
=
+ 2e

+
* current in inner circuit is due to ions
. Anode Cathode
Overalloxn -

In(s) + Cu 2/ag) 1 In (ap) + Cu(s)

of electrode
significance potential

NITESH DEVNANI
Anode II Cathode
of cell
- Representation (ag)(Intlagl
+
Electrode
In (s) 2H He
ly potential value
gives the tendency of an element to
get
+ +

In (s) 1 In cap) 11 Cu
*

(ag)/culs) L M

oxidised or .
reduced

/
- Oxidation
Salt
Bridge .

Anode reduction B 'B + + E =

1 3V
.

y
+2
+ 20
-

> Y E =
1 TV
.

Note-Electrode is formed of solid substance. Cathode

always
L tendency to get oxidised reduced
In (5) / In
+

(ag) II H+
(ag) / H2 (g) ,
Pt(s)
More wants to
get move

Inext electrode .
Better
Reducing Agent Better
oxidising Agent
*
Anode In(s) < In
(aq) + ze-

*
Cathode Cu (ag) + 22- Culs)
+ *
Overall -xn In (s) + Cu Culs)
(ag) (aq)
< In +

@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194

-
 ELECTROCHEMISTRY Relation b/w AG

E cell and
Kea -
Spontaneous
AGicO"Ecell0 <Keq > 1
Non-spontaneous
E'cell-RT enQ
<
Ecell = Reaction Quotient AGO'EcellCO'Kepc1
F
Trick L
F-Faraday's constant At
equilibrium AG O
=

T-Temperature concentration
of electrons solid-Ignore Aqueous
-

n-no .

Ecell 0
Electrolysis
=

substance
4-Reaction Quotient
R-Universal Gas constant Gaseous Partial pressure
Breakdown of a
using electricity
e--ignore
-

O =

Keq -
Electrolysis is
non-spontaneous

c
+

(aq
+
Cu ! Cu(s)
4
In (s) + > In
(ag) +
E cell 0 0591
log Keq Battery
= .

&
[In 2]
+

- D
=

L Nerst equ
Nerst equ at 298K [Cu+2]
Ecell Excell 0 0591
10G &
.
= -

of H20
R
Electrolysis of Molten Nach Electrolysis
+
Oxidation -

H2(g)'2H (ag) + ze- EOM2/H + =

0

2H
it
Anode /Oxidation) H2O
+ 02(g) 22-
+ : + +
Reduction
H2(g)
:
-

24 (aq) + 22- E H
+
/H2 =
0 Cathode Anode
Reduction potential
Hydrogen E 0
- = ·

cathode (reduction)
H2(g)
: 22- + 2H20 > + 20H-
Standard electrode is zero.
Hydrogen SHE 0
=
-
2
PHz I
& = = -
[H +)
- . . . - -

is taken as reference.
[H ]
+ 2
Chtyz Because
hydrogen
-
- - - -

m
&
- Anode Cathode
H2(g)
>

+02(g)
-----

>

Hydrogen potential
-
. . . - -

- - - - -

- - - -

E =
-0 0591 x.

PH Reduction
f Anode-In(s)

Cathode
+
> In (aq) + ze
cation move towards cathode
Faraday's law

Hydrogen In 15)
>
In (aq)
+ 22-

NITESH DEVNANI
towards anode
-

Anion move

Reduction Oxidation
concentration cell =
E cell =
0 Charge on 1 mole electron >
96500C 1
Faraday
cathode Nat +e Nalsl
concentration cell >
-
-
-

+ +
Overalloxn In (ap) > In
(aq) on
passing If
charge one
gram equivalent
is
deposited
-

E
E -0 0591 X
PH + 0 0591 X
PH
= =

Anode-ci'"[C(z(g)
. . ,

+ er

I
In Anode In cathode
↓ C2 Cl

eq cot
.
=
Molar mass

9 [In +2) Rf
C
= =

E cell C2 [In +2]

0 0591
log
= .
- - -
- -

- - - -

== =
- - - -

--
- -
L Cl
- -
-

- - - - - -

- - - ---
- >
-

InSO4 InSO4

Cl C2 @niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194

 ELECTROCHEMISTRY Electrolysis
First law of
Second law of Electrolysis
WXG I=
t "i
W 29
V
=
Swiss V

cathode
case-2
Using HG as
:

9 =
It (same current) - -

=I
- - - -

Inest electrode = -- Well Ecu

case-1
Using W [It
=
: I

Nat Cl-CNach
- - - - - -

Waq
- - - - - - -

Electrolysis of Nach
E
EAq
- - -

Nat C' ageous I =

-
NaCl
Ag
>
+ EXIXt Cu
H OH H2O
-

>
W =
96500

I
+
H20 > H OH-
Anode, ci
96500 We Ep .
cot Cu
[Ck2(g)
< +

cathode >
22 + 2H20 H2 + 20H
-

>
-

cot
Wag x Eq AG

(
.

N
Anode : C1-"1 Cl2 + e- Cathode (Natter : Na(s)
conductance of solution
electrolytic N
L
2
of foundation of
Na-Hg
area of cross section
es
Amalgam .

- - - - - -
Electrolysis
- - - -

Case 2 H2SO4

I (
Conc cell
Electrolytic
-
-
- - -

- - - -

- - -

H2SO4 HT 5042-
H2O H OH- Resistance (R) R =
Sl Unit :
okm
case 1 -Dil. Heson' same as water
7
-
A
Relation /W Am and XE :

H2SO4 H
+
SO4 Cathode-H2(g)
Resistivity (s)
Xm K X 1000
S208
=

H2O H
+
OH- Anode-250 : < + zet
N
MXNf
=

of H2504 M
Electrolysis Marshal's
-
Conductance (G) G =
1
R
cathode
-H2(g) &E =
K X 1000

Y
Acid H2S208

**
N
Anode-H20 >
102
+ 2H + 2 conductivity (k) Kappa GX

XE =
K X 1000

Conductance Cell constant

Conductivity MX
=
x
f
copper electrodes
Using
t
Case 2 :

NITESH DEVNANI
XE Am
XMf
=

case I'

cut2 304
Using
-
Inest electrode
2 >
- Cathode
-
Manode
If Cathode

Cut +
-

2
-

>
Cu(s)
-
L
Pure
n Cl
CU
Impure
H
+
OH- Electrolysis of
ap CUSO4
.

CU Anode- Molar
Conductivity (xm) Equivalent conductivity (E)

of
I solution
conductivity gram equivalent
- . . .

culs)(cutap)
--

Cathode Cut +
2e-'Cu(s)
<
molar solution
+ ze-
conductivity of
-
- - -

1
-

L
- -
- -
- -

+
L
Cut2

Anode-H20"102 22- + zM Mass of anode yes 1E <x 1000 Unit-Sm2egt

- -

+
unit-Sm2mol
- -
=
0 0 0 0
-
CUSO4 aq I - Am =
KX 1000
60 O
o o o
N
M
V Mass of cathode ↑ es
Anode muc of a
Refining
All Pt)
(Ag , ,

@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194

ELECTROCHEMISTRY
variation of conductivity with conc Electrolyte -
weak
electrolyte
Metallic conductor Am increases on dilution
decreases with decrease in conc /dilution
Conductivity
↑ ↑ >
-

Resistance Conductance I

of Ions)
increase) of both weak and
strong electrolytes
.
↓ Ostwald's dilution law

on dilution of weak
electrolyte
Electrolytic Conduction
(Mobility Conco > Dilution 4
of dissociation increases
TP Conductance ↑ I Strong Electrolyte Degree
K < conc x

Dilution No of Ions increases

.

Xm increases on dilution
Am increases
.
On dilution distance b/w cation

4
,

Kohlrausch law : AB and anion increases

valid for both and weak electrolyte

strong Variation
Force of att decreases
Am

(m) :
* Ions can move
freely

↓
*

(Xm) AB
= + +
(1m) B-

(E) AB =
(e) " A ++ (E) B- a Concl
L
VonG
Am dil *

-
-

For weak
electrolyte
E
we cannot find Xm' or Am
conck VONC

NITESH DEVNANI
di)
Degree of dissociation (X
variation of molar
conductivity
graphically
Xi =
molar
conductivity at zero conc
X Am conc
Xm molar
conductivity Increases with decrease in
conductivity at infinite dilution
Co
molar
=
=
Xm =

Xm
Xm Increases with dilution
molar
conductivity at
(c) '
=

Xm =
Am -A
keq CX
=

Xm Dilution
I I I

x 1 <
infinite dilution
1 -
x .
Conce ↓

@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194