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Electrochemis
try
Electrochemistr
y
Is the study of the relationship between electricity
and chemical reaction
Chemical reactions involved in electrochemistry are :
Reduction
Oxidation
REDOX REACTION
REDOX Reaction
REDUCTION
OXIDATION
gain of electron
loss of electron
Reaction at cathode
Reaction at anode
Remember
RED CAT
= REDuction
at CAThode
RED
CAT
Example:
Cu2+ + 2e- Cu
Oxidation no.
Example:
Example
Reduction : Cu2+(aq) + 2e- Cu(s)
Oxidation :
Overall cell
2+
2+
Cu
+
Zn
Cu
+
Zn
(aq)
(s)
(s)
(aq)
reaction :
Half-cell
reaction
Cells
There are 2 type of cells
Electrochemical
Cells
where chemical reaction
produces electricity
Electrolytic
Cells
Uses electricity to
produce chemical
reaction
Also called;
Galvanic cell or Voltaic cell
Chemical
Energy
Electrical
Energy
Electrical
Energy
Chemical
Energy
Galvanic cell
Voltmeter
Cu
electrode
Zn
electrode
Zn2+
ZnSO4(aq)
solution
Cu2+
Salt
bridge
CuSO4(aq)
solution
Zinc dissolves.
Oxidation occurs at the Zn electrode.
Zn2+ ions enter ZnSO4 solution.
Zn is the ve electrode since it is a source
of electrons anode.
Reactions Involved:
Anode
Cathode :
Overall cell
Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)
reaction :
Salt bridge
An inverted U tube containing a gel
permeated with solution of an inert
electrolyte such as KCl, Na2SO4,
NH4NO3.
Functions : Salt bridge helps to maintain electrical
neutrality
Completes the circuit by allowing ions
carrying charge to move from one half-cell
to the other.
ZnSO4(aq)
Zn2+
e
e
e
e
Cu
e
e
Cu2+
CuSO4(aq)
ANODE (-)
E = +1.10 V
Zn
ZnSO4(aq)
Zn2+
Cu
e
e
Cu2+
Salt bridge
(KCl)
CuSO4(aq)
Right Cell
Cu2+ (aq) + 2e- Cu (s)
Cu 2+ ions leave the solution.
Causing an overall excess of
-ve charge.
K+ ions from salt
bridge move into Cu
half cell
Electrochemical Cells
anode
oxidation
cathode
reduction
Spontaneous
Redox Reaction
half
19.2
Cell notation
Zn (s) + Cu2+ (aq)
Phase boundary
cathode
Cell notation
Exercise
For the cell below, write the reaction at
anode and cathode and also the overall
cell reaction.
Cell notation
3 Zn(s) 3Zn2+(aq) + 2e
6e- 2 Cr3+(aq) + 3e
6e- 2Cr(s)
X3
X2
Overall cell
3Zn(s) + 2Cr3+(aq) + 3Zn2+ (aq) +2Cr(s)
reaction:
Galvanic cell
Salt Bridge
measured by a
voltmeter
cell potential
Acts as electrical pressure that
pushes electron through the wire.
Electrode Potential
A measure of the ability of a half-cell to attract electrons towards it.
Cu2+(aq) + 2e Cu(s)
E ored = +0.34 V
Zn2+(aq) + 2e Zn(s)
E ored = -0.76 V
Standard reduction
potential
Cu2+(aq) + 2e Cu(s)
E ored = +0.34 V
Zn2+(aq) + 2e Zn(s)
E ored = -0.76 V
E0 = -0.76V
E0 = +0.34V
= +0.34 (-0.76)
= +1.10 V
= +0.34 + (+0.76)
= +1.10 V
Anode :
Cathode :
For example:
Cl2(g) + 2e- 2Cl-(aq)
E0 = +1.36 V
Cl2(g) + e- Cl-(aq)
E0 = +1.36 V
Cl-(aq) Cl2(g) + e-
E0 = -1.36 V
H2 gas
at 1 atm
H+ (aq)
1 M
Pt
electrode
E0 = +0.76
-
Zn
e
e
e
2+e
Zn
ZnSO4(aq)
1M
E0 = 0
+
H2 (g), 25oC,1
H+(aq),1 M
Pt
atm.
0
Ecell
= EH0+/H 2- EZn0 2+/Zn
0 2+
0.76 V = 0 - EZn
/Zn
0 2+ = -0.76 V
EZn
/Zn
Zn2+ + 2e- Zn
E0 = - 0.76 V
V-
E0 = 0
-
H2 (g) 25oC
1 atm.
Cu
Cu
CuSO4(aq)
1M
Pt
H+
(aq)1
M
H2 (1 atm)
2+
/Cu
EH 0/H+
0 2+
0.34 = ECu
/Cu - 0
0 2+
ECu
/Cu = 0.34 V
Cu (s)
Cu (s) + 2H+
0
0
0
Ecell
= Ecathode
- Eanode
0 = E0
Ecell
Cu
2H+ + 2e-
E0 = -0.76V
E0 = +0.34V
or
= +0.34 (-0.76)
= +1.10 V
= +0.34 + (+0.76)
= +1.10 V
Anode :
Cathode :
At standard-state condition
Exercise
Calculate the standard cell potential of the following
electrochemical cell.
Co(s) | Co2+(aq) || Ag+(aq) | Ag(s)
Ag+(aq) + e- Ag(aq)
Answer
+
Cathode (Red) : Ag (aq) + e Ag(aq)
E0 = +0.80V
E0 = -0.28V
E0 = +0.80V
E0ox = +0.28V
Increase
strength as
reducing
agent
Exercise
Arrange the 3 elements in order of increasing
strength of reducing agents
X3+ + 3e- X
E0 = -1.66 V
Y2+ + 2e- Y
E0 = -2.87 V
L2+ + 2e- L
E0 = +0.85 V
Answer :
L < X < Y
Example
Calculate the E0 cell for the reaction ::
Mg(p) | Mg2+(ak) || Sn4+(ak),Sn2+(ak) | Pt(p)
Given :
Mg2+(ak) + 2e
Sn4+(ak)
Mg(p)
E = -2.38 V
+ 2e Sn2+(ak) E= +0.15 V
Oxidation
: Mg(p)
Mg2+(ak)
Reduction
: Sn4+(ak)
+ 2e
+ 2e
Sn2+(ak)
Ecell = E o red
= +2.38 + 0.15
= +2.53 V
E o ox
Exercise
A cell is set up between a chlorine electrode and a
hydrogen electrode
Pt | H2(g, 1 atm) | H+(aq, 1M) || Cl2(g, 1atm) | Cl-(aq, 1M) | Pt
E0cell = +1.36 V
(a) Draw a diagram to show the apparatus and chemicals
used.
(b) Discuss the chemical reactions occurring in the
electrochemical cell.
Answer
E0cell =1.36V
H2 (g),
1 atm.
+
+
Pt
Cl2 (g),
1 atm.
Pt
H+(aq), 1M
Cl-(aq), 1M
Answer
Reduction (cathode)
Cl2 (g) + 2e- 2Cl- (aq)
Oxidation(anode)
H2 (g) 2H+ (aq) + 2e-
E0 = 0
Eocell =+1.36 V
Eocell = Eocathode - E0anode
+1.36 = Eocathode 0
E0cathode = +1.36 V
So the standard reduction potential for
Cl2 is:
Eo = +1.36 V
Zn + Sn4+
Sn2+ + Zn2+
Eo Zn2+/Zn = - 0.76V.
The two half-cells involved are:Anod : Zn Zn2+ + 2e
Eoox = +0.76 V
Cathode: Sn4+ + 2e Sn2+ Eo = +0.15 V
Zn + Sn4+
Eocell = Eo
Sn /Sn
4+
Zn2+ + Sn2+
2+
Eo Zn
= +0.15 (-0.76 )
= +0.91 V
spontaneous
Zn
2+/
Or
Reduction
Pb2+Pb
(aq)
+
2Cl
(aq)
Pb(s)
+
Cl
(g)
2+
2
(aq) + 2Cl (aq) Pb(s) + Cl (g)
2
Oxidation
cathode: Pb2+(aq) + 2e Pb(s)
anode: 2Cl-(aq) Cl2(g) + 2e
Eo = -0.13 V
Eoox = -1.36
Example :
Predict whether the following reactions occur
spontaneously :
2Ag(s) + Br2(aq)
2Ag+(aq)
+ 2Br-(aq)
0 +
EAg
/Ag = +0.8 V
Answer :
2Ag(s)
Br2(aq)
2Ag+(aq)
+ 2e
2Ag(s) + Br2(aq)
+
2Br
standard reduction
potential
2e
(aq)
2Ag+(aq) + 2Br-(aq)
E ox = - 0.80 V
E = +1.07 V
Esel = + 0.27 V
Exercise
A cell consists of silver and tin in a solution of 1 M
silver ions and tin (II) ions. Determine the spontaneity
of the reaction and calculate the cell voltage of this
reaction.
E0 = +0.80 V
E0 = -0.14 V
E0cell
(cathode)
(anode)
= +0.80 (-0.14)
= +0.94 V
= +ve ( reaction is spontaneous)
Nernst equation
Nernst equation can be used to calculate the E
for any chosen concentration :
Ecell = Eocell
RT
nF
ln
[ product ] x
[ reactant] y
0.0257
n
2.303 log
[ product ] x
[ reactant] y
cell
[ product ] x
log
[ reactant] y
n
[ product ]x
[ reactant]
Ecell = Eocell
0.0592
log Q
n
n = no of e- that are involved
Q = reaction quotient
Example
1
Answer
Zn(s)
+ Cu2+(aq)
Zn2+(aq)
+ Cu(s)
= +0.34 V + 0.76 V
= +0.34 V - (- 0.76 V)
= +1.10 V
= +1.10 V
E = Eo 0.0592
log [ Zn2+]
[ Cu2+]
= +1.10 V (-0.0385)
= +1.139 V
( 0.40)
At equilibrium:
~ No net reaction occur (Q=K)
~ Ecell = 0
Ecell = Eocell 0.0592
log K
n
0
= Eocell 0.0592
n
Ecell
0.0592
n
log K
log K
Example
2
2Ag+(ak)
Cu2+(ak)
Answer
At equilibrium, E cell = 0
Eocell = Eo cathode -
Eo anode
= +0.80 ( +0.34)
= +0.46 V
2Ag(s)
log K
2
0
= 0.46 0.0592
log K
2
0.0592 log K = 0.46
2
log K = 15.54
K = 3.467
x 1015
Electrolysis
Electrolysis is a chemical process that uses electricity
for a non-spontaneous redox reaction to occur.
Such reactions take place in electrolytic cells.
Electrolytic Cell
It is made up of 2 electrodes immersed in an
electrolyte.
A direct current is passed through the electrolyte
from an external source.
Molten salt and aqueous ionic solution are commonly
used as electrolytes.
Electrolytic Cell
+
Oxidation
Reduction
Electrolyte
(M+X-)
X-,OH-
Anion
M+,H+
Cation
A
n
o
d
e
Positive electrode
The electrode which is connected to the
positive terminal of the battery
Oxidation takes place
Electrons flow from anode to cathode
C
a
t
h
o
d
e
Negative electrode
The electrode which is connected to the
negative terminal of the battery
Reduction takes place
Electrode
as circuit connectors
as sites for the precipitation of insoluble
products
example: Platinum , Graphite (inert electrode)
Electrolyte
a liquid that conducts electricity due to
the presence of +ve and ve ions
must be in molten state or in aqueous
solution so that the ions can move freely
example: KCl(l), HCl(aq), CH3COOH(aq)
Anode
Electrochemical Ce
e-
Cathode
e-
Anode
e-
Cathode
Electrolytic Cell
Cathode = negative
Anode = positive
Electrochemical Ce
Cathode = positive
Anode = negative
Non-spontaneous redox
Spontaneous redox
reaction requires energy reaction releases energy
to drive it
Similarities:
Oxidation occurs at anode, reduction occurs
at cathode
Anions move towards anode, cations move
towards cathode.
Electrons flow from anode to cathode in an
external circuit.
Anion : Cl-
E0 = - 0.83 V
Oxidation :
2H2O (l)
E0 = - 1.23 V
concentration of electrolyte.
Na (s)
E0 = - 2.71 V
E0 = - 0.83 V
Anode
Cl2 (g) + 2eO2 (g) + 4H+ (aq) + 4e-
2Cl- (aq)
2H2O (l)
E0 = + 1.36 V
E0 = + 1.23 V
Reactions involved
2H
O
(l)
+
2e
2
Cathode:
Cell
6H2O(l)
reaction:
2H2O(l)
4 H2O
O2(g) + 2H2(g)
E0cell = - 2.06 V
Na (s)
E0 = - 2.71 V
E0 = - 0.83 V
Anode
Cl2 (g) + 2eO2 (g) + 4H+ (aq) + 4e-
2Cl- (aq)
2H2O (l)
E0 = + 1.36 V
E0 = + 1.23 V
Reactions involved
Cathode: 2H2O (l) + 2eAnode:
2Cl- (aq)
Cell
2H2O(l) + 2Clreaction:
E0 = -1.36 V
Exercise
Predict the electrolysis reaction when
Na2SO4 solution is electrolyzed using platinum electrodes.
Solution
Na2SO4 aqueous solution contains Na+ ion, SO42- ion
and water molecules
On electrolysis,
the cathode attracts Na+ ion and H2O molecules
the anode attracts SO42- ion and H2O molecules
Cathode
Na+ (aq) + e-
Na (s)
E0 = - 2.71 V
E0 = - 0.83 V
Anode
S2O82- (aq) + 2eO2 (g) + 4H+ (aq) + 4e-
2SO42- (aq)
2H2O (l)
E0 = + 2.01 V
E0 = + 1.23 V
Equation
Cathode: 2H2O (l) + 2e-
2H2O (l)
Cell
2H2O(l)
Reaction:
E0 = - 1.23 V
E0cell = - 2.06 V
Faradays Law of
Electrolysis
Faradays 1 Law
st
mQ
Q = electric charge in coulombs (C)
m = mass of substance discharged
Q = It
Q = electric charge in coulombs (C)
I = current in amperes (A)
t = time in second (s)
1 F = 96 500
C
Example
An aqueous solution of CuSO4 is electrolysed using a
current of 0.150 A for 5 hours. Calculate the mass
of copper deposited at the cathode.
Answer
Electric charge, Q = Current (I) x time (t)
Q = (0.150 A) x ( 5 x 60 x 60 )s
Q = 2700 C
1 mole of electron 1 F 96 500 C
No. of e passed through =
-
2700
96 500
= 0.028 mol