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Electrochemist
ry
Electrochemist
ry
Is the study of the relationship between electricity
and chemical reaction
Reduction
REDOX REACTION
Oxidation
Cu2+ + 2e- → Cu
Oxidation no. ↓
Electrochemical reaction consists of reduction
and oxidation.
These two reactions are called ‘half-cell
reactions’
The combination of 2 half reactions are called
‘cell reaction’
Example
Reduction : Cu2+ (aq) + 2e- → Cu(s)
Half-cell
Oxidation : Zn(s) → Zn2+ (aq) + 2e- reaction
Overall cell
reaction :
Cu2+
(aq) + Zn(s) → Cu(s) + Zn2+ (aq)
Cells
There are 2 type of cells
Electrochemical Electrolytic
Cells Cells
Also called;
Galvanic cell or Voltaic cell
Chemical Electrical Electrical Chemical
Energy Energy Energy Energy
Component and Operation
of Galvanic cell
Consists of :
1) Zn metal in an aqueous solution of Zn2+
Voltmeter
Cu
Zn
electrode
electrode
Zn2+ Cu2+
CuSO4(aq)
ZnSO4(aq)
solution
solution Salt
bridge
What happens at the zinc
electrode ?
Zinc is more electropositive than copper.
Tendency to release electrons: Zn > Cu.
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.
What happens at the copper
electrode ?
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.
What happened if there is no salt bridge?
Zn Cu
e
e
e e
Zn2+ e e Cu2+
ZnSO4(aq) CuSO4(aq)
E = +1.10 V
Zn - + Cu
e
Zn2+ e
ZnSO4(aq) Cu2+ CuSO4(aq)
Salt bridge
(KCl)
How does the cell maintains its electrical neutrality?
anode cathode
oxidation reduction
spontaneous
redox reaction
half 19.2
Cell notation
Cell notation
Exercise
For the cell below, write the reaction at anode
and cathode and also the overall cell reaction.
Cell notation
Zn (s) | Zn2+ (aq) || Cr3+ (aq) | Cr (s)
= +0.34 – (-0.76)
= +1.1 V
Zn2+ (aq) + 2e- → Zn (s) E0 = -0.76V
= +0.34 + (+0.76)
= +1.10 V
Half-cell equation at:
H2 gas
at 1 atm
Pt
H+ (aq) electrode
1 M
The standard reduction of SHE is 0 V
Standard reduction potential of Zinc half cell is
measured by setting up the electrochemical
cell as below.
E0 = +0.76
- V + E0 = 0
+
-
H2 (g), 25oC,1 atm.
Zn e
e
e H+(aq),1 M
Zn 2+ e
ZnSO4(aq) Pt
1M
Standard Electrode Potentials
Ecell
0
= E0H+/H 2 - EZ0n /Z2+n
0.76 V = 0 - E0Zn 2+
/Zn
+ V- E0 = 0
- H2 (g) 25oC
+
1 atm.
Cu
H+
Cu 2
(aq)1
M
CuSO4(aq) Pt
1M
Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)
Anode (oxidation): H2 (1 atm) 2H+ + 2e-
Cathode (reduction): 2e- + Cu2+ (1 M) Cu (s)
H2 + Cu2+ Cu (s) + 2H+
Ecell
0
= E0cathode - Ea0node
E0cell = E0Cu 2+
/Cu – EH0/H+ 2
0.34 = E0Cu 2+
/Cu -0
E0Cu 2+
/Cu = 0.34 V
The direction of half-reaction of SHE depends on the
other
half-cell connected on it.
The cell notation for SHE is either:
H+(aq) | H2(g) | Pt(s) when it is cathode
= +0.34 + (+0.76)
= +1.10 V
Half-cell equation at:
or
Answer :
L < X < Y
Example
Calculate the E0 cell for the reaction ::
Mg(p) | Mg2+ (ak) || Sn4+ (ak) ,Sn2+ (ak) | Pt(p)
Given :
E0cell = Ecathode - Eanode
Mg2+ (ak) + 2e→ Mg(p) Eθ = -2.38 V =+0.15- (-2.38)
Sn4+ (ak) + 2e → Sn2+ (ak) Eθ= +0.15 V
=+2.53V
Eθcell = E o red + E o ox
= +2.38 + 0.15
= +2.53 V
Exercis
A cell is set up between ae
chlorine electrode and a
hydrogen electrode
E0cell = +1.36 V
Pt Pt
H+(aq), 1M Cl-(aq), 1M
1. Show the process occur at anode and
cathode
- Half-cell reaction
2. Overall reaction
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
• Spontaneous & Non-Spontaneous
reactions
- Redox reaction is spontaneous when
Ecell is +ve.
- Non spontaneous is when Ecell is –ve.
Eocell = Eo Sn /Sn
4+ 2+ → Eo Zn/Zn2+ Eocell = Eored + Eoox
= (+0.15) + (0.76)
= +0.15 – (-0.76 ) Or = +0.91 V
= +0.91 V
spontaneous
Predict : Spontaneous or non-
spontaneous?
Oxidation
cathode: Pb2+ (aq) + 2e → Pb(s) Eo = -0.13 V
anode: 2Cl-(aq) → Cl2(g) + 2e Eoox = -1.36
= -1.48 V
Non-spontaneous
No Reaction
Example :
Predict whether the following reactions occur
spontaneously :
2Ag(s) + Br2(aq) 2Ag+(aq) + 2Br-(aq)
[ product ]x
= Q
[ reactant] y
Answer
= +1.10 V – (-0.0385)
= +1.139 V
At equilibrium:
~ No net reaction occur (Q=K)
~ Ecell = 0
0 = Eocell – 0.0592
log K
n
Eθcell = 0.0592
log K
n
Example
2
Calculate the equilibrium constant (K) for the
following reaction.
Answer
At equilibrium, E cell = 0
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- M+,H+
Anion Cation
A Positive electrode
n The electrode which is connected to the
o positive terminal of the battery
d
Oxidation takes place
e
Electrons flow from anode to cathode
C
a Negative electrode
t The electrode which is connected to the
h negative terminal of the battery
o Reduction takes place
d
e
Electrode
as circuit connectors
as sites for the precipitation of insoluble
products
example: Platinum , Graphite (inert electrode)
Electrolyte
Reduction :
2H2O (l) + 2e- H2 (g) + 2OH- (aq) E0 = -0.83 V
Oxidation :
2H2O (l) 4H+ (aq) + O2 (g) + 4e- E0 = -1.23 V
Predicting the products of electrolysis
Solution
Na2SO4 aqueous solution contains Na+ ion, SO42- ion
and water molecules
On electrolysis,
the cathode attracts Na+ ion and H2O molecules
Anode
S2O82- (aq) + 2e- 2SO42- (aq) E0 = +2.01 V
O2 (g) + 4H+ (aq) + 4e- 2H2O (l) E0 = +1.23 V
mαQ
Q = electric charge in coulombs (C)
m = mass of substance discharged
The End
Q = It
Q = electric charge in coulombs (C)
I = current in amperes (A)
t = time in second (s)
1 F = 96 500
C
Exampl
e is electrolysed using a
An aqueous solution of CuSO 4
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
Mr for Cu = 63.5
Mass of Copper deposited = 0.014 x 63.5
= 0.889 g