Electrochemistry
1
Content
Oxidation and reduction
Balancing net ionic equations for redox
reaction
Galvanic cells
Reduction potentials
Correlation between cell potentials and
thermodynamic values
Electrochemical decomposition
2
LESSON OUTCOMES
At the end of this lecture, students should
be able to:
• Identify the oxidizing and reducing agents
in a redox reaction
• Write equations for oxidation and reduction
halfreaction and use them to balance the
net equation.
• Describe galvanic cells
3
LESSON OUTCOMES
At the end of this lecture, students should
be able to:
• Draw cell diagram
• Write shorthand notation
• Calculate cell potential
• Calculate ΔG from cell potential
• Apply Nernst equation
4
Oxidation and reduction
LEO - Loss Electron Oxidation
GER - Gain Electron Reduction
0 +1 +2 0
9
The substance makes another substance to be oxidized is
called the oxidizing agent or oxidant.
The substance causing another substance to be reduced is
called a reducing agent or reductant.
0 +1 +2 0
Zn(s) are oxidised (LEO) = cause another substance to be
reduced: H+ is reduced (GER).
Therefore, Zn(s) is a reducing agent and H+(aq) is an
oxidizing agent.
0 +4 -2 +1 -2 +2 -2 +1 +2 -2 +1
2nd: balance
Cr2O7 2- (aq) 2Cr3+(aq)
Electron flow
Anode Cathode
- +
Porous barrier
Anions or salt bridge
Cations
Example
The following oxidation-reduction:
Cr2O72-(aq) + 14H+(aq) + 6I-(aq) 2Cr3+(aq) + 3I2 + 7H2O(l)
K2Cr2O7
KI
H2SO4
Salt bridge
Oxidation: I-(aq) I2
Balance - half-reaction method.
6I-(aq) 3I2(s) + 6e-
Solution
Anode (-ve) - Oxidation
6I- (aq) 3I2 (s) + 6e-
anion SO42- toward anode
Cathode (+ve) - Reduction
Cr2O7 2-(aq) + 14H+(aq) + 6e- 2Cr 3+(aq) + 7H2O
Cation K+ toward cathode
e-
- Salt bridge
+
SO42- anion cation K+ cathod
anode e
6I- (aq) 3I2 (s) + 6e- Cr2O7 2-(aq) + 14H+(aq) + 6e-
2Cr 3+(aq) + 7H2O
Cell EMF
Why e- flow spontaneously through the external circuit?
ZnSO4(aq) CuSO4(aq)
E°red = 0 V
PtH2(g)H+(aq) H+(aq)
Pt gauze coated
with Pt black
(To catalyse the reaction)
Standard Reduction Potential
Oxidation of Zn and reduction of H+
Zn (s) + 2H+ (aq) Zn2+ (aq) + H2 (g)
The Zn2+/Zn electrode is the anode and SHE is the
cathode.
The cell voltage is 0.76 V.
- using the E°red of H+ = 0, the standard reduction
potential E°red for Zn2+/Zn half-reaction.
Note:
Changing the stoichiometric coefficient in a half-reaction
does not effect the value of the standard reduction potential.
e.g: 2Zn 2+ (aq, 1 M) + 4e- 2Zn (s)
E°red = -0.76 V
Cell Potentials
Solution
E°cell = E°red (cathode) - E°red (anode)
1.10 V = E°red (cathode) - (-0.76 V)
E°red (cathode) = 1.10 V - 0.76 V = 0.34 V
Example
Calculate the E°cell for this reaction.
Cr2O72-(aq) + 14H+(aq) + 6I-(aq) 2Cr3+ + 3I2 + 7H2O
Solution
half-reaction:
Cathode:
Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+ + 7H2O
Anode:
6I-(aq) 3I2(s) + 6e-
Solution
E°red = Cr2O7 2- Cr3+ = 1.33 V
E°red = I2 I- = 0.54 V
Note:
The value of I2 I- is not multiplied by 3.
Intensive property: does not depend on the specific
stoichiometric coefficients.
Standard Reduction Potential (E°red)
More positive
potentials push e-
E°cell
through an external
E°red circuit.
Anode (oxidation)
More negative
Standard Reduction Potential (E°red)
The more positive the E value for a half reaction,
the greater the tendency for the reactant of the
half-reaction to be reduced and therefore to
oxidize another species.
Increasing strength of
F2(g) + 2e- 2F-(aq)
oxidizing agent
reducing agent
2H+(aq) + 2e- H2(g)
Li+(aq) + e- Li(s)
Most -ve
Strongest reducing
agent
Example
Determine which one of the three metals Zn, Fe, and Na
is the most active metal, given the following data:
Solution
E° = (1.36 V) - (0.54 V) = 0.82 V
E° is positive - this reaction is spontaneous and could be
used to build a voltaic cell.
EMF and Free-Energy Change
Gibbs free energy G is a measure of the spontaneity of
a process that occurs at constant temperature and
pressure.
EMF of a redox reaction indicates whether the reaction
is spontaneous.
Relationship exists between emf and the free-energy
change.
G
G =
= -nFE
-nFE
n = the no. of moles of electrons transferred in the reaction.
F = Faraday constant - quantity of electrical charge of 1 mol electron.
1 F = 96,500 C/mole = 96,500 J/V-mole
*n and F are positive quantities
EMF and Free-Energy Change
G
G =
= -nFE
-nFE
Solution
Reduction: F2(g) + 2e- + 2F-(aq) E°red = 2.87 V
Oxidation: 2Br-(aq) Br2(l) +2e- E°red = 1.06 V
RT lnQ
EE o
nF
Nernst Equation
RT lnQ T = in K
EE o
R = 8.21 J/molK
nF F = 96,500 J
E° = E°red (cathode) - E°red (anode)
The value of standard reduction potential is not
multiplied by stoichiometry coefficient.
Example: 6I-(aq) 3I2(s) + 6e-
From the table : I2 (s) + 2e- 2I- (aq)
E°red = 0.54 V
2.303RTlogQ
EE o
nF
0.0592 log Q
EE o
n
Nernst Equation
Consider: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
In this case n = 2 ( 2 e-s are transferred from Zn to Cu2+)
E 1.10
0.0592 V
log
Zn 2 Pure solids are
2 Cu 2 excluded
Given:
[Cr2O72-] = 2.0 M [H+] = 1.0 M
[I-] = 1.0 M [Cr3+] = 1.0 10-5 M
Solution
Find the standard EMF : Ecell = Ered (cathode) - Ered (anode)
= 5.0 10-11
Solution
We start by calculating the overall standard-state cell
potential for this reaction.
Zn Zn2+ + 2 e- Eored = -0.7628 V
2H+ + 2e- H2 Eored = 0.0000 V
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g) Eo = 0.7628 V 67
Solution
We then substitute into the Nernst equation
The reaction is at equilibrium: Qc = Kc, E = 0, n=2.
nE o
log K
0.0592
K = 5.9 x 1025
69
Electrochemical decomposition
The DC source serves as an ‘electron pump’,
pulling electrons away from one electrode and
pushing them through the external wiring onto
the other electrode
Amount of product = I t / nF
Where I = current (A), t = time (s)
n = mol electrons transferred
F= Faraday’s constant (96500 C mol-1) 73
THE END
74