Chapter 20

Overview
Oxidation-Reduction reactions
Balancing Redox Reactions
Half-Reaction method
Acidic Solution
Basic Solution
Voltaic Cells
Cell EMF--standard reduction potentials
Oxidizing & Reducing reagents
Spontaneity of Redox reactions
Effect of Concentration
Nernst Equation
Equilibrium Constants
Commercial Voltaic Cells
Electrolysis
Quantitative Aspects
Electrical Work

Redox Reactions
Involve a transfer of electrons
Oxidation loss of one or more electron(s)
oxidation state will increase
Reduction gain of one or more electron(s)
oxidation state will decrease
Must occur simultaneously
Zn
(s)
+ Cu
2+
(aq)
Zn
2+
(aq)
+ Cu
(s)

Zn Zn
2+
(aq)
+ 2e
-

oxidation rxn
Cu
2+
(aq)
+ 2e
-
Cu
(s)
reduction
oxidation
reduction rxn
You must know oxidation states:
(Review: Section 8.10)
What are the oxidation states of each atom in
the following:

H
2

CO
ClO
2
-

HC
2
H
3
O
2

H 0
C +2, O -2
Cl +3, O -2
H +1, C
1
+3, C
2
-3, O -2
Balancing Redox Reactions
Mass balance must be observed
e
-
-transfer must be balanced
Simple reactions:
Sn
2+
+ Fe
3+
Sn
4+
+ Fe
2+

Sn
2+
Sn
4+
+ 2e
-

Fe
3+
+ e
-
Fe
2+


oxidation rxn
reduction rxn x 2
2Fe
3+
+ 2e
-
2Fe
2+

Sn
2+
+ 2Fe
3+
Sn
4+
+ 2Fe
2+
Reactions involving H & O in acid:
MnO
4
-
+ C
2
O
4
2-


Mn
2+
+ CO
2

write both reactions
MnO
4
-


Mn
2+

C
2
O
4
2-


CO
2

mass balance (all except H & O)
MnO
4
-


Mn
2+
C
2
O
4
2-


2CO
2

add H
2
O & H
+
to balance O & H
8H
+
+ MnO
4
-


Mn
2+
+ 4H
2
O
C
2
O
4
2-


2CO
2


balance charge by adding electrons
5e
-
+ 8H
+
+ MnO
4
-


Mn
2+
+ 4H
2
O
C
2
O
4
2-


2CO
2
+ 2e
-

balance electrons transferred
10e
-
+ 16H
+
+ 2MnO
4
-


2Mn
2+
+ 8H
2
O
5C
2
O
4
2-


10CO
2
+ 10e
-

add half reactions
16H
+
+ 2MnO
4
-
+ 5C
2
O
4
2-
10CO
2
+ 2Mn
2+
+ 8H
2
O

check the balance

Reactions in base: MnO
4
-
+ CN
-
CNO
-
+ MnO
2

use exactly the same process
CN
-
CNO
-

MnO
4
-
MnO
2
3e
-
+
H
2
O +
+ 2H
2
O 4H
+
+
+ 2H
+
+ 2e
-

since H
+
cannot exist in basic solution, add OH
-
2OH
-
+ CN
-
CNO
-
+ H
2
O

+ 2e
-
3e
-
+ 2H
2
O + MnO
4
-
MnO
2
+ 4OH
-

balance electrons transferred & sum
6OH
-
+ 3CN
-
3CNO
-
+ 3H
2
O

+ 6e
-
6e
-
+ 4H
2
O + 2MnO
4
-
2MnO
2
+ 8OH
-

3CN
-
+ H
2
O + 2MnO
4
-
2MnO
2

+

3CNO
-
+2OH
-

check balance

Voltaic Cells
A spontaneous redox reaction that does
work
Anode
electrode at which oxidation occurs
loses mass
electrons released, sign is negative
Cathode
electrode at which reduction occurs
gains mass
electrons consumed, sign is positive

Cell EMF
Difference in potential energy of electrons at
the anode and cathode
Diff. in potential energy per electrical charge
measured in volts
1 V = 1 J
C
Potential difference = EMF, electromotive force
E
cell
= cell potential = cell voltage
E
cell
= cell potential under std. conditions
1 M, 1 atm, 25 C
Standard reduction potentials
E
red
in tables
E
cell
= E
red
(cathode) - E
red
(anode)
Based on standard hydrogen electrode
2H
+
(aq, 1M)
+ 2e
-
H
2(g, 1atm)
E
red
= 0 V
Zn
(s)
+ 2H
+
(aq)
Zn
2+
(aq)
+ H
2(g)
E
cell
= 0.76 V
0.76 V = 0 V - E
red
(anode)
Zn
2+
(aq, 1M)
+ 2e
-
Zn
(s)
E
red
(anode) = -0.76 V

Problem:
Calculate E
cell
for
2Al
(s)
+ 3I
2(s)
2Al
3+
(aq)
+ 6I
-
(aq)

Anode: 2Al 2Al
3+
+ 6e
-

Cathode: 3I
2
+ 6e
-
6I
-

E
cell
= E
red
(cathode) - E
red
(anode)
E
cell
= 0.54 V - (-1.66 V)
E
cell
= 2.20 V

Note: stoichiometric coefficient does not
affect the value of the E
red
(it is an intensive property)
E
ox
= - E
red

2Al
(s)
+ 3I
2(s)
2Al
3+
(aq)
+ 6I
-
(aq)

2Al 2Al
3+
+ 6e
-
E
ox
= +1.66 V
3I
2
+ 6e
-
6I
-
E
red
= +0.54 V
E
cell
= E
ox
+ E
red
= 2.20V
The more positive the E
cell
the more driving
force for the reaction

Oxidizing/Reducing Agents
Oxidizing agents cause oxidation
oxidizing agents are reduced
the more (+) the E
red
the better the ox. agent
Reducing agents cause reduction
reducing agents are oxidized
the more (-) the E
red
the better the red. agent
Which is the better oxidizing agent?
NO
3
-
+ 4H
+
+ 3e
-
NO + 2H
2
O E
red
0.96 V
Ag
+
+ e
-
Ag E
red
0.80 V
Cr
2
O
7
2-
+ 14H
+
+ 6e
-
2Cr
3+
+ H
2
O E
red
1.33 V
Which is the strongest reducing agent?
I
2
+ 2e
-
2I
-
E
red
+0.54 V
Fe
2+
+ 2e
-
Fe E
red
-0.44 V
MnO
4
-
+ 8H
+
+ 5e
-
Mn
2+
+ 4H
2
O E
red
+1.51 V
Spontaneity of Redox Reactions
Spontaneous redox rxns have positive
potentials
Non-spontaneous redox rxns have negative
potentials
Is this rxn spont. or non-spont.?
MnO
4
-
+ 8H
+
+ 5Fe
2+
5Fe
3+
+ Mn
2+
+ 4H
2
O
Fe
2+
Fe
3+
+ 1e
-
E
ox
= -0.77 v
MnO
4
-
+ 8H
+
+ 5e
-
Mn
2+
+ 4H
2
O E
red
= +1.51 v
E
ox
+ E
red
= + 0.74 v
Yes
EMF & Free Energy
If both DG & E are a measure of spontaneity,
they must be related
DG = - nFE
F is Faradays constant 1 F = 96,500 J/v mol e
-

remember: 1 C = 1 J/v
n = mol e
-
transferred
In the standard state DG = - nFE
Calculate the standard free energy change for
Hg + 2Fe
3+
Hg
2+
+ 2Fe
2+

n = 2 mol electrons transferred
Hg Hg
2+
+ 2e
-
E
ox
= - 0.854 v
2Fe
3+
+2e
-
2Fe
2+
E
red
= + 0.771 v
E
cell
= - 0.083 v
DG = - (2 mol e
-
)(-0.083 v)(96,500 J/v mol e
-
)
= + 16 kJ
Concentration & Cell EMF
Nernst Equation
relationship between DG & concentrations
DG = DG + RT ln Q Q = [prod]
x
/[react]
y

substitute -nFE for DG
E = E - (RT/nF) ln Q or
E = E - (2.303 RT/nF) log Q
2.303 RT/F = 0.0592 v-mol e
-
at std. temp.
E = E - (0.0592/n) log Q
Calculate the emf that the following cell
generates when [Mn
2+
] = 0.10 M & [Al
3+
] =
1.5 M 2Al + 3Mn
2+
2Al
3+
+ 3Mn
E = + 0.48 v
E = (+ 0.48 v) - (0.0592 v/ 6) log [(1.5)
2
/(0.10)
3
]
E = + 0.45 v
when [Mn
2+
] = 1.5 M & [Al
3+
] = 0.10 M
E = (+ 0.48 v) - (0.0592 v/ 6) log [(0.10)
2
/(1.5)
3
]
E = + 0.51 v
Equilibrium Constants
Remember DG = DG + RT ln Q, if Q = K,
then DG = 0, therefore -nFE = 0 and
0 = E - (RT/nF) ln K or
0 = E - (0.0592/n) log K
K can be calculated from cell potentials
log K = nE /0.0592

Calculate the equilibrium constant, K, for
2IO
3
-
+ 5Cu + 12H
+
I
2
+ 5Cu
2+
+ 6H
2
O
E = + 0.858 v
n = 10 mol e
-
transferred
log K = nE/0.0592
log K = 145
K = 1 x 10
145

Voltaic Cells
Lead storage battery
PbO
2
+ SO
4
-2
+ 4H
+
+ 2e
-
PbSO
4
+ H
2
O
Pb + SO
4
2-
PbSO
4
+ 2e
-

E
cell
= + 2.041 v
Dry cell
NH
4
+
+ 2MnO
2
+ 2e
-
Mn
2
O
3
+ 2NH
3
+ H
2
O
Zn Zn
2+
+ 2e
-

In an alkaline cell the NH
4
Cl is replaced with KOH
Ni-Cd
NiO
2
+ 2H
2
O + 2e
-
Ni(OH)
2
+ 2OH
-

Cd + 2OH
-
Cd(OH)
2
+ 2e
-

Fuel cells
4e
-
+ O
2
+ 2H
2
O 4OH
-

2H
2
+ 4OH
-
4H
2
O
Electrolytic Cells
Redox reactions that are not spontaneous
Must be driven by an outside source of
electrical energy
Cathode
reduction occurs
by sign convention, is negative
Anode
oxidation occurs
by sign convention, is positive
Quantitative Aspects
Redox reactions occur in stoichiometric
relationship to the transfer of electrons
Electrons put into a system through electrical
energy, can be quantized
Coulomb = quantity of charge passing through
electrical circuit in 1 s at 1 ampere (A) current
Coulomb = (amp) (seconds)

Problem: Calculate the mass of Mg formed
upon passage of a current of 60.0 A for a period of
4.00 x 10
3
s.
MgCl
2
Mg + Cl
2

Mg
2+
+ 2e
-
Mg 2Cl
-
Cl
2
+ 2e
-

we are concerned with the reduction
(60.0 A)(4 x 10
3
s)(1C/1 A-s) = 2.4 x 10
5
C
(2.4 x 10
5
C)(1 mol e
-
/ 96,500 C) = 2.49 mol e
-

(2.49 mol e
-
)(1 mol Mg/2 mol e
-
) = 1.24 mol Mg
(1.24 mol Mg)(24.3 g/mol) = 30.1 Mg
Electrical Work
DG = w
max
DG = - nFE w
max
= - nFE
Max work proportional to potential
w
max
= - n F E
J = (mol) (C/mol) (J/C)
Electrical work = (watt) (time)
1 watt (W) = 1 J/s or watt-s = J
1 kWh = 3.6 x 10
6
J