OXIDATION-REDUCTION

1
 DEFINITIONS
• Oxidation: Loss of electrons.
• Reduction: Gain of electrons.
• Reductant: Species that loses electrons.
• Oxidant: Species that gains electrons.
• Valence: the electrical charge an atom
would acquire if it formed ions in aqueous
solution.
2
 RULES FOR ASSIGNMENT OF
VALENCES
1) The valence of all pure elements is zero.
2) The valence of H is +1, except in hydrides,
where it is -1.
3) The valence of O is -2, except in peroxides,
where it is -1.
4) The algebraic sum of valences must equal
zero for a neutral molecule or the charge on
a complex ion.
3
 VARIABLE VALENCE ELEMENTS
• Sulfur: SO42-(+6), SO32-(+4), S(0), FeS2(-1), H2S(-2)
• Carbon: CO2(+4), C(0), CH4(-4)
• Nitrogen: NO3-(+5), NO2-(+3), NO(+2), N2O(+1), N2(0), NH3(-3)
• Iron: Fe2O3(+3), FeO(+2), Fe(0)
• Manganese: MnO4-(+7), MnO2(+4), Mn2O3(+3), MnO(+2), Mn(0)
• Copper: CuO(+2), Cu2O(+1), Cu(0)
• Tin: SnO2(+4), Sn2+(+2), Sn(0)
• Uranium: UO22+(+6), UO2(+4), U(0)
• Arsenic: H3AsO40(+5), H3AsO30(+3), As(0), AsH3(-1)
• Chromium: CrO42-(+6), Cr2O3(+3), Cr(0)
• Gold: AuCl4-(+3), Au(CN)2-(+1), Au(0)
4
 BALANCING OVERALL REDOX
REACTIONS
Example - balance the redox reaction below:
Fe + Cl2  Fe3+ + Cl-
Step 1: Assign valences,
Fe0 + Cl20  Fe3+ + Cl-
Step 2: Determine number of electrons lost or gained by
reactants.
Fe0 + Cl20  Fe3+ + Cl-
 
3e- 2e-
Step 3: Cross multiply.
2Fe + 3Cl20  2Fe3+ + 6Cl- 5
 HALF-CELL REACTIONS
The overall reaction:
2Fe + 3Cl20  2Fe3+ + 6Cl-
may be written as the sum of two half-cell reactions:
2Fe  2Fe3+ + 6e- (oxidation)
3Cl20 + 6e-  6Cl- (reduction)
All overall redox reactions can be expressed as the
sum of two half-cell reactions, one a reduction and
one an oxidation.
6
Another example - balance the redox reaction:
FeS2 + O2  Fe(OH)3 + SO42-
Fe+2S20 + O20  Fe+3(OH)3 + S+6O42-
 
15e- 4e-
4FeS2 + 15O2  Fe(OH)3 + SO42-
4FeS2 + 15O2  4Fe(OH)3 + 8SO42-
4FeS2 + 15O2 +14H2O  4Fe(OH)3 + 8SO42- + 16H+
This reaction is the main cause of acid generation in
drainage from sulfide ore deposits. Note that we get
4 moles of H+ for every mole of pyrite oxidized!
7
Final example:
C2H6 + NO3-  HCO3- + NH4+
C-32H6 + N+5O3-  2HC+4O3- + N-3H4+
 
14e- 8e-
8C2H6 + 14NO3-  2HCO3- + NH4+
8C2H6 + 14NO3-  16HCO3- + 14NH4+
8C2H6 + 14NO3- + 12H+ + 6H2O 16HCO3- + 14NH4+

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STRENGTH OF REDUCING AND
OXIDIZING AGENTS
Zn + Fe2+  Zn2+ + Fe
Which way will the reaction go?
Gr = -16.3 kcal/mole
Zn is a stronger reducing agent than Fe.

Fe + Cu2+  Fe2+ + Cu
Gr = -34.51 kcal/mole
Fe is a stronger reductant than Cu.
9
 ELECTROMOTIVE SERIES
Weakest oxidant Strongest reductant
Zn  Zn2+ + 2e-
Fe  Fe2+ + 2e-
Cu  Cu2+ + 2e-
Ag  Ag+ + e-
Strongest oxidant Weakest reductant

10
Figure 16.1 from Faure. Schematic diagram of a Zn-Cu electro-
chemical cell. The two metal electrodes are immersed in solutions
of ZnSO4 and CuSO4, which are prevented from mixing by a
porous partition.

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 ELECTROMOTIVE FORCE
Electromotive force (EMF): The electrical
potential generated by the half reactions of
an electrochemical cell.
Consider: Zn + Cu2+  Zn2+ + Cu
At equilibrium the electrochemical cell has to
obey 2
[ Zn ]
K 2
 10 37.24

[Cu ]
12
 G  2.3025 RT log K  50.8 kcal
o
r

G  nE
o
r
o

 (Faraday Constant) = 96,489 C mol-1

= 23.06 kcal/V-1 mol-1

Eo = Gro/(2)
= -50.8 kcal/(2 mol·23.06 kcal V-1 mol-1)
= -1.1 V

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 STANDARD HYDROGEN
ELECTRODE (SHE)
• In order to assign a ranking of half-cell reactions,
we arbitrarily set E = 0.00 V for the reaction:
H2(g)  2H+ + 2e-
when pH2 = 1 bar and pH = 0. In other words, Eo =
0.00 V. This is equivalent to the convention: Gfo
(H+) = Gfo (e-) = 0.00 kcal/mole.
• We then connect this SHE to any other electrode
representing a half-cell reaction and we can obtain
Eo for all half-cell reactions. This is called the
standard electrode potential.
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If we always write half-cell
reactions with the electrons on
the right hand side, E0 tells us
the position of the reaction in
the electromotive series relative
to SHE.

15
 THE NERNST EQUATION
• The value E0 refers to the EMF of a half-cell reaction
when all reactants are in the standard state, e.g., for
Zn  Zn2+ + 2e-
Eo is the EMF when aZn2+ = 1.0. What if this is not the
case?

2.3025 RT
EE  o
log( IAP )
n
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In this particular case
IAP = [Zn2+] and n = 2
so:
2.3025 RT
EE  o 2
log[Zn ]
2
At 25°C we have in this particular case:
0.0592 2
EE  o
log[Zn ]
2
 E 0  0.0296 log[Zn 2 ]
Or in the most general case at 25°C:
0.0592
EE  o
log( IAP )
n 17
 DEFINITION OF Eh
We define Eh to be the EMF between a half-cell
reaction in any state, and the SHE. For example,
Eh for the zinc reaction above is given defined by
the overall reaction: Zn + 2H+  Zn2+ + H2(g)
for which: 2
0.0592 [ Zn ] pH 2
Eh  E o
log
2 [ H  ]2
However, for the SHE by definition, pH2 = 1 bar and
[H+] = 1 mol L-1, so:
Eh  E  0.0296 log[Zn ]
o 2

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 STABILITY LIMITS OF WATER IN
Eh-pH SPACE
Upper limit
H2O(l)  2H+ + 1/2O2(g) + 2e-
Eh = E0 + 0.0295 log (pO21/2[H+]2)
E0 = Gro/(n) = -56.687/(2·23.06) = 1.23 V
Eh = 1.23 + 0.0148 log pO2 - 0.0592 pH
At the Earth’s surface, pO2 can be no greater than 1
bar so
Eh = 1.23 - 0.0592 pH
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Lower limit:

1/2H2(g)  H+ + e-
Eh = 0 + 0.059 log ([H+]/pH21/2)
Again, let pH2 = 1 bar.

Eh = -0.059 pH

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 T = 25oC
pH = 1 bar
2
Eh-pH diagram
1 O
2
pO = 1 bar
2
depicting the
HO
2 limits of stability
of liquid water.
Eh (volts)

HO
2
H
2

-1
0 2 4 6 8 10 12 14
pH 21
Eh-pH diagram
showing the
redox conditions
of various
natural
environments.

22
 Eh-pH DIAGRAM FOR THE SYSTEM Cd-
H2O-CO2

THERMODYNAMIC DATA
Species Gfo (kcal mol-1) Species Gfo (kcal mol-1)
CH4(aq) -8.28 Cd2+ -18.55
H2CO30 -149.00 Cd(OH)2(s) -113.19
HCO3- -140.24 CdO22- -67.97
CO32- -126.15 CdCO3(s) -160.00
C(graphite) 0 Cd(s) 0
H2O(l) -56.7

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 START WITH H2O-CO2 SYSTEM
H2CO30/HCO3- boundary:
H2CO30  HCO3- + H+
Gro = -140.24 - (-149.00) - (0.00) = 8.76 kcal mol-1
log K = -Gro/(2.3025RT)
= -8760/(2.3025·1.987·298.15) = -6.42
 
[ HCO ][ H ]
K 0
3
[ H 2CO3 ]
By definition [H2CO30] = [HCO3-] so K = [H+] and
pH = -log K = 6.42.
24
HCO3-/CO32- boundary:
HCO3-  CO32- + H+
Gro = -126.15 - (-140.24 ) - (0.00) = 14.09 kcal mol-1
log K = -Gro/(2.3025RT)
= -14090/(2.3025·1.987·298.15) = -10.33
2 
[CO ][ H ]
K 3

[ HCO3 ]

By definition [HCO3-] = [CO32-] so K = [H+] and pH

= -log K = 10.33.
25
 H2CO30/C(graphite) boundary:
C + 3H2O  H2CO30 + 4H+ + 4e-
Gro = -149.00 - 3(-56.7) = 21.10 kcal mol-1
E0 = Gro/(n) = 21.10/(4·23.06) = 0.229 volts

log[ H  ]4 [ H 2CO30 ]
0.0592
Eh  0.229 
4
We must assign a value to C. Here we assign C = 10-3
M. Because H2CO30 is predominant, [H2CO30]  C.

log103   0.0592 pH
0.0592
Eh  0.229 
4
Eh  0.184  0.0592 pH
26
 HCO3-/C(graphite) boundary:
C + 3H2O  HCO3- + 5H+ + 4e-
Gro = -140.24 - 3(-56.7) = 29.86 kcal mol-1
E0 = Gro/(n) = 29.86/(4·23.06) = 0.324 volts

log[ H  ]5 [ HCO3 ]
0.0592
Eh  0.324 
4
Because HCO3- is predominant, [HCO3-]  C = 10-3 M

log 10   0.074 pH

0.0592 3
Eh  0.324 
4
Eh  0.280  0.074 pH
27
 CO32-/C(graphite) boundary:
C + 3H2O  CO32- + 6H+ + 4e-
Gro = -126.15 - 3(-56.7) = 43.95 kcal mol-1
E0 = Gro/(n) = 43.95/(4·23.06) = 0.476 volts

log[ H  ]6 [CO32 ]
0.0592
Eh  0.476 
4
Because CO32- is predominant, [CO32-]  C = 10-3 M

log 10   0.089 pH

0.0592 3
Eh  0.476 
4
Eh  0.432  0.089 pH
28
 CH4(aq)/C(graphite) boundary:
CH4(aq)  C + 4H+ + 4e-
Gro = -(-8.28) = 8.28 kcal mol-1
E0 = Gro/(n) = 8.28/(4·23.06) = 0.0898 volts

log[ H  ]4 [CH 4 ( aq)]1 

0.0592
Eh  0.0898 
4
Because CH4(aq) is predominant, [CH4]  C = 10-3 M

log 10   0.0592 pH

0.0592
Eh  0.0898  3

4
Eh  0.134  0.0592 pH
29
CH4(aq)/HCO3- boundary:
CH4(aq) + 3H2O(l)  HCO3- + 9H+ + 8e-
Gro = -140.24 - (-8.28) - 3(-56.7) = 38.14 kcal mol-1
E0 = Gro/(n) = 38.14/(8·23.06) = 0.207 volts
0.0592  [ H  ]9 [ HCO3 ] 
Eh  0.207  log 
8  [CH 4 ( aq)] 
By definition [CH4(aq)] = [HCO3-], so

Eh  0.207  0.0667 pH

30
CH4(aq)/CO32- boundary:
CH4(aq) + 3H2O(l)  CO32- + 10H+ + 8e-
Gro = -126.15 - (-8.28) - 3(-56.7) = 52.23 kcal mol-1
E0 = Gro/(n) = 52.23/(8·23.06) = 0.283 volts
0.0592  [ H  ]10 [CO32 ] 
Eh  0.283  log 
8  [CH 4 ( aq)] 
By definition [CH4(aq)] = [CO32-], so

Eh  0.283  0.074 pH

31
 1.4 T = 25oC
1.2
O
pH = 1 bar
2 Eh-pH diagram
pO = 1 bar
depicting fields of
2
HO
1.0 2 2

C = 10-3 M
0.8
predominance and
0.6

H2CO30
stability in the
Eh (volts)

system C-O-H.
0.4 -
HCO3

0.2 graphite
CO32-
0.0 HO
2
H
-0.2 2 CH
4 (aq
)
-0.4

-0.6

-0.8

-1.0
0 2 4 6 8 10 12 14
pH 32
 NOW ADD Cd
Cd2+/CdCO3(s) boundary (H2CO30 field):
CdCO3(s) + 2H+  Cd2+ + H2CO30
Gro = -149.00 - 18.55 - (-160.00) = -7.55 kcal mol-1
log K = -Gro/(2.3025RT)
= 7550/(2.3025·1.987·298.15) = 5.53
0 2
[ H 2CO ][Cd ]
K 3
[ H  ]2
We assign C = 10-3 M and Cd = 10-3 M. Now
log K = 2pH + log [H2CO30] + log [Cd2+]
5.53 = 2pH - 3 - 3
pH = 5.77 33
Cd2+/CdCO3(s) boundary (graphite field):
Cd2+ + C + 3H2O(l)  CdCO3(s) + 6H+ + 4e-
Gro = -160.0 - (-18.55) - 3(-56.7) = 28.65 kcal mol-1
E0 = Gro/(n) = 28.65/(4·23.06) = 0.311 volts

0.0592  [ H  ]6 
Eh  0.311  log 
2 
4  [Cd ] 
We assign Cd = 10-3 M.

log103   0.0889 pH
0.0592
Eh  0.311 
4
Eh  0.355  0.0889 pH
34
Cd2+/CdCO3(s) boundary (CH4 field):
Cd2+ + CH4(aq) + 3H2O(l)  CdCO3(s) + 10H+ + 8e-
Gro = -160.0 - (-18.55) - 3(-56.7) - (-8.28)
= 36.93 kcal mol-1
E0 = Gro/(n) = 36.93/(8·23.06) = 0.200 volts

0.0592  [ H  ]10 
Eh  0.200  log 2

8  [Cd ][CH 4 ] 
We assign Cd = 10-3 M and C = 10-3 M.

log106   0.074 pH
0.0592
Eh  0.200 
8
Eh  0.244  0.074 pH
35
Cd(OH)2(s)/CdCO3(s) boundary (CO32- field):
Cd(OH)2(s) + CO32- + 2H+  CdCO3(s) + 2H2O(l)
Gro = -160.0 + 2(-56.7) - (-113.19) - (-126.15)
= -34.06 kcal mol-1
log K = -Gro/(2.3025RT)
= 34060/(2.3025·1.987·298.15) = 24.97

1
K
[ H  ]2 [CO32 ]
We assign C = 10-3 M. Now
log K = 24.97 = 2pH - log [CO32-] = 2pH + 3.0
pH = 10.98
36
Cd(OH)2(s)/CdCO3(s) boundary (CH4 field):
Cd(OH)2(s) + CH4(aq) + H2O(l)  CdCO3(s) + 8H+ + 8e-
Gro = -160.0 - (-56.7) - (-113.19) - (-8.28)
= 18.17 kcal mol-1
E0 = Gro/(n) = 18.17/(8·23.06) = 0.098 volts
0.0592  [ H  ]8 
Eh  0.098  log 
8  [CH 4 ( aq)] 
We assign C = 10-3 M.
Eh  0.098  0.0074( 3)  0.0592 pH

Eh  0.120  0.0592 pH
37
Cd(OH)2(s)/Cd2+ boundary:
Cd(OH)2(s) + 2H+  Cd2+ + 2H2O(l)
Gro = -18.55 + 2(-56.7) - (-113.19)
= -18.76 kcal mol-1
log K = -Gro/(2.3025RT)
= 18760/(2.3025·1.987·298.15) = 13.75
2
[Cd ]
K  2
[H ]
We assign Cd = 10-3 M. Now
log K = 13.75 = log [Cd2+] + 2pH = -3 + 2pH
pH = 8.38
38
Cd(OH)2(s)/CdO22- boundary:
Cd(OH)2(s)  CdO22- + 2H+
Gro = -67.97 - (-113.19)
= 45.22 kcal mol-1
log K = -Gro/(2.3025RT)
= -45220/(2.3025·1.987·298.15) = -33.15
2  2
K  [CdO ][ H ]
2

We assign Cd = 10-3 M. Now

log K = -33.15 = log [CdO22-] - 2pH = -3 + 2pH
pH = 15.08
This boundary does not plot on our diagram.
39
 o
1.4 Cd = 10-3 M T = 25 C
1.2
pH = 1 bar
Eh-pH diagram
2

pO = 1 bar
1.0 2

0.8
C = 10-3 M depicting fields of
0.6
predominance and
2+
stability in the
Eh (volts)

0.4 Cd CdCO3(s)
system Cd-C-O-

Cd(OH)2(s)
0.2

0.0
H.
-0.2

-0.4

-0.6

-0.8

-1.0
0 2 4 6 8 10 12 14
40
pH
Eh-pH diagram
depicting fields of
predominance and
stability in the
system Cd-C-S-O-H.
The conditions are
C = 10-3 M, S =
10-3 M, Cd = 10-8 M

41