Oxidation-Reduction

Biology
Industry
Environment
Biology
Biology
0
Industry
Synthesis of different compounds
Extraction of elements
Environment
Redox reactions - transfer of electrons between species.
All the redox reactions have two parts:
Oxidation
Reduction
The Loss of Electrons is Oxidation.
An element that loses electrons is said to be oxidized.
The species in which that element is present in a
reaction is called the reducing agent.

The Gain of Electrons is Reduction.
An element that gains electrons is said to be reduced.
The species in which that element is present in a
reaction is called the oxidizing agent.
Cu
2+
Cu
Mg Mg
2+

Balancing Redox Equations
1. Assign oxidation numbers to each atom.
2. Determine the elements that get oxidized and reduced.
3. Split the equation into half-reactions.
4. Balance all atoms in each half-reaction, except H and O.
5. Balance O atoms using H
2
O.
6. Balance H atoms using H
+
.
7. Balance charge using electrons.
8. Sum together the two half-reactions, so that: e
-
lost = e
-

gained
9. If the solution is basic, add a number of OH
-
ions to each
side of the equation equal to the number of H
+
ions shown
in the overall equation. Note that H
+
+ OH
-
H
2
O
Fe
2+
+ MnO
4
-
+ H
+
Mn
2+
+ Fe
3+
+ H
2
O
Example
Fe
2+
+ MnO
4
-
+ H
+
Mn
2+
+ Fe
3+
+ H
2
O
MnO
4
-
Mn
2+
Reduction half reaction
(+7) (+2)
Fe
2+
Fe
3+
Oxidation half reaction

MnO
4
-
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O

5Fe
2+
5Fe
3+
+5e
5Fe
2+
+ MnO
4
-
+ 8H
+
Mn
2+
+ 5Fe
3+
+ 4H
2
O
Nernst Equation
aOx
1
+bRed
2
aRed
1
+ bOx
2

Q =
[Red
1
]
a
[Ox
2
]
b

[Ox
1
]
a
[Red
2
]
b

E = E
0
- ln Q
RT
nF
E
0
= Standard Potential
R = Gas constant 8.314 J/K.mol
F- Faraday constant = 94485 J/V.mol
n- number of electrons
G
0
= - n F E
0
Note: if G
0
< 0, then E
0
must be >0
A reaction is favorable if E
0
> 0
Reaction is favorable
2H
+
(aq) + 2e H
2
(g) E
0
(H
+
, H
2
) = 0
Zn
2+
(aq) + 2e Zn(s) E
0
(Zn
2+
, Zn) = -0.76 V
2H
+
(aq) + Zn(s) Zn
2+
(aq) + H
2
(g) E
0
= +0.76 V
(a)
(b)
(a-b)
Hydrogen Electrode
consists of a platinum
electrode covered with
a fine powder of
platinum around
which H
2(g)
is bubbled.
Its potential is defined
as zero volts.
Hydrogen Half-Cell
H
2(g)
= 2 H
+
(aq)
+ 2 e
-

reversible reaction
Galvanic Cell
-
Diagrammatic presentation of potential data
Latimer Diagram
Frost Diagram
Latimer Diagram
* Oxidation number decrease from left to right and the E
0
values
are written above the line joining the species involved in the
couple.
* Written with the most oxidized species on the left, and the most
reduced species on the right.
A
+5
B
+3
C
+1
D
0
E
-2

x
y z
w
-
0.44
Fe
2+
+ 2e Fe -0.440
Fe
3+
+ e Fe
2+
+0.77
Fe
3+
+ 3e Fe
Iron +2 and +3
What happens when Fe(s) react with H
+
?
G = -nFE
-2 x F x -0.44 = 0.88 V
-1 x F x +0.771 = -0.771 V
+ 0.109 F
= -3 x F x 0.036
Fe
Fe
3+

+0.036
Fe
2+
+0.44
Fe
3+

Fe
2+
Fe
-0.036
+0.77 -0.44
-0.440
-0.771
Fe
3+

Fe
2+

-0.036
+0.77 -0.44
Fe
[Fe(CN)
6
]
3-

[Fe(CN)
6
]
4-

-1.16
0.36
Oxidation of Fe(0) to Fe(II) is considerably more favorable in the
cyanide/acid mixture than in aqueous acid.

(1) Concentration
(2) Temperature
(3) Other reagents which are not inert
Oxidation of elemental copper
Latimer diagram for chlorine in acidic solution
ClO
4
-
ClO
3
-
HClO
2
HClO Cl
2
Cl
-
+1.2
+1.18 +1.65 +1.63 +1.36
+7
+5
+3
+1
0
-1
ClO
4
-
ClO
3
-
+1.2
HClO Cl
2
+1.63
2 HClO(aq) + 2 H
+
(aq) + 2 e
-
Cl
2
(g) + 2 H
2
O(l) E
0
= +1.63 V
Can you balance the equation?
balance the equation
ClO
4
-
ClO
3
-
HClO
2
HClO Cl
2
Cl
-
+1.2
+1.18 +1.65 +1.63 +1.36
+7
+5
+3
+1
0
-1
Write the balanced equation for the first couple
Write the balanced equation for the second couple
1
2
HClO(aq) + H
+
(aq) + e Cl
2
(g) + H
2
O(l) +1.63 V
Cl
2
(g) + e Cl
-
(l) +1.36 V
G = G

+ G

-FE = -

FE

- FE
E = E+ E
+
Find out the oxidation state of chlorine
E = 1.5 V
How to extract E
0
for nonadjacent oxidation state?
E
0
=?
Identify the two reodx couples
0
-1 +1
ClO
4
-
ClO
3
-
ClO
2
-
ClO
-
Cl
2
Cl
-

+0.37 +0.3 +0.68 +0.42 +1.36
+0.89
ClO
-
Cl
2

+0.42
2ClO
-
(aq) + 2H
2
O(l) + 2e
-
Cl
2
(g) + 4OH
-
(aq) E
0
= 0.42 V
Latimer diagram for chlorine in basic solution
ClO
4
-
ClO
3
-
HClO
2
HClO Cl
2
Cl
-
+1.2
+1.18 +1.65 +1.63 +1.36
+7
+5
+3
+1
0
-1
+0.89
Balance the equation
Find out the E
0

+0.89
ClO
4
-
ClO
3
-
ClO
2
-
ClO
-
Cl
2
Cl
-

+0.37 +0.3 +0.68 +0.42 +1.36
Disproportionation
Element is simultaneously oxidized and reduced.
2M
+
(aq)
M
2+
(aq) M(s)
E
0

E
0

2 M
+
(aq) M(s) + M
2+
(aq)
the potential on the left of a species is less positive than that on
the right- the species can oxidize and reduce itself, a process known
as disproportionation.
ClO
-
Cl
2
Cl
-

+0.42 +1.36
ClO
4
-
ClO
3
-
ClO
2
-
ClO
-
Cl
2
Cl
-

+0.37 +0.3 +0.68 +0.42 +1.36
Cl
2
+ 2OH
-
ClO
-
+ Cl
-
+ H
2
O
ClO
-
Cl
2
Cl
-

+0.42 +1.36
E = E
0
(Cl
2
/Cl
-
) E
0
(ClO
-
/Cl
2
) = 1.36 - +0.42 = 0.94
Reaction is spontaneous
Cl
2
(g) + 2 e
-
2Cl
-
(aq) +1.36
2ClO
-
(aq) 2H
2
O(l) +2e
-
Cl
2
(g) + 4OH
-
(aq) +0.42
Latimer diagram for Oxygen
1.23 V
the potential on the left of a species is less positive than that on the
right- the species can oxidize and reduce itself, a process known
as disproportionation.
Disproportionation
H
2
O
2
(aq) + 2H
+
(aq) +2e
-
2H
2
O(aq) +1.76 V

O
2
(g) + 2H
+
(aq) +2 e
-
H
2
O
2
(aq) +0.7 V

H
2
O
2
(aq) O
2
(g) + H
2
O(l) +0.7 V
Yes the reaction is spontaneous
Is it spontaneous?
2 Cu
+
(aq) Cu
2+
(aq) + Cu(s)
Cu
+
(aq) + e
-
Cu(s) E
0
= + 0.52 V
Cu
2+
(aq) + e
-
Cu
+
(aq) E
0
= =0.16 V
Cu(I ) undergo disproportionation in aqueous solution
Another example
Comproportionation reaction
Ag
2+
(aq) + Ag(s) 2Ag
+
(aq) E
0
= + 1.18 V
Reverse of disproportionation
we will study this in detail under Frost diagram
Frost Diagram
Graphically illustration of the stability of different oxidation
states relative to its elemental form (ie, relative to oxidation
state= 0)
Arthur A. Frost
X
N
+ Ne
-
X
0


NE
0
= -G
0
/F
Look at the Latimer diagram of nitrogen in acidic solution
a
b c
d e
f g h
N
2

a
b
c
d
e
f
g
h
G = G

+ G

-nFE = -n

FE

- nFE
E = nE+ nE
n+n
NO
3
-

+ 6H
+
+ 5e
-

N
2
+ 3H
2
O E
0
= 1.25V

N
2
O
4
+ 4H
+

+ 4e
-

N
2
+ 2H
2
O E
0
= 1.36V

HNO
2
+ 3H
+

+ 3e
-

N
2
+ 2H
2
O E
0
= 1.45V

NO + 2H
+

+ 2e
-

N
2
+ H
2
O E
0
= 1.68V

N
2
O + H
+

+ e
-
N
2
+ H
2
O E
0
= 1.77V

N
2
+ 2H
+

+ H
2
O + e
-

NH
3
OH
+

E
0
= -1.87V

N
2
+ 5/2 H
+

+ 2e
-

N
2
H
5
+

E
0
= -0.23V

N
2
+ 4H
+

+ 3e
-
NH
4
+

E
0
= 0.27V
a
b
c
d
e
f
g
h
N(V): NO
3
-
(5 x 1.25, 5)

N(IV): N
2
O
4
(4 x 1.36, 4)

N(III): HNO
2
(3 x 1.35, 3)

N(II): NO (2 x 1.68, 2)

N(I): N
2
O (1 x 1.77, 1)

N(-I): NH
3
OH
+
[-1 x (-1.87), -1]

N(-II): N
2
H
5
+
[-2 x (-0.23), -2]

N(-III): NH
4
+
(-3 x 0.27, -3)
Oxidation state: species NE
0
, N
Frost Diagram N
2

the lowest lying species corresponds to
the most stable oxidation state of the
element
What do we really get from the Frost diagram?
Slope of the line joining any two points is equal to the std
potential of the couple.
N
NE
0

NE
0

N
Slope = E
0
=
NE
0
-NE
0

N-N
3, 4.4
2, 3.4
Slope = E
0
=
NE
0
-NE
0

N-N
1 V
E
0
of a redox couple
HNO
2
/NO
The oxidizing agent - couple with more positive slope - more
positive E
The reducing agent - couple with less positive slope
If the line has ive slope- higher lying species reducing agent

If the line has +ive slope higher lying species oxidizing agent
Oxidizing agent? Reducing agent?
Identifying strong or weak agent?
NO Strong oxidant than HNO
3

Disproportionation
Element is simultaneously oxidized and reduced.
2M
+
(aq)
M
2+
(aq) M(s)
E
0

E
0

2 M
+
(aq) M(s) + M
2+
(aq)
the potential on the left of a species is less positive than that on
the right- the species can oxidize and reduce itself, a process known
as disproportionation.
Disproportionation
What Frost diagram tells about this reaction?
A species in a Frost diagram is unstable with respect to disproportionation
if its point lies above the line connecting two adjacent species.
Disproportionation. another example
Comproportionation reaction
Comproportionation is spontaneous if the intermediate species
lies below the straight line joining the two reactant species.
Favorable?
NE
0

Disproportionation
Comproportionation
In acidic solution
Mn and MnO
2

Mn
2+

Rate of the reaction hindered
insolubility?
In basic solution
MnO
2
and Mn(OH)
2

Mn
2
O
3

* Thermodynamic stability is found at the bottom of the diagram.
Mn (II) is the most stable species.
* A species located on a convex curve can undergo disproportionation
example: MnO
4
3-
MnO
2
and MnO
4
2-
(in basic solution)

Any species located on the upper right side of the diagram will be
a strong oxidizing agent. MnO
4
-
- strong oxidizing agent.
Any species located on the upper left side of the diagram will be
a reducing agent. Mn - moderate reducing agent.
From the Frost diagram for Mn.
* Changes in pH may change the relative stabilities of the species.
The potential of any process involving the hydrogen ion will
change with pH because the concentration of this species is
changing.

* Under basic conditions aqueous Mn
2+
does not exist. Instead
Insoluble Mn(OH)
2
forms.
* Although it is thermodynamically favorable for permanganate
ion to be reduced to Mn(II) ion, the reaction is slow except in the
presence of a catalyst. Thus, solutions of permanganate can be
stored and used in the laboratory.
*All metals are good reducing agents

*Exception: Cu
*Reducing strength: goes down
smoothly from Ca to Ni
*Ni- mild reducing agent

*Early transition elements: +3 state
Latter +2 state

*Fe and Mn many oxidation states
*High oxidation state:
Strong oxidizing agents