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Oxidation-Reduction

Biology

Industry

Environment

Biology

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Biology
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Industry Extraction of elements Synthesis of different compounds

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Environment

Redox reactions - transfer of electrons between species.

All the redox reactions have two parts:

Oxidation Reduction

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• 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.

Mg Mg2+

Cu2+ Cu

Balancing Redox Equations

Fe2+ + MnO4- + H+ Mn2+ + Fe3+ + H2O

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 H2O.
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-  H2O

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Example

Fe2+ + MnO4- + H+ Mn2+ + Fe3+ + H2O

MnO4- Mn2+ Reduction half reaction

(+7) (+2)

Fe2+ Fe3+ Oxidation half reaction

MnO4- + 8H+ + 5e Mn2+ + 4H2O

5Fe2+ 5Fe3+ +5e

5Fe2+ + MnO4- + 8H+ Mn2+ + 5Fe3+ + 4H2O

Disproportionation
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.

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Is it spontaneous?

H2O2(aq) + 2H+ (aq) +2e- 2H2O(aq) +1.76 V

O2(g) + 2H+(aq) +2 e- H2O2(aq) +0.7 V

H2O2(aq) O2 (g) + H2O(l) +0.7 V

Yes the reaction is spontaneous

Another example…

2 Cu+(aq) Cu2+(aq) + Cu(s)

Cu+(aq) + e- Cu(s) E0 = + 0.52 V

Cu2+(aq) + e- Cu+(aq) E0 = =0.16 V

Cu(I) undergo disproportionation in aqueous solution

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Comproportionation reaction

Reverse of disproportionation

Ag2+(aq) + Ag(s) 2Ag+(aq) E0 = + 1.18 V

…we will study this in detail under Frost diagram

Nernst Equation

aOx1 +bRed2 a’Red1 + b’Ox2

[Red1]a’ [Ox2]b’ RT
Q= E = E0 - nF ln Q
[Ox1]a [Red2]b

E0 = Standard Potential
R = Gas constant 8.314 J/K.mol
F- Faraday constant = 94485 J/V.mol
n- number of electrons

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G0 = - n F  E0

Note: if G0 < 0, then  E0 must be >0

A reaction is favorable if  E0 > 0

(a) 2H+ (aq) + 2e H2(g) E0 (H+, H2) = 0

(b) Zn2+ (aq) + 2e Zn(s) E0 (Zn2+, Zn) = -0.76 V

(a-b) 2H+ (aq) + Zn(s) Zn2+(aq) + H2(g) E0 = +0.76 V

Reaction is favorable

Hydrogen Electrode

• consists of a platinum
electrode covered with
a fine powder of
platinum around
which H2(g) is bubbled.
Its potential is defined
as zero volts.
Hydrogen Half-Cell
H2(g) = 2 H+(aq) + 2 e-
reversible reaction

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Galvanic Cell

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Diagrammatic presentation of potential data

Latimer Diagram

Frost Diagram

Latimer Diagram
* Written with the most oxidized species on the left, and the most
reduced species on the right.

* Oxidation number decrease from left to right and the E0 values

are written above the line joining the species involved in the
couple.

x y z
A+5 w B+3 C+1 D0 E-2

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What happens when Fe(s) react with H+?

Iron +2 and +3 G = -nFE

Fe2+ + 2e Fe -0.440 -2 x F x -0.44 = 0.88 V

Fe3+ + e Fe2+ -0.771 -1 x F x +0.771 = -0.771 V

Fe3+ + 3e Fe + 0.109 F
= -3 x F x –0.036
+0.036 Fe3+
Fe
+0.44 Fe2+

-0.036
+0.77 Fe2+ -0.44 Fe
Fe3+

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-0.036

Fe3+ +0.77 Fe2+ -0.44 Fe

0.36
[Fe(CN)6]3- -1.16
[Fe(CN)6]4-

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

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Latimer diagram for chlorine in acidic solution

+1.2 +1.18 +1.65 +1.63 +1.36

ClO4- ClO3- HClO2 HClO Cl2 Cl-
+7 +5 +3 +1 0 -1

+1.2
ClO4- ClO3-

Can you balance the equation?

+1.63
HClO Cl2
balance the equation

2 HClO(aq) + 2 H+(aq) + 2 e- Cl2(g) + 2 H2O(l) E0 = +1.63 V

How to extract E0 for nonadjacent oxidation state?

E0 =?
+1.2 +1.18 +1.65 +1.63 +1.36
ClO4- ClO3- HClO2 HClO Cl2 Cl-
+7 +5 +3 +1
+1 00 -1
-1

1
Identify the two reodx couples 2

Find out the oxidation state of chlorine

Write the balanced equation for the first couple

HClO(aq) + H+(aq) + e ½ Cl2(g) + H2O(l) +1.63 V
Write the balanced equation for the second couple
G = G’ + G’’
½ Cl2(g) + e Cl- (l) +1.36 V -FE = - ’FE’ - ’’FE’’
E = ’E’+ ’’E’’
’+ ’’
E = 1.5 V

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Latimer diagram for chlorine in basic solution

+1.2 +1.18 +1.65 +1.63 +1.36

ClO4- ClO3- HClO2 HClO Cl2 Cl-
+7 +5 +3 +1 0 -1

+0.37 +0.3 +0.68 +0.42 +1.36

ClO4- ClO3- ClO2- ClO- Cl2 Cl-

+0.89
+0.89
+0.42
ClO- Cl2
Balance the equation…

2ClO- (aq) + 2H2O(l) + 2e- Cl2(g) + 4OH-(aq) E0 = 0.42 V

Find out the E0

+0.89

Disproportionation
Element is simultaneously oxidized and reduced.
2 M+(aq) M(s) + M2+(aq)
E0 E0’
M(s) 2M+(aq) M2+(aq)

+0.37 +0.3 +0.68 +0.42 +1.36

ClO4- ClO3- ClO2- ClO- Cl2 Cl-

‘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’.
+0.42 +1.36
ClO- Cl2 Cl-

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+0.37 +0.3 +0.68 +0.42 +1.36

ClO4- ClO3- ClO2- ClO- Cl2 Cl-

+0.42 +1.36
ClO- Cl2 Cl-

Cl2(g) + 2 e- 2Cl-(aq) +1.36

2ClO (aq) 2H2O(l) +2e-
- Cl2(g) + 4OH-(aq) +0.42

Cl2 + 2OH- ClO- + Cl- + H2O

E = E0 (Cl2/Cl-) –E0 (ClO-/Cl2) = 1.36 - +0.42 = 0.94

Reaction is spontaneous

Latimer diagram for Oxygen

1.23 V

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Disproportionation
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.

Is it spontaneous?

H2O2(aq) + 2H+ (aq) +2e- 2H2O(aq) +1.76 V

O2(g) + 2H+(aq) +2 e- H2O2(aq) +0.7 V

H2O2(aq) O2 (g) + H2O(l) +0.7 V

Yes the reaction is spontaneous

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Another example…

2 Cu+(aq) Cu2+(aq) + Cu(s)

Cu+(aq) + e- Cu(s) E0 = + 0.52 V

Cu2+(aq) + e- Cu+(aq) E0 = =0.16 V

Cu(I) undergo disproportionation in aqueous solution

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Comproportionation reaction

Reverse of disproportionation

Ag2+(aq) + Ag(s) 2Ag+(aq) E0 = + 1.18 V

…we will study this in detail under Frost diagram

Frost Diagram
Arthur A. Frost
Graphically illustration of the stability of different oxidation
states relative to its elemental form (ie, relative to oxidation
state= 0)

XN + Ne- X0

NE0 = -G0/F

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Look at the Latimer diagram of nitrogen in acidic solution

a b c d e

f g h

c
a

b
d
g
G = G’ + G’’
-nFE = -n’FE’ - n’’FE’’
N2 E = n’E’+ n’’E’’
f n’+n’’

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a NO3- + 6H+ + 5e- ½ N2 + 3H2O E0 = 1.25V

b ½ N2O4 + 4H+ + 4e- ½ N2 + 2H2O E0 = 1.36V

c HNO2 + 3H+ + 3e- ½ N2 + 2H2O E0 = 1.45V

d NO + 2H+ + 2e- ½ N2 + H2O E0 = 1.68V

e ½ N2O + H+ + e- ½ N2 + ½ H2O E0 = 1.77V

f ½ N2 + 2H+ + H2O + e- NH3OH+ E0 = -1.87V

g ½ N2 + 5/2 H+ + 2e- ½ N2H5+ E0 = -0.23V

h ½ N2 + 4H+ + 3e- NH4+ E0 = 0.27V

Oxidation state: species NE0, N

N(V): NO3- (5 x 1.25, 5)

N(IV): N2O4 (4 x 1.36, 4)

N(III): HNO2 (3 x 1.35, 3)

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

N(I): N2O (1 x 1.77, 1)

N(-I): NH3OH+ [-1 x (-1.87), -1]

N(-II): N2H5+ [-2 x (-0.23), -2]

N(-III): NH4+ (-3 x 0.27, -3)

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Frost Diagram – N2

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What do we really get from the Frost diagram?

the lowest lying species corresponds to

the most stable oxidation state of the
element

Slope of the line joining any two points is equal to the std
potential of the couple.

N’E0’

N’

N”E0’’
N’E0’-N”E0”
N’’ Slope = E0=
N’-N”

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E0 of a redox couple
HNO2/NO

3, 4.4

2, 3.4

N’E0’-N”E0”
Slope = E0=
N’-N”
1V

Oxidizing agent? Reducing agent?

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

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Identifying strong or weak agent?

NO – Strong oxidant than HNO3

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Comproportionation

In acidic solution…
Mn and MnO2

Mn2+
Rate of the reaction hindered
insolubility?

In basic solution…
MnO2 and Mn(OH)2

Mn2O3

From the Frost diagram for Mn….

* 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: MnO43- MnO2 and MnO42- (in basic solution)

•Any species located on the upper right side of the diagram will be
a strong oxidizing agent. MnO4- - strong oxidizing agent.

•Any species located on the upper left side of the diagram will be
a reducing agent. Mn - moderate reducing agent.

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Disproportionation
Element is simultaneously oxidized and reduced.
2 M+(aq) M(s) + M2+(aq)
E0 E0’
M(s) 2M+(aq) M2+(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’.

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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.

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Disproportionation…. another example

Comproportionation reaction

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Comproportionation is spontaneous if the intermediate species

lies below the straight line joining the two reactant species.

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Favorable?

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NE0

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Disproportionation

Thank You

Best wishes……

OC - 105 (Ph 83338)

Organic Chemistry Bldg.
Dept. of Chemistry
(Behind RTC)

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