Oxidation-Reduction

Biology
Industry
Environment

Biology

Biology
0

Extraction of elements
Industry

Synthesis of different compounds

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.
Mg
Cu2+

Mg2+
Cu

Balancing Redox Equations

Fe2+ + MnO4- + H+

Mn2+ + Fe3+ + H2O

1.
2.
3.
4.
5.

Assign oxidation numbers to each atom.

Determine the elements that get oxidized and reduced.
Split the equation into half-reactions.
Balance all atoms in each half-reaction, except H and O.
Balance O atoms using H2O.

6.
7.
8.

Balance H atoms using H+.

Balance charge using electrons.
Sum together the two half-reactions, so that: e- lost = egained
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

9.

Example
Fe2+ + MnO4- + H+
MnO4-

Mn2+

(+7)

(+2)

Fe2+

Fe3+

MnO4- + 8H+ + 5e
5Fe2+

Mn2+ + Fe3+ + H2O

Reduction half reaction
Oxidation half reaction
Mn2+ + 4H2O

5Fe3+ +5e

5Fe2+ + MnO4- + 8H+

Mn2+ + 5Fe3+ + 4H2O

Nernst Equation
aOx1 +bRed2

Q=

[Red1]a [Ox2]b
[Ox1]a [Red2]b

aRed1 + bOx2
RT

E = E0 - nF ln Q

E0 = 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 E0
Note: if G0 < 0, then E0 must be >0
A reaction is favorable if E0 > 0
(a) 2H+ (aq) + 2e
(b) Zn2+ (aq) + 2e
(a-b) 2H+ (aq) + Zn(s)

H2(g)

E0 (H+, H2) = 0

Zn(s)

E0 (Zn2+, Zn) = -0.76 V

Zn2+(aq) + H2(g)

Reaction is favorable

E0 = +0.76 V

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 ereversible reaction

Galvanic Cell

Galvanic Cells

anode

cathode

oxidation

reduction

spontaneous
redox reaction

19.2

Galvanic Cells
The difference in electrical potential between the anode and
cathode is called:

cell voltage
electromotive force (emf)
cell potential
Cell Diagram
Zn (s) + Cu

2+

(aq)

Cu (s) + Zn

2+

(aq)

2+
2+
[Cu ] = 1 M & [Zn ] = 1 M
2+
2+
Zn (s) | Zn (1 M) || Cu (1 M) | Cu (s)
anode

cathode
19.2

Standard Electrode Potentials

Zn (s) | Zn

2+

+
(1 M) || H (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation):

Zn (s)

Zn

2+

(1 M) + 2e

+
2e + 2H (1 M)

Cathode (reduction):
+
Zn (s) + 2H (1 M)

Zn

2+

H2 (1 atm)

+ H2 (1 atm)
19.3

Standard Electrode Potentials

0
Standard reduction potential (E ) is the voltage associated with a reduction reaction at an electrode when all
solutes are 1 M and all gases are at 1 atm.

Reduction Reaction
+
2e + 2H (1 M)

H2 (1 atm)

0
E =0V

Standard hydrogen electrode (SHE)

19.3

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 E 0 values
are written above the line joining the species involved in the
couple.

A+5

B+3

C+1

D0

E-2

-0.44

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

Iron
+2 and +3
-0.440

G = -nFE

-2 x F x -0.44 = 0.88 V

-0.771 -1 x F x +0.771 = -0.771 V

Fe3+ + 3e

+ 0.109 F
= -3 x F x 0.036

Fe

+0.036

Fe3+

Fe
+0.44

Fe2+

-0.036
Fe3+

+0.77 Fe2+

-0.44

Fe

-0.036
Fe3+

[Fe(CN)6]3-

+0.77 Fe2+

0.36
[Fe(CN)6]4-

-0.44

Fe

-1.16

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

ClO4
+7

- +1.2

ClO3

- +1.18

+5

HClO2

+1.65

HClO
+1

+3

- +1.2
ClO4

+1.63

Cl2
0

+1.36

Cl-1

ClO3-

Can you balance the equation?

HClO

+1.63

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 =?

ClO4
+7

- +1.2

ClO3

- +1.18

+5

HClO2

+1.65

+3

HClO

+1.63

+1
+1

Identify the two reodx couples

Cl2

+1.36

Cl-1
-1

00

Find out the oxidation state of chlorine

Write the balanced equation for the first couple
HClO(aq) + H+(aq) + e

Cl2(g) + H2O(l)

+1.63 V

Write the balanced equation for the second couple

G = G + G

-FE
=

FE
- FE
Cl2(g) + e
Cl (l)
+1.36 V
E = E+ E
+
E = 1.5 V

Latimer diagram for chlorine in basic solution

ClO4

- +1.2

+5

+7

ClO4

ClO3

- +1.18

+0.37

ClO3

HClO2

+1.65

+1

+3

+0.3

ClO2

HClO

+1.63

+0.68

ClO

Cl2

+1.36

Cl-1

+0.42

Cl2

+1.36

Cl-

+0.89
+0.89
ClO

+0.42

Cl2

Balance the equation

2ClO- (aq) + 2H2O(l) + 2eFind out the E0
+0.89

Cl2(g) + 4OH-(aq)

E0 = 0.42 V

Disproportionation
Element is simultaneously oxidized and reduced.
2 M+(aq)
M(s)
ClO4

+0.37

E0

ClO3

M(s) + M2+(aq)
E0

2M+(aq)
+0.3

ClO2

+0.68

ClO

M2+(aq)
-

+0.42

Cl2

+1.36

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.
ClO

+0.42

Cl2

+1.36

Cl-

ClO4

+0.37

ClO

+0.42

ClO3
Cl2

+0.3

+1.36

ClO2

+0.68

ClO

+0.42

Cl2

+1.36

Cl-

Cl-

Cl2(g) + 2 e2Cl-(aq)
2ClO- (aq) 2H2O(l) +2e-

Cl2 + 2OH-

+1.36
Cl2(g) + 4OH-(aq)

ClO- + Cl- + H2O

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

Reaction is spontaneous

+0.42

Latimer diagram for Oxygen

1.23 V

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
spontaneou
H2O2(aq) + 2H+ (aq) +2es?
O2(g) + 2H+(aq) +2 eH2O2(aq)

2H2O(aq)

+1.76 V

H2O2(aq)

+0.7 V

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

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 + NeNE0 = -G0/F

X0

Look at the Latimer diagram of nitrogen in acidic solution

c
a

e
b
d

N2

G = G + G
-nFE = -nFE - nFE
E = nE+ nE
n+n

f
h

NO3- + 6H+ + 5e-

N2 + 3H2O

E0 = 1.25V

N
O
+
4H
+
4e
2
4
b

N2 + 2H2O

E0 = 1.36V

c HNO2 + 3H+ + 3e-

N2 + 2H2O

E0 = 1.45V

d NO + 2H+ + 2e-

N2 + H2O

E0 = 1.68V

e N2O + H+ + e-

N2 + H2O

E0 = 1.77V

f N + 2H+ + H O + e2
2

NH3OH+

E0 = -1.87V

g N + 5/2 H+ + 2e2

N2H5+

E0 = -0.23V

NH4+

E0 = 0.27V

N2 + 4H+ + 3e-

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)

Frost Diagram N2

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.

NE0
N
NE0
N

0
0
NE
-NE
Slope = E0=
N-N

E0 of a redox couple
HNO2/NO
3, 4.4
2, 3.4
NE0-NE0
Slope = E =
N-N
0

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

Identifying strong or weak agent?

NO Strong oxidant than HNO3

Disproportionation
Element is simultaneously oxidized and reduced.

M(s)

2 M+(aq)
E0

M(s) + M2+(aq)
2M+(aq)

E0

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.

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?
Favorable

NE0

Disproportionation

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: MnO43MnO2 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.

* 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.
* 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 Mn2+ does not exist. Instead
Insoluble Mn(OH)2 forms.

*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