Oxidation-Reduction

Biology

Industry

Environment
Biology
Biology
0
Industry Extraction of elements 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 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
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

 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
 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
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
2+ 2+
Zn (s) + Cu (aq) Cu (s) + Zn (aq)

2+ 2+
[Cu ] = 1 M & [Zn ]=1M

2+ 2+
Zn (s) | Zn (1 M) || Cu (1 M) | Cu (s)

anode cathode

19.2
 Standard Electrode Potentials

2+ +
Zn (s) | Zn (1 M) || H (1 M) | H2 (1 atm) | Pt (s)

2+ -
Anode (oxidation): Zn (s) Zn (1 M) + 2e

- +
Cathode (reduction): 2e + 2H (1 M) H2 (1 atm)

+ 2+
Zn (s) + 2H (1 M) Zn + 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 E0 values

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

w x y z
A+5 B+3 C+1 D0 E-2
-0.44
 What happens when Fe(s) react with H+?
Iron +2 and +3 G = -nFE

-0.440 -2 x F x -0.44 = 0.88 V

-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+
 -0.036
+0.77 Fe2+ -0.44 Fe
Fe3+

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
 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

Identify the two reodx couples 1 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
 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

ClO 4
-
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

ClO 4
-
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-
 +0.37 +0.3 +0.68 +0.42 +1.36
ClO 4
-
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
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

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 + Ne- X0

NE0 = -G0/F
Look at the Latimer diagram of nitrogen in acidic solution

a b c d e

f g h
 c
a

g d

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

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

b ½ N2 O4 + 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 N + 2H+ + H O + e-       NH3OH+ E0 = -1.87V

2 2

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

2

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)

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.

N’E0’

N’

N”E0’’
N’E0
’-N”E0”
N’’ Slope = E0=
N’-N”
 E0 of a redox couple
HNO2/NO

3, 4.4

2, 3.4

N’E0’-N”E0”
Slope = E =
0
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
Identifying strong or weak agent?
NO – Strong oxidant than HNO3
 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’.
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: 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.
* 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