Inorganic Chemistry (CY11003)

3a-Oxidation-Reduction/Redox Chemistry

Books to Refer:
Inorganic Chemistry by Shriver & Atkins

Prof. Madhab Chandra Das

Department of Chemistry
High Pressure Lab (Ground Floor)
IIT Kharagpur
Ph: 03222-282894
Email: [email protected]
Biology
0
Industry Extraction of metals Dry & wet batteries

Fe
Na
Al

Fe2O3(s) + 3CO(g) → 2Fe(s) +3CO2(g)

hematite
Redox reactions - transfer of electrons between species.

All the redox reactions have two parts (half reactions):

Oxidation (ON increases) Reduction (ON decreases)
Mg -2e Mg2+
Cu2+ + 2e Cu

Mg: reducing agent: reduces others but get oxidized itself

Cu2+: oxidizing agent: oxidizes others but get reduced itself
ON= oxidation no
 Balancing Redox Equations
Fe2+ + MnO4- + H+ Mn2+ + Fe3+ + H2O

1. Determine the elements that get oxidized and reduced.

2. Split the equation into half-reactions.
3. Balance all atoms in each half-reaction, except H and O.
4. Balance O atoms using H2O.
5. 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 Do it by yourself

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

 Standard oxidation/ reduction/ redox potential

•The emf which determines the tendency or power of any atom towards
e loss or gain under standard conditions is called std oxd or std red potential.

• Std condition: Ions in unit activity, Metal are solid, Gas at 1 atm/25 oC

•Algebraic sum of the std oxd & std red potentials are called std redox
potential

Std H Electrodes: The electrodes whose potential is arbitrarily assumed

and with respect to which the potential of all other electrodes are
determined : 2 H+(aq) + 2 e- = H2(g) E0 H+/1/2H2 = 0.0 V

International convention: std reduction potential

Fe3+ +e Fe2+ E0 Fe Fe = 0.77 V OR
3+/ 2+

Eo (Fe3+, Fe2+) = 0.77 V

-
 Application of std reduction potential value
G0 = - n F E0

Spontaneous reaction: G0 < 0, then E0 must be >0

A reaction is favorable if E0 > 0

(a) 2H+ (aq) + 2e H2(g) E0 (H+, H2) = 0.0 V

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

(a-b) 2H+ (aq) + Zn(s) Zn2+(aq) + H2(g) E0cell = +0.76 V

Reaction is favorable

High std reduction potential: Highly oxidizing agent

Note: this is full redox reaction: e are cancelled out
 Galvanic Cell: a electrochemical cell
Electricity: by cost of redox reactions

Test Question: Predict if Ag

will be oxidized when
immerged In CuSO4 solution.
E0 (Cu2+, Cu) = 0.34 V
E0 (Ag+, Ag) = 0.80 V

Oxdn occurs at anode

Redn occurs at cathode

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

Cu2+ (aq) + 2e Cu(s) E0 (Cu2+, Cu) = 0.34V

Cu2+ + Zn Zn 2+ + Cu E0cell = 0.34 – (-0.76) = 1.10V

(high + ve value, spontaneous)
Diagrammatic presentation of potential data

Latimer Diagram (reduction potential diagram)

Frost Diagram (oxidation state diagram)

 Latimer Diagram

*The numerical value of std red pot (in v) is written over a horizontal line
(or arrow) connecting species with the element in different OS

* 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
 What could be extracted from Latimer Diagram…

??
+0.77 Fe2+ -0.44 Fe
Fe3+

G = -nFE
2+
Fe + 2e Fe Eo = -0.440 -2 x F x -0.44 = 0.88F

Fe3+ + e Fe2+ Eo = 0.77 -1 x F x +0.77 = -0.77F

Fe3+ + 3e Fe -3 x F x E0 Fe3+/Fe = + 0.11 F

 E0 Fe3+/Fe = -0.036
-0.036

Fe3+ +0.77 Fe2+ -0.44 Fe

Note: this is HALF reaction: e are NOT cancelled out
What could be extracted from Latimer Diagram…

-2 x F x E0

??

E0 Cu 2+/Cu = 0.34 V
No need to go to lab for EXPT
 Latimer diagram for chlorine in acidic solution
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

HClO(aq) + H+(aq) + e ½ Cl2(g) + H2O(l) Eo = +1.63 V

½ Cl2(g) + e Cl- (l) Eo = +1.36 V

G = G′ + G′′
-nFE = -n′ FE′ - n′′FE′′
Simple formula E = n′ E′ + n′′ E′′
n′+n ′′
Write the balanced equation for the
HClO(aq) + H+(aq) + 2e Cl-(l) + H2O(l) Eo = 1.5 V
 Latimer diagram for chlorine in basic solution

+0.37 +0.3 +0.68 +0.42 +1.36

ClO4 - ClO3 - ClO2 - ClO- Cl2 Cl-

??
+0.89

Balance the half reactions…

2ClO- (aq) + 2H2O(l) + 2e- Cl2(g) + 4OH-(aq) E0 = 0.42 V
Cl2 + 2e 2Cl- E0 = 1.36 V

Why not ½ Cl2 like before?

Try it out: same result Eo = +0.89
Disproportionation
Element is simultaneously oxidized and reduced.
2 M+(aq) M(s) + 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’.
 Continued……

Cl2(g) + 2 e- 2Cl-(aq) E0 = +1.36 V

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

Cl2 + 2OH- ClO- + Cl- + H2O E0 = 0.94 V

Full rkn Reaction is spontaneous as E0 is positive

Note: this is full redox reaction: e are cancelled out

Disproportionation
Is it spontaneous?

H2O2(aq) + 2H+ (aq) +2e- 2H2O(aq) E0 = +1.76 V

H2O2(aq) O2(g) + 2H+(aq) +2 e- E0 = - 0.70 V

-1 0 -2
2H2O2(aq) O2 (g) + 2H2O(l) E0 = +1.06 V

Yes the reaction is spontaneous

Auto-decomposition of H2O2 in lab
 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)

FD of an element X is a plot of NE0 for the couple

XN/X0 against the oxd no N, of the element.
Look at the Latimer diagram of nitrogen in acidic solution

a b c d e

f g h

From Latimer diagram, you can make the Frost Diagram

 c
a

g d

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

h
 By using the equation in Latimer diagram we can calculate….

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

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

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

2

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

e ½ N O + H+ + e- ½ N2 + ½ H2O E0 = 1.77V
2

f ½ N + 2H+ + H O + e- NH3OH+ E0 = -1.87V

2 2

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

h ½ N + 4H+ + 3e- NH4+ E0 = 0.27V

2
Oxidation state: species N x E0, 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(0): N2 (0, 0)

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

the lowest lying species corresponds to

the most stable oxidation state of the
element
Conclusion: Higher oxides & oxo-acids are unstable
in acidic sol but relatively stable in basic sol
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
E0 HNO2/NO = ??

3, 4.4

2, 3.4

N’E0’-N”E0”
Slope = E0=
N’-N”
1 V
(chk back)
Identifying strong or weak agent?
NO – Strong oxidant than HNO3
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

this is peroxide auto decomposition

Comproportionation reaction

In comproportionation, the reverse of disproportionation,

two species with the same element in different OS
form a product in which the element is in intermediate OS
Comproportionation is spontaneous if the intermediate species
lies below the straight line joining the two reactant species.
Construction of Frost diagram of Mn from the following Latimer diagram
Comproportionation: In acidic solution… Mn + Mn3+ Mn2+
In basic solution… MnO2 + Mn(OH)2 Mn2O3

From diagram comment on

Stability of Mn3+ in acidic sol
disproportionation

Mn3+ lies above the line joining MnO2

& Mn2+
 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- - oxidizing agent.

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