Redox reactions

Heshani Mudalige (BSc,MSc University of Colombo),

MSc(Oregon State University/USA)
 Oxidation - reduction

Oxidation is loss of electrons Reduction is gain of electrons

Oxidation Reduction
O R
I Is
I Is
L Loss of electrons G Gain of electrons
 Oxidation numbers

An “oxidation number” is a positive or negative number

assigned to an atom to indicate its degree of oxidation or
reduction.
 Rules for assigning oxidation numbers

 Oxidation number of any uncombined element is zero

Eg: Na 0

 H2 , O2 , N2 , Cl2 ,Br2 , I2 and F2 exist as diatomic molecules in the elemental state and have
oxidation states of 0

 Group one elements are always +1 in compounds or as free (aq) ions.

Ex: In NaCl each Na+ has an oxidation state of +1.

In K2SO4 each K+ has an oxidation state of +1.
A Li+ (aq) free ion has an oxidation number of +1.
 
 Group 2 elements have an oxidation state +2 in compounds and as free(aq) ions
Eg: In BaCl2 each Ba2+ has an oxidation state of +2
In Ca3(PO4)2 each Ca2+ has an oxidation state of +2.
A free Mg2+ has an oxidation state of +2.

 The oxidation number of a monatomic ion equals its charge.

Eg: Fe3+ +3
Cl- -1

 The oxidation number of Hydrogen in compounds is +1.Except in metal hydrides

 (LiH, NaH, CaH2, and LiAlH4)
Eg: NaH , That H -1

 Oxidation number for halogens is usually -1

Eg : F- -1
 The oxygen rules:

• Oxygen has usually an oxidation state of -2 for most compounds such as

oxides, water and acids(Contain O)
Eg: MgO -2
H2O -2
H2SO4 -2
• When oxygen is contained in a peroxide, it has an oxidation state of -1
Eg:     H2O2, Li2O2, K2O2 are peroxides, each O is -1

• When oxygen contained in a superoxide it has an oxidation state of -1/2

Eg: KO2 is a superoxide O has -1/2

• In OF2 that O is +2
 The sum of the oxidation numbers of the atoms in the compound must
equal to 0

Eg: NaNO3 KIO3

+1 + x + 3(-2) = 0 +1 + x + 3(-2) = 0
+1 +x - 6 = 0 +1 +x - 6 = 0
x = +5
x = +5
 The sum of the oxidation numbers in the formula of a polyatomic ion
is equal to its ionic charge

CrO42- SO42-

x + -2(4) = -2 x + -2(4) = -2
x = +6 x = +6
Oxidation numbers for common Nitrogen
and Sulphur containing compounds

N(I)
-

N2O

S8
Question 1: Assign oxidation states to following
elements

N2O4 SO3 Cl2O7

-
MnO2 NH3 MnO4

Cr2O72- C2O42- PO43-

ClO3- HSO3- HCO3-

Assigning oxidation numbers
More about oxidation numbers for Carbon
containing compounds
Thiosulphate ion(S2O32-) Tetrathionate ion(S4O62-)
 Oxidizing and Reducing agents

Oxidizing agents oxidize and are themselves reduced

Reducing agents reduce and are themselves oxidized
S is the oxidizing
agent S is reduced, Gains electrons, becomes a S2- ion

Mg(s) + S(s) MgS(s)

Mg is the reducing
agent
Mg is oxidized, Loses electrons, becomes a Mg2+ ion
 What is meant by half-reaction?

A half-reaction is simply one which shows either reduction OR

oxidation, but not both

2Ag+ + Cu 2Ag + Cu2+

Oxidation reaction Reduction reaction
Cu Cu + 2e¯
2+ Ag+ + e¯ Ag
+1 0
0 +2
Oxidation number increases Oxidation number decreases
 Half-Reactions Practice Problems

Question 2 :Balance the following half reactions

1) Cl2 Cl¯
2) Sn Sn2+
3) Fe3+ Fe2+
4) I3¯ I¯
 Reaction between Zn and CuSO4

Zn(s) Zn2+(aq) + 2e

Cu2+(aq) + 2e Cu(s)
 Question 3:Identify each of the following as
1) oxidation or 2) reduction.

A. Sn(s) Sn4+(aq) + 4e−

B. Fe3+(aq) + e− Fe2+(aq)
C. Cl2(g) + 2e− 2Cl-(aq)

D. Cs(s) Cs+(aq) + e−
E. F2(g) + 2e- 2F−(aq)

F. Al3+ + 3e− Al
G. Br + e− Br −
 Balancing Redox equations in acidic medium

STEP 1: The unbalanced equation

Cr2O72 (aq)  Cl  (aq )  Cr 3 (aq )  Cl2 (aq )

Dichromate ion reacts with chloride ion to produce chlorine and chromium (III)
STEP 2: identify the oxidized and reduced and write the half
reactions

Oxidation half-reaction


Cl (aq )  Cl2 (aq )
Reduction half-reaction

2 3
Cr2O (aq )  Cr (aq)
7
 STEP 3: Balance the half reactions(Acidic medium)


2Cl (aq )  Cl2 ( aq )  2e
 2  3
14 H (aq )  Cr2O (aq )  6e  2Cr (aq )  7 H 2O(l )
7
STEP 4: Multiply by factors to balance total electrons

3 Cl (aq)  Cl2 (aq )  2e

2
 


 2  3
14 H (aq )  Cr2O (aq )  6e  2Cr (aq )  7 H 2O(l )
7
 STEP 5: Add half reactions and eliminate common items

 
6Cl (aq )  3Cl2 (aq)  6e
+
14 H  (aq)  Cr2O72 (aq)  6e   2Cr 3 (aq)  7 H 2O(l )

14 H  (aq )  Cr2O72 (aq)  6Cl  (aq)  2Cr 3 (aq)  3Cl2 (aq)  7 H 2O(l )
Atoms and charges are balance
 Overall redox equation

14 H  (aq )  Cr2O72 (aq)  6Cl  (aq )  2Cr 3 (aq)  3Cl2 (aq)  7 H 2O(l )
Eg:
Redox reactions are reactions in which one species is
reduced and another is oxidized

Cl- is oxidized to Cl2

Cr2O72- is reduced to Cr3+

Things to remember in acidic medium(Reduction)

Cr2O72- Cr3+

CrO42- Cr3+

MnO4- Mn2+
Question 4:Balance the following redox reaction in the acidic
medium and write the complete reaction

MnO4-  + HCl + H2S Mn2+ + S + H2O

 Answer

2MnO4- + HCl + 5H2S 2Mn2+ + 5S

2KMnO4 + 6HCl + 5H2S 2MnCl2 + 5S +2KCl + 8H2O

 Balancing Redox equations in basic medium

 Write a balanced equation to represent the oxidation of iodide ion (I-) by

permanganate ion (MnO4-) in basic solution to yield molecular iodine (I2) and
manganese (IV) oxide (MnO2)

I- + MnO4- I2 + MnO2
STEP 1:Identify the oxidation and reduction reactions

Oxidation half-reaction

2I - I2 + 2e

Reduction half-reaction

MnO4- + 2H2O + 3e MnO 2 + 4OH-

Step 2: Multiply by factors to balance total electrons

3(2I - I2 + 2e)

2(MnO4- +2H2O + 3e MnO2 + 4OH-)

STEP 3: Add half reactions and eliminate common items
6I- 3I2 + 6e
2MnO4- + 4H2O + 6e 2MnO2 + 8OH-

2MnO4- + 4H2O + 6I- 2MnO2 + 8OH

+ -3I2

2KMnO4 + 4H2O + 6KI 2MnO2 + 8KOH + 3I2

Things to remember in basic medium

MnO4 - MnO2 (Reduction)

Cr3+ CrO 4
2- (Oxidation)
Question 5:Write balanced equations to represent the following
reactions in a basic solution

(a) Fe(OH)2 + MnO4-  MnO2 + Fe(OH)3

(b) Bi(OH)3 + SnO22-  SnO32- + Bi

 Answers

(a) 3Fe(OH)2 + MnO4- + 2H2O  MnO2 + 3Fe(OH)3 + OH-

3Fe(OH)2 + KMnO4 + 2H2O  MnO2 + 3Fe(OH)3 + KOH

(b) 2Bi(OH)3 + 3SnO22-  2Bi + 3H2O + 3SnO32-

2Bi(OH)3 + 3Na2SnO2  2Bi + 3H2O + 3Na2SnO3

 Disproportionation Reactions

In redox reactions, a single substance can be both

oxidized and reduced. These are known as
disproportionation reactions
Eg;

2H2O2(aq) 2H2O(l) + O2(g)