Summary

Redox Reactions

Classical Idea of Redox Reactions

 Oxidation: Addition of oxygen/electronegative element to a substance or removal of

hydrogen/electropositive element from a substance.
2Mg(s) + O2 (g)  2MgO(s)
 Reduction: Removal of oxygen/electronegative element from a substance or addition of
hydrogen/electropositive element to a substance.
2 Hg  s  

 2 Hg  l   O2  g 

Redox Reactions in Terms of Electron Transfer Reactions

 Oxidation : Loss of electrons(s) by any species

 Reduction : Gain of electrons(s) by any species

 Oxidising agent: Species which oxides other species and reduces itself by accepting electrons.
 Reducing agent: Species which reduces other species and oxidises itself by giving electrons.
 Oxidation Number: It denotes the oxidation state of an element in a compound.

Rules for the Calculation of Oxidation Number

 Each atom in H2, O2, Cl2, O3, P4, S8, Na, Mg, Al has the oxidation number zero.
 Alkali metals have oxidation number of +1 and all Alkaline earth metals have an oxidation
number of +2. Aluminium is regarded to have an oxidation number of +3 in all its compounds.
 Oxidation number of oxygen in most compounds is –2.
In peroxides like H2O2 and Na2O2 each oxygen atom is assigned an oxidation number of –1.
1
In superoxides like KO2, RbO2 each oxygen atom is assigned an oxidation number of (- 2 ).
 In compounds like oxygen difluoride (OF2), the oxidation number of Oxygen is +2 and in
dioxygen difluoride (O2F2) has an oxidation number of +1.
 The oxidation number of hydrogen is +1, except when it is bonded to metals. Example, in LiH,
NaH and CaH2, its oxidation number is –1.
 Fluorine has an oxidation number of –1.
(Cl, Br and I) also have an oxidation number of –1 but when these combined with oxygen, for
example in Oxoacids and Oxoanions then these have the positive oxidation number.

Redox Reactions 1
  The algebraic sum of the oxidation number of all the atoms in a compound must be zero. In
polyatomic ion, the algebraic sum of all the oxidation numbers of atom of the ion must equal
the charge on the ion.
Group 1 2 13 14 15 16 17
Element Na Mg Al Si P S Cl
Compound NaCl MgSO4 AlF3 SiCl4 P4O10 SF6 HClO4

Highest oxidation +1 +2 +3 +4 +5 +6 +7
number/state of the group
element

Fractional oxidation number: Fractional oxidation state is the average oxidation state of the element.

Type of Redox Reactions

Combination Reactions: Two or more element or compounds combine to form a new substance.

Decomposition Reactions: Breakdown of a compound into two or more components.

Displacement Reaction: An ion (or an atom) in a compound is replaced by an ion (or an atom) of
another element.

 Metal displacement:

 Non–metal displacement:

 Disproportionation reactions:

 Balancing Redox Reactions: Two methods are used to balance chemical equations for redox
processes.

 Oxidation Number Method :

Step 1: Write the correct formula for each reactant and product.
 Cr 3  SO42
Cr2O72  SO32– 

Redox Reactions 2
 Step 2: Assign the oxidation number to all elements in
the reaction showing a change in O.S.

Step 3: Calculate the increase or decrease in the oxidation number per atom and for the
entire molecule/ion in which it occurs. If these are not equal then multiply by suitable
number so that these become equal.
Cr2O72–  3S32–  Cr 3  3SO42–

Step 4: If the reaction is carried out in acidic solution, use H+ ions in the equation; if in
basic solution, use OH– ions on the appropriate side, so that the total ionic charges of
reactants and products are equal.
CrO72–  3SO32–  8H  
 2Cr 3  3SO42–

Step 5: Make the numbers of hydrogen and oxygen atoms in the expression on the two
sides equal by adding water (H2O) molecules to the reactants or products.

 Half Reaction Method: In this method, the two half equations are balanced separately and
then added together to give balanced equation.

Step 1: Produce unbalanced equation for the reaction in ionic form:

Fe2  aq   Cr2O72  aq  
 Fe3  aq   Cr 3  aq 

Step 2: Separate the equation into half reactions:

Oxidation half :

Reduction half :

Step 3: Balance the atoms other than O and H in reach half reaction individually multiply
the Cr3+ by 2 to balance Cr atoms.
Cr2O72–  aq  
 2Cr 3  aq 
Step 4: For reactions occurring in acidic medium, add H2O to balance O atoms and H+ to
balance H atoms.
Cr2O72–  aq   14H   aq  
 2Cr 3  aq   7 H 2O 1

Step 5: Add electrons to one side of the half reaction to balance the charges.
Now, the oxidation half reaction
Fe2  aq  
 Fe3  aq   e –
In the reduction half reaction there are net twelve positive charges on the left hand side and
only six positive charges on the right hand side. So add six electrons on the left side.
Cr2O72–  aq   14H   aq   6e – 
 2Cr 3  aq   7 H 2O l 
To equalise the number of electrons multiply the oxidation half reaction by 6 and write as:
6 Fe2  aq  
 6Fe3  aq   6e –
Redox Reactions 3
 Step 6: The net ionic equation as:
6 Fe2  aq   Cr2O72–  aq   14H   aq  
 6Fe3  aq   2Cr 3  aq   7 H 2O l 
Step 7: Verify that the equation in a basic medium, first balance the atoms as is done in
acidic medium. Then for each H+ ion, add an equal number of OH– ions to both sides of the
equation. Where H+ and OH– appear on the same side of the equation, combine these to
give H2O.

 A negative E° means that the redox couple is a stronger reducing agent than the H+/H2 couple.
 A positive E° means that the redox couple is a weaker reducing agent than the H+/H2 couple.
 KMnO4 acts as an oxidant in every medium with different strength.
Order: acidic medium > neutral medium > alkaline medium
 Act as both oxidising and reducing agents: SO2, H2O2, O3, NO2, etc.

 Nature of oxides based on oxidation number:

(i) Lowest oxidation state  Basic (MnO)
(ii) Intermediate oxidation state  Amphoteric (Mn3O4, MnO2)
(iii) Highest oxidation state  Acidic (Mn2O7)

Reaction between oxidising

Estimation of Reaction
agent and reducing agent
Titrating solution is Na2S2O3.5H2O(Hypo)
I2 (Iodometry) I2  2I–  2Na2S2O3
I2 + 2Na2S2O3  2NaI + Na2S4O6
CuSO4
2CuSO4 + 4KI  Cu2I2 + 2K2SO4 + I2 2CuSO4  I2  2I–  2Na2S2O3
(Iodimetry)

Redox Reactions 4
  In mixed oxides like Fe3O4, the metal exists in two different
oxidation states. Fe3O4 is an equimolar mixture of FeO and Fe2O3 and thus, Fe exist in +2 and
+3 oxidation states.
 If an element is in intermediate oxidation state, then that compound can act as both oxidising
and reducing agent, e.g. H2O2, H2O3, HNO2, SO2 etc.

Redox Reactions 5