REDOX REACTIONS

Where there is oxidation, there is always

reduction
 OXIDATION AND REDUCTION
• Oxidation: Addition of oxygen/electronegative element to a
substance or removal of hydrogen/ electropositive element from
a substance.
• Reduction: Removal of oxygen/electronegative element from a
substance or addition of hydrogen/ electropositive element to a
substance.
 Identify reactions
• 2 Mg (s) + O2 (g) = 2 MgO (s)
• Mg (s) + F2 (g) = MgF2 (s)
• 2K4 [Fe(CN)6](aq) + H2O2 (aq) =2K3[Fe(CN)6](aq) +KOH (aq)
• 2 HgO (s) = 2 Hg (l) + O2 (g)
• 2 FeCl3 (aq) + H2 (g) = 2 FeCl2 (aq) + 2 HCl(aq)
• CH2 = CH2 (g) + H2 (g) = H3C – CH3 (g)
• 2HgCl2 (aq) + SnCl2 (aq) = Hg2Cl2 (s)+SnCl4
 Redox Reactions
• Oxidation and reduction always occur
simultaneously
• (i) H2S(g) + Cl2(g) =2 HCl(g) + S(s)
• (ii) 3Fe3O4(s) + 8 Al (s)= 9Fe(s) +4Al2O3(s)
• (iii) 2Na(s) + H2 (g) =2NaH (s)
 REDOX REACTIONS IN TERMS OF
ELECTRON TRANSFER REACTIONS
• 2Na + Cl2 = 2NaCl
• 4Na + O2= 2Na2O
• 2Na + S=Na2S

Half reactions that involve

loss of electrons are called
oxidation reactions. Similarly,
the half reactions that involve
gain of electrons are called
reduction reactions.
 Definitions
• Oxidation: Loss of electron(s) by any species.
• Reduction: Gain of electron(s) by any species.
• Oxidising agent : Acceptor of electron(s).
• Reducing agent : Donor of electron(s).
 Competitive Electron Transfer
Reactions

Metal activity series or electrochemical series: The arrangement of elements on the

basis of their tendency to release electrons to other elements.
 OXIDATION NUMBER
• Oxidation number denotes the oxidation state of an element in a
compound ascertained according to a set of rules formulated on
the basis that electron pair in a covalent bond belongs entirely to
more electronegative element.
 Rules for calculation of oxidation
number
1. In elements, in the free or the uncombined state, each atom bears an oxidation number of zero.
Evidently each atom in H2, O2, Cl2, O3, P4, S8, Na, Mg, Al has the oxidation number zero.
2. For ions composed of only one atom, the oxidation number is equal to the charge on the ion.
Thus Na+ ion has an oxidation number of +1, Mg2+ ion, +2, Fe3+ ion, +3, Cl– ion, –1, O2–
ion, –2; and so on. In their compounds all 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.
3. The oxidation number of oxygen in most compounds is –2. Exceptions: peroxides and
superoxides. in peroxides (e.g., H2O2, Na2O2), each oxygen atom is assigned an oxidation
number of –1, in superoxides (e.g., KO2, RbO2) each oxygen atom is assigned an oxidation
number of –(½). The second exception appears rarely, i.e. when oxygen is bonded to fluorine.
In such compounds e.g., oxygen difluoride (OF2) and dioxygen difluoride (O2F2), the oxygen is
assigned an oxidation number of +2 and +1, respectively.
 Rules for calculation of oxidation
number
4. The oxidation number of hydrogen is +1, except when it is bonded to
metals in binary compounds (that is compounds containing two elements).
For example, in LiH, NaH, and CaH2, its oxidation number is –1.
5. In all its compounds, fluorine has an oxidation number of –1. Other
halogens (Cl, Br, and I) also have an oxidation number of –1, when they
occur as halide ions in their compounds. Chlorine, bromine and iodine
when combined with oxygen, for example in oxoacids and oxoanions, have
positive oxidation numbers.
6. 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 atoms of the ion must equal the charge on the ion. Thus, the
sum of oxidation number of three oxygen atoms and one carbon atom in
the carbonate ion, (CO3)2– must equal –2.
 Rules for calculation of oxidation
number
• If two or more than two atoms of an element are present in the
molecule/ion such as Na2S2O3/Cr2O72– , the oxidation number of the
atom of that element will then be the average of the oxidation number
of all the atoms of that element
• The oxidation number/state of a metal in a compound is sometimes
presented according to the notation given by German chemist, Alfred
Stock. It is popularly known as Stock notation. According to this, the
oxidation number is expressed by putting a Roman numeral
representing the oxidation number in parenthesis after the symbol of
the metal in the molecular formula. Thus aurous chloride and auric
chloride are written as Au(I)Cl and Au(III)Cl3. Similarly, stannous
chloride and stannic chloride are written as Sn(II)Cl2 and Sn(IV)Cl4.
 Calculate oxidation number
• HAuCl4, Tl2O, FeO, Fe2O3, CuI, CuO, MnO
and MnO2
 Definitions in terms of oxidation
number
• Oxidation: An increase in the oxidation number of the element in the given
substance.
• Reduction: A decrease in the oxidation number of the element in the given
substance.
• Oxidising agent: A reagent which can increase the oxidation number of an
element in a given substance. These reagents are called as oxidants also.
• Reducing agent: A reagent which lowers the oxidation number of an
element in a given substance. These reagents are also called as reductants.
• Redox reactions: Reactions which involve change in oxidation number of
the interacting species.
 Revision
Justify that the reaction:
2Cu2O(s) + Cu2S(s) 6Cu(s) + SO2(g)
is a redox reaction. Identify the species
oxidised/reduced, which acts as an oxidant and
which acts as a reductant.
 Types of Redox Reactions
• Combination reactions
• Decomposition reactions
• Displacement reactions
• Disproportionation reactions
Combination reactions
 Decomposition reactions
• Breakdown of a compound into two or more
components at least one of which must be in
the elemental state.
• All decomposition
reactions are not redox
reactions.
 Displacement reactions
• An ion (or an atom) in a compound is replaced by an ion
(or an atom) of another element.

• Two categories:
a) Metal displacement: metal displace other metal
b) Non-metal displacement: Hydrogen displacement
and a rarely occurring reaction involving oxygen
displacement
 Disproportionation reactions
• An element in one oxidation state is simultaneously oxidised and
reduced. One of the reacting substances in a disproportionation reaction
always contains an element that can exist in at least three oxidation states. The
element in the form of reacting substance is in the intermediate oxidation
state; and both higher and lower oxidation states of that element are formed
in the reaction.
 Disproportionation reactions

Among halogens, fluorine does not show a disproportionation tendency.

Classify following redox reactions
 Balancing of Redox Reactions
• Oxidation Number Method
• Half Reaction Method
 Oxidation Number Method
• Step 1: Write the correct formula for each reactant and
product.
• Step 2: Identify atoms which undergo change in
oxidation number in the reaction by assigning the
oxidation number to all elements in the reaction.
• 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.
• Step 4: Ascertain the involvement of ions if the reaction is taking
place in water, add H+ or OH– ions to the expression on the
appropriate side so that the total ionic charges of reactants and
products are equal. If the reaction is carried out in acidic solution, use
H+ ions in the equation; if in basic solution, use OH– ions.
• Step 5 : Make the numbers of hydrogen atoms in the expression on
the two sides equal by adding water (H2O) molecules to the reactants
or products. Now, also check the number of oxygen atoms. If there
are the same number of oxygen atoms in the reactants and products,
the equation then represents the balanced redox reaction.
 Oxidation Number Method
• FeCl3 + H2S FeCl2 +S+ HCl
• MnO2 +HCl MnCl2 + Cl2 + H2O
• Zn + HNO3 Zn(NO3)2 + NH4NO3+ H2O
• Cu + HNO3 Cu(NO3)2 + NO2+ H2O
• K2Cr2O7 + HCl KCl +CrCl3+Cl2 + H2O
• Cr2O72-+ SO2 +H+ Cr3+ +HSO4- +H2O
 Half Reaction Method
• 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
• Step 2: Separate the equation into half reactions: Oxidation half, Reduction half.
• Step 3:Balance the atoms other than O and H in each half reaction individually.
• Step 4: For reactions occurring in acidic medium, add H2O to balance O atoms and
H+ to balance H atoms.
• Step 5: Add electrons to one side of the half reaction to balance the charges. If need
be, make the number of electrons equal in the two half reactions by multiplying one or
both half reactions by appropriate number.
• Step 6: Add the two half reactions to achieve the overall reaction and cancel the
electrons on each side.
 Half Reaction Method
• Al + Ni2+ Al3+ + Ni
• Zn + BrO3- Zn2+ + Br-