Redox reactions

Where there is oxidation, there is always reduction- Chemistry is essentially a study of redox systems.
Redox = red + ox, ‘red’ from reduction and ‘ox’ from oxidation. The reactions in which reduction and oxidation takes place
simultaneously are called redox reactions.

Concepts of the process of oxidation and reduction:

Oxidation Reduction

Addition of oxygen or any electronegative element Removal of oxygen or any electronegative element

Removal of hydrogen or any electropositive element Addition of hydrogen or any electropositive element

Loss of electron Gain of electron

Increase oxidation number or oxidation state Decrease oxidation number or oxidation state

eg. ZnO + C → Zn + CO ; in this reaction ZnO is reduced to Zn and C is oxidized to CO (Write five more examples?)

Oxidation number: The charge that an atom of the element has in its ion or appears to have when present in the combined state
with other atoms.
Rules for calculating oxidation number (O.N.)/ oxidation state (O.S.):

Rule 1 In elements free or combined state, each atom bears O.N. zero. For e.g. Each atom in H2, O2, Cl2, P4, S8, Na, Mg, Al has O.N.
zero.
Rule 2 For ions composed of only one atom, the O.N. is equal to the charge on the ion. For e.g. Na+, Mg2+, Al3+, Cl-, O2-, N3- O.N. +1,
+2, +3, -1, -2, -3 respectively
Rule 3 Alkali metals (group 1 elements) always have +1 O.N. in their compounds. Alkaline earth metals (group 2 elements) always
have +2 O.N. in their compounds. Aluminium always has +3 O.N. in its compounds.
Rule 4 O.N. of oxygen is -2 except in peroxide (-1), superoxide (- ½ ) and compounds with F, oxygen bears positive O.S.
Rule 5 O.S of hydrogen is +1 except the compounds with highly electropositive metals like Na, Ca, Li O.S. of hydrogen is – 1.
Rule 6 O.S. of F is always – 1. Other halogens bears O.S. – 1 when they exist as halide ion but when bonded with more
electronegative element they bears positive O.S.
Rule 7 The algebraic sum of the oxidation number of all the atoms present in a compound must be equal to zero.
Rule 8 In case of polyatomic ions. the algebraic sum of the oxidation number of all the atoms present in the ion must be equal to
the charge on the ion.

Calculation of oxidation number (Some common examples)

Example Calculation Result

1. Find O.N. of Let O.N. of S be x, O.N. of Na, +1 and O, -2 O.N. of S in Na2S2O3 is +2

S in Na2S2O3 Therefore 2(+1) + 2x + 3 (-2) = 0, => x = +2

2. Find O.N. of Let O.N. of Mn be x, O.N. of K, +1 and O, -2 O.N. of Mn in KMnO4 is +7

Mn in KMnO4 Therefore +1 + x + 4 (-2) = 0, => x = +7
 3. Find O.N. of Let O.N. of Cr be x, O.N. of O, -2 O.N. of Cr in Cr2O72- +6
Cr in Cr2O72- Therefore 2x + 7 (-2) = - 2, => x = +6

4. Find O.N. of Let O.N. of Fe be x, O.N. of O, -2 Here the result is to be rationalize and therefore, 2 Fe, +3 O.S
Fe in Fe3O4 Therefore 3x + 4 (-2) = 0, => x = + 8/3 and 1 Fe, +2 O.S.

5. Find O.N. of Let O.N. of C be x, O.N. of H, +1 and O, -2 Sum total of charge of 2 C-atoms is zero. O.N. of each carbon
C in CH3COOH Therefore 2x + 4 (+1) + 2 (-2) = 0, => x = 0 is to be calculated by the structural formula CH3-COOH. The C
in -CH3 bears O.S. -3 and C in -COOH bears O.S. +3.

Oxidizing agent (oxidant) and reducing agent (reductant): In a redox reaction the substance that oxidizes other and itself get
reduced are called oxidizing agent or oxidant and the substance that reduces other and itself get oxidised are called reducing agent
or reductant. For e.g.
(i) In the reaction, MnO2 + 4 HCl → MnCl2 + 2 H2O + Cl2; MnO2 is oxidizing agent & HCl is reducing agent.
(ii) In the reaction, ZnO + C → Zn + CO ; ZnO is oxidizing agent and C is reducing agent.
Redox reaction includes various types of reactions:
Types of Examples Redox Justification/Explanation
reaction (Yes /No)
Combination Mg + O2 → 2 MgO Yes, Combination of two elements to form a compound is always a redox
Reactions reaction because addition takes place between one electropositive and
one electronegative element so there is a transfer of electrons. In the
given example
Mg → Mg2+ + 2 e- (oxidation) and O + 2 e-→ O2- (reduction)
CaO + CO2 → 2 CaCO3 No, Combination of two compounds to form another new compound may
not be a redox reaction because charge (oxidation number/state) of the
species remains same. In the given example, oxidation number of Ca, O
and C in both sides are +2, -2 and +4 respectively.
Decomposition 2 NaCl → 2 Na + Cl2 Yes Decomposition of a compound into its constituent elements is always a
reactions redox reaction, because there is transfer of electrons from anion to
cation. In the given example,
2Cl- → Cl2 + 2 e- (oxidation) and 2 Na+ + 2 e-→ 2 Na (reduction)
CaCO3 -Δ→ CaO + CO2 No Decomposition of a compound to form two new compounds may or may
not be a redox reaction. Charge of the species remains same in both
sides. In the given example, oxidation number of Ca, O and C in both
sides are +2, -2 and +4 respectively.
2Pb(NO3)2 → 2PbO + 4NO2 + O2 Yes In the given example, oxidation number of N reduced to +4 from +5 and
two O-atoms O.S. increases from -2 to zero to form O2.
Displacement Zn + CuSO4 → ZnSO4 + Cu Yes Displacement reaction is always a redox reaction. In the given example,
reactions Zn → Zn2+ + 2 e- (oxidation) and Cu2+ + 2 e- → Cu (reduction).
Double NaCl + AgNO3 → AgCl + NaNO3 No Double displacement reaction is not a redox reaction because here
displacement exchange of ions takes place but charge of the ions remains same in
reactions both sides. In the given example Na+, Cl-, Ag+ and NO3- remains same in
both sides.
Disproportionation reactions: the redox reaction in which one element in one oxidation state simultaneously oxidized and reduced.
For e.g. 2 H2O2 → H2O + O2 , here peroxide ion (O.S. of O, -1) is oxidized to O2 (O.S. of O, zero) and reduced to water (O.S. of O, -2)
P4 + 3 OH- + 3 H2O → PH3 + 3 H2PO2- , here P (O.S. of O, zero) is oxidized to H2PO2- (O.S. of P, -1) and reduced to PH3 (O.S. of P, -3)
Balancing redox reactions (by ion-electron method or half reaction method)
Example 1: Balance the equation MnO4- + Fe2+ → Mn2+ + Fe3+ in acidic medium
Steps Solution Remark
1. Write the unbalanced oxidation To identify the species oxidized and reduced we may
equation in ionic form MnO4- + Fe2+ → Mn2+ + Fe3+ compare O.N. of the species in both side of the equation.
 and identify oxidation Reduction (Or some time addition or removal of oxygen and hydrogen
and reduction process. if involved in the reaction or using other suitable concept)

2. Write oxidation and Reduction half, We should first balance the atoms other than O & H. Then O
reduction half MnO4- + 8 H+ + 5 e- → Mn2+ + 4 H2O & H are balanced by adding H+ and H2O for acidic medium.
separately and balance Oxidation half, Finally charge should be balanced by adding e-(oxidation
them Fe2+ → Fe3+ + 1e- ] x 5 process, in the right side and reduction process, in left side)

3. Add two half reactions Before adding we should equalize electrons (loss and gain in
after equalizing the MnO4- + 5Fe2+ + 8 H+ → Mn2+ + 5Fe3+ + 4H2O oxidation and reduction half respectively) we multiply the
electrons in both equations by suitable number, here only oxidation half
equations reaction is multiplied by 5.

Example 2: Balance the equation N2H4 + ClO3- → NO + Cl- in basic medium

Steps Solution Remark
4. Write the unbalanced reduction To identify the species oxidized and reduced we may
equation in ionic form N2H4 + ClO3- → NO + Cl- compare O.N. of the species in both side of the equation.
and identify oxidation oxidation (Or some time addition or removal of oxygen and hydrogen
and reduction process. if involved in the reaction or using other suitable concept)

5. Write oxidation and Reduction half, We should first balance the atoms other than O & H. Then O
reduction half ClO3- + 3 H2O + 6 e- → Cl- + 6 OH- ] x 4 & H are balanced by adding OH- and H2O for basic medium.
separately and balance Oxidation half, While balancing O, add double no. of OH- on the side where
them N2H4 + 8 OH- → 2 NO + 6 H2O + 8 e- ] x 3 less O-atom, and add require no. of H2O on the other side.
For balancing H-atom, add as many H2O molecules on the
side lack of H-atom and required no. of OH- on the other
side. Charge should be balanced as mentioned above.
6. Add two half reactions Before adding we should equalize electrons (loss and gain in
after equalizing the 3 N2H4 + 4 ClO3- → 6 NO + 4 Cl- + 6 H2O oxidation and reduction half respectively) we multiply the
electrons in both equations by suitable number, here oxidation half reaction is
equations multiplied by 3 and reduction half reactionby 4.

Balancing redox reactions (by oxidation number method)

Example 1: Balance the equation Cr2O72- + SO2 → Cr3+ + SO42- in acidic medium
Steps Solution Remark
1. Write the unbalanced Cr2O72- + SO2 → Cr3+ + SO42-
equation in ionic form O.S +6 -2 +4 -2 +3 +6 -2
and write O.S. of all
the species.

2. Indicate increase and O.N. increased by 2

decrease in O.N. Cr2O72- + SO2 → Cr3+ + SO42-
O.N. decreased by 3
3. Balancing increase and While balancing increase and decrease in O.N. we should
decrease in O.N. Cr2O72- + 3 SO2 → 2 Cr3+ + 3 SO42- take care of no. of atoms and formula in the either side.

4. Balancing O and H. Cr2O72- + 3 SO2 + 2 H+ → 2 Cr3+ + 3 SO42- + H2O Acidic medium, O & H are balanced by adding H+ and H2O.

Example 2: Balance the equation P4 + OH- → PH3 + H2PO2- in basic medium

Steps Solution Remark
1. Write the unbalanced P4 + OH- → PH3 + H2PO2-
equation in ionic form O.S 0 -2 +1 -3 +1 +1 +1 -2
 and write O.S. of all
the species.

2. Indicate increase and O.N. decreased by 3

decrease in O.N. P4 + OH- → PH3 + H2PO2-
O.N. increased by 1
3. Balancing increase and While balancing increase and decrease in O.N. we should
decrease in O.N. P4 + OH- → PH3 + 3 H2PO2- take care of no. of atoms and formula in the either side.

4. Balancing O and H. P4 + 3 OH- + 3 H2O → PH3 + 3 H2PO2- Basic medium, O & H are balanced by adding OH- and H2O.

Redox titration: In redox systems, the titration method can be used to determine strength of oxidant/reductant by titrating it against
standard solution of reductant/oxidant using a redox sensitive indicator.
Examples Reactions and mathematical formula for calculation Indicator used
To determine the Oxidation half, C2O42- → 2 CO2 + 2 e- ] x 5 MnO4- acts as the
strength of KMnO4 using Reduction half, MnO4- + 8 H+ + 5 e- → Mn2+ + 4 H2O ] x 2 self indicator. The
standard solution of Overall reaction, 2 MnO4- + 5 C2O42- + 16 H+ → 2 Mn2+ + 10 CO2 + 8 H2O visible end point in
oxalic acid Mathematical formula for calculation, 5(VKMnO4 x MKMnO4) = 2(Voxalic acid x Moxalic acid) this case is achieved
To determine the Oxidation half, Fe2+ → Fe3+ + 1e- ] x 5 after the last of the
strength of KMnO4 using Reduction half, MnO4- + 8 H+ + 5 e- → Mn2+ + 4 H2O ] reductant.
standard solution of Overall reaction, MnO4 + 5Fe + 8 H → Mn + 5Fe + 4H2O
- 2+ + 2+ 3+

Mohr’s salt. Mathematical formula for calculation, 5(VKMnO4 x MKMnO4) = (Vmohs’s salt x Mmohr’s salt)
Limitations of Concept of Oxidation Number:
The concept of redox processes has been evolving with time. This process of evolution is continuing. In fact, in recent past the
oxidation process is visualized as a decrease in electron density and reduction process as an increase in electron density around the
atom(s) involved in the reaction

Redox reaction and electrode process:

Let us consider the reaction Zn metal dipped in copper sulphate solution, Zn + CuSO4 → ZnSO4 + Cu, here Zn → Zn2+ + 2 e- (oxidation)
and Cu2+ + 2 e- → Cu (reduction) takes place. Now we modify the experiment in such a manner that transfer of electrons takes place
indirectly by separating of zinc metal from copper sulphate solution. We take copper sulphate solution in a beaker and put a copper
strip or rod in it and zinc sulphate solution in another beaker and put a zinc rod or strip in it. Now reaction takes place in either of the
beakers and at the interface of the metal and its salt solution in each beaker both the reduced and oxidized forms of the same
species are present (redox couple) represented as Zn2+/Zn and Cu2+/Cu. Now we put the beakers side by side and connect solutions
in two beakers by a salt bridge containing a solution of potassium chloride or ammonium nitrate. This provides an electric contact
between the two solutions without allowing them to mix with each other. The zinc and copper rods are connected by a metallic wire
with a provision for an ammeter and a switch. This is known as Daniell cell (electro chemical cell). When the switch is in the off
position, no reaction takes place in either of the beakers and no current flows through the metallic wire. As soon as the switch is in
the on position, we make the following observations:
1. The transfer of electrons now does not take place directly from Zn to Cu2+ but through the metallic wire connecting the two rods
which indicates the flow of current.
2. The electricity from solution in one beaker to solution in the other beaker flows by the migration of ions through the salt bridge.
Electrochemical cell: the device which produce electric current due to chemical reaction (redox reaction).
Electrode potential: The potential associated with each electrode is known as electrode potential. Electrode potential is expressed in
terms of reduction potential that means tendency of metal ion to gain electrons. Mn+ + ne- → M.
Standard electrode potential: If the concentration of each species taking part in the electrode reaction is unity (if any gas appears in
the electrode reaction, it is confined to 1 atmospheric pressure) and further the reaction is carried out at 298K, then the potential of
each electrode is said to be the Standard Electrode Potential
Cell potential: The flow of current is possible only if there is potential difference between the electrodes, this is known as cell
potential and is given by Ecell = Ecat - Ean. For the cell, Zn2+/Zn ‖ Cu2+/Cu, Ecell = ECu2+/Cu – EZn2+/Zn
Standard cell potential (E0cell): Cell potential at the standard state that is the concentration of each species taking part in the
electrode reaction is unity (if any gas appears in the electrode reaction, it is confined to 1 atmospheric pressure) and further the
reaction is carried out at 298K. E0cell = E0cat - E0an
Standard hydrogen electrode (SHE): it is the reference electrode whose potential is taken zero. In this electrode H2 gas under 1 atm
pressure is bubbled through 1 M HCl (aq) using Pt electrode. Reactions are at 2H+(aq) + e- → H2(g) and H2(g) → 2H+(aq) + 2 e-.
The electrode potential value for each electrode process is a measure of the relative tendency of the active species in the process to
remain in the oxidised/reduced form. A negative E0 means that the redox couple is a stronger reducing agent than the H+/H2 couple.
A positive E0 means that the redox couple is a weaker reducing agent than the H+/H2 couple.

Exercise

Answer the following questions:

1. What is oxidation and reduction? Explain with example.
2. What are redox reactions? Give examples.
3. What are oxidizing agent (oxidant) and reducing agent (reductant)? Explain with an example.
4. What is oxidation number? Is there any difference between oxidation number and oxidation state?
5. Is combination reaction a redox reaction? Explain with suitable example.
6. Is decomposition reaction a redox reaction? Explain with suitable example.
7. Is displacement reaction a redox reaction? Explain with suitable example.
8. Is double displacement reaction a redox reaction? Explain with suitable example.
9. What is disproportionation reaction? Explain with an example.
10. Identify the substances that are oxidized and the substances that are reduced in the following reactions.
(i) 4 Na(s) + O2(g) → 2 Na2O(s)
(ii) CuO(s) + H2(g) → Cu(s) + H2O(l)
(iii) H2S + Cl2 → 2HCl + S
(iv) H2O + F2 → HF + HOF
(v) ZnO + H2 → Zn + H2O
11. Assign oxidation number to the underlined elements in each of the following species:
(a) NaH2PO4 (b) NaHSO4
(c) H4P2O7 (d) K2MnO4
12. What is the oxidation number of the underlined elements in each of the following and how do you rationalise
your results?
(a) KI3 (b) H2S4O6 (c) Fe3O4
(d) CH3CH2OH (e) CH3COOH
13. Justify that the following reactions are redox reactions:
(a) CuO(s) + H2(g) → Cu(s) + H2O(g)
(b) Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)
(c) 4 NH3(g) + 5 O2(g) → 4NO(g) + 6H2O(g)
14. Write formulas for the following compounds:
(a) Mercury(II) chloride (b) Nickel(II) sulphate
 (c) Tin(IV) oxide (d) Thallium(I) sulphate
(e) Iron(III) sulphate (f) Chromium(III) oxide
15. Balance the following redox reactions by ion - electron method :
(a) MnO4- (aq) + I- (aq) → MnO2 (s) + I2(s) (in basic medium)
(b) H2O2 (aq) + Fe2+ (aq) → Fe3+ (aq) + H2O (l) (in acidic solution)
(c) Cl2O7 (g) + H2O2(aq) →ClO–(aq) + O2(g) + H+
16. Arrange the following metals in the order in which they displace each other from the solution of their salts. Al,
Cu, Fe, Mg and Zn.
17. Given the standard electrode potentials, K+/K = -2.93V, Ag+/Ag = 0.80V, Hg2+/Hg = 0.79V Mg2+/Mg = -2.37V. Cr3+/Cr
= -0.74V arrange these metals in their increasing order of reducing power.
18. Depict the galvanic cell in which the reaction Ni(s) + 2Ag+(aq) → Ni2+(aq) +2Ag(s) takes place, Further show:
(a) which of the electrode is negatively charged,
(b) the carriers of the current in the cell, and
(c) Individual reaction at each electrode.