References:
ions is equal to the charge of the ion
Chemistry by:
Brescia, Arents, Meislich & Turk
Brown, Lemay, Bursten, Murphy & Woodward
Chang
Petruccci, Harwood & Herring
McQuarrie, McQuarrie & Rock
Mortimer
Silberberg
Determination of Grades:
Q 30%
A, SW, RW, R 30%
TE 40%
Course Content:
Redox ,Electrochemistry and Energy
Nuclear Chemistry and Energy
Crystal Structure
Metals
The Chemistry of the Environment
Fuels, polymers & nanomaterials
Redox, Electrochemistry and Energy
REDOX: OXIDATION-REDUCTION REACTION
OXIDATION involves loss of electrons
increase in oxidation number
species involved is a reductant
or reducing agent (electron
donor)
REDUCTION involves gain of electrons
decrease in oxidation number
species involved is an oxidant or
oxidizing agent (electron
acceptor)
RULES IN DETERMINING THE OXIDATION STATE
OF AN ATOM
(1) An atom in its free or elemental state
has an oxidation number of zero e.g. Ne
has an oxidation number of zero; the
oxidation number of P in P4 is zero.
(2) The oxidation number of monatomic
e.g. the oxidation number of Na+, Al3+
and S2- is +1, +3 and -2, respectively.
(3) Fluorine in all its compounds, always
has an oxidation number of -1. F in XeF 4
and CaF2 has an oxidation number of -1.
(4) Li, Na, K, Rb, Cs, in all their compounds
have an oxidation number of +1 e.g.
each Na atom in Na2SO3 has an
oxidation number of +1.
(5) Be, Mg, Ca, Sr, Ba, and Ra in all their
compounds have an oxidation number
of +2 e.g. Ba in BaCO3 and Ca in CaCl2
has an oxidation number of +2.
(6) Cl, Br and I have an oxidation number of
-1 in their binary compounds with
metals e.g. each Cl atom in FeCl3 has an
oxidation number of -1.
(7) In most of the compounds of oxygen
like BaO, H2O, CO2, and MnO2 oxygen
has an oxidation number of -2 except in
the following cases
a. In its compounds with fluorine,
oxygen has a positive oxidation
number; in OF2, the O atom has an
oxidation number of +2.
b. In peroxide like H2O2, the O atom
has an oxidation number of -1.
c. In the superoxide ion O2- , the O
atom has an oxidation number of (-
1/2).
(8) Hydrogen in most of its compounds like
H2O, NH3, HF, NaHCO3, has an oxidation
number of +1. However, in hydrides
like NaH and MgH2, the oxidation
number of H is -1.
(9) For other atoms in compounds or
complex ions which are not covered by
the above rules, their oxidation
numbers of all the atoms in a
 compound or complex ion is equal to
the net charge of the species.
BALANCING REDOX REACTIONS BY THE CHANGE
IN OXIDATION NUMBER METHOD
(1) Identify the species that changed in
oxidation number and indicate their
oxidation numbers on both sides of the
equation.
(2) Find the number of electrons gained or
lost per formula unit of the oxidizing
agent and reducing agent respectively.
(3) Make the number of electrons gained
equal to the number of electrons lost by
adjusting the coefficients of the
oxidizing agent and reducing agent.
(4) Balance the elements that changed in
oxidation number by adjusting the
coefficient of the corresponding
products.
(5) Balance the other elements by
inspection.
(6) Check if the number of elements and
the total charge in each side of the
equation is balanced.
Balance the following redox equation
HNO3 + H2S ----> NO + S + H2O
HNO3 1(+1) + 1(N) + 3(-2) = 0
N = +5
NO 1(N) + 1(-2) = 0
N = +2
H2S 2(+1) + 1(S) = 0
S = -2
S 0
HNO3 + H2S ---> NO + S + H2O
+5 -2 +2 0
Nitrogen is reduced (from +5 to +2, a decrease
of 3), and sulphur is oxidized (from -2 to 0, an
increase of 2)
The lowest common multiple of 3 and 2 is 6
2HNO3 + 3H2S ---> NO + S + H2O
2HNO3 + 3H2S ---> 2NO + 3S + H2O
2HNO3 + 3H2S ----> 2NO + 3S + 4H2O
Balance the following redox equation
H2O + I2 + ClO3- ----> IO3- + Cl- + H+
ClO3- 1(Cl) + 3(-2) = -1 ----> Cl = +5
IO3- 1(I) + 3(-2) = -1 ---> I = +5
H2O + I2 + ClO3- ----> IO3- + Cl- + H+
0 +5 +5 -1
Each iodine atom undergoes an increase of 5
(from 0 to +5), but there are two iodine atoms
in I2. The increase in oxidation number is
therefore 10. Chlorine undergoes a decrease of
6 (from +5 to -1). The lowest common multiple
of 6 and 10 is 30. Therefore, 3I2 molecules must
be indicated (a total in crease of 30) and 5ClO 3-
ions are needed (a total decrease of 30)
H2O + 3I2 + 5ClO3- ----> IO3- + Cl- + H+
H2O + 3I2 + 5ClO3- ----> 6IO3- + 5Cl- + H+
Balance the oxygen
3H2O + 3I2 + 5ClO3- ----> 6IO3- + 5Cl- + H+
Balance the hydrogen
3H2O + 3I2 + 5ClO3- ----> 6IO3- + 5Cl- + 6H+
An ionic equation must indicate charge balance
as well as mass balance. Since the algebraic
sum of the charges on the left (-5) equals that
on the right (-5), the equation is balanced.
BALANCING REDOX REACTIONS BY HALF
REACTION (ION –ELECTRON) METHOD
(1) Identify the species that changed in
oxidation number. Write the skeleton
equation of the oxidation and reduction
half reaction based on these changes.
(2) Balance each half reaction separately.
(2.1) Balance all elements
except oxygen and hydrogen.
(2.2) Balance oxygen using H2O.
(2.3) Balance hydrogen using
H+.
 (2.4) If the medium is acidic:
change H+ to H3O+ by adding
H2O to both sides of the
equation. H2O will convert H+ to
H3O+ as in the following
equation: H+ + H2O ----> H3O+. If
the medium is basic add OH- to
both sides of the equation. The
OH- will neutralize the H+ to
produce H2O as in the following
equation: H+ + OH- ----> H2O.
(2.5) Balance charges using
electrons.
(3) Multiply each half reaction by the
appropriate integer to make the number of
electrons in the oxidation half reaction equal to
the number of electrons in the reduction half
reaction
(4) Add the two half reactions. Eliminate
duplication in the product and in the reactant
side of the equation.
(5) Finally, to be sure that the equation is
balanced, check the number of elements and
the total charge in each side of the equation.
Balance the following reaction that occurs in
acid solution
Cr2O72- + Cl- ----> Cr+3 + Cl2
Skeleton partial equations:
Cr2O72- ----> Cr3+ Cl- ----> Cl2
Cr2O72- ----> 2Cr3+ 2Cl- ----> Cl2
Cr2O72- ----> 2Cr3+ + 7H2O
14H+ + Cr2O72- ----> 2Cr3+ + 7H2O
+ 2- 3+
14H2O + 14H + Cr2O ----> 2Cr + (14+7)H2O
7 10Br- + 12H2O + 10e-
14H3O+ + Cr2O72- ----> 2Cr3+ + 21H2O
6e- + 14H3O+ + Cr2O72- ----> 2Cr3+ + 21H2O
2Cl- ----> Cl2 + 2e-
The number of electrons gained must equal the
number of electrons lost
6e- + 14H3O+ + Cr2O72- ----> 2Cr3+ + 21H2O
3(2Cl- ----> Cl2 + 2e-)
6e- + 14H3O+ + Cr2O72- + 6Cl- ----> 2Cr3+ + 21H2O
+ 3Cl2 + 6e-
14H3O+ + Cr2O72- + 6Cl- ----> 2Cr3+ + 21H2O + 3Cl2
14H+ + Cr2O72- + 6Cl- ----> 2Cr3+ + 7H2O + 3Cl2
Balance the following equation in alkaline
(basic)solution
Br2 -----> BrO3- + Br-
In this reaction the same substance is both
oxidized and reduced. Such reactions are called
disproportionation or auto-oxidation –reduction
reactions.
Br2 -----> BrO3-
Br2 -----> Br-
Br2 -----> 2BrO3-
Br2 -----> 2Br-
Br2 -----> 2BrO3-
6H2O + Br2 -----> 2BrO3-
6H2O + Br2 -----> 2BrO3- + 12H+
12OH- + 6H2O + Br2 -----> 2BrO3- + 12H+ + 12OH-
12OH- + 6H2O + Br2 -----> 2BrO3- + 12H2O
12OH- + 6H2O + Br2 -----> 2BrO3- + 12H2O + 10e-
2e- + Br2 -----> 2Br-
The number of electrons gained must equal the
number of electrons lost
12OH- + 6H2O + Br2 -----> 2BrO3- + 12H2O + 10e-
5(2e- + Br2 -----> 2Br-)
12OH- + 6H2O + Br2 + 5Br2 + 10e- -----> 2BrO3- +
12OH- + 6Br2 -----> 2BrO3- +10Br- + 6H2O
or by reducing the coefficients to the lowest
possible terms:
6OH- + 3Br2 -----> BrO3- +5Br- + 3H2O
Balance the following using the ion-electron (3) H2O + P4 + HOCl ----> H3PO4 + Cl- + H+
method (4) Cu + H+ + NO3- -- Cu2+ + NO + H2O
(1) MnO4- + As4O6 ----> Mn2+ + H3AsO4 (in
acid solution) STOICHIOMETRY OF REDOX REACTION
-
(2) MnO4 + N2H4 ----> MnO2 + N2 (in alkaline Just like any other reactions, stoichiometric
solution) calculations can be done in a redox reaction.
-
(3) ReO2 + Cl2 ----> HReO4 + Cl Calculations can be done based
- 2- -
(4) CO(NH2)2 + OBr ----> CO3 + N2 + Br (a) on the balanced redox reaction or
Balance the following using the change in (b) on the idea that the number of
oxidation number method electrons gained is equal to the
- - -
(1) H2O + MnO4 + ClO2 ----> MnO2 + ClO4 + number of electrons lost.
-
OH
(2) PbO2 + HI ----> PbI2 + I2 + H2O
COMPARATIVE STRENGTHS OF THE REDUCING AGENTS AND OXIDIZING AGENTS
Reduction half Standard
reaction reduction
potential
Increasing Mg2+ + 2e- -->Mg Increasing -2.37V
2+ - +
strength as Cu + 2e -->Cu strength as +0.15V
oxidizing agent Ag+ + e- --> Ag reducing agent +0.80V