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 XeF4
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 5ClO3-
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 STOICHIOMETRY OF REDOX REACTION
method
(1) MnO4- + As4O6 ----> Mn2+ + H3AsO4 (in Just like any other reactions, stoichiometric
acid solution) calculations can be done in a redox reaction.
(2) MnO4- + N2H4 ----> MnO2 + N2 (in alkaline Calculations can be done based
solution) (a) on the balanced redox reaction or
(3) ReO2 + Cl2 ----> HReO4 + Cl- (b) on the idea that the number of
(4) CO(NH2)2 + OBr- ----> CO32- + N2 + Br- electrons gained is equal to the
number of electrons lost.
Balance the following using the change in What weight of HNO3 (FW 63.0) is needed to
oxidation number method react with 250g of Cu (63.5)? The reaction is
(1) H2O + MnO4- + ClO2- ----> MnO2 + ClO4- + 3 Cu+8 HN O3=3 Cu ¿
OH-
(2) PbO2 + HI ----> PbI2 + I2 + H2O Formula Weight of HNO3 :1 ( H ) +1 ( N )+3 ( O )
63.0 g HNO3
(3) H2O + P4 + HOCl ----> H3PO4 + Cl- + H+ FW =1 ( 1.0 ) +1 ( 14.0 ) +3 ( 16.0 )=
1 mol HNO3
(4) Cu + H+ + NO3- -- Cu2+ + NO + H2O
250 g Cu ( 1 mol Cu
63.5 g Cu )(
8 mol HN O3
3 mol Cu )( 1 mol HN O3)
63.0 g HN O3
=661 g H

Common Oxidizing Agents and Their Products

Reactant Medium Products
+¿ ¿
−¿+ H ¿ +2
Mn O4 acid Mn + H 2 O
−2 +¿¿ +3
C r 2 O7 + H acid Cr + H 2 O
+4 +3
Ce acid Ce
+ ¿¿
−¿+H ¿ −¿+H O ¿
C lO 3 acid Cl 2

+ ¿¿
−¿+H ¿ −¿+H O ¿
BrO 3 acid Br 2

+¿ ¿
−¿+ H ¿ −¿+H O ¿
IO3 acid I 2

+ ¿¿

NO 3
−¿+H ¿
acid NO+ H 2 O ¿
+¿ ¿
H 2 O 2+ H acid H2 O
MnO2 (s) + H +¿¿ Acid +2
Mn + H 2 O
PbO 2(s) + H +¿ ¿ acid +2
Pb + H 2 O
+3 +2
Fe Fe

Common Reducing Agents and Their Products

Reactant Medium products
+ ¿¿
HNO2 + H 2 O acid −¿+H
NO 3
¿

−¿¿
I acid or neutral I2
 C 2 O4
−2
acid CO 2
H2 S acid S(s) + H +¿¿
SO 2+ H 2 O acid −2
SO 4 + H
+¿¿

+ ¿¿
H 3 ASO 3 + H 2 O acid or neutral H 3 ASO 4 + H
6 for I 2 , ( SO 4 )
−2
S2 O 3
acid or neutral S4 O−2 −2

+2 +3
Fe acid Fe
+2 +4
Sn acid Sn
Zn(s ) acid Zn
+2

Normality=N=
equivalents solute
=
( equivalent weight solute )
grams solute

liters of solutions liters of solution

formula weight of solute

equivalent weight of solute=
a
a=number of moles ofelectrons lost∨gained by a mole of
the reactant ¿ ¿ a formulaunit undergo ¿
+¿ ( aq ) supplied by one mole of the acid ¿
¿ the number moles of H
−¿ ( aq ) supplied by one mole¿
¿ the number of moles ofOH
of the base (for neutralizationreaction)
grams solute
liters of solution x normality =equivalents of solute=
equivalent weight solute
liters of solution x normality x equivalent weight of solute=grams of solute
Normality=a (Molarity)
What weight of pure potassium dichromate is needed for the preparation of 500ml of 0.1000N solution?
+3

C r 2 O−2
7 +H
+¿=Cr + H 2O ¿

−2 +3
C r 2 O7 =Cr
−2 +3
C r 2 O7 =2 Cr
−2 +3
C r 2 O7 =2 Cr +7 H 2 O
+3

C r 2 O−2
7 +14 H
+¿=2Cr +7 H 2O ¿

+3
−¿=2Cr +7 H 2 O ¿
−2 +¿+6 e ¿
C r 2 O7 +14 H

formula weight of K 2 Cr 2 O 7 294.21

equivalent weight of K 2 Cr 2 O7 = =
number of electrons gained∨lost 6

Other method to calculate equivalent weights:

−2
K 2 Cr2 O7−−−→ C r 2 O7
+3

C r 2 O−2
7 +H
+¿=Cr + H 2O ¿
 −2
C r 2 O7
2 ( Cr )+7 (−2 )=−2
2 ( Cr )=12
Cr=+6
C r (reactant )−−−−−−→ Cr( product)
(+6)−−−−−−−−−−(+3)
drop∈the oxidationnumber of Cr=3(that is 3 per chromium unit )
total change ( ¿ drop ) ∈the oxidation number of Cr=2 x 3=6(since there are 2 units of Cr per K 2 Cr 2 O7 unit )
FW K Cr O
equivalent weight of K 2 Cr 2 O7 = 2 2 7

( ( ))
gram K 2 Cr 2 O7
g
294.21
mole
6 ¿
¿ of K 2 Cr 2 O7 mole
0.1000 =
Liter solution
( 1000
500
) Liter
gram K 2 Cr 2 O7=2.452 g

In redox reactions, the number of equivalents of the oxidizing agent is equal to the number of
equivalents of reducing agents

A 0.4308 g sample of iron ore is dissolved in acid and the iron converted to the Fe2 +¿¿ state. The
solution is reacted with a solution of potassium permanganate. The oxidation of the iron requires 27.35
ml of 0.1248 N potassium permanganate solution. What is the mass percent of iron in the ore?

The number of equivalents of KMnO 4 used is the same as the number of equivalents of iron in the ore
equivalents of oxidizing agent=equivalents of reducing agent
equivalents of KMnO 4 =equivalents of Fe
equivalents of KMnO 4 =( VxN ) KMnO = ( 0.02735 L ) ¿4
3+ ¿¿
2 +¿−−−−→ Fe ¿
Fe
grams solute
equivalents of solute=
equivalent weight solute
−3
3.413 x 1 0 𨠨
gram Fe=0.1906 g Fe
gram of Fe 0.1906 g
% Fe ∈ore= x 100= x 100=44.24 %
gramof ore 0.4308 g
A solution of permanganate is 0.1000 N, 40.00 ml of this solution is added to an acidified solution which
contains excess potassium iodide. The iodine liberated is titrated by 35.00 ml sodium thiosulfate
solution. What is the normality of the latter?
+2
+¿=Mn + H2 O( oxidizingagent )¿
−¿+ H ¿
Mn O4
−¿=I 2 ( reducing agent ) ¿
I
−¿(oxidizing agent)¿
I 2=I
−2 −2
S2 O3 =S 4 O6 (reducing agent )
+2
−¿=2Mn +8 H O +5 I ¿
+ ¿+10 I 2 2
¿
−¿+16 H ¿
2 Mn O 4
−2

I 2+ 2 S2 O−2
3 =2 I
−¿+S O 4 6 ¿

−2

equivalent Mn O−¿=equivalents
4
I =equivalent S O 2 2 3 ¿

( NxV )Mn O =( NxV ) ¿ −¿

4 S2 O3
−2

0.1000 ¿ x
40.00
L 1000 (
L=N S O x
35.00
1000 )L
2
−2
3 ( )
N S O =0.1143 ¿ −2
2
L 3

What is the normality of an oxidizing agent of a solution of potassium dichromate containing 9.806 gram
per liter, and what volume 0.1000 N ferrous ammonium sulphate will 300.00 ml of the dichromate
oxidize in the presence of acid? How many grams of FeSO 4 . ( NH 4 )2 SO 4 .6 H 2 O (FW=392.15) are
contained in each millilitre of the ferrous solution?

COMPARATIVE STRENGTHS OF THE REDUCING AGENTS AND OXIDIZING AGENTS

Reduction half Standard
reaction reduction
potential
Increasing Mg2+ + 2e- -->Mg Increasing -2.37V
strength as Cu2+ + 2e- -->Cu+ strength as +0.15V
oxidizing agent Ag+ + e- --> Ag reducing agent +0.80V

Low reduction potential, poor tendency to be reduced, high tendency to be oxidized, better electron donor, better reducing agent
High reduction potential, high tendency to be reduced, better electron acceptor, better oxidizing agent

ELECTROCHEMICAL CELLS It consists essentially of two electrodes which

An electrochemical cell produces electricity are immersed either into the same solution or
directly from an oxidation-reduction reaction into two different solutions in electrolytic
It involves an oxidation half reaction and a contact with one another
reduction half reaction
Electrodes are used to enable electrons to enter
or leave an electrochemical cell
The electron transfer processes occur at the
electrodes
The reduction half reaction takes place at the
cathode; the oxidation half reaction takes place
at the anode
Salt bridges are used to make an electrical
connection between two different electrolyte
solutions in a cell
By convention, the half reaction of the left
electrode of the cell is written as an oxidation
half reaction, and the half reaction for the right
electrode of a cell is written as a reduction half
reaction (oxidation at the left electrode,
reduction at the right electrode)
The net cell reaction is given by the sum of the
two electrode half reactions adjusted so that
the number of electrons is the same in both half
reactions
The cell voltage depends on the concentrations
of the reactants and products of the cell
reaction
The cell voltage is a quantitative measure of the
driving force of the cell reaction

GALVANIC VS ELECTROLYTIC CELLS

galvanic electrolytic
Current in the form of moving ions can pass Spontaneity spontaneous nonspontaneous
through the salt bridge from one electrolyte of reaction
solution to the other Overall emf positive negative
Current within the cell electrolyte(s) is carried Energy CE  EE EE  CE
by ions Anode oxidation oxidation
A cell must be designed such that the reducing reaction
Cathode reduction reduction
agent (the one oxidized)and the oxidizing agent
reaction
(the one reduced) are physically separated
Polarity of negative Positive
Discharge denotes that current is drawn from the anode
the cell Polarity of positive negative
Electric current flows spontaneously through the cathode
metallic conductors from a region of negative
electrical potential to a region of positive
electrical potential
A cell diagram is used to represent an
electrochemical cell
(Std = all substances are at unit activity)
Use electrode potential to determine whether
the following proposed reactions are
spontaneous with all substances present at unit
activity:
−¿(aq)+ I 2(s )¿
( )
(a) Cl 2(g) +2 I −¿ aq −→ 2Cl ¿

+¿ (aq ) + H2( g)¿

(b) 2 A g(s )+ 2 H +¿−→2 A g ¿

0
−¿ (aq ) E cell ¿

( a ) Cl 2 (g )+ 2 e−¿=2 Cl ¿

¿+1.360 V
0
−¿E cell=−0.536 V ¿
−¿ ( aq ) =I 2( s) +2 e ¿
2I
−¿ ( aq )+ I 2( s) ¿

Cl 2( g )+ 2 I −¿ ( aq) → 2Cl ¿

emf =+ 0.824 V
Since the overall emf is positive, the reaction is
spontaneous
Gibbs Free Energy Change and electromotive
Force
0
The reversible emf of a cell, Ecell , is a measure
of the decrease in Gibbs free energy for the cell
reaction: ∆ G0 =nFE 0
1 F =96,500 coulombs , 1 V (C )=1 Joule
Use electrochemical data to calculate the value
of ∆ G0 for the reaction
2 Ag ( s ) +C l 2 ( g )−−→ 2 AgCl (s )
0 0
∆ G =nFE =2 ( 96,500 C ) (+ 1.137 )=−219,400 J
The Nernst equation is used to determine the
emf of the cell in which the constituents are
present in concentrations other than standard
 Erxn =− ( RT
nF ) ( K )
ln
Q

Other form

Erxn =E0rxn− ( 2.303nFRT ) log Q=¿ E −( 0.0592V

0
rxn
n ) log Q ¿
wW xX −−→ yY + zZ
Q=¿ ¿
When the activities of all substances are unity
0
(standard states): Erxn =Erxn