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STOICHIOMETRY
AND
REDOX
H2 CHEMISTRY (9729)
CURRICULUM FRAMEWORK
ASSESSMENT
Duration
Marks Weighting
(%)
Multiple Choice
1h
30
15
Structured
Questions
2h
75
30
Free Response
Questions
2h
80
35
Practical
2 h 30 min
55
20
LECTURE RULES
Attitude
Respect the speaker by listening.
Be attentive. The devil is in the details.
Preparedness
Guard your lecture notes.
Complete take-home tasks given by the
lecturer.
5
Punctuality
Alert tutor if the lesson before goes
overtime.
ANNOUNCEMENTS
ANNOUNCEMENTS
ANNOUNCEMENTS
UNITS OF MEASUREMENT
Heaviest baby from China
(2012)
Weight
7.04 kg
15.5 pounds
1.11 stones
MASS
International standard
that defines the
fundamental unit of mass
Made from platinum and
platinum-iridium alloy
Kept near Paris
10
CHEMISTRY UNITS
Consider the chemical equation:
2H2 + O2 2H2O
Mass
2g
1g
1.125g
(1.875g unreacted H2)
Moles
2
1
2
11
MOLE CONCEPT
12
MOLE DAY
13
CONSIDER THIS
14
15
Part 1:
Definition of terms
The Mole concept
Empirical formula and molecular
formula
Stoichiometric calculations
FAMILIAR TERMS
Nucleon number (A)
The total number of protons and neutrons in
an atom, also known as the mass number.
A
Z
16
1 DEFINITION OF TERMS
17
Isotopes
Atoms of the same element with the same
number of protons but different number of
neutrons.
13
1
2
18
16
Examples: 12
C , 6C ; 1H , 1H ; 8O , 8O
6
Different physical properties, identical chemical
properties (due to same number of electrons)
Relative abundance in naturally occurring
elements
1 DEFINITION OF TERMS
18
19
1 DEFINITION OF TERMS
EXAMPLE 1
Given the following data and that the Ar of chlorine
is 35.5, calculate the percentage abundance of
each of the 35Cl and 37Cl isotopes.
Relative isotopic mass
34.96885
36.96534
20
Isotope
35
Cl
37
Cl
EXAMPLE 1
Let the percentage abundance of 35Cl be x % and
the percentage abundance of 37Cl be (100 x) %.
x = 73.4
21
1 DEFINITION OF TERMS
22
1 DEFINITION OF TERMS
23
EXAMPLE 2
Calculate the Mr of C6H5Cl.
24
1 DEFINITION OF TERMS
Relative formula mass (Mr)
The average mass of one formula unit of one
mole of compound relative to the mass of one
mole of 12C atoms.
A formula unit is the smallest group of
atoms/ions from which the formula of a
compound can be established.
Sum of the individual relative atomic/ionic mass
of all the atoms/ions in the formula unit.
25
EXAMPLE 3
Calculate the relative formula mass of
calcium hydroxide, Ca(OH)2.
Mr of Ca(OH)2 = 40.1 + 2 16.0 + 2 1.0
= 74.1
26
Note:
All relative masses, i.e. Ar and Mr, are ratios
and have no units.
THE MOLE
Mass of
Substance
(g)
Molar mass
of substance
(g mol1)
27
Amount of
substance
(mol)
28
Avogadros constant
The number of 12C atoms in exactly 12 g of 12C
L = 6.02 1023 mol1
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
= 12 g of
pencil lead
= 1 mole of
carbon
atoms
44
602 earth
sized
planets
covered 1
m deep
with peas
EXAMPLE 4
Calculate the number of atoms in 1 g of 12C.
No. of
particles
Amount
of
6.02 1023
particles
(mol1)
(mol)
45
46
The Mole
A mole is the amount of substance that contains
Avogadro number (6.02 1023) of particles.
OR
A mole is the amount of substance which
contains the same number of particles as there
are atoms in 12.0 grams of 12C.
Examples:
1 mol of Mg contains:
6.02 1023 Mg atoms.
0.5 mol of NO2 contains:
3.01 1023 NO2 molecules
3.01 1023 N atoms
6.02 1023 O atoms
9.03 1023 atoms (both N and O atoms).
0.5 mol of NaCl contains:
3.01 1023 Na+ ions
3.01 1023 Cl ions
6.02 1023 ions (both Na+ and Cl ions).
47
EXAMPLE 5
In 10 g of NH4NO3, calculate the following:
(i) number of NH4+ ions
Ar (N): 14.0
Mr of NH4NO3 = (14.0 2) + (1.0 4) + (16.0 3)
Ar (H): 1.0
= 80.0
Ar (O): 16.0
Amount of NH NO = = 0.125 mol
4
48
NH4NO3 NH4+
Number of NH4+ ions = 7.53 1022
EXAMPLE 5
In 10 g of NH4NO3, calculate the following:
(ii) total number of ions (both NH4+ and NO3 ions)
NH4NO3 NH4+ NO3
Number of NO3 ions = 7.53 1022
49
EXAMPLE 5
In 10 g of NH4NO3, calculate the following:
(iii) total number of atoms
Total number of atoms in 1 formula unit of NH4NO3
=9
50
51
52
Molar Mass
Mass of 1 mole of the specified substance
(atoms, molecules, formula units, ions)
Units for molar mass: g mol1
Molar mass is numerically equal to Ar or Mr.
Molar mass (M) is NOT the same as relative
molecular mass (Mr) which is defined as the
average mass of one mole of molecules relative
to the mass of one mole of 12C atoms.
EXAMPLE 6
Calculate the molar mass of
(i) aluminium chloride, AlCl3;
(ii) sulfate ions, SO42.
(i) Molar mass of AlCl3 = 27.0 + 3 35.5
= 133.5 g mol1
53
54
Molar gas
volume /
dm3 mol1
22.7
24
55
EXAMPLE 7
Calculate the volume occupied by 2 mol of H 2(g) at
(i) s.t.p.
(ii) r.t.p.
(i) Volume occupied by 2 mol of H2(g) at s.t.p.
= 2 22.7
= 45.4 dm3
56
57
Applications in solutions
The concentration of a solute in a solution is the
mass/amount of solute in a given volume of
solution.
Concentration is usually expressed in g dm3
or mol dm3.
EXAMPLE 8
2.00 g of sodium hydroxide is dissolved in water
and made up to 250 cm3 in a volumetric flask.
Calculate the concentration of sodium hydroxide in
the solution in (i) g dm3 (ii) mol dm3.
(i) Concentration of NaOH = 2.00
= 8.00 g dm3
Note:
Square brackets are usually used when concentration
is expressed in mol dm3.
58
EXAMPLE 9
The concentration of aluminium sulfate, Al2(SO4)3,
in an aqueous solution was determined to be
0.0200 mol dm3.
59
Calculate
(i) the respective concentration of Al3+ and SO42 in
mol dm3,
(ii) the respective amount of Al3+ and SO42 in
25.0 cm3 of the solution.
EXAMPLE 9
(i) Al2(SO4)3(aq) 2Al3+(aq) + 3SO42(aq)
Al2(SO4)3 2Al3+ 3SO42
[Al3+] = 0.0200 2
= 0.0400 mol dm3
60
[SO42] = 0.0200 3
= 0.0600 mol dm3
EXAMPLE 9
Al3+
SO42
61
(ii)
62
Concentration =
amount of solute
volume of solution
EXAMPLE 10
10.0 cm3 of a 1.00 mol dm3 aqueous sodium
chloride solution is diluted with distilled water to
make up to 250 cm3. What is the concentration of
sodium chloride in the diluted solution in mol dm 3?
NaCl
10-2 mol
63
EXAMPLE 11
Find the volume of water (in cm3) that should be
added to 100 cm3 of a 0.500 mol dm3 hydrochloric
acid to form a 0.200 mol dm3 solution.
HCl in 100 cm3 of 0.500 mol dm-3 solution
mol
64
EXAMPLE 12
65
EXAMPLE 12
Total volume of resultant mixture = 20 + 80
= 100 cm3
[Na2SO4] in resultant mixture
= 0.0200 mol dm-3
66
amount of
substance, n
(in mol)
n=
n=
number of particles
Avogadro constant (in mol-1)
67
n=
68
EXAMPLE 13
Calculate the percentage composition by mass of
N, H, S and O in ammonium sulfate, (NH4)2SO4.
Express all answers to 1 decimal place.
Molar mass of (NH4)2SO4
= 2 14.0 + 8 1.0 + 32.1 + 4 16.0
= 132.1 g mol1
69
EXAMPLE 13
Percentage composition by mass of H
70
71
Empirical formula
The formula of a chemical compound that
shows the simplest whole-number ratio of the
number of atoms of each element present in the
substance.
72
73
EXAMPLE 14
74
EXAMPLE 14
Element
Mass ratio
60.0
8.0
32.0
Mole ratio
= 5.00
= 8.00
= 2.00
= 2.50
= 4.00
75
Simplest
ratio
= 1.00
EXAMPLE 14
Let molecular formula be C5nH8nO2n.
n = 200.0 (5 12.0 + 8 1.0 + 2 16.0)
=2
76
EXAMPLE 15
An organic compound, X, which contains only
carbon, hydrogen and oxygen has a molar mass
of about 85 g mol1. When 0.43 g of X is burnt in
excess oxygen, 1.10 g of CO2 and 0.45 g of water
are formed.
77
EXAMPLE 15
X + O2 CO2 + H2O
Mass of C in 0.43 g of X =
1.10
= 0.300 g
Mass of H in 0.43 g of X =
0.45
= 0.0500 g
78
EXAMPLE 15
Element
Mass ratio
C
0.300
H
0.0500
O
0.0800
= 0.0250
= 0.0500
= 0.00500
= 5.00
= 10.0
= 1.00
10
Mole ratio
Simplest
ratio
79
EXAMPLE 15
(b)What is the molecular formula of X?
Let molecular formula be C5nH10nOn.
n = 85 (5 12.0 + 10 1.0 + 16.0)
= 0.988
= 1 (nearest integer)
80
4 STOICHIOMETRIC
CALCULATIONS
81
Stoichiometry
Stoichiometry is the quantitative relationship
between quantities of reactants and products
involved in a chemical reaction.
It is based on the balanced chemical equation.
Substances react in a simple ratio of their
amounts.
EXAMPLE 16
Calculate the volume of hydrogen gas evolved at
s.t.p. when 36 g of magnesium react with an
excess of hydrochloric acid.
Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
Mg H2
Mg reacted = 36 24.3 = 1.48 mol
H evolved = 1.48 mol
2
82
EXAMPLE 17
Isooctane
(C8H18)
undergoes
combustion
efficiently in automobile engines. It is given an
octane number of 100. What is the mass of
oxygen used in the complete combustion of 2.0 g
of isooctane and what is the volume of CO2
produced at s.t.p.?
O2 8CO2 + 9H2O
C8H18
O2 8CO2
83
C8H18 +
EXAMPLE 17
CH
8
18
O2
4 STOICHIOMETRIC
CALCULATIONS
85
Limiting reagents
The exact amount of a substance required or
produced by a chemical reaction as determined
by the coefficients in the balanced equation is
known as the stoichiometric amount.
Reactants are not always added in
stoichiometric amounts. The reactant that is
completely consumed at the end of the reaction
is the limiting reagent.
4 STOICHIOMETRIC
CALCULATIONS
Limiting reagents
2
20
+ 15
10
?
limiting reagent
86
EXAMPLE 18
Sodium and chlorine react together according to
the equation shown:
Na(s) + Cl2(g) NaCl(s)
87
EXAMPLE 18
(i) Which reagent is the limiting reagent?
Na in 11.5 g = 11.5 23.0
= 0.500 mol
88
EXAMPLE 18
(ii) What is the mass of the product formed?
Mass of NaCl formed = 0.500 (23.0 + 35.5)
= 29.3 g
(iii) Calculate the mass of reactant present that
remained unreacted.
89
4 STOICHIOMETRIC
CALCULATIONS
90
Theoretical yield
The maximum amount of product that can be
formed from known amounts of reactants in a
reaction according to the chemically balanced
equation (stoichiometrically determined).
The quantity of product that is calculated to
form when all the limiting reagent is used up.
4 STOICHIOMETRIC
CALCULATIONS
Actual yield
The quantity of product that is actually obtained
in the reaction during an experiment
(experimentally determined)
Usually less than the theoretical yield due to:
91
- incomplete reaction
- undesirable side reactions
- product loss during the separation and
purification processes
4 STOICHIOMETRIC
CALCULATIONS
Percentage yield
Actual yield expressed
theoretical yield:
percentage
100%
92
Percentage yield =
as
EXAMPLE 19
An aqueous solution containing 15.0 g of barium
chloride was added to another aqueous solution
containing 10.0 g of iron(III) sulfate. 15.6 g of
barium sulfate was precipitated. Calculate the
percentage yield of barium sulfate.
93
Ar (Ba): 137.3
Ar (Cl): 35.5
Ar (Fe): 55.8
Ar (S): 32.1
Ar (O): 16.0
EXAMPLE 19
3BaCl2(aq) + Fe2(SO4)3(aq)
3BaSO4(s) + 2FeCl3(aq)
3BaCl2 Fe2(SO4)3
BaCl
Fe (SO )
2
4 3
in 10.0 g
EXAMPLE 19
Theoretical BaSO
95
= 92.9%
4 STOICHIOMETRIC
CALCULATIONS
Eudiometry
Hydrocarbons burn in excess oxygen according
to the general equation:
96
4 STOICHIOMETRIC
CALCULATIONS
Eudiometry
97
4 STOICHIOMETRIC
CALCULATIONS
Eudiometry
Before combustion
excess O2 V4
excess O2
V1
O2 reacted
V3
excess O2
CO2
formed
CxHy
Volume of oxygen reacted = V2 V4
Volume of carbon dioxide produced = V3 V4
98
V2
After cooling
After passing
through KOH
4 STOICHIOMETRIC
CALCULATIONS
Eudiometry
99
EXAMPLE 20
100
EXAMPLE 20
Volume of hydrocarbon = V1 = 20 cm3
Total volume of oxygen = V2 = 150 cm3
Volume of CO2 and excess O2 = V3 = 130 cm3
101
EXAMPLE 20
Before combustion
20
O2 reacted
130
90
excess O2
CO2
formed
CxHy
102
150
After cooling
excess O2
excess O2
After passing
through NaOH
EXAMPLE 20
(i) What is the volume of carbon dioxide produced
in the explosion?
VCO produced = 130 90 = 40 cm3
2
103
EXAMPLE 20
(iii) What is the molecular formula of the
hydrocarbon?
Let the molecular formula of the hydrocarbon
be CxHy.
CxHy(g) + (x + )O2(g) xCO2(g) + H2O(l)
60 cm3
40 cm3
CxHy(g) xCO2(g)
CxHy(g) (x + )O2(g)
x = 40 20
=2
2 + = 60 20
y=4
Molecular formula of the hydrocarbon is C2H4.
104
20 cm3
EXAMPLE 21
When 10.0 cm3 of but-1-ene, C4H8, were exploded
with an excess of oxygen, there was a contraction of
x cm3. A further contraction of y cm3 took place when
the residual gas was passed through aqueous
sodium hydroxide. Deduce the values of x and y,
assuming all volumes measured at 25 C and 1 atm
pressure.
C4H8(g) + 6O2(g) 4CO2(g) + 4H2O(l)
105
EXAMPLE 21
Before combustion
excess O2
excess O2
60.0
10.0
After passing
After cooling through NaOH
O2 reacted 40.0
excess O2
CO2
formed
x
CxHy
106
107
Part 2:
Volumetric Analysis
Redox
5 VOLUMETRIC ANALYSIS
108
Introduction
A quantitative chemical analysis method
employed to determine the concentration of a
solute in a given solution.
Depends
essentially
on
the
accurate
measurement of the volumes of 2 solutions
which react together completely according to
the stoichiometry of the chemical equation
5 VOLUMETRIC ANALYSIS
109
End point:
The point during titration when the indicator
changes colour.
Delivery of the titrant is stopped and the volume
of titrant added is recorded.
End-point is indicated by a suitable indicator
which undergoes a colour change.
Sometimes, one of the 2 solutions undergoes a
colour change, and the titration is therefore selfindicative, e.g. redox titration involving acidified
potassium manganate(VII).
110
5 VOLUMETRIC ANALYSIS
5 VOLUMETRIC ANALYSIS
111
5 VOLUMETRIC ANALYSIS
Choice of indicators for acid-base titrations:
Colour of indicator at
Working
pH Range
pH below
working pH
range
pH 3 5
red
methyl orange
screened
pH 3 5
violet
methyl orange
phenolphthalein pH 8 10 colourless
thymol blue
orange
pH above
working pH
range
yellow
grey
green
End point
pale pink
yellow (when
acid is added
to strong base)
pH 8 10 yellow/red
blue (when
strong base is
added to acid)
pink
blue
112
Indicator
5 VOLUMETRIC ANALYSIS
113
5 VOLUMETRIC ANALYSIS
14
114
5 VOLUMETRIC ANALYSIS
115
Universal indicator
A mixture of indicators which give a gradual
change in colour over a wide range of pH
EXAMPLE 22
116
EXAMPLE 22
2NaOH + H2SO4 Na2SO4 + 2H2O
2NaOH H2SO4
in 10.00 cm3 =
H2SO4
-3
neutralised
=
2
1.00
10
NaOH
= 2.00 10-3 mol
117
EXAMPLE 23
118
EXAMPLE 23
HxA + xNaOH NaxA + xH2O
HxA
NaOH
119
5 VOLUMETRIC ANALYSIS
Acid-carbonate and acid-hydrogencarbonate
titrations
Acid-hydrogencarbonate titrations can be
represented by the following equation:
HCO3(aq) + H+(aq) CO2(g) + H2O(l)
120
5 VOLUMETRIC ANALYSIS
Acid-carbonate and acid-hydrogencarbonate
titrations
Acid-carbonate titrations can be represented by
the following equation:
CO32(aq) + 2H+(aq) CO2(g) + H2O(l)
121
5 VOLUMETRIC ANALYSIS
CO32(aq) + H+(aq) HCO3(aq)
Equivalence point 1: thymol blue/
phenolphthalein
Equivalence point 2:
methyl orange
2x
Volume of acid added /cm3
122
14
13
12
11
10
9
8
pH 7
6
5
4
3
2
1
0
EXAMPLE 24
123
EXAMPLE 24
CO32(aq) + H+(aq) HCO3(aq)
pH
124
EXAMPLE 24
Na2CO3 + 2HCl 2NaCl + CO2 + H2O
Na2CO3
Na2CO3
in 250 cm3 =
= 1.32 10-2 mol
in 25.0 cm3 = 1.32 10-2
= 1.32 10-3 mol
125
126
EXAMPLE 25
EXAMPLE 25
CO32(aq) + H+(aq) HCO3(aq)
pH
19.20
127
EXAMPLE 25
Reaction(s) that K2CO3 undergo
K2CO3(aq) + HCl(aq) KHCO3(aq) + KCl(aq)
8.40 cm3
(phenolphthalein)
KHCO3(aq) + HCl(aq) CO2(g) + H2O(l) + KCl(aq)
8.40 cm3 19.20 cm3 (methyl orange)
128
EXAMPLE 25
Using phenolphthalein as indicator:
K2CO3 + HCl KHCO3 + KCl
(this step required 8.40 cm3 of HCl(aq) to
react with the amount of K2CO3)
129
EXAMPLE 25
K2CO3
Concentration of K2CO3
= [(8.40 10-4) ] (2 39.1 + 12.0 + 3 16.0)
= 5.80 g dm-3
NaHCO3
130
Concentration of NaHCO3
= [(1.08 10-3) ] (23.0 + 1.0 + 12.0 + 3 16.0)
= 4.54 g dm-3
5 VOLUMETRIC ANALYSIS
131
Back titrations
In back titrations, a known amount of reagent A
is added in excess to reagent B. The amount of
A that remained unreacted by reagent B is
determined by titration. By subtracting the
excess amount of A from the initial amount of A
added, the exact amount of A that reacted with
reagent B can be determined.
5 VOLUMETRIC ANALYSIS
Back titrations
132
5 VOLUMETRIC ANALYSIS
Back titrations
A+B C
+
A (excess)
133
C + unreacted A
EXAMPLE 26
FA 1 is a mixture of NaCl(s) and NaHCO3(s). FA 2
is an aqueous solution containing 30.0 g of FA 1
per dm3. 40.0 cm3 of 0.200 mol dm-3 HCl(aq) was
added to 25.0 cm3 of FA 2 in a conical flask and
the resultant solution required 21.60 cm 3 of 0.150
mol dm3 NaOH(aq) for complete neutralisation.
Calculate
(i) the number of moles of NaOH reacted.
NaOH
EXAMPLE 26
(ii) the number of moles of HCl that reacted
the NaHCO3 in 25.0 cm3 of FA 2.
with
i
n
40.0
cm
of
FA
2
=
0.200
HCl
= 8.00 10-3 mol
135
EXAMPLE 26
(iii) the number of moles of NaHCO3 in 25.0 cm3
of FA 2.
NaHCO3 + HCl NaCl + CO2 + H2O
NaHCO3 HCl
136
EXAMPLE 26
(iv)
= 53.3%
EXAMPLE 27
138
EXAMPLE 27
(NH4)2SO4 + 2NaOH 2NH3 + Na2SO4 + 2H2O
NaOH + HCl NaCl + H2O
NaOH
NaOH
(NH4)2SO4
139
= 0.0425 mol
140
6 REDOX
6 REDOX
Simultaneous occurrence of reduction and
oxidation
Reduction
Loss in oxygen
Gain in hydrogen
Gain in electrons
Decrease in
oxidation state
141
Oxidation
Gain in oxygen
Loss in hydrogen
Loss in electrons
Increase in
oxidation state
6 REDOX
Oxidising agent
Zn
Cu2+
Zn2+
Cu
142
Reducing agent
Oxidising Agent
(reduced)
Cr2O72- Cr3+
Reducing Agent
(oxidised)
I- I 2
MnO4- Mn2+
(acidic medium)
S2O32- S4O62-
MnO4 MnO2
(neutral/alkaline medium)
H2O2 H2O
M Mn+
(reactive metals)
H2O2 O2
Fe3+ Fe2+
Fe2+ Fe3+
143
6 REDOX
6 REDOX
144
6 REDOX
Assigning oxidation state/number
3. The algebraic sum of the oxidation states of all
the atoms in a chemical species is equal to its
charge.
E.g. the sum of the oxidation states of
carbon and three oxygen atoms in carbonate
ion (CO32) is -2;
145
6 REDOX
Element
Group I metals
(e.g. Li, Na, K)
Group II metals
(e.g. Be, Mg, Ca)
O.S.
Exceptions
+1
No exceptions
+2
No exceptions
146
Element
O.S.
fluorine
chlorine &
bromine
oxygen
hydrogen
+1
Exceptions
no exceptions (fluorine is the most
electronegative element)
when bonded to a more electronegative
element (e.g. BrF5, where Br has
oxidation state of +5)
peroxides (e.g. H2O2, Na2O2) where O
has oxidation state of 1;
superoxides (e.g. NaO2, KO2) where O
has oxidation state of ;
OF2 where O has oxidation state of +2
metal hydrides (e.g. NaH, MgH2) where
H has oxidation state of 1
147
6 REDOX
6 REDOX
Assigning oxidation state/number
5. In any chemical species consisting of 2
elements only, the more electronegative
element has the negative oxidation state.
Electronegativity is a measure of the ability of an
atom in a molecule to attract the shared pair of
electrons in a bond to itself.
148
EXAMPLE 28
Calculate the oxidation state of
(i) phosphorus in PO43
Let the oxidation state of phosphorus in PO43 be x.
x + 4(2) = 3
149
x = +5
EXAMPLE 28
Calculate the oxidation state of
(ii) lead in Pb3O4
Let the oxidation state of lead in Pb3O4 be x.
3(x) + 4(2) = 0
3x = +8
x=+
150
EXAMPLE 29
Is the following reaction a redox reaction?
Explain your answer.
2CrO42 + 2H+ Cr2O72 + H2O
+6 2
+1
+6
+1 2
151
6 REDOX
Disproportionation
A redox reaction in which one species is
simultaneously oxidised and reduced.
Examples of disproportionation reactions:
(i) Cl2 + 2OH ClO + Cl + H2O
152
6 REDOX
Disproportionation
Examples of disproportionation reactions:
(ii) 2H2O2 2H2O + O2
153
6 REDOX
Balancing equations for redox reactions
Two criteria:
Mass balance / material balance
154
Charge balance
6 REDOX
Half-equation method (acidic medium):
1. Separate the equation into two incomplete
half-equations, one for oxidation and the other
for reduction.
155
6 REDOX
Half-equation method (acidic medium):
3. Multiply the balanced half-equations by
appropriate integers such that the number of
electrons in both half-equations are equal.
156
EXAMPLE 30
Balance the following equations for reactions that
occur in an acidic medium.
Cr2O72 is reduced to Cr3+
(i) Cr2O72 + Fe2+ Cr3+ + Fe3+
157
EXAMPLE 30
Step 1:
Separate the equation into two incomplete halfequations, one for oxidation and the other for
reduction.
Oxidation half-equation
Fe2+ Fe3+
Reduction half-equation
Cr2O72 Cr3+
Step 2(i):
Balance the elements being reduced/oxidised.
Cr2O72 2Cr3+
158
Fe2+ Fe3+
EXAMPLE 30
Step 2(ii):
Balance oxygen atoms by adding H2O.
Cr2O72 2Cr3+ + 7H2O
Fe2+ Fe3+
Step 2(iii):
Balance hydrogen atoms by adding H+.
Fe2+ Fe3+
overall charge = + 12
overall charge = + 6
159
Step 2(iv):
Balance charges by adding electrons.
Fe2+ Fe3+ + e
6e + Cr2O72 + 14H+ 2Cr3+ + 7H2O
EXAMPLE 30
Step 3:
Multiply
the
balanced
half-equations
by
appropriate integers such that the number of
electrons in both half-equations are equal.
Fe2+ Fe3+ + e ( 6)
6Fe2+ 6Fe3+ + 6e
160
EXAMPLE 30
Step 4:
Combine the resulting half-equations together,
eliminate any common species on both sides to
obtain the overall balanced equation.
6Fe2+
6Fe3+ + 6e
161
EXAMPLE 30
Balance the following equations for reactions that
occur in an acidic medium.
MnO4 is reduced to Mn2+
(ii) MnO4 + H2O2 Mn2+ + O2
162
H2O2 is oxidised to O2
EXAMPLE 30
Step 1:
Separate the equation into two incomplete
half-equations, one for oxidation and the other for
reduction.
Oxidation half-equation
H2O2 O2
Reduction half-equation
MnO4 Mn2+
Step 2(i):
Balance the elements other than H and O.
MnO4 Mn2+
163
H2O2 O2
EXAMPLE 30
Step 2(ii):
Balance oxygen atoms by adding H2O.
H2O2 O2
MnO4 Mn2+ + 4H2O
Step 2(iii):
Balance hydrogen atoms by adding H+.
H2O2 O2 + 2H+
8H+ + MnO4 Mn2+ + 4H2O
164
Step 2(iv):
Balance charges by adding electrons to the side
with the greater overall positive charge.
H2O2 O2 + 2H+ + 2e
EXAMPLE 30
Step 3:
Multiply
the
balanced
half-equations
by
appropriate integers such that the number of
electrons in both half-equations are equal.
H2O2 O2 + 2H+ + 2e ( 5)
5H2O2 5O2 + 10H+ + 10e
5e + 8H+ + MnO4 Mn2+ + 4H2O ( 2)
165
EXAMPLE 30
Step 4:
Combine the resulting half-equations together,
eliminate any common species on both sides to
obtain the overall balanced equation.
Overall equation:
6
5H2O2 + 16H+ + 2MnO4 + 10e
2Mn2+ + 8H2O + 5O2 + 10H+ + 10e
2MnO4 + 6H+ + 5H2O2 2Mn2+ + 8H2O + 5O2
166
5H2O2
5O2 + 10H+ + 10e
10e + 16H+ + 2MnO4 2Mn2+ + 8H2O
6 REDOX
Half-equation method (alkaline/neutral medium):
167
6 REDOX
Half-equation method (alkaline/neutral medium):
3. Multiply the balanced half-equations by
appropriate integers such that the number of
electrons in both half-equations are equal.
168
EXAMPLE 31
Balance the following equations for reactions that
occur in an alkaline medium.
Cl2 is reduced to Cl
(i) Cl2 ClO3 + Cl
169
EXAMPLE 31
Cl2 ClO3
Cl2 2ClO3
2(ii)
Cl2 2Cl
2(iii)
Cl2 2Cl
Step
Cl2 Cl
1
Cl2 2Cl
2(i)
EXAMPLE 31
Step
2(v) Cl2 + 2e 2Cl
3 5Cl2 + 10e 10Cl
Cl2 + 12OH
2ClO3 + 6H2O + 10e
Cl2 + 12OH
2ClO3 + 6H2O + 10e
Overall equation:
5Cl2 + 10e + Cl2 + 12OH
10Cl + 2ClO3 + 6H2O + 10e
3Cl2 + 6OH 5Cl + ClO3 + 3H2O
171
EXAMPLE 31
Balance the following equations for reactions that
occur in an alkaline medium.
(ii) MnO4 + Fe2+ MnO2 + Fe3+
Reduction half-equation
MnO4 MnO2
4OH + 4H+ + MnO4 MnO2 + 2H2O + 4OH
172
EXAMPLE 31
Balance the following equations for reactions that
occur in an alkaline medium.
(ii) MnO4 + Fe2+ MnO2 + Fe3+
Oxidation half-equation
Fe2+ Fe3+
Fe2+ Fe3+ + e
MnO4 + 2H2O + 3Fe2+ MnO2 + 4OH + 3Fe3+
173
Overall equation:
6 REDOX
174
6 REDOX
(i) manganate(VII) titrations
Manganate(VII) ion is a powerful oxidising
agent.
In acidic medium,
MnO4 + 8H+ + 5e Mn2+ + 4H2O
pale pink
(but appears
colourless in
diluted solutions)
175
purple
6 REDOX
(i) manganate(VII) titrations
Sulfuric acid is used to provide the acidic
medium for manganate(VII) titrations.
Nitric acid and hydrochloric acid are not
used, as nitric acid is an oxidising agent
itself, and hydrochloric acid can be oxidised
by manganate(VII).
176
6 REDOX
(i) manganate(VII) titrations
The end-point for manganate(VII) titration
(if other reducing agent and product are also
colourless) occurs when one excess drop of
purple KMnO4(aq) turns the solution in the
conical flask from colourless to pale pink.
177
6 REDOX
(ii)dichromate(VI) titrations
Dichromate(VI) ion is a weaker oxidising agent
than manganate(VII) ion.
In acidic medium,
Cr2O72 + 14H+ + 6e
orange 2Cr3+ + 7H O
2
178
green
6 REDOX
(iii)
iodine-thiosulfate titrations
179
brown
6 REDOX
(iii)
iodine-thiosulfate titrations
180
6 REDOX
(iii)
iodine-thiosulfate titrations
181
6 REDOX
(iii)
iodine-thiosulfate titrations
182
EXAMPLE 32
183
EXAMPLE 32
Reduction half equation:
Cr2O72 + 14H+ + 6e 2Cr3+ + 7H2O
Oxidation half-equation:
C2O42 2CO2 + 2e
Overall equation:
Cr2O72 + 14H+ + 3C2O42 2Cr3+ + 7H2O + 6CO2
184
Cr2O72 3C2O42
EXAMPLE 32
C2O42
185
6 REDOX
EXAMPLE 33
Vanadium(II) ions, V2+, can be oxidised
quantitatively by acidified manganate(VII) ions to a
higher oxidation state. 25.0 cm3 of an aqueous
solution of V2+ ions of concentration 0.0200 mol
dm3 was found to react with 15.00 cm3 of 0.0200
mol dm3 acidified manganate(VII) ions. Determine
the oxidation state of vanadium in the product.
MnO4
V2+
EXAMPLE 33
In acidic medium, MnO4 is reduced according to
the equation as shown:
MnO4 + 8H+ + 5e Mn2+ + 4H2O
MnO4 5e
e involved = 3.00 10-4 5 = 1.50 10-3 mol
V2+ ? + 3e
Oxidation state of V in the product = +2 ( 3)
= +5
188
189
THE END