1

Atomic structure
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 2)
1 number of protons in the nucleus of an atom
2 a) 1, +1
b) 1 , −1
1840
c) 1, 0
3 a) atoms with the same number of protons but a different number
of neutrons
b) 17 protons; 17 electrons and 20 neutrons
4 a) 2, 8, 5
b) 2, 1
c) 2, 6
d) 2, 8, 8, 1
e) 2, 8, 8
f) 2
g) 2, 8, 3
5 phosphorus or 31
15P

●● TEST YOURSELF 2 (PAGE 6)

1 a) 19 protons;  19 electrons;  20 neutrons
b) 9 protons;  9 electrons;  10 neutrons
c) 56 protons;  56 electrons;  81 neutrons
d) 88 protons;  88 electrons;  138 neutrons
2 a)
Isotope atomic number mass number % abundance 1

35 79 50.5

81
35Br

b) 79.99
3 a) 69.2%
b) 63.62
 4 107.96
5 7.1
6 10B is 20%; 11B is 80%

●● TEST YOURSELF 3 (PAGES 11–2)

1 20.2; neon
2 207
3 a) 58
b) 43
c) i) 58
ii) C4H10

●● TEST YOURSELF 4 (PAGE 17)

1 i) 1s2
ii) 1s2 2s2 2p6 3s2 3p6
iii) 1s2 2s2 2p6
iv) 1s2 2s2 2p6
v) 1s2 2s2 2p6 3s2 3p6 3d6
vi) 1s2 2s2 2p6 3s2 3p6 3d5
vii) 1s2 2s2 2p6 3s2 3p6 3d8
viii) 1s2 2s2 2p6 3s2 3p6 3d9
ix) 1s2 2s2 2p6 3s2 3p6 3d3
Atomic structure

x) 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6

2 B
3 i) B
ii) A
iii) C
1

iv) C

v) A
2 vi) D
vii) D
viii) D
ix) B
x) B
xi) A
xii) D
●● TEST YOURSELF 5 (PAGE 24)

PRACTICE QUESTIONS (PAGES 25–6)

1 The first ionisation energy is the energy required to remove one mole of
electrons from one mole of gaseous atoms to form one mole of gaseous
1+ ions.
2 kJ mol−1
3 a) Si(g) → Si+(g) + e−
b) K+(g) → K2+(g) + e−
c) C2+(g) → C3+(g) + e−
4 M2O3

●● PRACTICE QUESTIONS (PAGES 25–6)

1 C (1)
2 B (1)
3 D (1)
4 a) Al(g) → Al+(g) + e− (1)
b) Li2+(g) → Li3+(g) + e− (1)
c) only three electrons (1)
5 a) B(g) → B+(g) + e− (1)
b) For sodium the atomic radius is larger than for lithium (1)
There is increased shielding by inner electrons (1)
So less energy is required to remove the electron (1)
c) Oxygen atoms have a p4 arrangement (1)
The repulsion of two electrons in the same p orbital leads to
less energy being required to remove the outer electron (1)
d) up for Mg but less than Be (1)
down again for Al but less than B (1)
up again for Si bit less than C (1)
e) smallest atomic radius (1)
highest nuclear charge in a period (1)
most energy required to remove the electron (1)
3
6 a) atomic radius decreases (1)
nuclear charge increases (1)
more energy required to remove electron (1)
b) boron has a p1 electronic configuration (1)
outer electrons further from the nucleus/shielded by inner s2
electrons (1)
c) 1s2 2s2 2p3 (1)
 7 a) (9.4 × 50)+(72.5 × 52)+(14.5 × 53)+(3.6 × 54) (1)
100
= 52.0 (1)
b) chromium (1)
c) 54Cr+ (1)

8 a) 43 (1)
b) 60 (1)
9 a) second electron removed from an energy level closer to
the nucleus (1)
less shielding by inner electrons (1)
b) Na(g) → Na+(g) + e− (1)
c) magnesium (1)
d) i) 1s2 2s2 2p6 3s2 3p6 3d10 (1)
ii) Zn2+ (2)
Cu+ (1)
Atomic structure
1

4
 2 Amount of substance
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 27)
1 a) Na(s)
b) Hg(l)
c) He(g)
d) Cl2(aq)
2 a) H2O(l)
b) CO2(g)
c) H2O(s)
d) NaCl(aq)

●● TEST YOURSELF 2 (PAGE 29)

1 a) NaF
b) MgO
c) K2O
d) BaCl2
2 a) hydroxide
b) oxide
c) chloride
d) aluminium
e) sulfate
3 a) CuCl2
b) ZnO
c) CuSO4 5
d) Fe(OH)3
4 a) carbon dioxide
b) potassium nitrate
c) copper(ii) carbonate
d) hydrogen fluoride
e) magnesium sulfate
 5 a) (NH4)2SO4
b) SO2
c) CaCO3
d) Al2(SO4)3

●● TEST YOURSELF 3 (PAGE 32)

1 a) 2KOH + H2SO4 → K2SO4 + 2H2O
b) 2Ca + O2 → 2CaO
c) 2Al + 3Cl2 → 2AlCl3
2 a) BaCl2 + K2SO4 → BaSO4 + 2KCl
b) Ba2+ + SO42– → BaSO4
3 a) Ca(OH)2 + 2HCl → CaCl2 + 2H2O
b) Al2O3 + 3H2SO4 → Al2(SO4)3 + 3H2O
c) Zn + 2HCl → ZnCl2 + H2
4 Zn2+ + 2OH− → Zn(OH)2
5 a) Mg + Cu2+ → Mg2+ + Cu
b) Zn + 2H+ → Zn2+ + H2

●● TEST YOURSELF 4 (PAGE 36)

1 a) 6.02 × 1021
b) 4.23 × 1023
Amount of substance

c) 4.84 × 1022
2 3.01 × 1022
3 a) 3.03 × 1023
b) 1.51 × 1023
4 0.729 g

●● TEST YOURSELF 5 (PAGE 39)

2

1 0.808 g

2 0.382 g
6
3 0.0341 g
4 5.17 g
●● TEST YOURSELF 6 (PAGE 42)

TEST YOURSELF 10 (PAGE 68)

1 79.8%
2 10.1 kg
3 68.1%
4 5.14 g

●● TEST YOURSELF 7 (PAGE 50)

1 0.301 mol dm−3
2 8.715 g
3 a) 40.1
b) calcium
4 0.13 dm3

●● TEST YOURSELF 8 (PAGE 59)

1 37.3 cm3
2 48.4 g dm−3
3 a) 3.54 × 10−3 mol
b) 0.142 mol dm−3
c) 1.42 mol dm−3

●● TEST YOURSELF 9 (PAGE 64)

1 8.04 dm3
2 13.7 g
3 a) 0.0168 mol
b) 0.0504 mol
c) 1.05 dm3

●● TEST YOURSELF 10 (PAGE 68)

1 SO3
2 x = 6
7
3 Pb3O4
4 a) NH2
b) N2H4
 ●● TEST YOURSELF 11 (PAGE 71)
1 16.3 %
2 22.7 %
3 A

●● ACTIVITY (PAGES 57–8)

Finding the concentration of diluted vinegar
1 • Rinse out pipette with deionised water and then with commercial
vinegar. Using a safety pipette filler, transfer 25.0 cm3 of commercial
vinegar into a 1 dm3 volumetric flask.
• Add deionised water to the flask until the water is just below the line.
• Using a disposable pipette, add deionised water very slowly until the
bottom of the meniscus is on the line.
• Stopper the flask and invert to mix thoroughly.
2 Rinse out pipette with diluted vinegar solution. Using a safety pipette
filler, transfer 25.0 cm3 of diluted vinegar solution into a conical flask.
3 Colourless to purple
4 17.50 cm3
5 CH3COOH + NaOH → CH3COONa + H2O
6 Moles = 17.50 × 0.10/1000 = 0.00175
7 Ratio 1:1 moles = 0.00175
Amount of substance

8 Moles = 0.00175 = 25.0 × conc/1000 = 0.07 mol dm−3

9 dilution factor = × 100; 0.07 × 100 = 7 × Mr = 7 × 60.0 = 420 g dm−3

●● ACTIVITY (PAGES 70–1)

Finding the formula of titanium oxide
1 Relights a glowing splint.
2 Mass of container and mass of container and titanium.
2

3 Powder would react faster.

4 Mass would increase due to titanium oxide forming.

8 5 Allow the container to cool before weighing and so prevent burns.
6 Repeat the experiment.
7 Pass the oxygen through a u-tube, containing a drying agent, (e.g.
anhydrous sodium sulfate) before entering the test tube.
 8 mass of oxygen = 8.0 − 4.8 = 3.2 g
3.2

PRACTICE QUESTIONS (PAGES 73–4)

moles of oxygen = = 0.20
16.0
4.8
moles of titanium = = 0.10
47.9
ratio of moles 0.10 Ti : 0.20 O 1 : 2 empirical formula is TiO2
titanium(IV) oxide.
47.9 47.9
9 a) × 100 = 37.5%; × 100 = 59.9%
127.9 79.9
b) The second reaction has a higher atom economy so there is less
waste, however it does use a substantial amount of electricity.
Other useful information is the toxicity or environmental hazard of
any products.
c) 100%
d) Electrolysis – electricity is expensive.
e) It is non-toxic and safe to use in the body, corrosion resistant,
strong, low density.

●● PRACTICE QUESTIONS (PAGES 73–4)

1 B
2 D
3 B
4 A
5 a) mass of P = 1.24 g
mass of O = 2.84 − 1.24 = 1.60 g (1)
1.24 1.60
moles of P = = 0.04  moles of O = = 0.1 (1)
31.0 16.0
P2O5 (1)
b) P4O10 (1)
6 2Sr(NO3)2 → 2SrO + 4NO2 + O2 (1)
0.1
7 moles of water = = 0.00556 mol (1)
18.0
molecules of water = 0.00556 × 6.02 × 10−23 = 3.35 × 1021 (1)
250 000
8 a) moles of CaSO4 = = 1835.54 mol (1)
136.2
moles of C = 4 × 1835.54 = 7342.16 mol (1)
mass of C = 7432.16 × 12.0 = 88105.92 g = 88.11 kg (1) 9
72.2
b) × 100 (1)
184.2
= 39.2% (1)
 25.0 × 7.80
9 a) = 0.195 mol (1)
1000
0.195
b) = 0.0244 mol (to three significant figures) (1)
8
c) T = 298 K
p = 100 000 Pa (1)
nRT 0.0244 × 8.31×298
V= so V = (1)
P 100 000
V = 6.04 × 10−4 m3 = 604 cm3 (1)
1.50
10 moles of P4 = = 0.0121 mol (1)
124.0
theoretical yield of PCl5 = 0.0121 × 4 × 208.5 = 10.09 g (1)
actual yield
Percentage yield = ×100
theoretical yield
8.34
So percentage yield = × 100 = 82.7% (1)
10.09
15.7 × 0.200
11 a) = 0.00314 mol (1)
1000
b) 0.00314 mol (1)
c) 0.00314 × 40 = 0.1256 mol dm−3 (1)
d) 0.1256 × 25 = 3.14 mol dm−3 (1)
234.0 × 0.100
12 moles of NaOH = = 0.0034 mol (1)
1000
moles of HCl reacting with NaOH = 0.0034
moles of HCl in 250 cm3 = 0.034 mol (1)
50.0 × 1.00
moles of HCl added initially = = 0.05 mol (1)
1000
moles of HCl which reacted with CaCO3 = 0.05 − 0.034 = 0.016 mol (1)
0.016
Amount of substance

moles of CaCO3 in the sample = = 0.008 mol (1)

2
mass of CaCO3 in the sample = 0.008 × 100.1 = 0.801 g (1)
0.801
percentage purity = = 80.1% (to 3 significant figures) (1)
1.00
13 a) 122.612 − 122.400 = 0.212 g (1)
0.212
b) = 0.002 (1)
106.0
c) 122.900 − 122.612 = 0.288 g (1)
0.288
d) = 0.016 (1)
2

18.0
e) x = 8 (1)

993.6
14 a) × 100 = 88.28% (1)
1125.6
10 b) i) moles of Pb = 0.522 mol (1)
mass of Pb = 0.522 × 207.2 = 108.16 g (1)
ii) T = 335 K and p = 125000 Pa (1)
nRT 0.522 × 8.31 × 335
V= = (1)
P 125 000
V = 0.0116 m3 = 11.6 dm3 (1)
 0.050
15 a) moles of Mg = = 0.002058 mol (1)
24.3

PRACTICE QUESTIONS (PAGES 73–4)

moles of HCl = 0.002058 × 2 = 0.004116 mol (1)
n × 1000 0.004116 × 1000
volume of HCl = = = 20.6 cm3 (1)
c 0.200
b) moles of H2 = 0.002058 mol (1)
T = 293 K and p = 110000 Pa (1)
nRT 0.002058 × 8.31 × 293
V= = = (1)
P 110 000
V = 4.555 × 10−5 m3 = 45.6 cm3 (1)

11
 3 Bonding
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 75)
1 a) nitride ion
b) calcium ion
c) sulfide ion
d) bromide ion
e) rubidium ion
f) hydride ion
2 shared pair of electrons
3 a) sodium oxide
b) calcium fluoride
c) magnesium iodide
d) potassium chloride
4 a) 1
b) 4
c) 2

●● TEST YOURSELF 2 (PAGES 82–3)

1 a) 1s2 2s2 2p6 3s2 3p6 4s1
Cl 1s2 2s2 2p6 3s2 3p5
Potassium atom gives an electron to a chlorine atom
K+ 1s2 2s2 2p6 3s2 3p6
Cl− 1s2 2s2 2p6 3s2 3p6
The ionic bond is the attraction of oppositely charged ions.
12 b) Water is polar and ionic substances have charged particles which
like to dissolve in polar solvents;
c) High melting point/high boiling point;
cannot conduct electricity when solid/conduct electricity when
molten or dissolved in water;
crystalline/brittle
2 a) Na+
b) 1s2 2s2 2p6
 3 name of compound formula formula of formula of
positive ion negative ion

TEST YOURSELF 4 (PAGE 92)

magnesium oxide MgO

AgF Ag+ F–

lithium carbonate Li2CO 3

zinc bromide ZnBr2

4 a) The ionic bond is the attraction between oppositely charged ions

b) The ionic bonds between the positive and negative ions are strong
and require a large amount of energy to break
5 The Mg2+ ion is smaller than the Ca2+ ion.
The larger ion leads to a weaker ionic bond in calcium oxide.
Less energy is needed to break the weaker ionic bond.

●● TEST YOURSELF 3 (PAGE 90)

1 shared pair of electrons
2 a) CO2 N2 O2
b) H3O+ NH4Cl
3 Lone pair of electrons

H N H
+
+ +

H
Bonding pair of electrons

4 Two electrons in the bond come from the same atom

●● TEST YOURSELF 4 (PAGE 92)

1 Regular structure showing Mg2+ ions with delocalised electrons
between them. The metallic bond is the attraction between the positive
ions and the delocalised electrons.
Magnesium

Mg2+ Mg2+ Mg2+ Mg2+ Mg2+

e– e– e–
e– e
–

Mg Mg Mg Mg2+ Mg2+
2+ 2+ 2+ 13
e– e– e– e– e
–

Mg Mg Mg Mg Mg2+
2+ 2+ 2+ 2+

e– e– e– e– e
–

Mg Mg Mg Mg Mg2+
2+ 2+ 2+ 2+

2 metallic bonding = attraction between positive ions and delocalised

electrons
metallic structure = regular lattice arrangement of positive ions held
together by delocalised electrons
 3 Delocalised electrons can move and carry charge.
4 a) A substance can be hammered into shape without breaking.
b) A substance which can be drawn out into wires.
5 a) The layer of positive ions can slide over each other without
disrupting the bonding.
b) Sodium has delocalised electrons which can move and carry charge.

●● TEST YOURSELF 5 (PAGE 97)

1 ice/iodine
2 covalent bonds between the atoms in I2
van der Waals’ forces between the molecules
3 a) Mg2+
b) Mg2+ and O2−
4 a) macromolecular covalent
b) ionic
c) molecular covalent
d) metallic
5 A large amount of energy is needed to break the many strong covalent
bonds in diamond

●● TEST YOURELF (PAGE 105)

1 a) bent, 104.5°
b) tetrahedral, 109.5°
c) pyramidal, 107°
d) trigonal planar, 120°
Bonding

2 a) pyramidal, 107°
b) tetrahedral, 109.5°
c) tetrahedral, 109.5°
3

d) bent, 104.5°

14
●● TEST YOURSELF (PAGE 115)
1 van der Waals’ forces are due to induced dipole–dipole forces caused
by movement of electrons in atoms and molecules
2 The attraction between a lone pair of electrons on one electronegative
atom and an H atom bonded to either N, O of F.
3 a) van der Waals’ forces
b) hydrogen bonds
c) hydrogen bonds
 d) permanent dipole–dipole forces

ACTIVITY (PAGE 108)

e) van der Waals’ forces
f) hydrogen bonds
4 Ice has a lower density than water
The hydrogen bonds in ice are fixed
The water molecules in ice are further apart than the water molecules
in water.
5 The Mr and number of electrons increases from F2 to I2
There are increased induced dipole-dipole forces
There are increased van der Waals’ forces of attraction between the
molecules.

●● ACTIVITY (PAGE 108)

Testing a liquid for polarity
1 a) ‘Polar bond’ means that there is a slight positive charge and slight
negative charge on each atom due to unequal sharing of electrons
in a covalent bond.
b) The oxygen is more electronegative than the hydrogen and attracts
the bonding electrons in the covalent bond to itself, resulting in a
slight positive charge on the hydrogen and a slight negative charge
on the oxygen.
Rod
2
+ δ−
O
H H
δ+ δ+
δ−
O
Rod H H
− δ+ δ+
3 a) Ethanol is a polar molecule as it contains a polar OH bond
Hexane is a non polar molecule it contains no polar bonds – there
is little electronegativity difference between C and H
15
Trichloromethane has polar C-Cl bonds and is not symmetrical so
it is a polar molecule.
 b) Liquid Is the stream deflected?

Water yes

Ethanol, CH3CH2OH yes

Hexane, C6H14 no

Trichloromethane, CHCl 3 yes

4 a) C–Cl
b) The stream will not be deflected by the rod even though it contains
polar bonds due to the symmetrical nature of the polar bonds
around the central atom (tetrahedral-shaped).

●● ACTIVITY (PAGE 115)

Comparing the viscosity of liquids
1
burette

stopwatch alcohol

beaker
Bonding

2 Open the tap and at the same time start the stopwatch. Record the time
taken for, for example, 30 cm3 of liquid to flow from the burette. Repeat
the measurement and find the average.
3

Calculate the flow rate by dividing the volume of liquid by the time
taken, which will give the flow rate in cm3 s−1

Repeat for each alcohol.

16 mass
3 density =
volume
mass
0.79 =
2.0
Mass = 1.58 g
1.58
Moles = = 0.0343 mol s−1
46.0
0.0343 × 60 = 2.058 = 2.1 mol/min−1 (to 2 significant figures)
 4 a) Hydrogen bonds occur between a hydrogen atom (which is
covalently bonded to O, N or F) in one molecule and an O, N or F

PRACTICE QUESTIONS (PAGES 116–7)

atom in another molecule. Hydrogen bonds are an extreme case of
permanent dipole attractions.
b) H3C O
δ–
C Hδ+ Hydrogen bond
H2
O CH3
δ–
δ+H C
H2

5 There are more –OH groups in propane-1,2,3-triol than in ethane-

1,2-diol; ethanol has the least number of –OH groups of these three
compounds. More –OH groups lead to more H-bonding and therefore
higher viscosity.
6 Use a liquid which has the same number of OH groups and so the same
hydrogen bonding but different RMMs. Compare the flow rates – they
should be different if the RMM affected the flow rate.

●● PRACTICE QUESTIONS (PAGES 116–7)

1 B
2 D
3 A
4 B
5 a) There are stronger hydrogen bonds between ammonia molecules. (1)
PH3 shows weaker van der Waals’ forces (and permanent
dipole–dipole forces) between molecules. (1)
More energy is required to break the stronger hydrogen bonds
between ammonia molecules. (1)
b) There is an increase in Mr and the number of electrons. (1)
There is an increase in van der Waals’ forces between molecules. (1)
More energy is required to break the greater van der Waals’ forces. (1)
6 The hydrogen bonds in ice are fixed whereas in water they are
constantly being broken and reformed. (1)
The water molecules in ice are further apart than the water
molecules in water. (1)
17
7 a) When molten, the ions can move and carry charge. (1)
When solid, the ions are held in an ionic lattice and cannot
move and carry charge. (1)
b) ionic lattice (1)
c) The ionic bonds between the positive and negative ions are strong (1)
and require a large amount of energy to break (1)
 8 a) van der Waals’ forces (1)
b) van der Waals’ forces and permanent dipole-dipole forces (1)
c) The van der Waals’ forces of attraction are weaker (1)
than the permanent dipole-dipole forces between propanone
molecules (1)
more energy is require to break the bond between the molecules
of propanone (1)
9 a) tetrahedral (1)
b) methane (1)
c) ammonium ion (1)
d) eight electrons in the outside shell so 4 electron pairs (1)
electron pairs repel each other (1)
four bonding pairs of electrons repel each other equally (1)
the tetrahedral shape minimises the repulsions between the
pairs of electrons (1)
10 a) magnesium has a stronger metallic bond than sodium (1)
as magnesium has more outer shell electrons which can be
delocalised (1)
b) metallic (1)
c) The strong ionic bonds (1)
between the small 2+ and 2− ions (1)
require a lot of energy to break (1)
d) The iodide ion is larger than the chloride ion (1)
the ionic bond is less strong in magnesium iodide (1)
as the ions are not a close together (1)
Bonding

11 a) i) weak van der Waals’ forces of attraction (1)

between the molecules (1)
require little energy to break (1)
3

ii) bonding is covalent (1)

structure is molecular (1)(5)

b) i) SF2 + Cl2 + 2NaF → SF4 + 2NaCl (1)

18
ii) bent (1)
electron pairs repel each other, the two lone pairs of
electrons repel more than the two bonding pairs of electrons (1)
the molecule takes up the bent shape (104.5°) to minimise
the repulsions (1)
iii) SF2 is molecular covalent (1)
NaF is ionic (1)
 4 Energetics
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 118)
1 a) endothermic
b) exothermic
c) exothermic
2 a) exothermic
b) exothermic
c) exothermic
d) endothermic

●● TEST YOURSELF 2 (PAGE 123)

1 100 kPa and a stated temperature
2 same reaction
1 3
3 N2(g) + H2(g) → NH3(g)
2 2
1
4 a) Ca(s) + O2(g) → CaO(s)
2
1
b) Na(s) + Cl2(g) → NaCl(s)
2
1
c) H2(g) + O2(g) → H2O (l)
2
1
d) C(s) + O2(g) → CO(g)
2
1
e) 2C(s) + 3H2(g) + O2(g) → C2H5OH(l)
2
f) 4C(s) + 5H2(g) → C4H10(g)
1
5 a) CO(g) + O2(g) → CO2(g)
2
b) C2H4(g) + 3O2(g) → 2CO2(g) + 2H2O(l)
c) CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
1 1 19
d) K(s) + O2(g) → K2O(s)
4 2
1
e) H2(g) + O2(g) → H2O(l)
2
f) C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l)

●● TEST YOURSELF 3 (PAGES 131–2)

1 q = mc∆T
q = 120 × 4.18 × 10.1 = 5066.16 J
 5066.16
per mol of methanol = = 298009.4 J mol−1
0.017
or −298 kJ mol−1
2 a) moles of C3H8 = 0.0136 mol
b) q = mc∆T = 100 × 4.18 × 65.0 = 27170 J
27 170
c) = 1 997 794.118 J mol−1
0.0136
−2000 kJ mol−1 (accept −1998 kJ mol−1)
3 moles of propanone = 0.01724 mol
q = mc∆T = 150 × 4.18 × 45.5 = 28528.5 J
per mole of propanone = 1654785.393 J mol−1
−1650 kJ mol−1
4 q = mc∆T = 50 × 4.18 × 13.0 = 2717 J
per mole of water = 54340 J mol−1 = −54.3 kJ mol−1
5 q = mc∆T = 25 × 4.18 × 6.1 = 637.45 J
per mol of NaOH = 42 496.67 J mol−1
−42.5 kJ mol−1

●● TEST YOURSELF 4 (PAGE 137)

1 a) −572 kJ mol−1
b) −822 kJ mol−1
c) −394 kJ mol−1
d) −788 kJ mol−1
e) −858 kJ mol−1
2 −891 kJ mol−1
Energetics

3 −2234 kJ mol−1

●● TEST YOURSELF 5 (PAGE 142)

1 The mean bond enthalpy is a measure of the energy required to break
4

one mole of a covalent bond measured in kJ mol−1 averaged across

many compounds containing the bond

2 a) Shorter bond is a stronger bond (or converse).

20
b) 6472 − 8522 = −2050 kJ mol−1
3 4719 − 5990 = −1271 kJ mol−1
4 a) 4556 − 5990 = −1434 kJ mol−1
b) Mean bond enthalpy values not specific to the molecules in this
reaction.
Water not a gas in this equation.
●● ACTIVITY (PAGES 125–6)

ACTIVITY (PAGES 125–6)

Measuring and evaluating the enthalpy change for the
neutralisation of sodium hydroxide and hydrochloric
acid.
1
35

30

25

Temperature (ºC) 20

15

10

0
0 2 4 6 8 10 12
Time (mins)

2 21.1 °C
3 21.1 °C
4 35 °C
5 35.0 − 21.1 = 13.9 °C
6 q=mc∆T
50 × 4.18 × 13.9 = 2905.1 J
7 1.0 × 25.0/1000 = 0.025 moles
8 2905.1 J for 0.025 moles
116 204 J for 1 mole = 116.204 kJ
0.1 0.1
9 × 100 = × 100=0.719% (to 3 d.p.)
answer from Q5 13.9
10 It is possible to extrapolate with confidence because the lines go
through most of the points, no anomalies.
11 To improve reliability of results. Repeating allows for possible 21
anomalies in a single experiment to be eliminated.
12 Heat loss through the open beaker to the surroundings.
13 To provide support and additional insulation.
14 Use a pipette or burette, either is accurate to one decimal place.
 ●● PRACTICE QUESTIONS (PAGES 142–3)
1 C (1)
2 D (1)
3 C (1)
4 q = mc∆T = 200 × 4.18 × 51.6 = 43137.6 J (1)
1.0
moles of C6H14 = =0.01163 mol (1)
86.0
43 6
energy change per mole = = 3 709 165.95 J mol−1 (1)
0.01163
3 709 165.95
energy change in kJ per mole =
1000
= −3710 kJ mol−1 to 3 significant figures (1)
5 a) i) the enthalpy change when 1 mole of a substance is burned
completely in excess oxygen with all substances in standard
states under standard conditions. (1)
ii) CH3CH2CH2CH2OH(l) + 6O2(g) → 4CO2(g) + 5H2O(l) (1)
0.600
b) moles of butan-1-ol = = 0.00811 mol (1)
74.0
q = mcT = 250 × 4.18 × 19.40 = 20273 J (1)
20 273
energy change per mole = = 2 499 753.391 J mol−1 (1)
0.00811
2 499 753.391
energy change in kJ per mole =
1000
= −2499.75 kJ mol−1 (1)
0.750
6 moles of benzene = = 0.009615 mol (1)
78.0
q = mc∆T = 200 × 4.18 × 43.7 = 36533.2 J (1)
36533.2
energy change per mole = = 3 799 604.784 J mol−1 (1)
0.009615
3799604.784
energy change in kJ per mole = = −3799.6 kJ mol−1 (1)
1000
1
7 a) i) Ba(s) + C(s) + 1 O2(g) → BaCO3(s) (1)
Energetics

2
1
ii) Ba(s) + O2(g) → BaO(s) (1)
2
iii) C(s) + O2(g) → CO2(g) (1)
b) +1216 (1) + (−554) + (−394) (1) = +268 kJ mol−1
4

8 a) 4(+178) (1) + 2(−824) + 8(−297) (1) = −3312 kJ mol−1 (1)

b) it is an element (1)

22
9 2(−359) − 2(−468) = +218 kJ mol−1
10 Bonds broken = 6635 (1)
Bonds made = 8522 (1)
Energy change = +6635 − 8522 = −1887 kJ mol−1 (1)
 5 Kinetics
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 144)
1 Three from: increasing concentration
Increasing temperature
Adding a catalyst
Grinding up a solid reactant
2 a) Faster with powdered magnesium
b) Greater surface area with powdered magnesium
3 a) Increase the rate of the reaction
b) Increase the rate of the reaction

●● TEST YOURSELF 2 (PAGE 147)

1 The activation energy is the minimum amount of energy which the
reactant particles require for a reaction to occur.
2 A catalyst increases the rate of the reaction by providing a different
reaction route with a lower activation energy.
3 Increasing temperature increases the energy of the reactant particles.
There are more collisions with energy greater than or equal to the
activation energy.
4 A collision must occur with energy at least equal to the activation energy.
5 More reactant particles present in the mixture. Therefore more particles
with energy greater than or equal to the activation energy.

●● TEST YOURSELF 3 (PAGE 151)

1 It provides an alternative reaction route with a lower activation energy.
2 Temperature 23

3 A small increase in temperature can cause a large increase in the rate of

reaction as there is significant increase in the number of molecules with
enough energy to undergo a successful collision.
4 a) Most probable energy (peak) is shifted to the left and the height of
the curve is higher.
b) Increase temperature increases the number of molecules with
energy greater than or equal to the activation energy.
 ●● PRACTICE QUESTIONS (PAGES 152–4)
1 A (1)
2 A (1)
3 a) A and C (1)
b) D (1)
c) endothermic as enthalpy increase/∆H is positive (1)
4 a) i) Most probable energy (peak) is shifted to the left and the
height of the peak is higher. (1)
ii) Fewer molecules with energy greater than or equal to the
activation energy. (1)
Area under the graph above Ea decreases. (1)
b) Provides an alternative reaction route of lower activation energy. (1)
More molecules with energy greater than or equal to the
activation energy/area under the graph above Ea increases. (1)
c) Exothermic as ∆H is negative. (1)
d) Zero molecules have zero energy. (1)
5 a) Substance which increases the rate of a chemical reaction
without being used up. (1)
b) i) A (1)
ii) D (1)
iii) Starts at (0,0); lower than line; ends up at 24 cm3. (1)
iv) Starts at (0,0); lower than X; ends up at 24 cm3 after X. (1)
6 a) i) Number of molecules (1)
ii) Activation energy (1)
b) i) n (1)
Kinetics

ii) Ea (1)
iii) n would increase. (1)
5

E and Ea would remain unchanged. (1)

c) catalyst provides an alternative reaction route of lower

activation energy. (1)

24
d) Increasing temperature increases the energy of the reactant
particles. (1)
Therefore there are more collisions with energy greater than
or equal to the activation energy. (1)
 6 Chemical equilibria
and le Chatelier’s
principle
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 155)
1 A reaction in which the reactants change into the products but the
products can change back into the reactants.
2 a) Sulfur dioxide and oxygen
Sulfur trioxide
b) Reversible arrow

●● TEST YOURSELF 2 (PAGE 157)

1 Concentrations of the reactants and products remain constant.
The rates of the forward and reverse reactions are equal.
2 The reactants and products are all in the same state/all gases.
3 Two from: temperature/concentration/pressure.

●● TEST YOURSELF 3 (PAGE 163)

1 If a factor is changed which affects a system in equilibrium, the
position of equilibrium will move in a direction so as to oppose the
change.
2 A catalyst increases the rate of the forward and reverse reaction equally.
3 3 moles of gas on the left and 5 moles of gas on the right;
increase in pressure shifts the position of equilibrium to the side with a
smaller gas volume; 25

position of equilibrium moves from right to left;

yield of hydrogen decreases.
4 a) Forward reaction is endothermic;
increasing temperature shifts the position of equilibrium in the
direction of the endothermic reaction to absorb the heat;
position of equilibrium moves from left to right;
concentration of NO2 increases.
 b) 1 mole of gas on the left and 2 moles of gas on the right;
increase in pressure shifts the position of equilibrium to the side
with a smaller gas volume;
position of equilibrium moves from right to left;
concentration of NO2 decreases.
5 a) Compromise between rate of reaction and yield of product;
lower yield (as forward reaction is exothermic) but higher rate of
reaction.
1
b) 1 2 moles of gas on the left and 1 mole of gas on the right;
increase in pressure shifts the position of equilibrium to the side
with a smaller gas volume;
position of equilibrium moves from left to right;
yield of SO3 increases.

●● TEST YOURSELF 4 (PAGE 165)

Chemical equilibria and le Chatelier’s principle

1 a) C2H4(g) + H2O(g) C2H5OH(g)

Stare symbols not required
b) concentrated phosphoric acid
c) high pressure and moderate temperature
d) hydration
2 a) methanol
b) 3 moles of gas on the left and 1 mol of gas on the right;
increase in pressure shifts the position of equilibrium to the side
with a smaller gas volume;
position of equilibrium moves from left to right;
yield of CH3OH increases.
c) Compromise between rate of reaction and yield of product;
lower yield (as forward reaction is exothermic) but higher rate of
6

reaction.
3 Equal number of moles of gas on each side of the equilibrium.

26 ●● PRACTICE QUESTIONS (PAGES 166–7)

1 B (1)
2 a) C and D (1)
b) C and D (1)
c) none (1)
 3 a) Concentrations of the reactants and products remain constant (1)

PRACTICE QUESTIONS (PAGES 166–7)

The rates of the forward and reverse reactions are equal (1)
b) i) endothermic; (1)
as position of equilibrium moves from left to right, when
temperature is increased, to absorb the heat. (1)
ii) Energy of the particles increases; (1)
more collisions with energy greater than or equal to the
activation energy (1)
c) 1 mole of gas on the left and 2 moles of gas on the right; (1)
a decrease in pressure shifts the position of equilibrium to the
side with a larger gas volume; (1)
position of equilibrium moves from left to right. (1)
4 a) 3 moles of gas on the left and 2 moles of gas on the right; (1)
an increase in pressure shifts the position of equilibrium to the
side with a smaller gas volume (1)
position of equilibrium moves from left to right, therefore the
amount of NO2 increases. (1)
b) Forward reaction is exothermic; (1)
decrease in temperature shifts the position of equilibrium in the
direction of the exothermic reaction; (1)
position of equilibrium moves from left to right and so more
brown NO2. (1)
5 a) 2 moles of gas on the left and 4 moles of gas on the right; (1)
an increase in pressure shifts the position of equilibrium to the
side with a smaller gas volume; (1)
position of equilibrium moves from right to left and yield of H2
decreases. (1)
b) The position of equilibrium moves from left to right to remove
the excess hydrogen; (1)
the equilibrium yield of CH3OH increases. (1)
6 a) 9 moles of gas on the left and 10 moles of gas on the right; (1)
an increase in pressure shifts the position of equilibrium to
the side with a smaller gas volume; (1)
27
position of equilibrium moves from right to left. (1)
b) Forward reaction is exothermic; (1)
increase in temperature shifts the position of equilibrium in the
direction of the endothermic reaction; (1)
position of equilibrium moves from right to left. (1)
c) A catalyst has no effect on the position of equilibrium. (1)
d) The reaction is exothermic (1)
 7 a) vanadium(V) oxide/ V2O5 (1)
b) Increases the rate of the reaction/equilibrium attained more
rapidly. (1)
c) i) reaction is exothermic; (1)
a lower temperature shifts the position of equilibrium in the
direction of the exothermic reaction (1)
position of equilibrium moves from left to right/higher
yield of SO3 (1)
ii) Compromise between rate of reaction and yield of product; (1)
lower yield (as forward reaction is exothermic) but higher
rate of reaction. (1)
1
d) i) 1 2 moles of gas on the left and 1 mole of gas on the right; (1)
an increase in pressure shifts the position of equilibrium to
the side with a smaller gas volume; (1)
Chemical equilibria and le Chatelier’s principle

position of equilibrium moves from left to right/yield of

SO3 increases. (1)
ii) Pressure is expensive (1)
due to the cost of the pumps to apply it and the
equipment and valves needed to withstand it. (1) (2)
6

28
 7 Equilibrium constant,
Kc, for homogeneous
systems
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 169)
1 The concentrations of the reactants and products remain constant and
the rates of the forward and reverse reactions are equal.
2 If a factor is changed which affects a system in equilibrium, the position
of equilibrium will move in a direction so as to oppose the change.
3 a) Position of equilibrium moved in the direction of the reverse
endothermic reaction;
the position of equilibrium moves from right to left;
the yield of C decreases.
b) 3 moles of gas on the left side and 1 moles of gas on the right side;
an increase in pressure shifts the position of equilibrium to the side
with a smaller gas volume;
increasing pressure moves the position of equilibrium from left to
right to oppose the increase in pressure;
the yield of C increases.
c) A catalyst increases the rate of reaction of both the forward and
reverse reactions.
Equilibrium is attained more quickly but a catalyst does not affect
the position of equilibrium.
d) All the reactants and products are in the same state (or phase).

●● TEST YOURSELF 2 (PAGE 172) 29

[H]2
1 a) Kc =
[F]2[G]
b) mol  dm3
−1

[CO2][H2]4
2 a) Kc =
[CH4][H2O]2
b) mol2 dm−6
[HBr]2
3 a) Kc =
[H2][Br2]
b) Equal number of moles on both sides of the equation and they
cancel each other out in the Kc expression.
 ●● TEST YOURSELF 3 (PAGE 176)
[C][D]
1 a) Kc = ; mol−2 dm6
[A]2[B]2
b) A = 0.6; B = 0.6; D = 0.2
[PCl3][Cl2]
2 a) Kc =
[PCl5]
b) mol dm−3
c) i) PCl3 = 6.0; Cl2 = 6.0
ii) [PCl5] = 1.6 mol dm−3; [PCl3] = [Cl2] = 2.4 mol dm−3
[NO]4[H2O]6
3 a) Kc =
[NH3]4[O2]5
b) mol dm−3
c) i) NH3 = 1.20; O2 = 1.50; H2O = 1.20
ii) [NH3] = 0.06 mol dm−3
EQUILIBRIUM CONSTANT, KC, FOR HOMOGENEOUS SYSTEMS

[O2] = 0.075 mol dm−3
[NO] = 0.04 mol dm−3
[H2O] = 0.06 mol dm−3

●● TEST YOURSELF 4 (PAGE 180)

[SO3]2
1 a) Kc =
[SO2]2[O2]
(0.82)2
b) Kc = = 7.94 mol−1 dm3
(0.240)2(1.47)
[PCl3][Cl2]
2 a) Kc =
[PCl5]
b) PCl5 = 0.80; PCl3 = 1.2
c) [PCl5] = 0.08 mol dm−3; [PCl3] = 0.12 mol dm−3; [Cl2]
= 0.12 mol dm−3
(0.12)(0.12)
d) Kc = = 0.18 mol dm−3
0.08
3 a) B = 0.60; C = 0.40
b) [A] = 0.04 mol dm−3
[B] = 0.12 mol dm−3
7

[C] = 0.08 mol dm−3

[C]
c) Kc =
[A]2[B]
30 0.08
d) Kc = = 417 mol−2dm6
(0.04)2 (0.12)
●● TEST YOURSELF 5 (PAGES 182–3)

TEST YOURSELF 6 (PAGE 187)

[C][D]
1 Kc =
[A][B]2
K c × [A] × [B]2 12.4 × (1.20) × (0.55)2
[C]= =
[D] (2.10)
= 2.14 mol dm−1
[C][D]
2 Kc =
[A][B]2
[C][D] (0.940)(2.52)
[B]2 = = = 0.5127
[A] × Kc (0.440)(10.5)
[B] = 0.716 mol dm−3
[H ][I ]
3 a) Kc = 2 22
[HI]
b) Equal number of moles on both sides of the equation and they
cancel each other out in the Kc expression.
[H ][I ]
c) [HI]2 = 2 2
Kc
[H2] = 0.0200 mol dm−3; [I2] = 0.0200 mol dm−3
(0.0200)(0.0200)
[HI]2 = = 5.369 × 10−5
7.45
[HI] = 0.0073 mol dm−3

●● TEST YOURSELF 6 (PAGE 187)

1 If a factor is changed which affects a system in equilibrium, the
position of equilibrium will move in a direction so as to oppose the
change
2 a) increases
b) decreases
c) i) no effect
ii) increases
3 a) increases
b) no effect
c) decreases

31
 ●● ACTIVITY (PAGES 183–4)
Determination of the value of Kc when ethanol reacts
with ethanoic acid
1 Ethanoic acid  d = m/v  1.05 = m/6.0  m = 6.3 g 
moles = 6.3/60.0 = 0.105
Ethanol  d = m/v  0.79 = m/6.0  m = 4.74 g 
moles = 4.74/46.0 = 0.103
Water  d = m/v  1.0 = m/8.0  m = 8.0 g moles = 8.0/18.0 = 0.444
16.50 × 0.1
2 = 0.00165
1000
34.65 × 0.1
3 = 0.003465
1000
4 0.003465−0.00165 = 0.001815
5 0.105−0.001815 = 0.103185
EQUILIBRIUM CONSTANT, KC, FOR HOMOGENEOUS SYSTEMS

6 0.103−0.001815 = 0.101185
7 0.444+0.001815 = 0.4458515
8 0.103185/0.02 = 5.16
9 0.101185 /0.02 =5.05
10 0.09
11 22.29
22.9 × 0.09
12 = 0.08 no units
(5.16×5.05)
13 Kc is temperature dependent, and the temperature may have changed
in the laboratory, and may not have been 298 K.

●● PRACTICE QUESTIONS (PAGES 188–9)

1 B (1)
2 B (1)
[PCl3][Cl2] Kc × [PCl5]
3 a) Kc = ; so [Cl2] = (1)
[PCl5] [PCl3]
0.185 × 0.220
[Cl2] =  (1)
0.0120
7

= 3.39 mol dm−3 (1)

[PCl3][Cl2]
b) [PCl5] =  (1)
Kc
32 [PCl3] = 0.0750 mol dm−3
and [Cl2] = 0.0450 mol dm−3 (1)
0.0750 × 0.0450
[PCl5] =  (1)
0.185
= 0.0182 mol dm−3 (1)
Moles of PCl5 in 2 dm3 = 0.0182 × 2 = 0.0364 mol (1)
 [SO3]
4 a) Kc = (1)
[SO2][O2]
1

PRACTICE QUESTIONS (PAGES 188–9)

2

b) decreases (1)
[SO3]
c) [SO2] = (1)
Kc × [O2]
1
2

(2.4)
[SO2] = (1)
(2.8 × 102)(0.54)
1
2

= 0.012  mol dm−3 (1)

d) Kc for the reverse reaction is for the forward reaction
1
Kc =
2.8 × 102
=3.6 × 10−3 (1)
[C]
5 a) Kc = (1)
[A]2 [B]
b) mol−2 dm6 (1)
(1.04)
c) i) Kc = (1)
(0.35)2 (0.77)
= 11 (1)
ii) As Kc decreases with increasing temperature (1)
reaction is exothermic (1)
[HI]2
6 Kc = (1)
[H2][I2]
moles of HI at equilibrium = 3.00
moles of H2 = 0.300
moles of I2 = 0.300
[HI] = 1.50 mol dm−3
[H2] = [I2] = 0.150 mol dm−3 (1)
(1.50)2
Kc = =100
(0.150)(0.150)
 for calculation (1)
 for answer (1)
7 a) moles of SO2Cl2 = 0.00750 (1)
moles of SO2 = 0.0345 (1)
[SO2][Cl2]
b) Kc = (1)
[SO2Cl2]
c) [SO2Cl2] = 0.00375 mol dm−3 (1)
[SO2] = [Cl2] = 0.01725 mol dm−3 (1)
33
(0.01725)(0.01725)
Kc = (1)
(0.00375)
= 0.0794 (1)
d) mol dm−3 (1)
[H2O][CO]
8 a) Kc = (1)
[H2][CO2]
b) CO2 = 0.20; H2O = 0.80; CO = 0.80; all correct = [2]

( )( )
0.80
c) Kc = 0.20
V
0.80
V
0.20 (1) = 16 (1)
( )( )
V V
 8 Oxidation, reduction
and redox equations
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 190)
1 Sulfur gains oxygen and the gain of oxygen is oxidation.
2 Chlorine gains hydrogen and the gain of hydrogen is reduction.
3 a) Magnesium loses electrons and the loss of electrons is oxidation.
b) Copper ions gain electrons and the gain of electrons is reduction.

●● TEST YOURSELF 2 (PAGE 194)

1 a) +5
b) +4
c) +1
d) −3
e) −3
2 a) +4
b) +2
c) +6
d) −2
f) +6
3 Na2Cr2O7; BaFeO4; K2MnO4
4 a) 0
b) +3

34 c) +5
d) +5
e) −3
5 +3; +4; +5; +6; +7
●● TEST YOURSELF 3 (PAGE 195)

TEST YOURSELF 4 (PAGE 197)

1 +6
2 NaClO4
3 magnesium stannate(iv)
4 a) 3
b) 1
c) 3
d) 4
e) 4

●● TEST YOURSELF 4 (PAGE 197)

1 a) N changes from −3 in NH3 to +2 in NO
Increase in oxidation state is oxidation
O changes from 0 in O2 to −2 in NO and H2O
Decrease in oxidation state is reduction
Redox is oxidation and reduction occurring simultaneously in the
same reaction
b) I changes from −1 in HI to 0 in I2
Increase in oxidation state is oxidation
S changes from +6 in H2SO4 to 0 in S
Decrease in oxidation state is reduction
Redox is oxidation and reduction occurring simultaneously in the
same reaction
c) Br changes from −1 in NaBr to 0 in Br2
Increase in oxidation state is oxidation
Cl changes from 0 in Cl2 to −1 in NaCl
Decrease in oxidation state is reduction
Redox is oxidation and reduction occurring simultaneously in the
same reaction
2 a) Hydrogen changes from 0 in H2 to +1 in H2O
35
Increase in oxidation state is oxidation
b) Sodium changes from 0 in Na to +1 in Na2O
Increase in oxidation state is oxidation
3 No changes in oxidation state
 ●● TEST YOURSELF 5 (PAGE 199)
1 N changes from −3 in NH3 to 0 in N2
Increase in oxidation state is oxidation
Cu changes from +2 in CuO to 0 in Cu
Decrease in oxidation state is reduction
Redox is oxidation and reduction occurring simultaneously in the same
reaction
2 Ag changes from 0 in Ag to +1 in AgNO3
Increase in oxidation state is oxidation
N changes from +5 in HNO3 to +2 in NO
Decrease in oxidation state is reduction
Redox is oxidation and reduction occurring simultaneously in the same
reaction
3 Cl2, 0; HCl, −1; HOCl, +1
4 a) +4; +7; +6; +2
OXIDATION, REDUCTION AND REDOX EQUATIONS

b) manganate(VII)/MnO4–

●● TEST YOURSELF 6 (PAGE 203)

1 a) Br2 + 2e− → 2Br−
b) Zn → Zn2+ + 2e−
c) Fe → Fe3+ + 3e−
2 a) VO +2 + 2H+ + e− → VO2+ + H2O
b) VO2+ + 2H+ + e− → V3+ + H2O
c) SO2-
4 + 4H + 2e → SO2 + 2H2O
+ −

d) Cr3+ + 4H2O → CrO2–

4 + 8H + 3e
+ −

e) NO–3 + 4H+ + 3e− → NO + 2H2O

f) Cl2 + 2H2O → 2OCl− + 4H+ + 2e−
8

●● TEST YOURSELF 7 (PAGE 206)

1 a) CH3CH(OH)CH3 + [O] → CH3COCH3 + H2O

36
b) CH3OH + 2[O] → HCOOH + H2O
c) CH3CH2CH2CH2OH + [O] → CH3CH2CH2CHO + H2O
2 a) CH3COCH2CH3 + 2[H] → CH3CH(OH)CH2CH3
b) CH3CHO + 2[H] → CH3CH2OH
c) CH3CH2COOH + 2[H] → CH3CH2CHO + H2O
3 CH3CH(OH)CH2CH2CH3 → CH3COCH2CH2CH3 + 2H+ + 2e−
●● TEST YOURSELF 8 (PAGE 211)

ACTIVITY (PAGES 206–8)

1 2H2O2 + N2H4 → N2 + 4H2O
2 H2O2 +2H+ + 2I− → I2 + 2H2O
3 Cl− + 2OH− + 2HBrO + 2H+ → Br2 + 3H2O + ClO−
or
Cl− + 2HBrO → Br2 + H2O + ClO−
4 2MnO–4 + 16H+ + 5C2O2-
4 → 2Mn + 8H2O + 10CO2
2+

●● ACTIVITY (PAGES 206–8)

Redox reactions in photochromic glass
1 AgCl → Ag+ + Cl−
2 Moles of = 0.287/143.4 = 0.00200
Mass of silver ions = 0.00200 × 107.9 = 0.2160 g
3 Cl− → Cl + e− The oxidation state of chlorine in chloride ions is −1.
The oxidation state of chlorine atoms is 0. The reaction is an oxidation
reaction because the oxidation state has increased.
4 Ag+ +e− → Ag. The silver ions gain electrons to form silver atoms.
Gain of electrons is reduction.
5 The chlorine atoms may combine and produce molecules of chlorine
gas Cl2.
6 Cu+ + Cl → Cu2+ + Cl−
Copper changes in oxidation state from +1(in Cu+) to +2 (in Cu2+) .
This is an increase in oxidation state and so it is oxidised.
Chlorine changes in oxidation state from 0 (in Cl) to −1 (in Cl−). This is
a decrease in oxidation state and so it is reduced.
7 Cu2+ + Ag → Ag+ + Cu+
Copper changes in oxidation state from +2 (in Cu2+) to +1 (in Cu+).
This is a decrease in oxidation state and so it is reduced.
Silver changes in oxidation state from 0 (in Ag) to +1 (in Ag+). This is
an increase in oxidation state and so it is oxidised.
8 Goggles and gloves when using concentrated acid.
9 The oxidation number of copper changes from +2 (in CuO) to +1 37
(in CuCl). This is a decrease in oxidation state so it is reduced.
The oxidation state of copper changes from 0 (in Cu) to +1 (in
CuCl). This is an increase in oxidation state so it is oxidised. It is a
disproportionation reaction because the same element (Cu) is oxidised
and reduced in the same reaction.
10 Copper(I) chloride is insoluble in water.
11 Decanting separates the insoluble solid from the water. It means to pour off
the liquid, leaving the insoluble copper(I) chloride behind in the beaker.
 ●● PRACTICE QUESTIONS (PAGES 211–2)
1 B (1)
2 B (1)
3 D (1)
4 a) +5; +5; 0; +3 (4)
b) P4 + 5O2 → P4O10 (1)
c) P4O10 + 6H2O → 4H3PO4 (1)
No change in oxidation state (1)
d) H3PO4 + 2H+ + 2e− → H3PO3 + H2O (1)
5 a) i) 2; 4; 2 (1)
ii) 8; 4; 4 (1)
b) MnO2- 2-
4 + 2SO2 → Mn + 2SO4 (1)
2+

6 a) in VO2Cl; oxidation state of V is +5 (1)

VO2+ in VOCl2 and VOSO4; oxidation state of V is +4 (1)
OXIDATION, REDUCTION AND REDOX EQUATIONS

b) iodine (1)
−1 in NaI to 0 in I2 (1)
7 a) Magnesium oxidised (1)
Hydrogen reduced (1)
b) Chlorine oxidised (1)
Chlorine also reduced (1)
c) Sulfur oxidised (1)
Chromium reduced (1)
8 a) +6; 0; +8 (1) each
b) same element/xenon oxidised and reduced in the same reaction (1)
9 a) no change oxidation state (1)
b) 2NaI + 3H2SO4 → 2NaHSO4 + I2 + SO2 + 2H2O (1)
8

c) I changes from −1 in HI to 0 in I2; oxidation (1)

S changes from +6 in H2SO4 to +4 in SO2; reduction (1)

38 d) iodine is a grey-black solid (1)

sulfur is a yellow solid (1)
e) H2SO4 + 8H+ + 8e− → H2S + 4H2O (1)
f) HI/hydrogen iodide/iodide ions (1)
 9 Periodicity and Group 2

●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 213)
1 The elements are arranged in order of increasing atomic number in the
modern Periodic Table.
2 a) magnesium
b) arsenic
c) neon
3 For the first 20 elements, the Period number is the same as the number
of energy levels and the Group number is the same number as the
number of electrons in the highest energy level/outer level.

●● TEST YOURSELF 2 (PAGE 218)

1 The atomic radius of the atoms from sodium to argon decreases.
2 The first ionisation energy is the energy required to remove one mole of
electrons from one mole of atoms in the gaseous state to produce one
mole of 1+ ions in the gaseous state. From sodium to argon:
•  nuclear charge increases
•  atomic radius decreases
•  electron requires more energy to remove it
3 The intermolecular forces between molecules of sulfur and between
molecules of phosphorus are van der Waals’ forces which increase as
Mr increases. S8 has a bigger Mr than P4.
4 a) silicon
b) sodium
c) sodium 39
5 a) p block
b) d block
c) s block

●● TEST YOURSELF 3 (PAGE 221)

1 a) Mg: 1s22s22p63s2
b) Ca: 1s22s22p63s23p64s2
 c) Sr: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 5s2
d) Ba: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6 6s2
2 a) The first ionisation energy is the energy required to remove one
mole of electrons from one mole of gaseous atoms to form one
mole of gaseous 1+ ions.
b) Atomic radius is larger for strontium
Increased shielding by inner electrons
So less energy is required to remove the electron
3 Fewer shells of electrons so outer electrons are closer to the nucleus.
4 a) Delocalised from outer
shells of metal atoms

+ + + + + Regular arrangement
of positive ions in
+ + + + layers surrounded by
delocalised electrons
+ + + + +

Metal ions

b) There is an attraction between the layers of regularly arranged

positive ions and the sea of delocalised electrons.
c) Melting point decreases down the group.
Going down the group the size of the positive ions increases.
Metallic bonding/attraction between ions and delocalised electrons
is weaker.
PERIODICITY AND GROUP 2

5 a) Metallic bonding in transition metals is stronger than the metallic

bonding in Group 2 metals.
b) Transition metals have more electrons which can be delocalised
than Group 2 metals.

●● TEST YOURSELF 4 (PAGE 224)

1 a) A calcium hydroxide
B calcium oxide
9

b) Ca + 2H2O → Ca(OH)2 + H2

c) Ca → Ca2+ + 2e−
40 d) As the group is descended the metals become more reactive with
water.
2 Group 2 hydroxides become more soluble as the group is descended
while the solubility of the Group 2 sulfates decrease as the group is
descended.
 3 a) Add hydrochloric acid followed by barium chloride solution to a
solution of the suspected sulfate ions. If sulfate ions are present a

ACTIVITY (PAGES 218–9)

white precipitate of barium sulfate will form.
Ba2+ + SO42− → BaSO4
b) The barium chloride is acidified to remove any ions which will also
give a white precipitate with barium ions such as carbonate ions.
c) Sulfuric acid contains sulfate ions and will give a white precipitate
of barium sulfate.

●● ACTIVITY (PAGES 218–9)

Trends in first ionisation energy across a period
1
2800
2600
2400 He
First ionisation energy/kJ mol–1

2200 Ne
2000
1800 F
1600 Ar
N Kr
1400 Cl
1200 H O Br
P
1000 Be Zn As
C Fe Ni
800 Mg S Cr
B Ca Ti Se Y
600 Si Ge Zr
Sc V Mn Co Cu
400 Li Na Al Ga Sr
200 K Rb
0
0 1 2 3 4 5 6 7 8 910 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42
Atomic number

2 Atoms of Group 1 elements are at troughs on the graph. They have the
have the lowest first ionisation energy in every period as they have the
greatest atomic radius and the lowest nuclear charge in a particular
period. Hence it takes less energy to remove the outermost electron.
3 Atoms of Group 0 elements are at peaks on the graph. They have the
highest first ionisation energy in every period they have the smallest
atomic radius and the highest nuclear charge in a period. Hence it takes
more energy to remove the outermost electron.
4 The general increase in first ionisation energy across period 2 is caused
by the increase in nuclear charge. There is no increased shielding and
the atomic radius is decreasing. The outer electron is closer to the
nucleus with a greater nuclear charge holding it so more energy is
required to remove it.
41
5 The general trend is the same, for the same reasons as in question 4.
6 For elements in a group, for example Group1 it is observed that
sodium has higher ionisation energy than potassium. As the group
is descended the ionisation energy decreases as the outer electron is
further from the positive charge of the nucleus and there is increased
shielding.
 7 a)
4600
Na
4400
4200
4000
3800
3600
3400
3200

Ionisation energy/kJ mol–1

3000
2800 Ar
2600
2400 He
S
2200 Ne Cl
2000 P
Al
1800 F
1600 Ar
N Kr
1400 Si Cl
Mg Br
1200 H O P
1000 Be Zn As
C Fe Ni
800 Mg S Cr
B Ca Ti Se Y
600 Si Ge Zr
Sc V Mn Co Cu
400 Li Na Al Ga Sr
200 K Rb
0
0 1 2 3 4 5 6 7 8 910 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42
Atomic number

b) The trend is similar to that of first ionisation energy

c) Once one electron is removed, a positive ion is formed. Removing
an electron from a positive ion is more difficult and requires more
energy than removing it from an atom.
d) Al+(g) → Al2+(g) + e−
PERIODICITY AND GROUP 2

●● ACTIVITY (PAGES 222–3)

Group 2 hydroxides
1 Measure 100 cm3 of water into a beaker
Place in a thermostatically controlled water bath at 25°C
Weigh a known mass of solid and add in portions to the water, stirring
until no more will dissolve.
Weigh the solid and determine how much has dissolved – this is the
9

solubility in g/100 cm3

2 3.890 g in 100 cm3  38.90 g in 1000 cm3

42 moles = 38.9/fm (171.3) = 0.02271 mol dm−3
3 Blue to yellow
4 Decrease/less acid needed
5 Safety glasses and gloves (or wash hands on contact) as barium
compounds are toxic
6 The first titration is a rough titration and could be anomalous
7 Ba(OH)2 + 2HNO3 → Ba(NO3)2 + 2H2O
●● PRACTICE QUESTIONS (PAGES 225–6)

PRACTICE QUESTIONS (PAGES 225–6)

1 D (1)
2 D (1)
3 a) p block (1)
b) 53 (1)
iodine (1)
4 a) neon (1)
b) carbon (1)
c) Be(g) → Be+(g) + e− (1)
d) The ionisation energy of boron is lower than expected as the
energy level is divided into subshells. The outer electron in
boron is in a 2p orbital. It is further away from the nucleus than
the 2s electrons and is shielded by the 2s electrons from the
attraction of the nuclear charge. (3)
5 a) The elements of Group 2 become more reactive in water as the
group is descended. (1)
b) When the H2O is steam, i.e. when the magnesium is heated in a
stream of steam. (1)
c) Ba(s) + 2H2O(l) → Ba(OH)2(aq) + H2(g) (1)
6 a) The hydroxide of Group 2 elements become more soluble as the
group is descended. (1)
b) The sulfates of Group 2 elements become less soluble as the
group is descended. (1)
c) Add hydrochloric acid followed by a solution of barium chloride
to the aqueous sulfate ions, a white precipitate will form. (2)
d) Barium sulfate insoluble in water; and is not absorbed into the
blood stream (1)
e) Barium sulfate is used as it absorbs X-rays. (1)
7 a) Going down the group the size of the positive ions increases. (1)
Metallic bonding/attraction between ions and delocalised
electrons (1) is weaker (1). (3)
b) Atomic radius is smaller for magnesium (1).
Decreased shielding by inner electrons (1) so more energy is
required to remove the electron. (2) 43
c) i) Ca(g) → Ca+(g) + e− (1)
ii) Ba+(g) → Ba2+(g) + e− (1)
8 a) Used as an antacid (1)
b) CaCO3 + 2H+ → Ca2+ + H2O + CO2 (1)
c) i) 2Mg + TiCl4 → 2MgCl2 + Ti (1)
Mg + H2SO4 → MgSO4 + H2 (1)
ii) Magnesium sulfate is soluble in water and can be washed off. (1)
 10 Halogens
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 227)
1 fluorine, chlorine, bromine, iodine and astatine
2 a) NaI
b) CaCl2
c) AlF3
d) FeCl3
e) LiBr
f) ZnCl2
3 Cl2 + 2KI → 2KCl + I2

●● TEST YOURSELF 2 (PAGE 229)

1 Halogen State at room Colour
temperature and
pressure
fluorine gas yellow

iodine solid grey-black

bromine liquid red-brown

chlorine gas yellow-green

2 a) Change of state from a solid directly to a gas on heating

b) Purple gas formed
3 a) The ability of an atom in a covalent bond to attract the bonding
44 electrons
b) The bonding electrons for a fluorine atom are closer to the nucleus
and there is less shielding (of the nucleus) by inner electrons.
4 They are toxic.
5 Greater Mr so greater number of electrons for iodine;
Greater van der Waals’ forces between the molecules;
Larger amount of energy required to break the bonds between the
iodine molecules.
●● TEST YOURSELF 3 (PAGE 237)

TEST YOURSELF 4 (PAGE 242)

1 Cl2 + H2O → HOCl + HCl
2 a) 2NaOH + Cl2 → NaCl + NaOCl + H2O
b) sodium chlorate(I)
c) bleach
3 a) I changes from −1 in KI to 0 in I2
S changes from +6 in H2SO4 to -2 in H2S
b) H2S/hydrogen sulfide
c) Iodide ions are a stronger reducing agent as the electrons being lost
are further from the nucleus/experience more shielding.
4 a) Cl2 + 2I− → 2Cl− + I2
b) 2I− → I2 + 2e−
c) Iodine in the presence of iodide ions is brown.

●● TEST YOURSELF 4 (PAGE 242)

1 a) silver(I) chloride
b) Ag+ + Cl− → AgCl
c) chloride ions/Cl−
2 a) sulfur/S
b) hydrogen sulfide/H2S
c) sodium iodide
3 To remove carbonate ions and hydroxide ions which also form a white
precipitate with Ag+ ions.
4 silver nitrate solution
5 a) misty fumes
b) Br changes from −1 in HBr to 0 in Br2;
an increase in oxidation state is oxidation;
S changes from +6 in H2SO4 to +4 in SO2;
a decrease in oxidation state is reduction;
a redox reaction is one where oxidation and reduction occurring 45
simultaneously in the same reaction.
 ●● ACTIVITY (PAGES 229–30)
Extraction of iodine from seaweed
0.01 × 1000
1 mass of iodine =
100
Mass of iodine = 0.1 g
0.1
Moles of iodine = = 0.0004
253.8
2 2I−(aq)) → I2(aq) + 2e−
2e− + 2H+(aq) + H2O2(aq) → 2H2O(l)
3 The oxidation state increases from −1 to 0. An increase in oxidation
state is oxidation.
4 Yellow-brown
5 Iodine is more soluble in organic solvents than in water and passes into
the cyclohexane. Iodine dissolved in cyclohexane is purple.
6 Iodine crystals; grey-black
7 Purple gas; iodine sublimes

●● ACTIVITY (PAGE 242)

1 Soluble, not a carbonate
Magnesium ion present/magnesium compound
Not a carbonate or hydrogen carbonate
Chloride ion
Sulfate ion
2 Magnesium chloride and magnesium sulfate.

●● PRACTICE QUESTIONS (PAGES 243–4)

10 HALOGENS

1 A (1)
2 A (1)
3 D (1)
4 a) Going down the group, the Mr is greater so there are a greater
number of electrons; (1)

Greater van der Waals’ forces between the molecules; (1)

46 More energy required to break the forces between the molecules. (1)
b) i) The ability of an atom in a covalent bond to attract the
bonding electrons (1)
ii) Decreases (1)
iii) Bonding electrons further from the nucleus; (1)
More shielding by inner electrons. (1)
 5 a) Cl2 + H2O  HOCl + HCl (1)

PRACTICE QUESTIONS (PAGES 243–4)

b) Chloric(I) acid (or hypochlorous acid) (1)
Hydrochloric acid (1)
c) In very low concentrations, it is not toxic to humans. (1)
d) 2Cl2 + 2H2O → O2 + 4HCl (1)
6 a) +1 (1)
b) sodium chlorate(I) (1)
c) Cl changes from 0 in Cl2 to +1 in NaOCl
Increase in oxidation state is oxidation (1)
Cl changes from 0 in Cl2 to −1 in NaCl
Decrease in oxidation state is reduction (1)
Oxidation and reduction occurring simultaneously in the same
reaction is known as a redox reaction. (1)
d) potassium bromide, potassium bromate(I) and water (1)
7 a) Solution changes from colourless to brown (1)
b) 2I− + Cl2 → 2Cl− + I2 (1)
c) I changes from −1 in KI/I− to 0 in I2 and increase in oxidation
state is oxidation (1)
Cl changes from 0 in Cl2 to -1 in KCl/Cl- and decrease in
oxidation state is reduction (1)
Oxidation and reduction occurring simultaneously in the same
reaction is known as a redox reaction. (1)
8 a) Ag+ + I − → AgI
b) (1) for each correct row
Halide Colour of silver halide Effect of adding dilute ammonia
solution to the silver halide
chloride white solid redissolves to form a
colourless solution
bromide cream no effect

iodide yellow no effect

9 a) NaCl + H2SO4 → NaHSO4 + HCl (1) 47

b) HCl/hydrogen chloride (1)

c) Any two from sulfur/hydrogen sulfide/sulfur dioxide/iodine/water (2)
 10 a) 2Br− → Br2 + 2e− (1)
H2SO4 + 2H+ +2e− → SO2 + 2H2O (1)
b) bromine/Br2 (1)
c) An oxidising agent gains electrons. (1)
d) The outer electron being lost is further from the nucleus in
bromide ion (1)
And experiences more shielding by inner electrons (1)
11 a) i)
NaClO and NaCl (1)
ii) AgI (1)
iii) HBr (1)
iv) NaCl (1)
v) NaClO (1)
vi) NaI (1)
b) i) NaF + H2SO4 → NaHSO4 + HF (1)
ii) HF formed/HF fumes react with moist air. (1)
10 HALOGENS

48
 11 Introduction to
organic chemistry
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 245)
1 A covalent bond is formed when two atoms share a pair of electrons,
one electron comes from each atom in the bond.
2 A molecule of methane:
H
+ +

H C H
+
+

H
3 Methane is tetrahedral. It has four pairs of bonded electrons in the
valence shell. The electron pairs move as far apart as possible to
minimise the repulsions. In a three-dimensional space this means
moving 109o apart to the corners of a tetrahedron.
4 Six hydrogen atoms
5 Four hydrogen atoms

●● TEST YOURSELF 2 (PAGE 249)

1 a)
Element Mass/g Number of moles Simplest ratio of moles

Carbon 8.27 8.27/12.0 = 0.689 0.689/0.689 = 1.00

Hydrogen 10.0-8.27=1.73 1.73/1.0 = 1.73 1.73/0.689 = 2.51

Empirical C 2 H5
formula 49

b)
relative molecular relative molecular mass of molecular formula
mass empirical formula unit
58.0 C2H5 = (12.0 × 2) + (1.0 × 5)= 29.0 There are two units of
C2H5 in the molecule.
58.0/29.0=2
C 4H10
 2 a) A hydrocarbon contains atoms of hydrogen and carbon only.
This compound also contains atoms of oxygen so cannot be a
hydrocarbon.
b)
Element Mass/g Number of moles Simplest ratio of moles

Carbon 7.98 7.98/12.0 = 0.665 0.665/0.665 = 1.00

Oxygen 10.68 10.68/16.0 = 0.668 0.668/0.665 = 1.00

Hydrogen 20 − (10.68 + 7.98) = 1.34 1.34/1.0 = 1.34 1.34/0.665 = 2.02

Empirical formula CH2O

c)
relative molecular mass relative molecular mass of empirical molecular formula
formula unit
60.00 CH2O = (12.0) + (1.0 × 2) + (16.0) = 30.0 There are two units of CH2O in the molecule.
60.0/30.0 =2
C2H4 O

●● TEST YOURSELF 3 (PAGE 252)

11 INTRODUCTION TO ORGANIC CHEMISTRY

X Y Z
1 a)
H H
H C H
H C H H
H H H H H H H
C C
H C C C C H H C C C C H H C H H C H
H O H H H H H H H H

b) H

50

c) C4H10O C5H12 C5H10

d) C4H10O C5H12 CH2

 2 a) C2H5OH

TEST YOURSELF 4 (PAGE 259)

b) C16H32
c) C8H18

●● TEST YOURSELF 4 (PAGE 259)

1 a) i) 1-bromopropane
ii) 2-chloropropane
iii) 3-iodoprop-1-ene. You may also have named this 1-iodoprop-
3-ene. This was a little tricky. Usually the lowest set of
numbers are used to describe positions of double bonds and
substituents but since the numbers are 1,3 or 3,1 the position
of the double bond is labelled using the lowest number as it
has a higher priority in naming as shown in Table 11.11.
iv) but-2-ene
v) 3-methylbutan-1-ol
vi) 2-methylhexan-3-ol
b) Compound iv) is the only hydrocarbon in the list of compounds
as it contains atoms of hydrogen and carbon only. All of the other
compounds contain atoms of other elements for example halogen
atoms of oxygen atoms.
2 a) Remember all of the bonds are shown. Sometimes the shape of the
double bond is incorporated into the diagram.
H
H H H H C H
C C C H or
C C
H H H
H H
b) Remember to draw the bond between the O atom and the H atom
in the OH group. This bond is frequently missed by candidates.
H H H H

H C C C C H
51

H O H H

H
 c) F H

C C C H

F Cl H
d) H H H H H

H C C C C C H

H O H H H

H
e) H H

H C C C C C C H
11 INTRODUCTION TO ORGANIC CHEMISTRY

H H H H H H
f) H H

H C C C C O H

H H H H
g)
H I
H I
C
H C C I

H C C C H
C

H H
H H
52
●● TEST YOURSELF 5 (PAGE 262)

TEST YOURSELF 5 (PAGE 262)

1 a) Isomers are molecules which have the same molecular formula but
a different structural formula.
b) H H H H H H
H C C C C C C H
H H H H H H
hexane

H H H H H
H C C C C C H
H H H H
H C H
H
2-methylpentane

H H H H H
H C C C C C H
H H H H
H C H
H
3-methylpentane

H
H C H
H H H
H C C C C H
H H H
H C H
H
2,3-dimethylbutane

H
H C H
H H H
53
H C C C C H
H H H
H C H
H
2,2-dimethylbutane

c) Chain isomerism
 2 a) Functional group isomerism
b) Positional isomerism
c) Chain isomerism

●● ACTIVITY (PAGE 259)

Preparation of limonene
1 C10H16
2 C5H8
3
H Cl
H C C Cl
H Cl
4 Limonene is non-polar, water is polar – like dissolves like – therefore
water will not dissolve limonene. No hydrogen bonds will form with
water.
or
Limonene and 1,1,1-triochloethane are both non-polar – they will
11 INTRODUCTION TO ORGANIC CHEMISTRY

dissolve in each other as like dissolves like.

5 The lower layer is 1,1,1-trichlorethane as its density is 1.3 g cm−3,
greater than that of water (1 g cm−3)
m
6 d = 1.2 cm3 = 0.8 × 1.2 = 0.96 g
v
0.96
× 100=0.8%
120.0
7 Some is lost in transfer, or in the distillation. It may not have been
distilled long enough to collect enough distillate or not enough
1,1,1-trichloroethane solvent may have been used.

●● PRACTICE QUESTIONS (PAGES 263–4)

1 B (1)
2 C (1)
3 a) i) A homologous series is a series of carbon compounds

which have:
54 same general formula;
a gradation in physical properties;
similar chemical properties;
same functional group.
Each member of a homologous series differs from subsequent
members by a –CH2 group. (1)
ii) A functional group is a group of atoms which are responsible
for the characteristic reactions of a molecule. (1)
 iii) A structural formula shows the arrangement of atoms in a
formula without showing the bonds. (1)

PRACTICE QUESTIONS (PAGES 263–4)

b) CH2O (1)
H O
H C C

H O H (1)
4 a) i) alcohol (1)
ii) aldehyde (1)
iii) ketone (1)
iv) alkene (1)
v) carboxylic acid (1)
vi) amine (1)
vii) nitrile (1)
b) i) propan-2-ol (1)
ii) propanal (1)
iii) butanone (1)
iv) pent-2-ene (1)
v) 3-methylbutanoic acid (1)
vi) ethylamine (1)
vii) propanenitrile (1)
5 a) i) A, E, H (1)
ii) I, G or B, F (1)
iii) C, G or C, I (1)
iv) B, D or A, H (1)
b) A – butan-2-ol
B – but-1-ene
C – 2-methylbutane
D – but-2-ene, however if you are familiar with E/Z isomerism
which is studied in the chapter on alkenes you will be able to 55
name this compound E-but-2-ene.
E – 2-methylpropan-2-ol
F – but-1-ene
G – pentane
H – butan-1-ol
I – pentane (3)
 12
Alkanes
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 265)
1 Molecules of methane are held together by van der Waals’ forces. These
are attractive forces which arise from an asymmetry in the electron
cloud of a molecule, which produces an instantaneous dipole. The
instantaneous dipole induces a dipole in a neighbouring molecule
which results in a small force of attraction.
2 a) Butane
b) H
H C H
H H
H C C C H
H H H

H H H H
H C C C C H
H H H H

●● TEST YOURSELF 2 (PAGE 267)

1 a) C14H30
b) It contains atoms of hydrogen and carbon only.
2 a) i) H H H H H

56
H C C C C C H

H H H H H
 ii) H

TEST YOURSELF 2 (PAGE 267)

H C H
H H
H C C C H
H H
H C H
H
iii) H H H H

H C C C C H

H H H H
b) i) The intermolecular forces between molecules of both butane
and pentane are van der Waals’ forces. Van der Waals’ forces
increase with increasing Mr. Pentane has a higher Mr than
butane and therefore a higher degree of van der Waals’ forces
ii) The intermolecular forces between molecules of both pentane
and 2,2-dimethylpropane are van der Waal’s forces. Pentane
and 2,2-dimethylpropane are structural isomers therefore
the relative molecular mass of both the molecules is the
same. However, the branched molecule will not be able to
approach as closely as the straight chain molecule therefore
the force of attraction due to van der Waal’s forces between
2,2-dimethylpropane will be less than the force of attraction
between molecules of pentane.
3 A homologous series is a series of carbon-based compounds which
have the same general formula and functional group. They have similar
chemical properties and show a gradation in physical properties with
successive members differing by a CH2 group. Alkanes are an example
of a homologous series. All members of the series have the general
formula CnH2n+2 While they do not strictly have a functional group, all
alkanes are saturated hydrocarbons containing only C-C or C-H single
bonds. They all react with halogens in UV light to form the hydrogen
halide and a halogenoalkane. As the series is descended the physical
properties change slightly; the first four members of the alkanes are
gases at room temperature, C5–C17 liquids and the remaining members 57
are waxy solids with increasing melting points.
 ●● TEST YOURSELF 3 (PAGE 270)
1 a) i) Fractional distillation is the continual evaporation and
condensation of a mixture causing the components to separate
because of a difference in boiling point.
ii) Cracking is a process where a long chain hydrocarbon
molecule is broken into a shorter chain molecule which is in
greater demand because it is more useful.
b) Many of the components of the fractional distillation of crude oil
are not in high demand as they have few uses. These long chain
molecules are cracked into more useful molecules which are in
higher demand.
c) i) Thermal cracking requires a temperature of between 1000K
and 1200K and a pressure of 70 atm for a period of 1 second.
ii) These conditions are extreme and could result in the complete
decomposition of the long chain hydrocarbon. By applying
these conditions for a short space of time the molecule is
broken into shorter chains and not into individual atoms.
iii) The product mixture of the thermal cracking process is rich in
alkenes and short chain alkanes
d) C10H22 → C6H14 + 2C2H4

●● TEST YOURSELF 4 (PAGE 273)

1 a) i) C8H18 + 1212O2 → 8CO2 + 9H2O
ii) C8H18 + 812O2 → 8CO + 9H2O
iii) C8H18 + 412O2 → 8C + 9H2O
b) C8H18 + 1012O2 → 4CO2 + 4CO + 9H2O
2 a) Carbon monoxide is a toxic gas which can lead to death but it is
colourless and odourless and cannot be detected by human senses.
12 ALKANES

b) The gas fired burner must be serviced regularly (once a year) to

certify that it always has a sufficient supply of air to ensure no CO
is produced as part of the combustion process. The exhaust flue
must be clear and all gases produced as part of the combustion
process are exhausted into the open environment.

3 Nitrogen oxides can only be produced in extremely high temperature

environments.
58
4 C6H12S2 + 11O2 → 6CO2 + 6H2O + 2SO2
5 The alkanes found in vehicle exhaust emissions are unburnt fuel
molecules.
●● TEST YOURSELF 5 (PAGE 276)

ACTIVITY (PAGES 276–7)

1 a) A catalytic convertor reduces the amount of carbon monoxide,
nitrogen oxides and unburnt hydrocarbons released into the air from an
internal combustion engine by converting them into less toxic gases.
b) i) 2NO(g) + 2CO(g) → 2CO2(g) + N2(g)
ii) 2NO2(g) + 4CO(g) → 4CO2(g) + N2(g)
iii) 2NO(g) + 2CO(g) → 2CO2(g) + N2(g)
iv) C5H12(g) + 16NO → 5CO2(g) + 4N2(g) + 6H2O(g)
c) The catalyst material is expensive. The honeycomb shape gives
the catalyst the maximum surface area thus maximising the rate of
reaction for the minimum amount of catalyst.
d) A thin layer of the catalyst is used. It is coated onto a ceramic
material which is in a honeycomb shape increasing the surface area
and ensuring efficient reaction.

●● ACTIVITY (PAGES 276–7)

Burning petrol in car engines
1 2,5-dimethylhexane
2 C8H18
3 Octane;
H H H H H H H H

H C C C C C C C C H

H H H H H H H H
4 2C8H18 + 25O2 → 16CO2 + 18H2O
5 Insufficient oxygen and the temperature is too low to burn all the
carbon – the smoke is particles of carbon
6 Green house effect/global warming/acid rain/smog
7 The straight chain has a higher boiling point. Branching the chain
makes the molecule more compact and decrease the surface area over
which intermolecular forces can act, hence the intermolecular forces
are smaller and so the boiling point of a branched molecule is less. 59

8 Carbon dioxide and nitrogen

9 It provides an alternative pathway with lower activation energy.
1.6
10 Moles = = 0.067
24.0
ratio – 4 moles NO :1 mole oxygen
0.068 : 0.017
0.017 × 24 = 0.4 dm3
 ●● PRACTICE QUESTIONS (PAGES 277–8)
1 B (1)
2 a) CnH2n+2 (1)
b) C6H14 (1)
c) Any two from: (4)
H

H C H
H H H H

H C C C C C H 2-methylpentane

H H H H H
H

H C H
H H H H

H C C C C C H 3-methylpentane

H H H H H
H

H C H
H H H

H C C C C H 2,2-dimethylbutane
12 ALKANES

H H H
H C H

H
60
H C H
H H H

H C C C C H 2,3-dimethylbutane

H H H
H C H

H
 3 a) Cracking is a process where a long chain hydrocarbon molecule is
broken into a shorter chain molecule which is in greater demand

PRACTICE QUESTIONS (PAGES 277–8)

because it is more useful. (1)
b) i) Thermal cracking (1)
ii) Thermal cracking requires a temperature of between 1000 K
and 1200 K and a pressure of 70 atm for a time of 1 second. (2)
c) Many of the components of the fractional distillation of crude oil
are not in high demand as they have few uses. These long chain
molecules are cracked into more useful molecules which are in
higher demand. (1)
4 a) The top of the column is the coolest part of the column. Shorter
chain hydrocarbons have lower boiling points than longer chain
hydrocarbons and therefore condense at lower temperatures. (2)
b) i) The process referred to in this question is catalytic cracking.
The additional conditions are: temperatures between 800K
and 1000K at a pressure between 1 and 2 atm for 2–4 seconds. (2)
ii) A zeolite has a honeycomb structure which gives it a large
surface area which further increases the rate of the reaction. (2)
5 a) C8H18 + 6½O2 → 4CO + 4C + 9H2O (1)
b) Carbon monoxide is a cumulative poison. When in the blood
stream it irreversibly reacts with the haemoglobin in the blood to
form carboxyhaemoglobin which cannot transport oxygen to body
cells for respiration. Small amounts can lead to head aches,
increasing amounts produce nausea and lack of energy, excessive
amounts of carbon monoxide in the blood stream can be fatal. (1)
c) i) 2NO(g) + 2CO(g) → 2CO2(g) + N2(g) (1)
ii) Platinium or rhodium (1)
iii) The honeycomb shape has a large surface area which increases
the rate of the reaction. The thin coating does indeed cost less
but a thin layer also conserves resources of rare metals. (1)
6 a) Any two from: a homologous series is a series of carbon-based
compounds which have the same general formula and functional
group; they have similar chemical properties and show a gradation
in physical properties; successive members differ by a CH2 group. (2)
b) i) The boiling points increase as the chain length increases.
The only intermolecular forces present between molecules of
alkanes are van der Waals’ forces. Van der Waals’ forces 61
increase with increase in relative molecular mass. (2)
ii) Fractional distillation (1)
c) i) Sulfur dioxide (1)
ii) Neutralisation (1)
d) i) C13H28 (1)
ii) Thermal cracking as the product mixture is rich in alkenes
and shorter chain alkanes. (1)
 13 Halogenoalkanes
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 279)
1 a) i) A saturated carbon compound is one which contains only
single bonds between the atoms in their molecules.
ii) A hydrocarbon is a molecule which contains only carbon and
hydrogen atoms.
iii) A homologous series is a series of compounds which have the
same general formula and the same functional group. They
show a gradation in physical properties and display similar
chemical properties and, in organic chemistry, each successive
member differs from the next by a –CH2group.
2 a) C7H16.
b) There are nine isomers with the molecular formula C7H16 (If you
have studied some optical isomerism, there are eleven isomers
counting all the enantiomers ) All of the isomers are chain isomers.
3 C6H14 + 9.5O2 → 6CO2 + 7H2O

●● TEST YOURSELF 2 (PAGE 281)

1 a) Cl H

Cl C C H

Cl H
b) H Br Br H

H C C C C H
62

H H H H
c) H Cl F

H C C C H

H H H
 2 H H H H

TEST YOURSELF 4 (PAGE 290)

H C C Cδ+ C H
H H Br H
3 The carbon-bromine bond is polar as there is a difference in
electronegativity between the two atoms. The carbon-chlorine bond is
more polar as the difference in electronegativity between the carbon
and chlorine atoms is larger than the difference in electronegativity
between the carbon and bromine atoms.
4 a) 1,3-dibromopropane
b) 3-chloro-2-iodopentane
c) 1,1dichloro-1-fluorobutane
d) 1,3-dibromo-3-methylbutane
5 a) C2H5Br
b) C2H5Br
c) CH3CH2CH2CH2Br

●● TEST YOURSELF 3 (PAGE 284)

1 a) free radical substitution
b) i) Cl2 → Cl● + Cl●
ii) Cl● + C2H6 → ●CH2CH3 + HCl
●CH CH
2 3 + Cl2 → Cl● +CH2ClCH3
iii) ●CH2CH3 + Cl● → CH2ClCH3
●CH CH
2 3 + ●CH2CH3 → CH3CH2CH2CH3
c) There are several different tri-substituted halogenoalkanes you can
draw. Ensure you have either two or four carbons in the molecule
each with three chlorine atoms. You can place a maximum of three
chlorine atoms on the end carbons and two on the carbons in the
chain.

●● TEST YOURSELF 4 (PAGE 290)

1 a) A mechanism is a detailed step-by-step sequence illustrating how
an overall reaction occurs. 63

b) A curly arrow shows the movement of a pair of electrons. It must

begin at a lone pair of electrons or in the centre of a covalent bond
and end at an atom or in the centre of a bond.
c) A nucleophile is an electron pair donor.
d) A base is a proton acceptor.
 2 a) H H H H H H H H
H C C Cδ+ C H H C C C C H + Br–
H H Brδ– H H H OH H
–
OH
b) reagent: sodium hydroxide
reaction conditions: aqueous
dissolve halogenoalkane in the minimum volume of ethanol
reflux gently
c) nucleophilic substitution
d) CH3CH2CHBrCH3 + NaOH → CH3CH2CH(OH)CH3 + NaBr
3 a) The halogenoalkane is dissolved in a minimum volume of ethanol.
The halogenoalkane-ethanol solution will mix with an aqueous
solution.
b) H H H H H H H H
H C C Cδ+ C H H C C C C H + Br–
H H Brδ– H H H C H
–
C N N
c) 2-methylbutanenitrile
d) CH3CHBrCH2CH3 + KCN → CH3CH2CHCNCH2CH3 + KBr
4 a) 2NH3 + CH3CHClCH3 → CH3CH(CH3)NH2 + NH4Cl
13 HALOGENOALKANES

b) 1-methylethylamine
c) The second molecule of ammonia accepts a proton from the
positively charged reactive intermediate.
d) Excess ammonia in a sealed tube under pressure.
e) The organic product is also a nucleophile and can react with the
2-chloropropane producing further substituted amines.

●● REQUIRED PRACTICAL (PAGES 290–1)

Preparation of 1-bromobutane
64 1 C4H9OH + HBr → C4H9Br + H2O
2 a) H2SO4 + NaBr → NaHSO4 + HBr
b) Sulfuric acid is reduced by the bromide ion
3 The reaction is exothermic, so this controls the reaction and prevents
violent spitting.
4 Anti-bumping granules
5 Add a still head, add a thermometer, move condenser from upright to
sideways position, put receiver on end of condenser.
 6 a) Shake in a separating funnel, invert and release the pressure,
remove the stopper and run off the layer.

ACTIVITY (PAGE 293)

b) Sulfuric acid
7 water
8 Moles of butanol = 21.8/74.0 = 0.29
Moles of sodium bromide = 40/102.9 (excess) = 0.39
Moles 1-bromobutane = 0.29 = mass/136.9; mass = 40 g
% yield = actual yield/theoretical yield = (3.55/40) × 100 = 8.9%
9 Practical – loss during transfer, loss during distillation.
Theoretical – side reactions produce a different product, reaction does
not go to completion

●● ACTIVITY (PAGE 293)

Preparation of methylpropene gas
1 H

H C H
H

H C C Cl

H
H C H

H
2 It cannot form hydrogen bonds with water
3 a) C4H9Cl + KOH → C4H8 + KCl + H2O
b) elimination
4 The volume of gas in the apparatus is less as it cools down, and water is
sucked back due to pressure differences.
Remove the delivery tube from the water after heating, or disconnect
the delivery tube 65

5 Density = mass/volume; 0.8 = mass/2; mass = 1.6 g

1.6
Moles = = 0.0173
92.5
Moles of methylpropene = 0.0173 (1 : 1 Ratio)
Volume methylpropene = 24 × 0.0173 = 0.415 dm3
6 a) C4H9Cl + NaOH → C4H9OH + NaCl
b) nucleophilic substitution.
 ●● PRACTICE QUESTIONS (PAGES 294–6)
1 a) ultraviolet light (1)
b) hydrogen chloride (1)
c) Initiation: Cl2 → Cl● + Cl●
Propagation: Cl● + CH4 → ●CH3 + HCl
●CH
3 + Cl2 → Cl● + CH3Cl
Termination: Cl● + ●CH3 → CH3Cl
●CH
3 +●CH3 → CH3CH3 (4)
d) free radical substitution reaction (1)
2 a) A nucleophile is an electron pair donor. (1)
b) i) CH3CH2Br + KOH → CH3CH2OH + KBr (1)
ii) CH3CH2Br + KCN → CH3CH2CN + KBr (1)
c)
H H
(1)

H C C C N
H H
d) Reacting a halogenoalkane with an aqueous solution of potassium
cyanide produces an organic product which has one more carbon
in the chain. This nitrile can be easily converted to other functional
groups. (1)
3
13 HALOGENOALKANES

Product Reagent Conditions Starting halogenoalkane

pent-2-ene KOH Dissolve reactants and reagents in ethanol 2-bromopentane(2)

propanenitrile KCN Dissolve reagent in water; dissolve halogenoalkane in a bromoethane(2)

minimum volume of ethanol; reflux gently
propan-2-ol NaOH Dissolve reagent in water; dissolve halogenoalkane in a 2-bromopropane(2)
minimum volume of ethanol; reflux gently
methylamine ammonia Reagent in excess; in a sealed tube under pressure bromomethane(2)

diethylamine ammonia Reagent and halogenoalkane in 1:1 ratio or halogenoalkane bromoethane(2)

66 in excess in a sealed tube under pressure

4 a) Br2 → Br● + Br●

Br● + C2H6 → ●CH2CH3 + HBr
●CH CH
2 3 + Br2 → Br● + CH2BrCH3
●CH CH
2 3 + Br● → CH2BrCH3 (4)
b) 1,1-dibromoethane and 1,2-dibromoethane (2)
c) ●CH CH
2 3 + ●CH2CH3 → CH3CH2CH2CH3 (1)
 1
5 2 2 Cl2 + C3H8 → CHCl2CHClCHCl2 (3)

PRACTICE QUESTIONS (PAGES 294–6)

6 a) (4)
propan-1-ol propene
H H
H H H
H C
H C C C O H C C H
H H H H H
b) Propan-1-ol is formed by a nucleophilic substitution mechanism
which is more probable when the potassium hydroxide is dissolved
in water and the halogenoalkane is dissolved in a minimum volume
of ethanol and the mixture refluxed gently. The alkene is formed by
an elimination reaction and is more probable when the reagent and
halogenoalkane are dissolved in ethanol and no water is present. (2)
7 a) i) Cl2 → ●Cl + ●Cl (1)
ii) CHCl3 + ●Cl → ●CCl3 + HCl
●CCl
3 + Cl2 → CCl4 (1)
iii) ●CCl3 + ●Cl → CCl4 (1)
b) Did you realise that this overall reaction was not for the reaction
you wrote the mechanism for in part a?
CH2Cl2 + 2Cl2 → CCl4 + 2HCl (1)
c) i) Tetrachloromethane is inert in the atmosphere at the surface
of the earth but it escapes into the stratosphere where it forms
chlorine free radicals. The chlorine free radicals react with
the ozone in the stratosphere in a free radical chain reaction
decomposing the ozone into oxygen. The ozone in the
stratosphere is essential as it absorbs wavelengths of ultraviolet
radiation from the sun that other gases do not absorb. These
wavelengths can cause skin cancer and damage plant tissue
and reduce plankton population in the oceans.
One chlorine free radical can decompose 100,000 molecules of
ozone.
●Cl + O3 → ClO● + O2
ClO● + O3 → ●Cl + 2O2
Overall
2O3 → 3O2 (3) 67
ii) Tetrachloromethane can also be used as a refrigerant or
a fire extinguisher. (2)
d) i) (1)
F H
F C C H

F F
 ii) Hydrofluorocarbons are also non-toxic with similar chemical
and physical properties to CFC’s but they do not harm the
ozone layer to the same extent as the compounds they replace.
(They do however contribute to another environmental problem,
Global Warming. Therefore the search goes on to find yet more
suitable refrigerants, solvents.) (1)
8 a) A nucleophile is an electron pair donor. (1)
b) Compound 1: propanenitrile (1)
Compound 2: ethanol (1)
Compound 3: ethylamine (1)
c) i) cyanide ions ( the reagent is potassium cyanide) (1)
ii) ammonia (1)
H H
d) i) (2)H H
H C Cδ+ Brδ– H C C O H + Br
–

H H H H
–
OH
H H
ii) (2)H H
H C Cδ+ Brδ– H C C C N + Br–
H H H H
–
CH
e) Reagent: sodium hydroxide
13 HALOGENOALKANES

Reaction conditions: dissolve the sodium hydroxide in water and

dissolve the bromoethane in a minimum volume of ethanol and
reflux gently. (1)
f) Compound 3 is a primary amine. A primary amine is favoured
by an excess of ammonia in an attempt to prevent the formation
of further substituted amines as the amines formed are also
nucleophiles and will react with the bromoethane. If the ammonia
is in excess there is a greater probability of the ammonia reacting
with the bromoethane rather than the substituted amines. (1)

g) i) Reagent: potassium hydroxide (1)

68 Reaction conditions: dissolve both reagent and bromoethane

in ethanol, no water present (1)
ii) elimination (1)
9 B
10 D
 14
Alkenes
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 297)
1 a) H H H H

H C C C C Br

H H H H
b) The source of the hydroxide ions is potassium hydroxide as it is
more soluble in ethanol than sodium hydroxide. The reagent and
the halogenoalkane are dissolved in ethanol.
c)
H H H H H H H
_
δ+ δ_
H C C C C Br H C C C C +H2O+ Br
H
H H H H H H H
–
OH
d) Butan-1-ol may be produced as elimination and nucleophilic
substitution reactions can occur but the elimination will be more
probable in ethanolic conditions.

●● TEST YOURSELF 2 (PAGE 301)

1 a) H H
H C
C C H
H H
69
b) H H H
H C C C C
H H Cl H
 c) H H H H
H C C C C C C H
H H H H
H C H
H C H
H
H
d)

2 a)
Structural isomers
H H H H H
C C C C H H C C C C H
H H H H H H H H
but-1-ene positional isomers but-2-ene

H
H C H
H H
C C C H
H H
2-methylprop-1-ene-a chain isomer

Steroisomers
H H H H
14 ALKENES

C H H C C H
H C C H C C
H C H H H H
H H
E-but-2-ene Z-but-2-ene

b) E-Z isomerism is a feature of the alkenes as they contain a

70 double bond and rotation is restricted about a double bond.
Halogenoalkanes do not contain a double so rotation is not
restricted.
3 a) The higher priority groups in this molecule are on the same side
of the plane of the double bond. Each carbon atom in the double
bond is considered separately.
On the left hand side the carbon is bonded directly to a carbon
atom above and below. These carbon atoms are each bonded
directly to a further carbon atom. At the top this carbon atom is
 bonded to a carbon and two hydrogens while at the bottom the
carbon is bonded to three hydrogen atoms. The top group is the

TEST YOURSELF 4 (PAGE 312)

higher priority group. Using the same reasoning the top group
on the right-hand side is the higher priority group. As the higher
priority groups are on the same side of the plane of the C=C the
molecule is classified as a Z isomer.
b) Z-4-ethyl-3-methylhept-3-ene

●● TEST YOURSELF 3 (PAGE 306)

1 a) poly(chloroethene)
b) poly(tetrafluroroethene)
2 drainpipes/window or door frames/clothing/electrical insulation for
wiring
3 a) H H
C C
H H
b) CH3H
C C
H H (CH3 in any position)

c) Cl H
C C
Cl H (Cl on same C atom)

●● TEST YOURSELF 4 (PAGE 312)

1 a) i) An electrophile is an electron pair acceptor.
ii) A nucleophile is an electron pair donor.
iii) Heterolytic fission is the breaking of a bond into two
differently charged fragments.
iv) Homolytic fission is the breaking of a bond into two free
radicals.
71
b) i) Br2 → Br− + Br+
ii) Br2 → ●Br + ●Br
 2 a) H H
H H
_
C C H C C H + Br
+
H H H
δ+ δ_
H Br

H H
H C C H
H Br
b) CH2CH2 + HBr → CH3CH2Br
c) bromoethane
d) electrophilic addition
e) carbocation
3 a) Bromine will react with ethene in the dark at room temperature in
an electrophilic addition reaction to produce 1,2-dibromoethane
and no other product. The bromine molecule is polarised when
it is in the proximity of the C=C of the alkene and undergoes
heterolytic fission to produce a bromide ion which adds to a
reactive carbocation intermediate.
Bromine will react with ethane in the presence of ultraviolet light
to form a mixture of brominated alkanes which may have one or
more bromine atoms, up to a maximum of six. Butane is also found
in the product mixture. Hydrogen bromide gas is also produced.
The reaction is a free radical substitution reaction. It is a chain
reaction which happens in three steps: initiation, propagation and
termination. In the initiation step UV light supplies the activation
energy to break the Br–Br bond homolytically to form two bromine
radicals, each with an unpaired electron.
14 ALKENES

b) i) Br2 + CH4 → HBr + CH3Br

There are various other equations which you can write
depending on the product as a mixture of brominated alkanes
are formed.
2Br2 + CH4 → 2HBr + CH2Br2

3Br2 + CH4 → 3HBr + CHBr3

72
4Br2 + CH4 → 4HBr + CBr4
ii) Br2 + CH3CHCHCH2CH3 → CH3CHBrCHBrCH2CH3
c) Add the organic compound to bromine water. The yellow-orange
bromine water will become colourless if the organic compound
contains a double bond.
●● TEST YOURSELF 5 (PAGE 315)

TEST YOURSELF 5 (PAGE 315)

1 a) i) A carbocation is a positive ion where the positive charge
centres on a carbon atom in the molecule.
ii) Carbocations can be classified according to the position of
the positively charged carbon in the molecule. A secondary
carbocation is one where the positively charged carbon atom is
along the carbon chain or is attached to two R groups.
b) Tertiary carbocations are more stable than secondary carbocations
which are more stable than primary carbocations due to the
positive inductive effect of the alkyl groups attached to the
positively charged carbon. Alkyl groups donate electron density
towards the C+ reducing the value of the positive charge and
stabilising the carbocation. Tertiary carbocations have three alkyl
groups attached while secondary carbocations have two and
primary carbocations have one or no alkyl group attached.
2 a) i) H H H H
H C C C C C C H
H H H H H H
ii)
H H H H H H
H C C H H C C C C H
H H C C H H H H H H
C C
H C C H
H H H H
E-hex-3-ene but-2-ene

b) Hex-2-ene is an asymmetrical alkene; E and Z hex-3-ene are

symmetrical alkenes.

73
 c)
H3CH2C CH2CH3
C C
H H
+ _
Hδ Brδ

H3CCH2 CH2CH3 H3CCH2 CH2CH3

H C C H H C C H
+ +
H H
_ _
Br Br
CH3CH2CH2CHBrCH2CH3 CH3CH2CHδCH2CH2CH3
3-bromohexane 3-bromohexane

d) H H H H
H C C C C C C H
H H H H H H
δ+ _
H Brδ

H H H H H H H H H H H H
H C C C C C C H H C C C C C C H
+ +
H H H H H H H H H H
_ _
Br Br
14 ALKENES

CH3CH2CHBrCH2CH2CH3 CH3CHBrCH2CH2CH2CH3
3-bromohexane 2-bromohexane

●● ACTIVITY (PAGES 301–2)

74
Making ethene
1 fractional distillation
2 The breaking up of large molecules into smaller ones using heat.
3 C10 H20 → C2H4 + C8H16
4 CH3–CH2–OH conc H2SO4 CH2=CH2 + H2O
5 The first portion of the gas evolved is displaced air from the apparatus.
6 As the gas cools it contracts and this would cause the solution in the
wash bottle to suck back. Sodium hydroxide and concentrated sulfuric
acid would be a dangerous violent reaction.
●● PRACTICE QUESTIONS (PAGE 316)

PRACTICE QUESTIONS (PAGE 316)

1 a) i)CH F (1)
3

C C
CH3CH3
2-fluoro-3-methylbut-2-ene (1)
ii) addition (1)
b) H CH2Cl (1)

C C
H Cl
2 This is a Z isomer as the higher priority groups are on the same side
of the plane of the double bond. If you did not get this question correct
look at how you assigned the priority of the groups. Remember you
must do each atom at a time. You cannot just add up the total Mr of
the groups attached. (1)
3 a) An electrophile is an electron pair acceptor. (1)
b) i) HBr, HCN (1)
ii) Br2 (1)
c) i) _
(3)
C C C C + X
+

δ+ _
H Xδ

C C
X
ii) electrophilic addition (1)

75
 4 a) Add the organic compound to bromine water. The orange bromine
water will become colourless if the organic compound contains a
double bond. (2)
b) _
(3)
C C C C + Br
+
Br
δ+ δ_
Br Br

C C
Br Br
5 a) i) B (1)
ii) The bromine molecule adds across the double bond. The
bromine atoms do not add to the same carbon atom. (1)
b) electrophilic addition (1)
6 a) H H H H H H (3)

H C C C H C C C H+
+
H H H H
δ+ δ– –
H O O O O
S S
H O O H O O

H H H
H C C C H
14 ALKENES

H H
O O
S
H O O

b) carbocation (1)
76 electrophilic addition (1)
c) Hydrolysis is the decomposition of a chemical compound by
reaction with water. (1)
d) Propan-1-ol is formed from 1-propyl hydrogensulfate. This is
formed from a primary carbocation which is not as stable as the
secondary carbocation which leads to the formation of 2-propyl
hydrogensulfate. The more stable carbocation remains in the
reaction mixture longer so there is a greater probability of it
remaining long enough to react. (2)
 7 a) Bromine will react with ethene in the dark at room temperature in
an electrophilic addition reaction to produce 1,2-dibromoethane

PRACTICE QUESTIONS (PAGE 316)

and no other product. The bromine molecule is polarised when
it is in the proximity of the C=C of the alkene and undergoes
heterolytic fission to produce a bromide ion which adds to a
reactive carbocation intermediate.
Bromine will react with ethane in the presence of ultraviolet light to
form a mixture of brominated alkanes which may have one or more
bromine atoms, up to a maximum of six. Butane is also found in
the product mixture. Hydrogen bromide gas is also produced. The
reaction is a free radical substitution reaction. It is a chain reaction
which happens in three steps: initiation, propagation and
termination. In the initiation step, UV light supplies the activation
energy to break the Br-Br bond homolytically to form two bromine
radicals, each with an unpaired electron. (4)
b) The product is 1,2-dibromoethane as the bromine molecule adds
across the double bond in an electrophilic addition mechanism.
Both the bromine atoms do not add to the same carbon atom. (1)
8 A (1)
9 B (1)

77
 15
Alcohols
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 317)
1 The boiling point of the Group IV hydrides increases from H2S to H2Te.
The only intermolecular force between the molecules in these three
compounds is van der Waals’ forces. As the Mr increases the force of
attraction between the molecules due to van der Waals’ forces increases
thus increasing the boiling point. If water were to fit into this pattern
it would have a boiling point of approximately −100 °C as it has the
lowest Mr of the group. However, hydrogen bonding is also present
between water molecules. Hydrogen bonds are much stronger forces of
attraction than van der Waals’ forces and more energy must be supplied
to overcome these attractive forces increasing the boiling point.
Hydrogen bonds in water arise because hydrogen atoms are directly
bonded to oxygen which is a much more electronegative atom. The
oxygen takes the greater share of electron density in the bond leaving
the hydrogen atom δ+ and the oxygen atom δ−. The δ+ hydrogen
atom accepts a lone pair of electrons from an oxygen atom of another
molecule forming what is known as a hydrogen bond.
2 a) 2-bromo-2-methylpropane
b) Reagent: potassium hydroxide
Conditions: dissolve the halogenoalkane and the reagent in ethanol
Mechanism: elimination
H CH3 H H CH3 H
H C Cδ+ C H C C C H
H Br Hδ_ H H
_ _
OH + H2O + Br
c) alcohol
78
d) Temperature, 600 oC; pressure, 60 atm
3 a) Fe2+ → Fe3+ + e−
b) MnO4− + 8H+ + 5e− → Mn2+ + 4H2O
c) Cr2O72− + 14H+ + 6e− → 2Cr3+ + 7H2O
●● TEST YOURSELF 2 (PAGES 319–20)

TEST YOURSELF 2 (PAGES 319–20)

1 a) ethanol, primary alcohol
b) 3-methyl-pentan-3-ol, tertiary alcohol
c) 2-methyl-propan-1-ol, primary alcohol
d) pentan-2-ol, secondary alcohol
2 H H H H H

H C C C C C O H

H H H H H
pentan-1-ol
primary alcohol

H H H H H

H C C C C C H

H H O H H

H
pentan-3-ol
secondary alcohol

H
H H H C H H

H C C C C H

H H O H

H
2-methyl-butan-2-ol
tertiary alcohol
79
3 a) heptan-1-ol, CH3CH2CH2CH2CH2CH2CH2OH
octane, CH3CH2CH2CH2CH2CH2CH2CH3
b) Octane and heptan-1-ol have similar Mr so the intermolecular
attractions due to van der Waals’ forces will be similar but heptan-
1-ol also has hydrogen bonding between the molecules. This is an
additional and stronger intermolecular force therefore more energy
must be supplied to overcome these forces and the boiling point
increases.
 4 a) Ethanol is soluble in water due to the polar OH group at the end
of the short hydrocarbon chain which hydrogen bonds with water.
Most polar molecules are soluble in water.
b) Hexan-1-ol is much less soluble in water than ethanol as it has a
longer hydrocarbon chain which dominates the physical properties
of the molecule.

●● TEST YOURSELF 3 (PAGE 322)

1 a) A: pentan-3-one, (CH3CH2)2CO
B: butanal, CH3CH2CH2CHO
C: hexanoic acid, CH3CH2CH2CH2CH2COOH
b) Cr2O72− + 14H+ + 6e− → 2Cr3+ + 7H2O
2 Without refluxing, the alcohol will evaporate before the reaction has
taken place. Refluxing continually returns the alcohol to the reaction
flask allowing it to react.

●● TEST YOURSELF 4 (PAGE 328)

1 a) Name of reagent observation with

propanal hexan-2-one

Fehling’s solution orange-red precipitate solution remains blue

forms

b) Fehling’s solution is freshly prepared in the laboratory. It is made

initially as two separate solutions which are added together
immediately before use.
c) Cu2+ + e− → Cu+
15 ALCOHOLS

d) Tollens’ reagent can be used to distinguish between an aldehyde

and a ketone. It is a colourless solution of silver(I) ions, which
when warmed gently (using a water bath) with an aldehyde are
reduced to silver atoms, leaving a silver mirror on the interior of
the reaction vessel. When Tollens’ reagent is warmed gently in the
presence of a ketone the solution remains colourless.

2 H H H H H H H
80 H C C C C C H C C C C C H
H H H H H H H H H H
pent-1-ene pent-2-ene

3 a) aluminium oxide or concentrated sulfuric acid

b) When using aluminium oxide the reaction should be carried out at
a temperature of 600 °C. When using concentrated sulfuric acid as
the catalyst the reaction should be carried out at a temperature of
170 °C.
●● TEST YOURSELF 5 (PAGE 330)

1 a) A catalyst is a substance that increases the rate of a chemical
reaction and remains chemically unchanged at the end of the

PRACTICE QUESTIONS (PAGES 333–4)

reaction. It decreases the activation energy for the reaction by
providing an alternative pathway or mechanism for the reaction.
b) Hydration is the addition of water to a compound. (This is
sometimes confused with hydrolysis which is the decomposition
of a compound by reaction with water)
c) CH3CHCH2 + H2O → CH3CH(OH)CH3
d) propan-2-ol

●● ACTIVITY (PAGES 322–3)

Preparation of ethanal
1 density = mass/volume
0.79 × 6 = 4.74 g
2 Sodium dichromate is orange, if it was not in excess it would be green.
3 a) ethanoic acid
b) The ethanal is distilled off as soon as it is formed preventing
further reaction.
4 Ethanal has a low boiling point
5 Fractional distillation
6 Cr2O72− + 14H+ + 6e− → 2Cr3+ + 7H2O
7 Moles = 4.74/46.0 = 0.103
0.103 × 44.0 = 4.53 g
1.32
× 100 = 29.1%
4.53
8 Ethanol and ethanal can hydrogen bond with water; they dissolve.
Ethanol and ethanal boil.

●● PRACTICE QUESTIONS (PAGES 333–4)

1 a) primary alcohols (1)
H H
b) H O H H H O
(2)
81
H C C C C H C C C C
H H H H H H H OH
butanal butanoic acid

c) i) CH3CH2CH2CH2OH → CH3CH2CH=CH2 + H2O (2)

ii) concentrated sulfuric acid (1)
 2 a) pentan-2-one (1)
b) functional group isomerism (1)
c) H OH (1)
H3C C
C C CH3
H H
d) This isomer has a C=C .There is restricted rotation about a C=C. (1)
e) You can describe two tests here either the test with Fehling’s
solution or the test with Tollens’ reagent.
Add Fehling’s solution to a sample of the compound and warm.
Isomer 2 will react and form an orange-red precipitate. Fehling’s
solution remains colourless in the presence of isomer 3.
Add Tollens’ reagent to a sample of the compound and warm.
Isomer 2 will react and form a precipitate of silver on the sides of the
reaction vessel, a silver mirror. Tollens’ reagent remains colourless
in the presence of isomer 3. (3)
3 a) electrophilic addition (3)

H H H H –
O O
C C H C C H + S
+
H H H H O O
δ+ δ–
H O O
S
H O O

H H
15 ALCOHOLS

H C C H
H
O O
S

H O O
82
b) ethanol  (1)
c) catalyst  (1)
d) Step 1: Add hydrogen bromide to ethene to form bromoethane.
This is an electrophilic addition reaction.
Step 2: Dissolve bromoethane in a minimum volume of ethanol.
Dissolve sodium hydroxide in water. Add and reflux gently.
This is a nucleophilic substitution reaction forming ethanol. (6)
 4 a) CH OH
(1)
2
COOH

+4[O] +2H2O
CH2OH COOH

PRACTICE QUESTIONS (PAGES 333–4)

H
b) O (1)
C

C
H O
c) Reaction 1: electrophilic addition
Reaction 2: nucleophilic substitution (2)
5 a) structural formula: CH3C(CH3)CHCH2CH2C(CH3)CHCH2OH (1)
molecular formula: C10H18O (1)
b) C10H18O + 14O2 → 10CO2 + 9H2O (2)
c) Stereoisomers are molecules which have the same molecular and
structural formula but have a different arrangement of their
groups in a three-dimensional space. (1)
d) primary alcohol (The OH group is at the end of the chain.) (1)
e) Reagent: acidified potassium dichromate; primary alcohol in
excess; product distilled immediately. (3)
6 A
7 D
8 a) The forward reaction is exothermic. If the temperature is lowered the
system will move to oppose this change, to increase the temperature.
The position of equilibrium will shift to the right thus forming
more ethanol. (2)
b) At low temperatures the rate of reaction is slow and the time taken
to reach equilibrium is long, therefore a compromise temperature
is reached, i.e. one which gives an appreciable rate of reaction and
yield of ethanol. (1)
c) If water was used it would dilute the acid catalyst and it would no
longer be concentrated and would not function as a catalyst. (1)

83
 16 Organic analysis
●●TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 335)
1 a) Carbonyl C=O
b) You can describe two tests here either the test with Fehling’s
solution or the test with Tollens’ reagent.
Add Fehling’s solution to a sample. Warm. An aldehyde will react
and form an orange-red precipitate. Fehling’s solution remains
colourless in the presence of a ketone.
Add Tollens’ reagent to a sample. Warm. An aldehyde reacts from a
precipitate of silver on the sides of the reaction vessel, a silver mirror.
Tollens’ reagent remains colourless in the presence of a ketone.
c) CH3COCH2CH2CH3 one possible isomer is pentanal
CH3CH2CH2CH2CHO
2 a) Warm with acidified potassium dichromate(VI). The ethanol will
change colour from orange to green. The 2-methylpropan-2-ol is a
tertiary alcohol and the potassium dichromate(VI) remains orange.
b) Bubble into orange bromine water. The cyclohexene will change
colour to colourless and the cyclohexane remains colourless.
3 a) m/z
b) i) 92Zr+

ii) 94Zr+

●● TEST YOURSELF 2 (PAGE 339)

1 a) Abundance
b) 46
c) 46
d) The molecule has not fragmented, nor has the Mr. It has simply lost
84 an electron.
2 C

●● TEST YOURSELF 3 (PAGE 343)

1 a) Bonds vibrate.
b) The functional groups can be identified using characteristic bond
absorptions. The finger print region is unique to each compound
and can be compared to a database.
c) It does not absorb infared.
 2 a) i) Propanoic acid. C=O 1680–1750 and OH acid absorption at
2500–3000

PRACTICE QUESTIONS (PAGES 347–8)

ii) Butanol. OH alcohol absorption at 3230–3350
b) i) Wavenumber on x axis
ii) Transmittance on y axis
c) It changes in parts
3 a) X propanone; Y ethanoic acid; Z propan-2-ol
b) i) C-H
ii) OH present of COOH group
4 X: C=O
Y: OH  CH3CH2COOH

●● TEST YOURSELF 4 (PAGE 346)

1 a) C=C
b) E
2 a) Bromine water room temperature
It changes from orange to colourless in the propene
b) Sodium carbonate, room temperature
Bubbles with ethanoic acid
c) Acidified potassium dichromate, warm
Colour change orange to green with propan-2-ol
d) Fehling’s/Tollen’s, warm
Red ppt/silver mirror with propanal

●● REQUIRED PRACTICAL (PAGE 345)

a) Immiscible with water
C=C present
Not oxidisable, not a primary alcohol or aldehyde
b) Orange
c) C=C
85
d) OH

●● PRACTICE QUESTIONS (PAGES 347–8)

1 C A D B (4)
2 A (1)
3 a) 3230–3550 OH peak (1)
b) Compare fingerprint region to database (2)
 4 a) Cl2 + CHCl3 → CCl4 + HCl (1)
b) CHCl3 has a C–H bond
CCl4 has no C-H bond
The infrared spectrum shows that the peak for C–H in range
2850 to 3300 is missing (2)
5 a) More absorption and less transmittance of infrared radiation by
water vapour
OR
broader absorption by OH/less absorption of infrared radiation by
carbon dioxide (2)
b) Contains C=O expected absorption for C=O is missing.
The peak (for C=O) is shifted to 2300 (2)
6 D (1)
7 a) CH3CH2CHOHCH3 + [O] → CH3CH2COCH3 + H2O (1)
b) Secondary (1)
16 ORGANIC ANALYSIS

86
 Thermodynamics:
18
Born-Haber cycles
TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGES 363–4)
1 a) Mg(s) + 12O2(g) → MgO(s)
b) 12H2(g) + 12Cl2(g) → HCl(g)
2 a) C3H8(g) + 5O2 (g) → 3CO2(g) + 4H2O(l)
b) CH3OH(l) + 112O2(g) → CO(g) + 2H2O(l)
3 a) Hess’s Law states that the enthalpy change for a chemical reaction is
independent of the route taken and depends only on the initial and
final states.
b) C2H6(g) + 312O2(g) → 2CO2(g) + 3H2O(l)
c) ΔcH1 = −1561 kJ mol−1
4 ΔcH1 = −1248.4 kJ mol−1
5 ΔcH1 = 6472 − 8522 = −2050 kJ mol−1

TEST YOURSELF 2 (PAGE 371)

1 a) Ca2+(g) + 2Cl−(g) → CaCl2(s)
b) F2(g) → 2F(g)
c) O(g) + e− → O-(g)
d) Ag(s) + 12F2(g) → AgF(s)
e) K(g) → K+(g) + e−
2 a) Second ionisation energy of calcium
b) Enthalpy of atomisation of sodium
c) First electron affinity of chlorine
d) Enthalpy of formation of sodium fluoride
e) Enthalpy of lattice formation of magnesium chloride 87

3 a) The enthalpy change when one mole of a compound is formed from its
elements when all reactants and products are in their standard states
under standard conditions.
b) The enthalpy change when one mole of an ionic compound is formed
from its constituent ions in the gaseous state.
c) The enthalpy change when one mole of an ionic compound is
separated into its component gaseous ions.
 d) The enthalpy change for the formation of one mole of gaseous chlorine
atoms, Cl(g) from the element, 12Cl2(g).
e) The enthalpy changes when one mole of gaseous lithium atoms forms
one mole of gaseous Li+ ions.

TEST YOURSELF 3 (PAGE 379)

1 a) Enthalpy of formation of rubidium chloride
b) +676 kJ mol−1
2 a) The K+ ion is smaller than the Rb+ ion
The ions in KCl pack closer together so attraction between the ions is
stronger in KCl.
b) +431 kJ mol−1
3 a) F2(g) → 2F(g)
b) The enthalpy change for the formation of one mole of gaseous fluorine
atoms, F(g) from the element, 12F2(g)
c) −269 kJ

TEST YOURSELF 4 (PAGE 384)

18 Thermodynamics: Born-Haber cycles

1 Silver chloride has some covalent character.

The theoretical value is lower as it assumes that the bonding in the lattice
is purely ionic.
Additional covalent bonding increase the experimental lattice enthalpy.
2 ΔsolH1 = +31 kJ mol−1
3 Fluoride ions are smaller than chloride ions so have a higher charge density.
The smaller ions have a greater attraction on the δ+ of the water
molecules.

ACTIVITY (PAGES 383–4)

Experimental determination of the enthalpy of
solution of sodium hydroxide and ammonium nitrate
1 Place a weighing boat on a balance and zero. Add ammonium nitrate

with a spatula until the reading is around 2 g – approximate. Record the
88 reading to 2 decimal places (2.02 g) – accurate.
2 Safety glasses and gloves – sodium hydroxide is very corrosive – if it
comes in contact with skin, wash off with water immediately
3 Na+, OH−, NH4+, NO3−
4 5.1°C, 1.4 °C
5 d = m
v
0.998 = m
100
m = 99.8 g
 6 q = mcΔT

PRACTICE QUESTIONS (PAGES 385–387)

q = 99.8 × − 5.1 × 4.18 = −2127.5 J = −2.128 kJ
q = 99.8 × 1.4 × 4.18 = 584.0 J = +0.584 kJ
 7 moles NaOH= 3.99 = 0.09975
40.0
2.128/0.09995 mol = −21.19 kJ mol−1
2.02
moles NH4NO3 = = 0.02525
80.0
0.584 kJ/0.02526 mol = +23.12 kJ mol−1
 8 NaOH: (44.20 – 21.19) × 100 = 52.0% error
44.20
NH4NO3:(25.40 – 23.12) × 100 = 8.98% error
25.40
 9 Heat loss.
Lid on polystyrene cup, extra insulation.
10 Increase.

PRACTICE QUESTIONS (PAGES 385–387)

1 C (1)
2 D (1)
3 a)   i) Li (g) → Li+ (g) + e− (1)
ii) Li (s) + 1
F
2 2
(g) → LiF (s) (1)
iii) F (g) + e− → F− (g) (1)
 iv) Li+ (g) + F− (g) → LiF (s) (1)
b) ΔLH1 = +348 − 79 −520 − 159 + (−612) (1)
= −1022 kJ mol−1 (1)
4 a)

Step Name of enthalpy change ΔH 1  /kJ mol−1

A Enthalpy of lattice dissociation of sodium chloride to be calculated
B Enthalpy of formation of sodium chloride     (1) −411
C Enthalpy of atomisation of sodium         (1) +109
D First ionisation energy/enthalpy of sodium      (1) +494
E Enthalpy of atomisation of chlorine +121
F First electron affinity of chlorine        (1) −364
89
b) ΔLH1 = 411 + 109 + 494 + 121 −364 (1)
= +711 kJ mol−1 (1)
c) Sodium ion is smaller than potassium ion. (1)
Ions in sodium chloride pack closer together so attraction
between the ions is stronger in NaCl. (1)
 Mg2+ (g) + 2e– + 2Cl (g) 5 a) All labelled correctly (4); −1 for each error

+242
b) ΔfH1 = +150 + 736 + 1450 + 242 + 2(−364) −2492 (2)
2+ (g) 2(–364)
Mg + 2e– + Cl2 (g) = −642 kJ mol−1 (1)
Mg2+ (g) + 2Cl– (g) 6 a) Bromide ions are smaller than iodide ions so have
+1450 a higher charge density. (1)

Mg+ (g) + e– + Cl2 (g)

The smaller ions have a greater attraction of the δ+ of the
water molecules. (1)
+736
Mg (g) + Cl2 (g) –2492 b) ΔsolH1 = enthalpy of lattice dissociation + ΔhydH1 (K+)
+ ΔhydH1(I−)
+150
Mg (s) + Cl2 (g) + 20.5 = ΔLH1 − 320 − 293 (1)
  ΔLH1 = + 633.5 kJ mol−1 (1)
MgCl2 (s)
Enthalpy of lattice formation = −633.5 kJ mol−1 (1)
c) ΔsolH1 = enthalpy of lattice dissociation + ΔhydH1(Fe2+)
+ 2ΔH1hyd(Cl−) −47 = + 2631 − 1950 + 2ΔhydH1 (Cl−) (1)
2ΔhydH1 (Cl−) = −47 − 2631 + 1950 = −728 kJ (1)
ΔhydH1 (Cl−) = −364 kJ mol−1 (1)
d) i) Ions are regarded as point charges or perfect spheres. (1)
18 Thermodynamics: Born-Haber cycles

ii) Iron(ii) chloride has covalent character. (1)

Forces of attraction in the lattice are stronger than simply
pure ionic interactions. (1)
7 Arrow down to 2Al3+(g) + 3e− + 3O−(g) (1)
Then arrow up to 2Al3+(g) + 3O2−(g) (1)
Then arrow down (as formation given) to Al2O3(s) (1)
ΔfH1 = 2ΔaH1(Al) + 2(ΔIE1H1 + ΔIE2H1 + Δ IE3H1) + 3ΔaH1 (O) +
3ΔEA1H1 + 3ΔEA2H1 + ΔLH1
or similar calculation of the type
−1675.7 = 2(+324.3) + 2(580+1800+2700) + 3(249.2) + 3(−141)
+ 3x + (−15178.9) (2)
3x = 2370 (1)
x = +790 kJ mol−1 (1)

Second electron affinity is endothermic (1)

90
due to repulsion between the negative O- ions and negative electrons (1)
whereas first electron affinity is exothermic. (1)
 Thermodynamics:
19 Gibbs free energy
change, ΔG, and
entropy change, ΔS
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 388)
1 +177 kJ mol−1
2 –46 kJ mol−1
3 a) −908 kJ mol−1
b) Oxygen is an element in its standard state.

●● TEST YOURSELF 2 (PAGE 394)

1 a) Decrease
b) Increase
c) Decrease
d) Increase
2 a) +243 J K−1 mol−1
b) −345 J K−1 mol−1
c) +330 J K−1 mol−1

●● TEST YOURSELF 3 (PAGE 399)

1 a) A
b) A and B
2 a) +122 kJ mol−1
b) +33 J K-1 mol−1 91

c) 3697 K
3 a) −137 kJ mol−1
b) –121 J K−1 mol−1
c) 1132 K
4 a) +90.6 J K−1 mol−1
b) 331.1 K
 ●● TEST YOURSELF 4 (PAGE 402)
1 −ΔS
2 Intercept on ΔG (y) axis
3 a) +80 kJ mol−1
b) Increase in entropy as gradient is negative
c) 580 K
19 THERMODYNAMICS: GIBBS FREE ENERGY CHANGE, ΔG, AND ENTROPY CHANGE, ΔS

●● ACTIVITY (PAGES 401–2)

The production of ammonia answers
1 2NH3 + H2SO4 → (NH4)2SO4
2 4NH3 + 5O2 → 4NO + 6 H2O
2NO + O2 → 2NO2
4NO2 + O2 + 2H2O → 4HNO3
3 a) Gradient of line = −ΔS1
Gradient = +0.1944 kJ K−1 mol−1

ΔS1 = −194.4 J K−1 mol−1
b) Graph crosses the ΔG1 axis at −92 kJ mol 1. At T = 0−K, ΔG1 = ΔH1
ΔH1 = −92 kJ mol−1
c) Line crosses the T axis at 460−K. At temperatures above this ΔG1
becomes positive, so the reaction is no longer feasible above 460 K.
d) Ammonia liquefies so the entropy data is different.
e) 4 mol of gas produces 2 mol of gas so the reaction becomes less
disordered and entropy decreases.

●● PRACTICE QUESTIONS (PAGES 403–4)

1 A (1)
2 D (1)
3 B (1)

4 a) i) +8.889 (kJ mol−1) (1)

92 ii) −17.68 (kJ mol−1) (1)

62
b)  (1)
0.1328
= 466.9 K (1)
5 a) 83.4 − (39.7+70) (1)
= −26.3 J K−1 mol−1 (1)
b) 2471 K (1)
6 a) ΔH1 (MgCO3) =  602 − 394 + 1096= +100 kJ mol−1

PRACTICE QUESTIONS (PAGES 403–4)

ΔH1 (BaCO3) =  554 − 94 + 1216 = +268 kJ mol−1 (1)
ΔS1 (MgCO3) = 27 + 214 − 66 = +175 J K−1 mol−1
ΔS1 (BaCO3) = 70 + 214 − 112 = +172 J K−1 mol−1 (1)
At 900 K
For MgCO3
ΔG = 100 – 900(0.175) = -57.5 kJ mol−1 feasible (1)
For BaCO3
ΔG = 268 − 900(0.172) = +113.2 kJ mol−1 not feasible (1)
b) MgCO3 = 100 (1)
0.175
= 571 K (1)
268
BaCO3 = (1)
0.172
= 1558 K (1)
  7 a) ΔH1 = +220 kJ mol−1 (1)
ΔS1 = +185 J K-1 mol−1 (1)
b) T = 1170 K (1)
c) 1170 K (1)
8 ΔG = 0 = 2.6 − 371(x − 0.051) (1)
2.6 = 371(x − 0.051)
2.6 = 371x − 18.921
371x = 2.6 +18.921
371x = 21.521
x = 0.0580 (1)
ΔS1 = +58.0 J K−1 mol−1 (1)
 9 a) +1669 −3(111) (1)
= +1336 kJ mol−1 (1)
b) It is an element (in its standard state). (1)
c) 2(28) + 3(198) − 51 − 3(6) (1)
= +581 J K−1 mol−1 (1)
93
d) ΔG1 = +1336 − 298(0.581) (1)
= +1162.862 kJ mol−1 (1)
e) ΔG1 >0 so reaction is not feasible. (1)
1336
f) (1)
0.581
= 2299.48 K (1)
 10 a) ΔS1 = 131 + 1 (205) − 189 =
2
+44.5 J K−1 mol−1 (1)
b) ΔG1 = ΔH1 − TΔS1
0 = ΔH1 − 5440(0.0445)
for expression use (1)
for ΔS1/1000 (1)
19 THERMODYNAMICS: GIBBS FREE ENERGY CHANGE, ΔG, AND ENTROPY CHANGE, ΔS

ΔH1 = +242.08 kJ mol−1 (1)

c)  (2)
ΔH1 = +286 − 242.08 = +43.92 kJ mol−1 (1)
H2O(l) H2O(g)

–286 [1] –242.08 [1]

H2(g) + 12 O2(g)

94
 20
Rate equations
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 405)
1 Temperature; concentration; presence of a catalyst; pressure;
2 Emp decreases
3 No effect
4 a) B
b) All reactants and products in the same state/phase.
5 Minimum energy required for the collisions between reactant particles to
cause a reaction.

●● TEST YOURSELF 2 (PAGE 407)

1 rate = k[D]2
2 a) rate constant
b) 2
c) 1
d) 3
3 a) 2
b) 0
c) mol−1 dm3 s−1
4 a) Concentration of A in mol dm−3
b) mol dm−3 s−1
c) x + y
d) s−1
e) mol−2 dm6 s−1

●● TEST YOURSELF 3 (PAGE 416) 95

1 a) Order with respect to C = 1

Order with respect to D = 2
b) mol−2 dm6 s−1
 2 Initial [A] / Initial [B] / Initial rate /
Experiment mol dm−3 mol dm−3 mol dm−3 s−1
1 1.5 × 10 −2 2.4 × 10 −2 1.2 × 10 −5
2 3.0 × 10 −2 2.4 × 10 −2 4.8 × 10 −5
3 3.0 × 10 −5 3.6 × 10 −2 4.8 × 10 −5

3 a) Order with respect to R = 1

Order with respect to S = 2
b) rate = k[R][S]2
c) 4 mol−2 dm6 s−1
4 k is the rate constant
A is the Arrhenius constant
R is the gas constant
T is the temperature
Ea is the activation energy

●● TEST YOURSELF 4 (PAGE 425)

1 Measuring gas volume against time
2 a) Measuring gas volume against time
b) Absorbance of iodine (brown) against time or pH against time
c) Measuring colour of iodine (brown) against time
using a colorimeter
using a calibration curve

●● TEST YOURSELF 5 (PAGE 427)

20 Rate equations

1 a) 2
b) 0
c) Step 1
Y not involved
2 a) 2

b) rate = k[CH3COOCH3][OH−]
96
c) mol−1 dm3 s−1
3 a) 2A + B → A2B
b)   i) 2
  ii) rate = k[A][B]
iii) Step 1
Contains A and B in 1:1 ratio
●● ACTIVITY (PAGE 424)

PRACTICE QUESTIONS (PAGES 428–9)

Investigation of the reaction of iodate(v) ions in acidic
solution with sulfate(iv) ions to determine the order of
the reaction with respect to hydrogen ions answers
1 t (s) 42 28 20 15 11 9
1/t (s -1) 0.0238 0.0357 0.0500 0.0667 0.0909 0.111
Log 1/t −1.62 −1.4 −1.30 −1.18 −1.04 −0.955
Log (vol) 1.40 1.54 1.65 1.74 1.85 1.93

2 log vol
1.4 1.5 1.6 1.7 1.8 1.9 2.0
0
–0.2
–0.4
–0.6
log 1/t

–0.8
–1.0
–1.2
–1.4
–1.6
–1.8

3 Gradient = 1.09 – this will depend on your own graph.

4 Keep the concentration of acid constant and vary the concentration of
iodate(v)
5 a) Error is 1 − 0.963 = 0.037 = 0.037/1 × 100 = 3.7%
b) The result error is greater than the apparatus error so the fault is due to
the person carrying out the experiment

●● PRACTICE QUESTIONS (PAGES 428–9)

1 C (1)
2 B (1)
3 a) order with respect to X = 2 (1)
order with respect to Y = 1 (1)
b) 3 (1)
c) rate = k[X]2[Y] (1)
rate 0.007 97
d) k = – = 7 (1)
[X] [Y] (0.1)2 (0.1)
2
units are mol−2dm6s−1 (1)
4 a) order with respect to A = 1 (1)
b) order with respect to B = 1 (1)
c) rate = k[A][B] (1)
3.760 × 10−4
d) k = rate = = 1.34 (1)
[A][B] (1.4 × 10−2 )(2.0 × 10−2 )
units are mol−1 dm3 s−1 (1)
 5 a) Order with respect to P = 1 (1)
Order with respect to Q = 1 (1)
b) rate = k[P][Q] (1)
rate 0.0020
c) k = = = 0.2 (1)
[P][Q] (0.10)(0.10)
units are mol−1 dm3 s−1 (1)
2.7 × 10−7
6 a) k = rate 2 = −2 −4 2
= 8.44 × 10−3 (1)
[B][C] (2.0 × 10 )(4.0 × 10 )
units are mol−2 dm6 s−1 (1)
b) rate = 8.44 × 10−3 × 4.0 × 10−2 × (5.0 × 10−2)2 = 8.44 × 10−7 (1)
E
− a
7 a) k = Ae RT (1)
b) Ea/R = 15024
Ea = 15024 × 8.31 = 124849 J mol−1 (1)
= 124.8 kJ mol−1 (1)
ln A = 21.4
A = e21.4 = 1.97 × 109 s−1 (1)
E
− a
c) k = Ae RT
E
Initially determine a . Ea = 128 849 J mol−1; R = 8.31 J K−1 mol-1 and
T = 300 K RT
Ea 124849 = 50.08 or shown in expression
= (1)
RT 8.31 × 300
Ea
−
k = Ae RT = 1.97 × 109 × e−50.08 = 3.51 × 10−13 s−1 (1)
If 124800 J mol−1 used for Ea, answer would be 3.58 × 10−13 s−1
20 Rate equations

With alternative answer k = 4.51 × 10−13 s−1.

8 a) tangent drawn (1)
0.600

0.500
[Ester]/mol dm–3

0.400

0.300

0.200

0.100

98 0.000
0
00

00

00

00

00

00

00

00
10

20

30

40

50

60

70

80

Time/s

gradient = 0.370 (1)

5500
= 6.73 × 10−5 (1)
Any sensible tangent and subsequent gradient calculation allowed
b) First (1)
9 a) (brown) colour of iodine (1)

PRACTICE QUESTIONS (PAGES 428–9)

Measured using a colorimeter (1)
b)   i) zero (1)
ii) any horizontal line drawn (1)

Rate of reaction
[I2]

c) i) Concentration of iodine has no effect on the rate of

the reaction. (1)
rate 1.20 × 10 −4
ii) k = + = = 3 × 10−5 (1)
[H ][CH3 COCH3 ] (0.50)(8.00)
Units are mol−1 dm3 s−1 (1)
10 a) Initial concentration Initial concentration Initial rate
Experiment of D (mol dm−3) of E (mol dm−3) (mol dm−3 s−1)
1 0.05 0.10 2.25 × 10 −3
2 0.05 0.20 9(.00) × 10−3 (1)
3 0.10 0.10 (1) 4.50 × 10 −3
4 0.15 (1) 0.20 2.70 × 10 −2
5 0.10 0.14 (1) 8.82 × 10 −3

2.25 × 10−3
b) k = = 4.5 mol−2 dm6 s−1 (1)
(0.50)(0.10)2
c) Let c = initial concentration of D
So 4c = initial concentration of E
rate = 4.5 × (c) × (4c)2 = 5.76 × 10−4
4.5 × 16c3 = 5.76 × 10−4
16c3 = 1.28 × 10−4
c3 = 8 × 10−6
c = 0.02 for calculation (2) 99

Initial concentration of D = 0.02 mol dm−3 (2)

Initial concentration of E = 0.08 mol dm−3 (2)
Using 10.0c =0.0153
Initial concentration of D = 0.0153 mol dm−3
Initial concentration of E = 0.0612/0.0613 mol dm−3
 21 Equilibrium constant
Kp for homogeneous
systems
●● TEST YOURSELF ON PRIOR KNOWLEGE 1
(PAGE 431)
1 Concentrations of the reactants and products remain constant and the
rates of the forward and reverse reactions are equal.
2 If a factor is changed which affects a system in equilibrium, the position
of equilibrium will move in a direction so as to oppose the change.
3 a) Position of equilibrium moved in the direction of the reverse
endothermic reaction.
The position of equilibrium moves from right to left.
The yield of C decreases
b) 3 mol of gas on the left hand side and 1 mol of gas on the right hand side.
An increase in pressure shifts the position of equilibrium to the side
with a smaller gas volume.
Increasing pressure moves the position of equilibrium from left to right
to oppose the increase in pressure.
The yield of C increases.
c) A catalyst increases the rate of reaction of both the forward and reverse
reactions.
Equilibrium is attained more quickly but a catalyst does not affect the
position of equilibrium.
d) All the reactants and products are in the same state (or phase).

100 [CO2 ][H2 ]4

4 a) Kc =
[CH 4 ][H2O]2
b) 1.41 mol2 dm−6

●● TEST YOURSELF 2 (PAGE 433)

1 mole fraction N2 = 0.533  mole fraction O2 = 0.467
2 60 kPa
 3 a) N2 = 0.0538 

PRACTICE QUESTIONS (PAGES 438–9)

H2 = 0.484   NH3 = 0.462
b) N2 =5.38 kPa 
H2 = 48.4 KPa  NH3 = 46.2 kPa

●● TEST YOURSELF 3 (PAGE 438)

1 a) 19.1 kPa
b) No effect
2 0.0408 no units
3 0.0126 MPa

●● PRACTICE QUESTIONS (Pages 438–9)

1 B (1)
2 D (1)
p(SO3 )2
3 K p = (1)
p(SO2 )2 p(O2 )

= (500)2 = 0.0434 (1) kPa−1 (1)

2
(240) (100)
4 Equilibrium moles of A = 1.00; B = 1.50; C = 1.50 or
Mole fractions of A = 0.250; B = 0.375; C = 0.375 (1)
p(C)3 (0.375)3
Kp = =
p(A) p(B) (0.250)2 (0.375)
2

Kp = 2.25 no units (1)

5 moles of N2 = 2.13 mol H2 = 6.4 mol NH3 = 1.48 mol

mole fractions of N2 = 0.213
H2 = 0.639
NH3 = 0.148 (1)
partial pressures of N2 = 28116 Pa
H2 = 84348 Pa NH3 = 19536 Pa (1)
2 3
p(NH3 ) (19536)
Kp = 3 =
p(N2 )p(H2 ) (28116)(84348)3
KP   = 2.26 × 10−11 Pa−2 (1) 101

6 Partial pressure of H2 and I2 are the same in all equilibria.

p(H2 )p(I2 )
Kp = (1)
p(HI)2

= x2 or similar (1)
(1.80)2

= 0.0185 (1)
 x2 = 0.05994 (1)
x = p(H2) = p(I2) = 0.245 MPa (1)
7 Equilibrium moles of CO = 1.00 − x; H2O = 1.00 − x; CO2 = x; H2 = x
p(CO2 )p(H)
Kp = (1)
p(CO)p(H2O)
x2
( )
x 2
  = 2 = 1.00 − x
= 0.0625 (1)
(1.00 – x )
x
(
      1.00 − x = 0.250 )
x = 0.250(1 − x)
1.25x = 0.250
x = 0.200 (1) moles of CO = 1.00 − x = 0.800 (1)
8 Equilibrium concentrations of CO = 0.117; H2 = 0.287; CH3OH =
21 EQUILIBRIUM CONSTANT KP FOR HOMOGENEOUS SYSTEMS

0.481 (1)
[CH3OH]
Kc = (1)
[CO][H2 ]2
0.481
= = 49.9 mol−2 dm6 (1)
(0.117)(0.287)2
Partial pressures of CO = 0.211 MPa; H2 = 0.515 MPa; CH3OH =
0.863 MPa
(p(CH3OH))
Kp =
(p(CO)p[(H2 )]2 )
0.863
= = 15.4 MPa−2 (1)
(0.211)(0.515)2
p(HI)2
9 a) i) Kp = (1)
p(H2 )p(I2 )3
ii) H2 = 2 − x
I2  = 2 − x
HI = 2x     Total equilibrium moles = 4 (1)
2–x
H2 =
4
2–x

   I2 =
4
x
102 HI = x or (1)
4 2
(2 x)2
Kp =
(2 − x)2
(2 x )2
= 0.106 (1)
(2 − x )2
2x
= 0.3256
2– x
x = 0.28 (1)
 H2 = 1.72 moles

PRACTICE QUESTIONS (PAGES 438–9)

I2 = 1.72 moles
HI = 0.560 moles
All three correct (1)
0.28
iii) × 100 = 14% (1)
2
(2 x )2 2x
b) = 0.0111 so = 0.105 (1)
(2 − x )2 2– x
x = 0.100 (1)
H2 = 1.900 remaining (1)
0.100
× 100 = 5% (1)
2

103
 22
Electrode potentials
and cells

TEST YOURSELF ON PRIOR KNOWLEGE 1

(PAGE 440)
1 a) +2
b) −3
c) +5
d) −2
e) −3
2 a) sodium sulfate(vi)
b) ammonium nitrate(v)
c) nitrogen(i) oxide
d) potassium chromate(vi)
3 a) E
b) D
c) A
d) C

TEST YOURSELF 2 (PAGE 444)

1 Inert; good conductor of electricity
2 100 kPa
298 K
1.00 mol dm−3 concentrations of ions in solution
104 3 Diagram to show salt bridge, external circuit with voltmeter, copper
metal dipping into a solution of 1.00 mol dm−3 Cu2+/CuSO4 at 298 K
and 100 kPa

TEST YOURSELF 3 (PAGE 451)

1 a) +1.53 V
b) Fe3+/Fe2+ or iron
c) Zn + 2Fe3+ → Zn2+ + 2Fe2+
d) Zn | Zn2+ || Fe3+, Fe2+ | Pt
 2 a) Fe → Fe2+ + 2e−

ACTIVITY (PAGE 452)

b) Cu2+ + 2e− → Cu
c) Fe + Cu2+ → Cu + Fe2+
d) +0.34 V
3 a) Zn
b) It becomes oxidised/loses electrons.
c) i) E1 (F2/F−) > E1 (O2/H2O) or the EMF of the cell is +1.64 V
ii) 2F2 + 2H2O → 4F− + 4H+ + O2
d) i) Zn | Zn2+ || Cl2 | Cl− | Pt
ii) +2.12 V

TEST YOURSELF 4 (PAGE 459)

1 a) Li + CoO2 → Li+[CoO2]−
b) Reaction B
Oxidation occurs at the negative electrode
2 Reagents supplied continuously; concentration of reagent(s) remain
constant.
3 a) H2(g) → 2H+(aq) + 2e−
b) O2(g) + 4H+(aq) + 4e− → 2H2O(l)
c) 2H2(g) → O2(g) → 2H2O(l)

ACTIVITY (PAGE 452)

Does the concentration of silver ions in a solution
affect the electrode potential of a cell?
1 It completes the electrical circuit. It allows an electrical connection
between the two beakers by allowing ions to flow, while preventing the
two solutions from meeting.
2 Filter paper strip dipped in potassium nitrate solution
3 The two electrodes generate the same electrode potentials, but since the
two oppose each other there is be no measurable potential – the tendency
for electrons to pass from one electrode to another is balanced by that for
electrons to flow in the reverse direction. 105
4 This allows only a small current to flow
Log[Ag+]B
–5 –4 –3 –2 –1
5 −5,−4,−3,−2,−1. The log scale converts a wide range of numbers 0.00001
0 to 0 to a smaller range scale −5 to −1 which is easier to plot
electrode potential/v

–0.05
6 The graph is a straight line showing that the electrode potential is
–0.1
directly proportional to Log [Ag+]B, hence place the unknown solution
–0.15 in beaker B, and read the electrode potential. Then use the graph to find
–0.2 Log [Ag+]B for this value, and hence determine the unknown silver ion
–0.25 concentration.
 PRACTICE QUESTIONS (PAGES 459–461)
1 B (1)
2 C (1)
3 C (1)
4 Diagram to include salt bridge (1)
voltmeter in external circuit (1)
1.00 mol dm−3 V3+ and 1.00 mol dm−3 V2+ ions (1)
Platinium contact in the solution (1)
100 kPa and 298 K (1)
5 a) Fe2+/Fe3+ or iron (1)
Oxidation occurs at the negative electrode (1)
b) Fe2+/Fe3+ or iron (1)
MnO−4 + 8H+ + 5e− → Mn2+ + 4H2O (1)
5Fe2+ + MnO4− + 8H+ → 5Fe3+ + Mn2+ + 4H2O (1)
c) EMF = + 0.74 = + 1.51 – x (x is the standard electrode potential).
x = 1.51 − 0.74 = +0.77 V (1)
6 a) Pt | VO2+, VO2+ || ClO3− , Cl− | Pt
22 Electrode potentials and cells

or Pt | VO2+, VO2+ , H+ ||   ClO3− , H+, Cl− | Pt (1)

b) ClO3− + 6VO2+ + 3H2O → Cl− + 6H+ + 6VO2+ (1)
−
c) Oxidising agent: ClO3 (1)
Reducing agent : VO2+ (1)
d) +0.45 V (1)
e) Vanadium electrode (1)
7 a) i) E1 (Au+/Au) > E1 (O2/H2O) or EMF = +0.45 V (1)
ii) 4Au+ + 2H2O → 4Au + O2 + 4H+ (1)
iii) Pt | H2O | O2 || Au+ | Au (1)
b) i) E1 (Cl2/Cl−) > E1(Ag+/Ag) or EMF is negative/−0.56 V (1)

ii) White precipitate (1)

106 iii) Ag+ + Cl− → AgCl (1)

c) i) Zn2+ (1)
and Fe (1)
3Zn + 2Fe3+ → 2Fe + 3Zn2+ (1)
ii) Fe3+ (1)
and Ag (1)
Fe + 3Ag+ → Fe3+ + 3Ag (1)
 iii) Cu2+  (1)

PRACTICE QUESTIONS (PAGES 459–461)

and Ag (1)
  Cu + 2Ag+ → Cu2+ + 2Ag (1)
8 a) i) Pt | V2+, V3+ || Cu2+ | Cu (2)
ii) Salt bridge (1)
iii) Left electrode is an oxidation/electrons released (1)
Travel to right-hand side reduction electrode (which consumes
electrons)(1)
iv) EMF = + 0.60 V (1)
v) 2V2+ + Cu2+ → 2V3+ + Cu (1)
b) i) EMF = +1.26 = x + 0.26 (1)
x = + 1.00 V (1) (as it is the reduction)
ii) VO2+ + V2+ + 2H+ → V3+ + VO2+ + H2O (2)
9 a) H2(g) + 2OH−(aq) → 2H2O(l) + 2e−; state symbols not required (1)
b) O2(g) + 2H2O(l) + 4e− → 4OH−(aq); state symbols not required (1)
c) 2H2(g) + O2(g) → 2H2O(l); state symbols not required (1)
d) i) EMF = +1.23 = +0.40 − x
x = 1.23 = 0.40 so x = −0.83V (1)
ii) Reagents supplied continuously (1)
Concentration of reagent(s) remain constant. (1)
10 a) i) Cr2O72− (1)
ii) salt bridge and voltmeter in external circuit (1)
1.00 mol dm−3 dichromate(vi) ions and 1.00 mol dm−3
chromium(iii) ions. (1)
Platinium contact in the solution (1)
100 kPa and 298 K (1)
iii) 6Fe2+ + Cr2O72− + 14H+ → 2Cr3+ + 6Fe3+ + 7H2O (2)
b) i) EMF = −0.14 + 0.44 = +0.30 V (1)
ii) Fe | Fe2+ || Sn2+ | Sn (2)
c) 107

i) E1 (Zn/Zn2+) > E1 (Fe/Fe2+) or EMF = +0.32 V (1)

Zinc oxidises instead of the iron (1)
ii) Zn + Fe2+ → Zn2+ + Fe (1)
 23 Acids and bases
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 462)
1 a) sulfuric acid; hydrochloric acid; nitric acid; ethanoic acid
b) ethanoic acid/CH3COOH
2 a) NaOH and KOH
b) copper(II) sulfate/copper sulfate
c) magnesium chloride
3 a) D
b) E
c) C
d) A
e) B

●● TEST YOURSELF 2 (PAGE 470)

1 pH = −log10[H+]
2 a) 1.62
b) 1.77
c) 1.55
3 a) 0.0158 (mol dm−3)
b) 0.316 (mol dm−3)
c) 0.629 (mol dm−3)
4 0.370 (mol dm−3)

●● TEST YOURSELF 3 (PAGE 474)

108
1 Kw = [H+][OH−]
2 a) 6.17
b) 11.56
3 3.98 × 10−14 (mol2 dm−6)
4 0.479 (mol dm−3)
●● TEST YOURSELF 4 (PAGE 477)

ACTIVITY (PAGE 487)

1 CH3COOH ⇋ CH3COO− + H+

[CH3 COO− ][H + ]

2 Ka =
[CH3 COOH]
3 2.66
4 0.00316 (mol dm−3)
5 2.54

●● TEST YOURSELF 5 (PAGE 482)

1 1.36
2 12.15
3 1.85
4 1.18

●● TEST YOURSELF 6 (PAGE 486)

1 24.0 (cm3)
2 a) Nitric acid or hydrochloric acid
b) Ammonia
c) Ethanoic acid
3 Colour change of indicator is not in range of equivalence region
of titration

●● TEST YOURSELF 7 (PAGE 494)

1 Buffers are solutions which can resist changes in pH when small
quantities of acid or base are added
2 A− reacts with H+ ions and removes them from solution so
maintaining pH
A− + H+ ⇋ HA
3 4.37
4 3.57
5 a) 4.31
109
b) 4.30

●● ACTIVITY (PAGE 487)

Investigating the change in pH when methanoic acid
reacts with sodium hydroxide
1 a) Idea that over time/after storage, the meter does not give accurate
readings.
 The reason for this is that the glass electrode does not give a
reproducible EMF over longer periods of time. Calibration should be
performed with at least two standard buffer solutions that span the
range of pH values to be measured.
b) HCOOH ⇋ HCOO− + H+
The reversible arrow shows that the dissociation is incomplete since
HCOOH is a weak acid.
[COO− ][H + ]
c) Ka =
[HCOOH]
d) pH = −log[H+]
2.37 = −log[H+]
[H+] = 4.27 × 10−3
(4.27 × 10 −3 )2
Ka = = 1.82 × 10−4
0.100
2 a) NaOH + HCOOH → HCOONa + H2O
b) To ensure that the solution is homogenous and the pH is uniform
throughout.
25.0 × 1.5 × 10−2
c) Moles of methanoic acid = = 3.75 × 10−4
1000
Ratio 1:1
30.0 × concentration
Moles NaOH = 3.75 × 10−4 =
1000
Conc = 0.0125 mol dm−3
d) The pH change at the end point is between 6 and 10. Metacresol
purple changes colour with in this range and is suitable to use.

●● PRACTICE QUESTIONS (PAGES 495–6)

23 Acids and bases

1 A (1)
2 B (1)
3 a) pH = −log10[H+] (1)
+ −
b) Ka = [H ][A ] (1)
[HA]
c) Kw = [H+][OH−] (1)
4 [H+]2 = Ka × [HX] (1)
2.45 × 10−4 × 0.215 = 7.258 × 10−3 mol dm−3

[H+] = (1)
pH = −log10[H+] = −log10(7.258 × 10−3) = 2.14 (1)
110
5 a) Kw = [H+][OH−] (1)
b) [H+] = 5.48 × 10−14 = 2.341 × 10−7 mol dm−3 (1)
pH = −log10[H+] = −log10(2.341 × 10−7) = 6.63 (1)
6 a) acid (1)
donating a proton (1)
b) HNO3 (1)
 50.0 × 0.200
7 a) moles of OH− = = 0.0100 (1)

PRACTICE QUESTIONS (PAGES 495–6)

1000
0.0100 × 1000
new [OH−] = = 0.0400 mol dm−3 (1)
250
Kw 1.0 × 10−14
[H+] = = = 2.50 × 10−13 (1)
[OH − ] 0.0400
pH = −log10[H+] = −log10(2.50 × 10−13) = 12.60 (1)
5.00 × 0.0520
b) moles of H+ = = 2.60 × 10−4 (1)
1000
2.60 × 10−4 × 1000
new [H+] = = 0.0104 mol dm−3 (1)
25.0
pH = −log10[H+] = −log10(0.0104) = 1.98 (1)
15.00 × 0.124
c) moles of H+ = × 2 (as diprotic acid)
1000
= 3.72 × 10−3 (1)
3.72 × 10−3 × 1000
new [H+] = = 0.0744 mol dm−3 (1)
50.0
pH = −log10[H+] = −log10(0.0744) = 1.13 (1)
10.00 × 0.150
8 moles of NaOH = = 1.50 × 10−3 (1)
1000
25.00 × 0.100
moles of HCl = = 2.50 × 10−3 (1)
1000
moles of HCl left over = 2.50 × 10−3 – 1.50 × 10−3 = 1.00 × 10−3 (1)
1.00 × 10−3 × 1000
[H+] = = 0.02857 mol dm−3 (1)
35.0
pH = −log10[H+] = −log10(0.02857) = 1.54 (1)
9 a) A− reacts with H+ ions/A− + H+ ⇋ HA (1)
and removes them from solution so maintaining pH. (1)
125 × 0.325
b) moles of HA = = 0.040625 (1)
1000
K × [HA]
[H+] = a − (1)
[A ]
1.74 × 10−5 × 0.040625
[H+]= = 2.608 ×10−5 mol dm−3 (1)
0.0271
pH = −log10[H+] = −log10(2.608 × 10−5) = 4.58 (1)
50.0 × 0.200
c) moles of H+ added = = 1.00 × 10−3 (1)
1000
125 × 0.325 111
Initial moles of HA = = 0.040625
1000
New moles of HA = 0.040625 + 1.00 × 10−3 = 0.041625 (1)
New moles of A– = 0.0271 – 1.00 × 10−3 = 0.0261 (1)
K × [HA]
[H+] = a − (1)
[A ]
1.74 × 10−5 × 0.041625
[H+] = = 2.775 × 10−5 (1)
0.0261
pH = –log10[H+] = –log10(2.775 × 10−5) = 4.56 (1)
 10 a) pH = −log10[H+] = −log10 (0.125) (1)
= 0.9 (1)
b) NaOH + HCl → NaCl + H2O (1)
25.0 × 0.125
c) moles of HCl = = 3.125 × 10−3 (1)
1000
moles NaOH = 3.125 × 10−3 (1)
−3
3.125 × 10 × 1000
[NaOH] = = 0.138 mol dm−3 (1)
22.7
d) [OH−] = 0.138 mol dm−3 (1)
Kw 1.00 × 10 −14
[H+] = = = 7.246 × 10−14 mol dm−3 (1)
[OH − ] 0.138
pH = −log10[H+] = −log10(7.246 × 10−14) = 13.14 (1)
If 0.145 is used, then pH = 13.16
11 a) i) 2 (1)
ii) 4 (1)
iii) 3 (1)
b) i) Phenolphthalein (1)
ii) Blue to yellow (1)
12 a) Base reacts with and removes H+ ions/H+ + OH− → H2O (1)
Position of equilibrium in buffer moves to replace the H+ ion so
maintaining pH/ HA ⇌ A− + H+ (1)
50.0 × 0.200
b) moles of HX = = 0.0100 (1)
1000
25.0 × 0.180
moles of KOH = = 4.50 × 10−3 (1)
23 Acids and bases

1000
moles of HX remaining = 0.0100 − 4.50 × 10−3 = 5.50 × 10−3 (1)
moles of KX formed = 4.50 × 10−3 (1)

K a × [HA] 2.74 × 10 −5 × 5.50 × 10 −3

[H+] = =
[A − ] 4.50 × 10 −3
   = 3.349 × 10−5 mol−dm−3 (1)

pH = −log10[H+] = −log10(3.349 × 10−5) = 4.48 (1)

112 c) moles of HX = 5.5 × 10−3 − 0.00240 = 3.10 × 10−3 (1)
moles of KX = 4.50 × 10−3 + 0.00240 = 6.90 × 10−3 (1)
K a × [HA] 2.74 × 10 −5 × 3.1 × 10 −3
[H+] = = =
[A − ] 6.90 × 10 −3
1.23 × 10−5 mol dm−3 (1)
pH = −log10[H+] = −log10(1.23 × 10−5) = 4.91 (1)
13 [H+] = 10−4.81 = 1.549 × 10−5 mol dm−3 (1)

PRACTICE QUESTIONS (PAGES 495–6)

[A−] = x (1)
[HA] = 0.124 − x (1)
[H + ][ A − ]
Ka =
[HA]
(1.549 × 10−5 )( x )
1.74 × 10−5 =
(0.124 − x )
1.74 × 10−5 (0.124 − x) = 1.549 × 10−5 x
2.1576 × 10−6 − 1.74 × 10−5 x = 1.549 × 10−5 x
2.1576 × 10−6 = 1.549 ×10−5 x + 1.74 × 10−5 x
2.1576 × 10−6 = 3.289 × 10−5 x (1)
2.1567 × 10−6
x= = 0.0656 mol (1)
3.289 × 10−5

113
 24 Properties of Period 3
elements and their
oxides
TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 497)
1 a) barium, sodium, magnesium
b) chlorine, neon, bismuth
c) 3
d) 1
2 Ba + 2H2O → Ba(OH)2 + H2
3 a) Yellow
b) White
c) White
4 a) Increases then decreases
b) Decreases
c) Decreases
d) Decreases

TEST YOURSELF 2 (PAGES 501–2)

1 Ionic lattice
2 Ionic bonding
3 a) Na2O + H2O → 2Na+ + 2OH-
b) 12–14
114
4 4Al + 3O2 → 2Al2O3
5 a) Al2O3 + 3H2SO4 → Al2(SO4)3 + 3H2O
b) Al2O3 + 2KOH + 3H2O → 2KAl(OH)4
c) Amphoteric
TEST YOURSELF 3 (PAGE 508)

PRACTICE QUESTIONS (PAGE 509)

1 a) SO2 + H2O → H2SO3
b) 0–2
c) SO2 + 2NaOH → Na2SO3 + H2O
2 a) P4O10 + 6H2O → 4H3PO4
b) Molecular covalent
3 Yellow solid melts to a red liquid; blue flame; misty pungent gas
4 a) NaHSO4
b) Mg3(PO4)2
c) K2HPO4
d) NaHSO3
5 P4O10 + 6Na2O → 4Na3PO4

ACTIVITY (PAGE 504)

1 P4 + 5O2 → P4O10
2 Bright white flame, white smoke
3 P4S3 + 8O2 → P4O10 + 3SO2
4 2KClO3 → 2KCl + 3O2
5 3P4S3 + 16KClO3 → 3P4O10 + 9SO2 + 16KCl
6 Place electrodes in a sample of molten magnesium oxide, and attach to a
cell and a lamp, the lamp should light showing that magnesium oxide is
ionic, and conducts electricity when molten – the lamp should not light
when the magnesium oxide is solid.

PRACTICE QUESTIONS (PAGE 509)

1 B (1)
2 B (1)
3 D (1)
4 D (1)
5 a) All are ionic structures (1)
115
Large amount of energy required to break the strong ionic bonds
between the ions. (1)
b) SiO2 is giant covalent and P4O10 is molecular covalent. (1)
Larger amount of energy required to break the many strong covalent

bonds in SiO2. (1)
Compared to the weaker van der Waals’ forces/permanent dipole-
permanent dipole attractions between the molecules in P4O10. (1)
 c) SO3 has greater Mr/more electrons than SO2. (1)
Stronger van der Waals’ forces of attraction between the molecules. (1) 
More energy required to break the van der Waals’ forces between
SO3 molecules. (1)
6 a) P4O10 + 6H2O → 4H3PO4 (1)
b) P4O10 + 6MgO → 2Mg3(PO4)2 (1)
500 × 0.15
c) Moles of H3PO4 =
1000
= 0.075 mol (1)

Moles of P4O10 required =

0.075
4
= 0.01875 mol (1)
Mass of P4O10 = 0.01875 × 284.0 = 5.325 g (1)
7 a) Sodium oxide is an ionic lattice. (1)
Sulfur dioxide is molecular covalent (1)
b) Large amount of energy is required to breaks the strong ionic bonds
between the ions. (1)
24 Properties of Period 3 elements and their oxides

Small amount of energy required to break the weak van der Waals’
forces/permanent dipole-permanent dipole attractions between the
molecules in SO2. (1)
c) Sodium oxide 12–14 (1)
Sulfur dioxide 3–5 (1)
d) Na2O + SO2 → Na2SO3 (1)
8 a) +6 (1)
b) +5 (1)
c) Acid A = sulfuric(vi) acid (1)
Acids B = phosphoric(v) acid (1)
d) SO3 + H2O → H2SO3 (1)
e) 2H3PO4 + 3CaO → Ca3(PO4)2 + 3H2O (1)
f) The S and P are in the highest oxidation possible. (1)
g) HSO−4 hydrogensulfate ion (1)
SO24− sulfate ion (1)
0.0300

9 Moles of sodium = = 1.30 × 10−3 mol (1)

23.0
116
[OH−] = 1.30 × 10−3 mol dm−3 (1)
1.00 × 10−14
[H+] = = 7.69 × 10−12 mol dm−3 (1)
1.30 × 10−3
pH = −log10[H+] = −log10(7.69 × 10−12) = 11.11 (1)
 25 Transition metals

TEST YOURSELF ON PRIOR KNOWLEDGE 1

(PAGE 510)
1 a) 1s2 2s2 2p6 3s2 3p6 3d1 4s2
b) 1s2 2s2 2p6 3s2 3p6 3d5 4s1
c) 1s2 2s2 2p6 3s2 3p6 3d8 4s2
d) 1s2 2s2 2p6 3s2 3p6 3d10 4s1
2 a) 1s2 2s2 2p6 3s2 3p6 3d2
b) 1s2 2s2 2p6 3s2 3p6 3d6
c) 1s2 2s2 2p6 3s2 3p6 3d7
d) 1s2 2s2 2p6 3s2 3p6 3d9
3 The pair of electron forming the bond come from one atom
4 a) Tetrahedral
b) Linear
c) Octahedral

TEST YOURSELF 2 (PAGE 519)

1 a) D
b) B
c) C
2 Fe2+
3 a) 6 and 4
b) Five particles in solution on the left and seven on the right Increase in
disorder so increase in entropy.

117
TEST YOURSELF 3 (PAGE 522)
1 A: tetrahedral; B: octahedral; C: linear; D: octahedral; E: octahedral; F:
square planar.
2 A: 4; B: 6; C: 2; D: 6; E: 6; F: 4.
3 A:+2; B: +2; C: +1; D: +3; E: +2; F +2.
4 F
5 E
 TEST YOURSELF 4 (PAGE 527)
1 4.42 × 10−19 J
2 Light is absorbed to excite electrons from ground state to excited state.
the complementary colour (blue) is the colour we observe
3 550 nm

TEST YOURSELF 5 (PAGE 533)

1 a) A and D
b) Green ppt
c) White ppt that redissolves to form a colourless solution.
d) Green ppt
2 a) 6
b) +3
c) Octahedral
d) Al(OH)3(H2O)3 + OH− → [Al(OH)4(H2O)2]− + H2O
3 a) [Fe(H2O)6]3+
b) Brown ppt and bubbles of a gas produced.
c) 2[Fe(H2O)6]3+ + 3CO23− → 2Fe(OH)3(H2O)3 + 3CO2 + 3H2O

ACTIVITY (PAGE 533)

1 Cu2+
25 Transition metals

2 [Cu(H2O)6]2+ octahedral
3 A white ppt with barium ions indicates that a sulfate ion is present. The
white ppt is barium sulfate. When silver nitrate is added the solution
remains colourless and no precipitate is formed, indicating that a halide
ion is not present.
Ba2+ + SO24− → BaSO4
4 Cu(OH)2(H2O)4
5 [Cu(H2O)6]2+ + 2OH− → Cu(OH)2(H2O)4 + 2H2O

blue ppt
118 Cu(OH)2(H2O)4 + 4NH3 → [Cu(NH3)4(H2O)2]2+ + 2H2O + 2OH−
deep blue solution
6 Copper(ii) carbonate
7 The solid is in the form of crystals so it is hydrated. On heating, the
crystals should turn to powder and beads of colourless liquid should
form on the test tube.
8 Hydrated copper(ii) sulfate
PRACTICE QUESTIONS (PAGES 534–5)

PRACTICE QUESTIONS (PAGES 534–5)

1 D (1)
2 D (1)
3 C (1)
4 D (1)
hc
5 a) ΔE = (1)
λ
−34
hc 6.63 × 10 × 3.0 × 108
b) ΔE = =  (1)
λ 420 × 10−9
= 4.74 × 10−19 J (1)
c) One colour of light is absorbed to excite the electron (1)
The remaining colour of light is transmitted (1)
d) any three from: identity of the metal; oxidation state of the metal;
identity of the ligands; coordination number; shape. (3)
6 a) Forms two coordinate bonds to the central metal atom or ion. (1)
b) [Ni(NH3)6]2+ (1)
c) [Cr(OH)6]3− (1)
d) [Ag(NH3)2]+ (1)
e) (b) and (c) are octahedral (2)
(d) is linear (1)
7 a) Forms multiple coordinate bonds to the metal ion or atom (1)
b) Two particles on the left-hand side and seven on the right-hand side (1)
Increase in disorder/entropy (1)
c) Coordinate (1)
d) Both are 6 (1)
8 a) [Fe(H2O)6]2+ + 2OH− → Fe(OH)2(H2O)4 + 2H2O (2)
b) Brown ppt (1)
c) i) Brown ppt (1); bubbles of gas/effervescence (1) (2)
ii) 2[Fe(H2O)6]3+ + 3CO23− → 2Fe(OH)3(H2O)3 + 3CO2 + 3H2O (2)
9 a) 4 (1) and square planar (1) (2)
b) [Pt(NH3)2Cl2] is cis-trans (1) 119

[Co(NH3)4Cl2]+ is cis-trans (1)

[Ni(H2NCH2CH2NH2)3]2+ is optical (1)
c) Cancer treatment (1)
d) Pt +2 oxidation state/Pt2+ ion (1)
2Cl− ligands cancel charge (1)
 10 a) To [Fe(H2O)6]2+ green ppt (1)
[Fe(H2O)6]2+ + CO23− → FeCO3 + 6H2O (2)
To [Fe(H2O)6]3+ brown ppt (1) and bubbles of gas evolved/
effervescence (1)
2[Fe(H2O)6]3+ + 3CO23− → 2Fe(OH)3(H2O)3 + 3CO2 + 3H2O (2)
b) Blue ppt [1]
[Cu(H2O)6]2+ + 2OH− → Cu(OH)2(H2O)4 + 2H2O (2)
Redissolves to form a deep blue solution (1)
Cu(OH)2(H2O)4 + 4NH3 → [Cu(NH3)4(H2O)2]2+ + 2OH− [2]
11 a) Reaction 1: Fe(s) → Fe2+(aq) + 2e− ×4
Reaction 2: O2 + 2H2O + 4e− → 4OH− ×2
Reaction 3: Fe2+ (aq) + 2OH− (aq) → Fe(OH)2 (s) ×4
Reaction 4: 4Fe(OH)2 (s) + O2(g) → 2Fe2O3.H2O(s) + 2H2O(l) ×1
4Fe(s) + 3O2(g) + 2H2O(l) → 2Fe2O3.H2O(s) (3)
b) Reaction 3 (1)
    No change in oxidation number (1)
c) i) Oxidation occurs/Mg → Mg2+ + 2e− (1)
ii) Mg|Mg2+||Fe2+|Fe (2)
iii) +1.93 V (1)
25 Transition metals

120
 26 Transition metals:
Variable oxidation
states

TEST YOURSELF ON PRIOR KNOWLEDGE 1

(PAGE 536)
1 a) +3
b) +7
c) +6
d) +6
2 4
3 a) Sodium dichromate(vi)
b) Manganese(iv) oxide
c) Cobalt(iii) oxide
4 Provides and alternative reaction route of lower activation energy

TEST YOURSELF 2 (PAGE 541)

1 a) +2 and violet
b) +3 and green
c) +5 and yellow
d) +5 and yellow
2 VO2+ + 2H++ e− → VO2+ + H2O
3 a) 2VO2+ + 4H+ + Zn → Zn2+ + 2V3 + + 2H2O
b) +1.10 V 121
c) Blue to green

TEST YOURSELF 3 (PAGE 546)

1 a) MnO−4 + 8H+ + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+
b) 0.0419 mol dm−3
2 0.119 g
3 7
 TEST YOURSELF 4 (PAGE 550)
1 V2O5 + SO2 → V2O4 + SO3
V2O4 + 1 O2 → V2O5
2
2 a) A: iron; B: Fe2+ or Fe3+; C: Mn2+
b) B and C
c) A
d) C
3 They do not show variable oxidation states in their compounds.

ACTIVITY (PAGE 546)

Finding the formula of Mohr’s salt
1 Titrations using permanganate are performed in acidic solutions rather
than basic solutions, as titrations in basic solutions tend to produce an
insoluble oxide, usually MnO2. This precipitate is black and makes it very
26 Transition metals: Variable oxidation states

hard to see what else is going on in the reaction; the acidic product is
soluble, and thus makes the progress of the reaction much easier to see.
2 It is a weak acid and does not provide sufficient hydrogen ions.
3 The ammonium ions make solutions of Mohr’s salt slightly acidic, which
slows the oxidation process
4
Rough Titration 1 Titration 2 Titration 3
Final volume 21.10 20.05 21.40 20.00
Initial volume 0.10 0.00 1.20 0.05
Titre/cm3 21.00 20.05 20.20 19.95

20.02 + 19.95
5 Mean = = 20.00 – do not use 20.02 as it is not concordant.
2
6 Colourless → pink. It is self indicating.
7 Percentage error = 0.25 × 100 = 1.25%
20.00
8 5Fe2+ + 8H+ + MnO−4 → 5Fe3+ + 4H2O + Mn2+
9 Moles of manganate(vii) = 20.00 × 0.02 = 0.0004
1000
Ratio 1 mol manganate to 5 mol Fe2+

5 × 0.0004 = 0.002
122
Moles Fe2+ = 0.002 = 25.0 × concentration
1000
Conc = 0.08 mol dm−3
0.08 mol dm−3 = 31.4 g dm−3 /Mr
31.4
Mr = = 392.5
0.08
Fe(NH4)2(SO4)2nH2O = 392.5
284.0 + n18 = 392.5
n=6
PRACTICE QUESTIONS (PAGES 551–2)

PRACTICE QUESTIONS (PAGES 551–2)

1 A (1)
2 C (1)
3 2MnO−4 + 6H+ + 5H2O2 → 2Mn2+ + 8H2O + 5O2 (1)
17.55 × 0.124
Moles of MnO−4 = = 2.1762 × 10−3 mol (1)
1000
Ratio of H2O2 : MnO−4 = 5 : 2
2.1762 × 10−3
So moles of H2O2 in 25.0 = × 5 = 5.4405 × 10−3 mol (1)
2
Concentration of H2O2 = 5.4405 × 10−3 × 40 = 0.218 mol dm−3 mol (1)
4 a) 2MnO−4 + 16H+ + 5C 2O24− → 10CO2 + 2Mn2+ + 8H2O (1)
b) Manganate(vii) ions are coloured/purple (1)
c) Shallow gradient at start (1)
Getting steeper (1)
Becomes steep (1)
Levels off (1)
Example:
Concentration of
MnO4–/Mol dm–3

Time/s

5 a) 2SO2 + O2 → 2SO3 (1)

b) It is not used up/it is reformed at the end (1)
c) It has variable oxidation states (1)
2−
6 a) 2MnO−4 + 16H+ + 5C 2O4 → 10CO2 + 2Mn2+ + 4H2O (1)
b) MnO−4 + 8H+ + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O (1)
c) 3MnO−4  : 5FeC2O4
25.25 × 0.0148
d) Moles of MnO−4 = = 3.737 × 10−4 mol (1)
1000
3.737 × 10−4
Moles of FeC2O4 in 25 cm3 = × 5 = 6.228 × 10−4 (1) 123
3
Moles of FeC2O4 in 500 cm3 = 6.228 × 10−4 × 20 = 0.01246 mol (1)
Mass of FeC2O4 = 0.01246 × 143.8 = 1.79 g (1)
If incorrect ratio used: answer would be 3.76 g
7 a) C (1)
b) Two negative ions (1)
Repel each other/activation energy high (1)
 c) Mn2+ formed (1)
Autocatalyst (1)
Increased rate of reaction/pathway of lower activation energy (1)
−
8 a) 5Fe2+ + MnO4 + 8H+ → 5Fe3+ + Mn2+ + 8H2O (2)
4.483
b) Moles of FeSO4.7H2O = = 0.01613 mol (1)
277.9
0.01613
Moles of Fe2+ in 25 cm3 sample = = 0.001613 mol (1)
10
Moles of MnO4 required = 0.001616 = 3.226 × 10−4 mol
−
(1)
5
3.226 × 10−4
Volume of KMnO4 solution = × 1000 = 25.4 cm3 (1)
0.0127
9 a) i) VO2+ reduced to VO2+/V(v) to V(iv) as EMF = +0.83 V (1)
VO2+ reduced to V3+/V(iv) to V(iii) as EMF = +0.17 V (1)
V3+ not reduced to V2+/no V(iii) to V(ii) as EMF = −0.43 V (1)
SO2 oxidised to SO24− (1)
ii) Yellow (to blue) to green (1)
26 Transition metals: Variable oxidation states

b) i) VO2+ reduced to VO2+/V(v) to V(iv) as EMF = +1.76 V (1)

VO2+ reduced to V3+/V(iv) to V(iii) as EMF = +1.1(0) V (1)
V3+ not reduced to V2+/no V(iii) to V(ii) as EMF = +0.5(0) V (1)
ii) VO2+ + 4H+ + 3e− → V2+ + 2H2O (2)
iii) 2VO2+ + 8H+ + 3Zn → 2V2+ + 4H2O + 3Zn2+ (2)

124
 27 Optical isomerism
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 553)
1 a) Molecules which have the same molecular formula but a different
structural formula are known as structural isomers.
b) There are 2. They are butane and 2-methylpropane.
2 a) 2-chloropropane CH3CHClCH3
b) H Cl H

H C C C H

H H H

c) H Cl H H

C C C C

Cl H Cl Cl

(E)-1,2-dichloroethene (Z)-1,2-dichloroethene

3 Stereoisomers are molecules which have the same structural formula but
a different arrangement of atoms in space.

●● TEST YOURSELF 1 (PAGE 556)

1 a) No
b) No
c) no
d) Yes
e) No
f) Yes
2 a) A carbon that has four different atoms or groups attached.
b) COOH HOOC 125

C C
H H
H3C CH3
OH HO

c) 109.5°
d) 2-hydroxypropanoic acid
 ●● TEST YOURSELF 2 (PAGE 557)
1 Pass plane polarised light into it – the plane of plane polarised light will
be rotated by a single enantiomer but it will be unaffected by a racemate.
2 a H H Br H

H C C C C H

H H H H

2-bromobutane
C4H9Br

b) The asterisk should be on the same carbon as the bromine.

c) Br Br

C C
CH3CH2 H H H2CH3C
CH3 H3C
mirror

d) The racemate is optically inactive as it contains equal amounts of each

isomer, and one isomer rotates plane polarised light to the right, the
other to the left and the two opposite effects cancel out.
3 Light in which all the waves vibrate in the same plane.

●● PRACTICE QUESTIONS (PAGE 558)

1 A (1)
2 A (1)
3 a) An optically active substance is one which can rotate the plane
27 Optical isomerism

of plane polarised light (1)

b) OH HO  (2)
C C
H3C COOH HOOC CH3
H H

c) H H H O  (1)
H C C C C

H H

4 a) An asymmetric carbon atom is chiral and has four different atoms or

126 groups attached. (1)
b) Optical isomers are stereoisomers which occur as a result of chirality in
molecules. They exist as non-superimposable mirror images and differ
in their effect on plane polarised light. (1)
c) H H H H  (1)
H C C C C H

H H OH H
d) H H  (2)

PRACTICE QUESTIONS (PAGE 558)

C C
CH3CH2 OH HO H2CH3C
CH3 H3C

e) Pass plane polarised light into a solution of the isomers; one isomer
rotates plane polarised light to the right, the other to the left. (2)
f) Orange to green (4)
H H H H

H C C C C H

H H OH H  
H H O H

H C C C C H

H H H

127
 28
The carbonyl group
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGES 559–60)
1 a) butan-2-ol
b) hept-3-ene
c) 2-Methylbutane
d) 2,3-dimethylhexane
e) 2-methylpropane
f) 1-bromo-1,2-dichloropropane
g) 1-bromo-1-chlorobutane
2 a) Structure (c) or (d)
b) Structure (e) or (g)
3 (a) Alcohol (b) C=C
4 CH3CH2CH2CH3
5 a) Orange to green
b) CH3CH2OH + 2[O] ⟶ CH3COOH + H2O
c) Ethanoic acid
d) Primary

●● TEST YOURSELF 2 (PAGES 568–9)

1 a) CH3CH2CH2CHO
b) CH3COCH3
c) CH3CHO
d) HCHO
128 e) CH3COCH2CH2CH3
f) CH3CH2CH(CH3)CHO
g) CH3CHClCH2CH2CHO
2 a) ethanol, propanone, butanone, propanal
b) ethanol, propanal
c) propanone, propanal
d) ethanol, propanal
 e) propanal, silver mirror

TEST YOURSELF 3 (PAGE 572)

f) propanone, propanal
3 HCHO + 2[H] ⟶ CH3OH
4 CH3CH(OH)CH3 + [O] ⟶ CH3COCH3 + H2O
5 CH3CH2CH2CHO + [O] ⟶ CH3CH2CH2COOH
6 Oxidising Primary Secondary Tertiary Aldehyde Ketone
agent alcohol alcohol alcohol
Acidified ✓ ✓ ✗ ✓ ✗
potassium
dichromate
Felhing’s ✗ ✗ ✗ ✓ ✗
solution
Tollens’ ✗ ✗ ✗ ✓ ✗
reagent

7 a) Propanal, propan-1-ol
b) Ethanoic acid ethanal
c) Butanoic acid
d) Propan-2-ol
e) Propan-1-ol, propan-2-ol and propanal, propanone
f) Ethanal propanal

●● TEST YOURSELF 3 (PAGE 572)

1 a) CH3CH2CHO + HCN ⟶ CH3CH2CH(OH)CN
b) 2-hydroxybutanenitrile

propanal + ??? addition

c) Nucleophilic
d) 
−O H+ OH
O

CH3CH2C CH3CH2C H CH3CH2C H

H CN CN
−
CN

e) The product is a racemate as it contains equal amounts of each isomer.

One isomer rotates plane polarised light to the right, the other to the
left and the two opposite effects cancel out. 129

2 a) NaBH4
b)  
−O H+ OH
O

CH3CH2C CH3CH2C H CH3CH2 C H

H H H
−
H
nucleophile : hydride ion

c) Propanol
 3 a) CH3CH2CH=CHCHO + Br2 ⟶ CH2CH2CHBrCHBrCHO
b) CH3CH2CH=CHCHO + HCN ⟶ CH3CH2CH=CHCH(OH)CN

●● TEST YOURSELF 4 (PAGE 577)

1 a) i) CH3CH2CHClCH2COOH
ii) CH3CH(CH3)CHCHCOOH
iii) CH3CHOHCOOH
iv) CH2OHCH2COOH
b Acid (iv)
c) Acid (ii)
2 a) CH3COOH ⇋ CH3COO− + H+
b) Ethanoate
c) Yes the ions can move and carry charge
3 a) KOH + CH3COOH ⟶ CH3COOK + H2O
b) 2CH3COOH + Na2CO3 ⟶ 2CH3COONa + H2O + CO2
c) MgO + 2CH3CH2COOH ⟶ (CH3CH2COO)2Mg + H2O
d) HCOOH + NH3 ⟶ HCOONH4
e) CH3COONH4 ⟶ CH2CONH2 + H2O; ethanamide
4 Add solid sodium carbonate to the solution and bubbles are observed and
the gas produced will turn colourless limewater milky.

●● TEST YOURSELF 5 (PAGES 582–3)

28 The carbonyl group

1 a) Ethyl ethanoate
b) Methyl methanoate
c) Ethyl propanoate
d) Ethyl methanoate
2 a) CH3COOH + CH3OH ⇋ H2O + CH3COOCH3
b) CH3CH2CH2CH2COOH + CH3CH2OH ⇋ H2O +
CH3CH2CH2CH2COOCH2CH3

c) CH3CH2CH2COOH + CH3CH2CH2OH ⇋
130 CH3CH2CH2COOCH2CH2CH3 + H2O
3 Concentrated sulfuric acid
4 a) HCOOCH2CH3 + NaOH ⟶ HCOONa + CH3CH2OH
b) HCOOC3H7 + H2O ⇋ HCOOH + C3H7OH
5 Propane-1,2,3-triol
6 Saponification is the alkaline hydrolysis of fats into glycerol and the salts
of the fatty acids present in the soap.
 7 a) H2C OH

ACTIVITY (PAGE 579)

HC OH

H2C OH + 3HOOC(CH2)7CH=CHCH2CH=CH(CH2)4CH3 3H2O +

CH2OOC(CH2)7CH=CHCH2CH=CH(CH2)4CH3

CHOOC(CH2)7CH=CHCH2CH=CH(CH2)4CH3

CH2OOC(CH2)7CH=CHCH2CH=CH(CH2)4CH3

b) It contains carbon–carbon double bonds;

c) CH3OOC(CH2)7CH=CHCH2CH=CH(CH2)4CH3

●● TEST YOURSELF 6 (PAGE 591)

1 a) Propanoyl chloride
b) Butanamide
c) Propanoic anhydride
d) Ethanoyl chloride
2 a) CH3COCl + CH3CH2CH2OH ⟶ CH3COOCH2CH2CH3 + HCl
b) CH3CH2CH2COCl + 2NH3 ⟶ CH3CH2CH2CONH2 + NH4Cl
c) CH3CH2COCl + CH3NH2 ⟶ CH3CH2CONHCH3 + HCl
d) (CH3CO)2O + CH3CH2OH ⟶ CH3COOCH2CH3 + CH3COOH
3 Nucleophilic addition-elimination: ethanoic acid
4 Recrystallization
5 Carry out a melting point experiment; if it is pure the melting point
should be sharp.

●● ACTIVITY (PAGE 579)

Preparation of an ester
1 The concentrated sulfuric acid on dilution gives out a great deal of heat,
the slow addition with cooling is necessary to avoid splashing if the
mixture gets hot.
2 It is a catalyst for the esterification.
3 CH3CH2OH + CH3COOH ⇋ CH3COOCH2CH3 + H2O
4 Anti-bumping granules are small pieces of silica or broken unglazed 131
pottery. This provides a nucleus on which gas bubbles grow, therefore
avoiding the sudden production of large gas bubbles that can lead to
‘bumping’, which could cause the liquid to splash over into the condenser
and therefore produce an impure product.
5 The distillate contains traces of unreacted ethanoic acid and concentrated
sulfuric acid. The sodium carbonate solution removes these.
6 The neutralisation with sodium carbonate produces carbon dioxide gas;
opening the tap releases this and avoids a build-up of pressure that might
blow the stopper out of the funnel.
 7 The ester has been dried.
8 To remove water.
9 Moles ethanol = 40.0 = 0.870 mol; moles ethanoic acid = 52.0 = 0.867
46 60.0
0.870 × 88.0 = 76.6 g theoretical yield % yield = 50.0 × 100 = 65.3%
76.6
●● ACTIVITY (PAGES 590–1)
The preparation of aspirin in the laboratory
 1 Catalyst
 2 Slowly/drop wise, wear gloves
 3 Open tap

Cold water
out
Liebig
condenser

Cold water in

Pear-shaped
flask
Anti-bumping
granules

Heat

 4 Number of moles aspirin = 5.0 = 0.0277

180.0
28 The carbonyl group

0.0277 × 100 = 0.041

70
Number of moles 2-hydroxybenzoic acid = 0.041
Mass of 2-hydroxybenzoic acid = 0.041 × 138.0 = 5.66 g
 5 (CH3CO)2O + H2O ⟶ 2CH3COOH
 6 To form crystals
 7 It is faster and gives drier product
 8 Dissolve in minimum volume of hot water, filter, cool and crystallise

 9 180.0 × 100 = 75%

132
180.0 + 60.0
10 Ethanoyl choride reacts violently and hydrogen chloride gas (corrosive)
is produced.
11 It is impure if a wide range of melting points and the value is below the
melting point of pure aspirin.
●● PRACTICE QUESTIONS (PAGES 591–3)

PRACTICE QUESTIONS (PAGES 591–3)

1 D (1)
2 B (1)
3 B (1)
4 a) A: acidified potassium dichromate(VI), warm (2)
B: acidified potassium dichromate(VI), warm (2)
C: hydrolysis by heating with dilute hydrochloric acid (2)
D: NaBH4, heat under reflux followed by adding dilute mineral acid (2)
E: propanol concentrated sulfuric acid catalyst, heat (2)
b) A, oxidation; B, oxidation; C, hydrolysis; D, reduction;
E, esterification (5)
5 a) A nucleophile is a lone pair donor. It is an atom or group which is
attracted to an electron deficient centre, where it donates the lone pair
to form a new covalent bond. (1)
b) The carbonyl group is polar and the carbon δ+ is susceptible to attack
by nucleophiles seeking such an electron deficient centre. (2)
c) CH3CH2CHO + HCN ⟶ CH3CH2CH(OH)CN;
2-hydroxybutanenitile
propanal + ??? (2)
d) (3)
−O H+ OH
O

CH3CH2C CH3CH2C H CH3CH2C H

H CN CN
−
CN

e) This is because the carbonyl bond is planar and the cyanide ion
could attack the carbon atom equally from either side. As a result, the
formation of each enantiomer is equally likely and so a racemate is
formed. (2)
f) i)  Reagent Formula of metal/ Formula of metal/  (4)
ion before test ion after test
Tollens’ Ag+ Ag
reagent
Fehling’s Cu2+ Cu+
solution
ii) Tollens’ reagent and Fehling’s solution (1) 133

6 a) i) Ethanoic acid forms a dimer as two hydrogen bonds form, between

two ethanoic acid molecules. The hydrogen bonds need a lot of
energy to break. Ethyl methanoate only has weaker dipole–dipole
attractions between the molecules which do not need as much
energy to break. (3)
ii) CH3COOH + KHCO3 ⟶ CH3COOK + CO2 + H2O
Bubbles heat, solid disappears to form a colourless solution. (2)
 b) i) CH3COOH + CH3OH ⇋ CH3COOCH3 + H2O (1)
use concentrated sulfuric acid as a dehydrating agent to remove
water and the reaction will move to the right
ii) O O  (4)
CH3 CH2 C CH3 C

OH OCH3

propanoic acid methyl ethanoate

iii) (CH3CO)2O + CH3OH ⟶ CH3COOCH3 + CH3COOH (1)

c) i)   Propane-1,2,3-triol (1)
ii) CH2OH CH2OOCR  (4)
CHOH + 3RCOOCl CHOOCR + 3HCl

CH2OH CH2OOCR

iii) CH2OOCC17H31  (1)

CHOOCC17H33 + 3 CH3OH

CH2OOCC17H29

HO CH2

HO CH + CH3OOC17H31 + CH3OOC17H33 + CH3OOC18H29

HO CH2

 7 C2H5COONH4 CH3CH2CH2OH CH3CH2COONa (3)

 8 B (1)
28 The carbonyl group

 9 a) O
− (3)
O O
CH3 C CH3 C Cl CH3 C + HCl

Cl +
CH3 N H N H

CH3NH2 H CH3

b) CH3CH2COCl + 2NH3 ⟶ CH3CH2CONH2 + NH4Cl (1)

10 a) A, ethene; B, bromoethane; C, propanenitrile; D, propanoic
acid; E, propanoyl chloride (5)
b) 1, Addition; 2, substitution (2)

c) Electrophilic addition (1)

134
d) Nucleophilic substitution (1)
e) 1, HBr; 2, KCN (2)
11 a) Add sodium carbonate = the methyl ethanoate has no reaction,
the acid bubbles producing carbon dioxide. (3)
b) React with water/ethanol – the butan-2-one has no reaction and
the propanoyl chloride has a vigorous reaction and fumes of HCl. (3)
 c) Warm with acidified potassium dichromate(vi) butan-2-ol orange
⟶ green and 2 methylpropan-2-ol has no reaction. (3)

PRACTICE QUESTIONS (PAGES 591–3)

12 a) Ethanoic acid is soluble as it can form hydrogen bonds between
the polar COOOH and lone pair on water. The long hydrocarbon
chain in dodecaonic acid breaks the hydrogen bonds between the
COOH and water and prevents it from dissolving. (2)
b) Add a spatula of sodium carbonate or sodium hydrogen carbonate
to the solution
If it is a carboxylic acid effervescence is observed.
The gas can be collected and bubbled into colourless limewater
which should turn milky, proving that the gas produced is carbon
dioxide. (2)
c) Place some of the solid in a melting point tube and attach to a
thermometer with a rubber band.
Place in melting point apparatus and heat slowly.
Record the temperature at which the solid starts to melt and the
temperature at which it finishes melting.
Repeat and average the temperatures.
A sharp melting point indicates a pure solid (3)
d) C11H23COOH + 4[H] ⟶ C11H23CH2OH + H2O; NaBH4 (2)
e) H O

H H C O C C11H23

H C OH O

3C11H23COOH + H C OH H C O C C11H23 + 3H2O

H C OH O

H H C O C C11H23

13 X propan-2-ol; NaBH4 nucleophilic addition (2)

H OH H

H C C C H

H H H
Y propene conc H2SO4 or conc H3PO4 elimination (2)
H H H

H C C C 135

H H

HBr electrophilic addition (2)

 29 Aromatic chemistry
●● TEST YOURSELF ON PRIOR KNOWLEDGE 1
(PAGE 594)
1 a) ethene + bromine 1,2-dibromoethane

H H H H

C C + Br2 H C C H

H H Br Br

b) Orange to colourless
c) 1,2-dibromoethane
2 a) C5H8
b) C5H8
c)

d) 2-methylbuta-1,3-diene
e) C5H8 + 2Br2 ⟶ C5H8Br4
f) Orange bromine water is decolourised

●● TEST YOURSELF 2 (PAGE 597)

1 Kekulé’s structure suggests alternate double and single bonds, however
X-ray diffraction shows that that all the bonds in benzene are the same
length, intermediate between that of a single and double bond.
2 Hexagonal planar; 120°
3 Each carbon uses three of its outer electrons to form sigma bonds to two
other carbon atoms, and one hydrogen atom. Each carbon also has one
electron in a p orbital. The p orbitals overlap sideways to form a ring of
charge above and below the plane. The 6p electrons spread across this
136
ring and are delocalised. This leaves each carbon atom with one electron
in a p orbital.

●● TEST YOURSELF 3 (PAGE 599)

1 a) 1,2-dichlorobenzene
b) 3-chloro-1-methylbenzene
c) 1-ethyl-2-methylbenzene
d) 1-bromo-4-chlorobenzene
 2 a) Bromine water

TEST YOURSELF 5 (PAGE 603)

b) With benzene it remains orange; with cyclohexene it goes from orange
to colourless.
3 To undergo addition reactions, the delocalised electron system would
be broken resulting in a loss of stability. Instead benzene undergoes
substitution reactions which retain the delocalised ring of electrons and
hence the stability of the benzene ring.
4 CH3

5 1-Bromo-2-chlorobenzene; alphabetical order of side groups

●● TEST YOURSELF 4 (PAGE 601)

1 a) Electrophilic substitution
b) Movement of a pair of electrons
c) 6; 4
d) A C-H bond breaks in the unstable intermediate and the two electrons
in the bond move back into the pi electron system, reforming the
stable delocalised electron ring. The hydrogen is lost as H+.
e) Explosives; amines for dyes
f) 50°C and a catalyst of concentrated sulfuric and concentrated nitric
acid.

●● TEST YOURSELF 5 (PAGE 603)

1 a) CH3CH2CH2COCl + C6H6 ⟶ C6H5COCH2CH2CH3 + HCl
b) Acylation is the process of replacing a hydrogen atom by an acyl group
(RCO−). Here the hydrogen atom is replaced by COCH2CH2CH3.
c) Aluminium chloride
+ −
CH3CH2CH2COCl + AlCl3 ⟶ CH3CH2CH2CO + AlCl4
−
d) H+ + AlCl4 ⟶ AlCl3 + HCl
e) Aluminium chloride hydrolyses
2 a) O 137

C CH2 CH3

b) C6H6 + CH3CH2COCl ⟶ C6H5COCH2CH3 + HCl

anhydrous conditions and aluminium chloride catalyst
 c) C9H10O O

d) Phenylpropanal
H

●● ACTIVITY (PAGE 603)

Preparation of methyl 3-nitrobenzoate
1 O OCH3 O OCH3
C C

+ HNO3 + H2O
O
N

2 Ester
3 C8H8O2; C4H4O
4 The temperature was kept low (less than 10 °C) to prevent further
nitration.
5 Methyl 3-nitrobenzoate Nitrobenzene
Temperature less than 10 °C Temperature 50 °C
Cool in ice Heat under reflux

6 To remove aqueous impurities, e.g. acid

29 Aromatic chemistry

7 Recrystallisation is used to purify the solid methyl-3-nitobenzoate. The

impurities dissolve in the hot solvent and remain there when the solid
crystallises out again.
8 moles of methyl benzoate = 2.7 = 0.020
136.0
Ratio 1 : 1; moles methyl 3-nitrobenzoate = 0.020
0.020 × 181.0 = 3.62 g
9 % yield = 2.1 × 100 = 58.0%
3.62
●● PRACTICE QUESTIONS (PAGES 604–5)

138 1 B (1)
2 B (1)
3 D (1)
4 a) C6H6 + 3H2 ⟶ C6H12 (1)
b) Benzene is more stable than cyclohexa-1,3,5-triene. The expected ΔH1
of hydrogenation of C6H6 is 3 x −120 = −360 kJ mol−1. The actual ΔH1
of C6H6 is −208 which is 152 kJ mol−1 less exothermic than expected.
This is because of the stability of the delocalised electron ring. (2)
 c) Bubble bromine water into both, in benzene it remains orange. In
cyclohexene the bromine water turns from orange to colourless. (2)

PRACTICE QUESTIONS (PAGES 604–5)

5 a) CH3 CH3 CH3 (4)
Br

Br

Br
2-bromomethyl benzene 3-bromomethyl benzene 4-bromomethyl benzene

b) To undergo addition reactions, the delocalised electron system would

be broken resulting in a loss of stability. Instead benzene undergoes
substitution reactions which retain the delocalised ring of electrons
and hence the stability of the benzene ring. (2)
6 a) i) Catalyst (1)
ii) Cl+ (1)
b) i) 2-methyl-1,3,5-trinitrobenzene (1)
ii) 2C7H5N3O6 + 10.5 O2 ⟶ 14CO2 + 3N2 + 5H2O (2)
c) i) Concentrated nitric acid and concentrated sulfuric acid. (2)
ii) HNO3 + 2H2SO4 ⟶ NO2+ + 2HSO4− + H3O+ (1)
iii) Nitronium ion (1)
d) i) Electrophilic substitution (1)
ii) (3)
H NO2
+
NO2
+ NO2 + H+

iii) 2-methyl nitrobenzene (1)

7 a) C6H6 + CH3COCl ⟶ C6H5COCH3 + HCl; phenylethanone (2)
b) Aluminium chloride (1)
+
c) CH3COCl + AlCl3 ⟶ CH3 CH2CH2CO + AlCl4− (1)

H C CH 3
+
C CH3
+ C CH 3 O + H+
O
O
139
d) Electrophilic substitution. (1)
+
8 a)  (1)
O
N O

b) The nitrogen atom should have 5 electrons in the outer shell. It has
lost one, so the ion is positive. (1)
 c) The nitronium ion is an electrophile as it is a group that is attracted to
an electron-rich centre where it accepts a pair of electrons to form a
new covalent bond. (1)
–
d) HNO3 + 2H2SO4 ⟶ NO2+ + 2HSO4 + H3O+ (1)
e) Substitution – a hydrogen atom on the benzene is replaced by a NO2
group. (2)
f) The hydrogen ion is regenerated at the end of the reaction. (1)
9 a) Propanoyl chloride; aluminium chloride
+ −
CH3 CH2COCl + AlCl3 ⟶ CH3 CH2CO + AlCl4 (3)
b) (3)
H C CH2CH3
+
C CH2CH3
+ C CH2CH3 O
O
O

c) No change; Fehling’s reagent remains a blue solution. (1)

d) Z is Tollens’ reagent. Structure X is given below: (3)

O
29 Aromatic chemistry

140
 30
Amines

●● TEST YOURSELF ON PRIOR KNOWLEDGE 1

(PAGE 606)
1 lone pair

H N H

2 It is a proton acceptor
3 a) 1,3-dibromo-2-chlorobutane
b) 1,2,3-trifluoropropane
c) 2-chloropropane
d) 2-bromopropane
e) 2-bromobutane
4 It has a lone pair which it can donate.

●● TEST YOURSELF 2 (PAGE 611)

1 a) ethylamine
b) phenylamine
c) dimethylamine
d) trimethylamine
e) 2-aminobutane
f) 2,4-diaminopentane
g) butylamine
h) 2-amino-2-methylethanoic acid.
2 141

Amine 1° 2° 3°
methylamine ✓
ethylamine ✓
dimethylamine ✓
phenylamine ✓
triethylamine ✓
 3
H NH2 H CH3
CH3

H C C C H HN N

CH2 CH3 H3C CH3

H H H
primary secondary tertiary

●● TEST YOURSELF 3 (PAGE 616)

1 a) Proton acceptor
b) i) CH3CH2NH2 + H2O ⇋ CH3CH2NH3+ + OH−
ii) The equilibrium lies to the left so there is a low [OH–] as ethylamine
is only slightly ionised
c) Ethylamine. The alkyl group is electron releasing/donating and this
increases the electron density on N and increases the availability of the
lone pair, so it can accept protons readily.
2 a i) methylammonium chloride
ii) Heat with sodium hydroxide.
b)

Compound Basicity

ammonia 3
dimethylamine 1
methylamine 2
phenylamine 4

c) CH3CH2NH2 + H2O ⇋ CH3CH2NH3+ + OH−

d) 2CH3NH2 + H2SO4 ⇋ (CH3NH3)2SO4
3 A, benzene; B, nitrobenzene; C, phenylamine; D, phenylammonium
30 Amines

chloride.
b) Concentrated nitric acid and concentrated sulfuric acid; tin and
concentrated hydrochloric acid; hydrochloric acid
c) Electrophilic substitution

4 The lone pair on N in Y is delocalised into the pi electron ring and is less
available for protonation than lone pair in Z
142

●● TEST YOURSELF 4 (PAGE 619)

1 CH3CONCH3 + CH3COOH
2 a) CH3CH2COCl + CH3CH2NH2 → CH3CH2CONHCH2CH3 + HCl
b) Nucleophilic addition-elimination
 c)
O−

ACTIVITY (PAGE 619)

O O
CH3 CH2C CH3 CH2 C Cl CH3 CH2 C + HCl

Cl CH3 CH2
+
N H N H

CH3 CH2NH2 H CH3 CH2

d) N-ethylpropanamide
3 a) dimethylamine
b) Nucleophilic substitution
H H H
+
H C Br H C N H + Br –

H H CH3

CH3NH2

c) Quaternary ammonium salt

d) Cationic surfactant; bactericide; detergent; fabric softener or
conditioner; hair conditioner

●● ACTIVITY (PAGE 619)

PARACETAMOL
1 2  a)
OH OH

NH2 H N C O

CH3
2 b)
OH OH

+ CH3 COCI + HCI

NH2 H N C O
143
CH3

c) Electrophilic substitution
3 It is less corrosive; it is less vulnerable to hydrolysis; it is less hazardous to
use as it gives a less violent reaction; it is cheaper than ethanoyl chloride;
it does not produce corrosive fumes of hydrogen chloride.
 ●● PRACTICE QUESTIONS (PAGES 620–1)
1 C (1)
2 D (1)
3 D (1)
4 a) i) butylamine CH3CH2CH2CH2NH2  (2)
ii) Lone pair donor (1)
iii) Where one atom or group is replaced by another. (1)
b) i) CH3CH2Br + KCN → CH3CH2CN + KBr  (1)
ii) Hydrogen with a nickel catalyst or LiAlH4. (1)
iii) propylamine (1)
iv) Reduction (1)
v) (1)
H H H H H H

H C C C N + 4[H] H C C C N

H
H H H H H

5 a) i) Proton acceptor (1)

ii) butylamine. The alkyl group is electron releasing and it increases the
electron density on nitrogen making the lone pair more available. (2)
b) (1)
H3C CH2CH3
N

CH3

  c) i) CH3(CH2)17N(CH3)3 (Br ) (1)

ii) Quaternary ammonium (salt) (2)
30 Amines

Cationic surfactant; fabric softener/water repellents; hair

conditioners; spermicidal; detergents.
d) Mechanism: (3)
−
O
O O

CH3 C CH3 C Cl CH3 C + HCl

144 Cl CH3
+
N H N H

CH3NH2 H CH3
6 a) Nδ−–Hδ+ (1)

PRACTICE QUESTIONS (PAGES 620–1)

  b) i) (5)

Amine Melting point (°C) Boiling point (°C) State at 25°C

methylamine −93 −61.8 Gas
ethylamine −81   17 Gas
propylamine −83   49 Liquid
dimethylamine −92   7 Gas
trimethylamine −117   3 Gas

ii) The lone pair of the nitrogen can form hydrogen bonds with
polar water. (1)
c) i) Nucleophilic substitution (1)
ii) Quaternary ammonium salt (1)
7 a) Method 1
Intermediate is propanenitrile
Reagent: KCN; condition: aqueous or ethanolic solution
Reagent: Hydrogen; condition: nickel catalyst or
LiAlH4; condition: in ether
Method 2
Reagent: ammonia; condition: excess ammonia (6)
b) Disadvantages method 1: KCN is toxic; it is a two-step process giving a
lower yield; LiAlH4 is expensive.
Disadvantage method 2: further substitution is likely and the product
must be separated out. (2)

145
 31 Polymers, amino
acids and DNA

●● TEST YOURSELF ON PRIOR KNOWLEDGE 1

(PAGE 622)
1 a) polythene or poly(ethene)
b) PVC or poly(chloroethene)
c) polystyrene or poly(styrene)
2 a) tetrafluoroethene
b)
F F F F

C C C C

F F F F

c) Addition
d) polytetrafluoroethene

●● TEST YOURSELF 1 (PAGE 628)

1 a) benzene-1,4-dicarboxylic acid and ethane-1,2-diol
b) hexanedioic acid and hexane-1,6-diamine
c) benzene-1,4-dicarboxylic acid and benzene-1,6-diamine
2
H H H H H

N C C N C C C C C

H H H H O H H H O
146
3 a)
O H H O

CI C C C C CI butanedioyl dichloride

H H
 b)

TEST YOURSELF 3 (PAGE 645)

H H H H

HO C C C C OH butane-1,4-diol

H H H H

c) polyester

●● TEST YOURSELF 2 (PAGE 638)

1 a)
CH3

CH2

H3C *CH

H2N *C COOH

b)
CH3

CH2

H3C CH
+
H3N C COOH

2 Alpha/α helix; beta/β-pleated sheet.

3 Distance moved by the spot divided by the distance moved by the
solvent.
4
CH3
+ –
H3N C COO

●● TEST YOURSELF 3 (PAGE 645)

1 Guanine, adenine, cytosine and thymine 147

2 Guanine with cytosine; adenine with thymine

3 2-Deoxyribose bonded to phosphate ion (bonded at carbon 5) and base
(bonded at carbon 1)
4

T C G A T A C G
A G C T A T G C
 ●● ACTIVITY (PAGES 632–5)
LYSINE
1 2,6-diaminohexanoic acid
2 A molecule with the ability to rotate the plane of plane polarised light.
3
CO2H HO2C

∗C C
H2N (CH2)4NH2 H2N(CH2)4 NH2
H H

4 It forms zwitterions and so there are strong ionic attractions between

oppositely charged ions, which take a substantial amount of energy to break.
5 A zwitterion is an ion with a positive and a negative charge.
6 a)

CH2 CH2 CH2 CH2 CH COO−

NH3+ NH3+

b) H2N(CH2)4CH(NH2)COO−
7 H2N(CH2)4CH(NH2)CONH(CH2)4CH(NH2)COOH
8 Moles of N = 10.5 = 0.75
14.0
31 Polymers, amino acids and DNA

5.3
Moles of H = = 5.3
1.0
36.1
Moles of C = = 3.01
12.0
48.1
Moles of O = = 3.01
16.0
Divide by 0.75 to get simplest ratio C4H7O4N

●● ACTIVITY (PAGE 639)

Urea
1 Pb(CNO)2 + 2NH3 + 2H2O → Pb(OH)2 + 2NH4CNO
420
2 moles NH4CNO = = 7.00
60.0
80% → 100% 7.00 × 100 = 8.75

80
(1 : 2) moles Pb(CNO)2 = 8.75 = 4.375
148 2
mass Pb(CNO)2 = 4.375 × 291.2 = 1274 g
3 a) Recrystallisation
b) The urea must be soluble in hot solvent but insoluble when solvent is
cold. The impurities remain in solution when cold.
c) Prevents loss of product.
 d) Filter by suction filtration and then dry in low temperature oven/
desiccator.

PRACTICE QUESTIONS (PAGES 646–7)

e) Place the sample in a capillary tube sealed at one end and heat slowly
(in an oil bath); a sharp melting point at 133 °C indicates purity.
4 a) 2NH3 + CO2 → H2NCOONH4
b) H2NCOONH4 → (NH2)2CO + H2O
c) % N = 2 × 14.0 × 100 = 46.67%
60.0
5
H O H O H H O H H

H N C N H + C C N C N C + H2O

H H H H

Urea Methanal Urea-methanal

●● PRACTICE QUESTIONS (PAGES 646–7)

1 C (1)
2 C (1)
3 a) Glycine (1)
b) (2)
COOH COOH

CH2OH CH2 CH2 CH2OH

H2N CH C N CH COOH or H2N CH C N CH COOH

O H O H

c) 2-aminobutanedioic acid (1)

d) 2-amino-3-hydroxypropanoic acid (1)
e) (1)
COO−

CH2

H2N CH COO−

f) (1)
149
COOH

CH2

H3N+ CH COOH

g) (2)
CH2OH

H3N+ CH C O CH3

O
 4 a) (1)
CH3

HO CH

H2N CH COOH

b) (1)
COOH

HO CH

H3N+ CH COOH

c)  (2)
O COOH

H3C C O CH

H3N+ CH COOH

5 a) i) thymine (1)
ii) C5H6N2O2 (1)
b) 2-deoxyribose (1)
c) i) adenine (1)
31 Polymers, amino acids and DNA

ii) (1)
O
OH
H3C
−O NH
P O

OCH2
N O
O
H H

H H
OH H

d) (1)
O
OH
H3C

−O NH
P O

150 OCH2
N O
O
H H

H H
OH H
 6 a) +2 (1)

PRACTICE QUESTIONS (PAGES 646–7)

b) Square planar (1)
c) i) N atom in guanine (or adenine) (1)
Binds to Pt (1) in cisplatin (1)
Prevents random replication of DNA (1)
ii) Any two of: Hair loss; sterility; skin problems; digestive problems
any two. (2)
7 a) i) (1)
H H

HO C C OH

H H

ii) (1)

HOOC COOH

b) For two repeating units (2)

For any ester group circled (1)

H H O O H H O O

C C O C C O C C O C C O

H H H H

c) Condensation (1)
d) i) (1)

ClOC COCl

ii) (2)

O O

ClOC COCl + CH3CH2OH CH3CH2 O C C O CH2CH3 + 2HCl

e) H3CC6H4H3 + 6[O] → HOOCC6H4OOH + 2H2O (2) 151

or

H3C CH3 + 6[O] HOOC COOH + 2H2O

 8 a) H H  (1)
O O
C C C C

Cl Cl
H H

b) butane-2,2-diol (1)
c) polyester (1)
9 a) phenylamine (1)
aspartic acid (1)
b) CH3 (1)
O

C O

CH2 C H

N H

C O

−OOC
CH2 C H

NH2

c) CH3 CH3 (1)

O O
31 Polymers, amino acids and DNA

C O C O

CH2 C H CH2 C H

N H HN+ H

C O C O

HOOC CH2 C H HOOC CH2 C H

H3N+ H3N+
  or  
d) CH3  (1)
O

C O
∗

CH2 C H

N H
152
C O

− OOC ∗
CH2 C H

NH2
e) i) CH3OH (2)

PRACTICE QUESTIONS (PAGES 646–7)

COOH

CH2

H3N+ CH COOH

H3N+ C COOH

CH2

ii) Second and third/the amino acids (1)

153
 Organic synthesis,
32
NMR spectroscopy
and chromatography

●● TEST YOURSELF ON PRIOR KNOWLEDGE 1

(PAGE 648)
1 a) ethanoic acid; carboxylic acid
b) propanenitrile; nitrile
c) pentan-2-one; ketone
d) methyl ethanoate; ester
e) propanal; aldehyde
f) but-1-ene; alkene
2 a) C=O
b) O–H
c) C≡N
3 Propene/C3H6

●● TEST YOURSELF 2 (PAGE 653)

1 a) Concentrated NH3
b) KCN
c) Sn/HCl
d) lithal/LiAlH4
2 a) ethanoic acid
b) hydrochloric acid and lithal
3 a) Butanenitrile
b) KCN; lithal/LiAlH4
154

●● TEST YOURSELF 3 (PAGE 662)

1 TMS/tetramethylsilane
2 quartet, triplet and singlet
3 2
4 a) butanone, pentan-3-one, butanal
b) pentan-3-one
●● TEST YOURSELF 4 (PAGE 667)

PRACTICE QUESTIONS (PAGES 667–9)

1 Silica gel
2 Ethanal
3 UV light/ninhydrin/chemical developing agent

●● ACTIVITY (PAGE 665)

Thin-layer chromatography of amino acids in myoglobin
1 To prevent contamination of the plate by amino-acids from the skin,
which would interfere with results.
2 The pencil line is insoluble and will not move with the solvent or
interfere with results.
3 Using a capillary tube, add a spot of the amino acid solution to the base
line, allow it to dry and re-apply the solution to make a concentrated spot.
4 If the solvent is too deep, it will dissolve away the mixture.
5 If the tank is open, solvent may evaporate and not advance up the
plate. Having a sealed environment also allows solvent to saturate the
atmosphere inside.
6 The solvent can be toxic or flammable.
7 Avoid breathing vapour; wear gloves; carry out procedure in a fume
cupboard.
8 Distance moved by spot 3 cm, distance moved by solvent 6 cm;
3
Rf value = = 0.5
6
X corresponds to asparagine.
9 Different retention on the silica gel; different solubility in the developing
solvent.

●● PRACTICE QUESTIONS (PAGES 667–9)

1 D (1)
2 D (1)
3 C (1)
4 a) Single peak (1) as all 1H/protons equivalent (1)
b) each error −1 (2) 155

Δ/ppm 1.0 3.2 5.0

Integration ratio 3 3 1
Spin-spin splitting Triplet Quartet Singlet

c) Triplet due to CH2 adjacent to CH3. (1)

Quartet due to CH3 adjacent to CH2. (1)
 5 a) 5 (1)
b) 4 (1)
c) 4-methylpentan-2-one (1)
d) Doublet (1)
e) Singlet (1)
f)
CH3 H

H3C C CH2 C CH3

H OH
32 Organic synthesis, NMR spectroscopy and chromatography

6 a) A is butan-2-ol (1) (plus (1) for structure)

H H H H

H C C C C H

H H OH H

B is but-1-ene (1) (plus (1) for structure)

H H H H

H C C C C H

H H

C is 1-bromobutane (1) (plus (1) for structure)

H H H H

H C C C C H

H H H Br

D is butan-1-ol (1) (plus (1) for structure)

H H H H

H C C C C H

H H H OH

b) Step 1: NaBH4 or LiAlH4 (1)

Step 2: conc H2SO4  (1)

Step 3: HBr or HCl (1)

156 Step 4: NaOH/OH−  (1)
7 a) 1: Rf = 0.3125 (1)
2: Rf = 0.5 (1)
3: Rf = 0.9 (1)
b) Propan-2-ol = 1; propanone = 2; ethyl propanoate = 3 (1 correct = (1))(1)
c) Oils/fats/chemicals from skin may contaminate sample/plate. (1)
8 a) CH3CO (1)

PRACTICE QUESTIONS (PAGES 667–9)

b) CH3CH2O (1)
c) (1)
H H O H

H C C C O C H

H H H

d) CCl4/CDCl3/CD2Cl2/C2D6 (1)
9 a) CH3CH2CH3 (1)
b) CH3CH2CH2OH and CH3CH(OH)CH2CH3 and CH3CH2CHO (1)
c) CH3CH2CH2Br and CH3CH2COOH (1)
d) CH3CH=CH2 (1)
e) CH3CH2COOH and CH3CH2CHO (1)
f) i) Propene (1) and propylamine/1-aminopropane (1)
ii) HCl/HBr (1); electrophilic addition (1)
Concentrated (1)
NH3 (1)
Nucleophilic substitution (1)
10 a) 2-methylbutanal (1)
H H CH3
O
∗
H C C C C

H
H H H

or any other option is acceptable, for example

for correct structure (1)
for correct placement of asterisk (1)
OH
∗
H3C C C C CH3

H H H

for correct structure (1)

157
for correct placement of asterisk (1)
for correct name (pent-3-en(e)-2-ol)  (1)
 b) Any acceptable answer with the correct formula. For example:
Z isomer (1)
H3C CH(OH)CH3

C C

H H

E isomer (1) ((1) for structure)

H CH(OH)CH3

C C

H3C H

c) Correct structure of pent-4-en(e)-1-ol (1)

32 Organic synthesis, NMR spectroscopy and chromatography

H H H

H C C C C C OH

H H H H H

d) 3-methylbutanal (1)

158