AS & A Level Chemistry Workbook Answers

CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: WORKBOOK
Exam-style questions and sample answers have been written by the authors. In examinations, the way marks are awarded
may be different.
Workbook answers
Chapter 1
Exercise 1.1
An atom contains a dense nucleus surrounded by d The nucleus is extremely small so very few
shells of electrons. The nucleus contains the nucleons particles get close enough to it to be repelled
(protons and neutrons). Protons are positively charged, completely.
electrons have a negative charge and neutrons are
uncharged. The protons and neutrons have the same e The neutrons would go straight through the
relative mass. The mass of an electron is negligible. foil because they are uncharged. They are not
deflected by the positive charge in the nucleus.
Exercise 1.2 f Atoms of the isotope with more neutrons have
a greater mass. So since density = mass/volume,
1 and C; 2 and B; 3 and D; 4 and A
the density of heavier isotopes is greater.
Exercise 1.3
a A 36, B 49, C 66, D 24, E 24, F 26 Exam-style questions
b i There is a mixture of isotopes present.
(Relative atomic mass is the weighted
Question 1
mean of these isotopes.) a There are 3 protons, which are positively
ii 52 charged. [1]
iii There are two more protons than There are 4 neutrons, which have no
electrons in the strontium ion. charge. [1]
c i 13 protons, 13 electrons, 14 neutrons There are 3 electrons, which are negatively

charged. [1]
ii 55 protons, 54 electrons, 78 neutrons
Protons and neutron have a relative
iii 8 protons, 10 electrons, 9 neutrons mass of 1. [1]
Electrons have hardly any mass / mass of
Exercise 1.4 about 1/2000 that of a proton. [1]
a 4 2+
2 He b The electron configuration is the same/
b Most of the atom is empty space because the there is the same number of outer shell
nucleus is extremely small. The electrons have electrons. [1]
a much smaller mass than the alpha-particles c 7 Li+ (1 mark for 7 and 3 in correct places,
so do not cause a change in their momentum 3
if they do collide. 1 mark for Li+) [2]
c The positive charge on the nucleus (protons) d It has 2 electrons and 3 protons / it has
repels the positive charge on the alpha-particle. one more proton than electrons. [1]
[Total: 9]
1 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020

Question 2 c i Cobalt-59 because it has 32 neutrons

whereas nickel-58 has 30 neutrons. [1]
a Nickel, because it has one more proton than
cobalt / nickel has 28 protons and cobalt ii Cobalt because the number of electrons
has 27 [1] equals the number of protons. [1]
b Relative atomic mass depends on the iii Co3+ [1]

weighted mean [1] d The beam is deflected [1]
of the isotopes / idea of isotopes. [1] towards the positive plate / away from the
Cobalt has greater proportion of (isotopes) negative plate. [1]
with higher mass / nickel has greater Electrons are negatively charged / like
proportion (of isotopes) with lower mass. [1] charges repel / unlike charges attract. [1]
[Total: 10]

may be different.
Workbook answers
Chapter 2
Exercise 2.1 f H
g Similar points further on in the curve have
a A 2; B 1s; C 2; D 18; E 3; F 3s, 3p, 3d;
lower values, e.g. I is lower than A, J is lower
b i 1s22s22p5 than B, K is lower than C, etc.
ii Si Exercise 2.3
iii 1s22s22p63s23p64s13d5
a i There is a sudden jump in ionisation
iv 1s22s22p6 energy when the second electron has been
removed (because that is in a shell closer
v 19
to the nucleus).
vi Br−
ii Removal of electrons 10 and 11 takes
vii 1s22s22p63s23p63d2 much more energy than the others
(because they are nearer the nucleus).
c i Group 2
iii There is a gradual change as electrons 2 to
ii Group 15
9 are removed / there are no sudden jumps
iii Group 17 in the ionisation energy on removal of
successive electrons from 2 to 9.
iv Group 18
b i Ca 3+ ( g ) → Ca 4+ ( g ) + e −
Exercise 2.2
ii P + ( g ) → P2+ ( g ) + e −
a Across a period, there is a general increase
in the value of IE1. This is because of the Exercise 2.4
increase in nuclear charge. Across a period
the electrons are added to the same principal a i They are higher up on the diagram.
quantum shell so the attractive forces between ii The arrows are shown pointing in the
the nucleus and the outer electrons increases opposite direction.
gradually. So the first ionisation energy
increases gradually. Across a period there is b i ii 3p iii 3p
not much difference in shielding because there
are the same number of inner shell electrons. 3s 3s
2p 2p 2p
b A and I (ionisation energy increases across a
period to a maximum at Group 18) 2s 2s 2s
c i A and B or I and J 1s 1s 1s
ii F and G
c Electrons in the same orbital repel each other
iii C and D or K and L more than electrons in separate orbitals. The
electron removed from P and S are from the
d C and K same 3p energy level. The 3 outer p electrons
e E in P are in separate 3p orbitals to minimise the

repulsion between the electrons. There are 4 This draws the outer electrons (in the ion)
outer p electrons in S. So two of the electrons nearer the nucleus. [1]
have to go into the same orbital. The electron
removed from sulfur is from a 3p orbital, d i Boron has lower first ionisation energy
which contains a pair of electrons in the same than beryllium because the 5th electron
orbital. The extra repulsion between this pair goes into a p subshell [1]
of electrons makes the atom more unstable so which is further from the nucleus [1]
it is easier to remove an electron. This effect
is greater that the effect of the greater nuclear so attractive force on nucleus on electron
charge of S compared with P. is less. [1]
Boron has lower first ionisation energy
Exercise 2.5 than carbon because it has a lower
a The principal energy levels nuclear charge [1]
b The spacing gets smaller / the lines get closer so attractive forces between the nucleus
together. and outer electrons greater. [1]
c Electrons falling from higher to lower energy Similar amount of shielding since outer
levels electrons are in the same principal
quantum shell. [1]
d A
ii B ( g ) → B+ ( g ) + e − Symbols [1]
e I
gas state symbols [1]
f The energy levels get closer.
e s is spherical shape [1]
g H
p is propeller / dumbbell shape (there
h It takes more energy to remove the electron
should be no electron density in the centre) [1]
from hydrogen as the electron is at a lower
energy level closer to the attractive force of the [Total: 17]
nucleus / it takes less energy to remove the outer
electron from a lithium atom since the outer Question 2
electron is further from the attractive force of
the nucleus. a i 1s22s22p63s23p6 [1]
ii 1s22s22p63s23p64s13d5 [1]
Exam-style questions iii 1s22s22p63s23p63d3 [1]
Question 1 b Argon [1]

c i The electrons are being removed from
a i 1s22s22p1 [1]
the same principal quantum shell. [1]
ii 1s22s22p63s23p63d104s24p1 [1]
There is a gradual increase in nuclear
iii 1s22s22p63s23p63d10 [1] charge [1]
b No / gallium ion is smaller (0 mark on own) so attractive force between the nucleus
because the outer electrons in the atom are and electrons gradually increases. [1]
further from the nucleus / the outer electrons
in the atom are not pulled in by the nuclear ii The 8th electron is in a quantum shell
charge as much. [1] nearer to the nucleus. [1]
c Gallium. When a gallium ion is formed from Attractive forces between the nucleus
a gallium atom the outer quantum shell of and the outer electrons are higher. [1]
electrons is removed. [1] Very little shielding. [1]
So there is a greater force of attraction between
the nucleus and the outer electrons. [1]

iii F2 + ( g ) → F3+ ( g ) + e − Symbols [1] Correct levels and correct number of orbitals
filled / partly filled [1]
gas state symbols [1]
correct number of electrons in each
[Total: 12] subshell [1]
Question 3 correct spin [1]
a The energy needed to remove one electron [Total: 18]

from each atom in one mole of an atoms Question 4
to form one mole of ions [1]
a Atomic radius decreases across a period. [1]
atoms and ions in gaseous state. [1]
The outer electrons are in the same principal
b B and C [1]
quantum shell but the nuclear charge
Because there is a large jump in ionisation increases across a period. [1]
energy between the first and second electrons
So there is a greater force of attraction
being removed [1]
between outer electrons and the nucleus. [1]
c B [1] b Decreases between groups 1 and 14 / decrease
d A [1] across the group for positive ions. [1]
Because there is a large jump in ionisation Large increase between groups 14 and 17 /
energy between the third and fourth negative ions larger than positive ions in the
electrons being removed [1] same period. [1]
So there are 3 electrons in the outer shell [1] Decreases between groups 14 and 17 / decrease
across the group for negative ions. [1]
Group 13 elements form stable ions by loss
of 3 electrons. [1] c Down the group, there is one extra shell of
electrons from Cl to Br to I. [1]
e Accept values between 9000 and 11 000. [1]
Greater number of inner shells means greater
Element is in Group 2. [1] amount of shielding. [1]
3rd, 4th and 5th ionisation energies are This is greater than the effect of increased
increasing steadily (so must have at least nuclear charge. [1]
8 electrons in this shell). [1]
d i Atom (or molecule) having one (or
f i 1s 2s 2p 3s 3p 4s 3d
2 2 6 2 6 2 3
[1] more) unpaired electrons [1]
ii V + ( g ) → V 2 + ( g ) + e − Symbols [1] ii 1s22s22p63s23p5 [1]
gas state symbols [1] (same as a Cl atom)
g [Total: 11]
3p
3s
2p
2s
1s

may be different.
Workbook answers
Chapter 3
Exercise 3.1
We compare the mass of atoms using the unified d i (NH4)2SO4
atomic mass unit. This is defined as one twelfth of the
mass of an atom of carbon-12. Relative atomic mass is ii Zn(NO3)2
the weighted average mass of atoms in a given sample. iii Ag3PO4
The number of atoms in exactly 12 grams of the
iv Ca(OH)2
isotope carbon-12 is called The Avogadro constant.
Its value is 6.02 × 1023 mol-1. So there are e i NiSO4•7H2O
6.02 × 1023 atoms of carbon in 12 g of the
carbon-12 isotope. A mole is the amount of ii anhydrous
substance that has the same number of defined iii water of crystallisation
particles as there are in exactly 6.02 × 1023 atoms
of carbon in 12 grams of the carbon-12 isotope. iv Heat the green nickel sulfate
Relative molecular mass is the weighted average
mass of a molecule to the unified atomic mass Exercise 3.3
unit. Relative molecular mass is found by adding a i (3 × 207.2) + (4 × 16.0) = 685.6
together the relative atomic masses of all the atoms
in the molecule. For ionic compounds we use the 41.12
ii = 0.0600 mol (to 3 significant
term relative formula mass. 685.6
figures)
Exercise 3.2 iii 0.0600 × 3 = 0.180 mol
a i HCO3− iv Mass = mol × molar mass = 0.180 × 207.2
= 37.3 g
ii OH−
35.61
b i Mol Sn = = 0.300 mol
iii SO42− 118.7
iv Ag+ 42.60
Mol Cl = = 0.600 mol
71
b i ammonium
78.21
Mol tin chloride = = 0.300 mol
ii phosphate 260.7
iii nitrate ii Ratio of moles = Sn = 1, Cl = 2, SnCl4 = 1
iv carbonate iii Equation: Sn + 2Cl2 → SnCl4
c i CO2
ii MgO
iii Ca3N2
iv Al2S3

Exercise 3.4 Exercise 3.6

a i Not the simplest ratio. The simplest ratio a R. (200 cm3 = 0.2 dm3) concentration
is C3H5Cl.
moles = 0.12
= = 0.6 mol dm−3
ii empirical formula mass of PNCl2 = 31 + volume 0.2
14 + 2 (35.5) = 116
S. Mol = concentration × volume (dm3)
ratio of molar mass to empirical formula = 0.4 × 1.5 = 0.6 mol
mass = 348/ 116 = 3 mol
T. Volume (dm3) = = 0.25
multiply empirical formula mass by concentration 0.05
3 = P3N3Cl6 = 5 dm3 = 5000 cm3
5.4
b i Mass of oxygen = 19.78 − 14.98 = 4.80 g U. 5.4 g NaOH = mol = 0.135 mol.
40
14.98 0.135
ii Mol As = = 0.20 mol Concentration = = 0.90 mol dm−3
74.9 0.15
4.8 V. Mol NaCl = 0.20 × 2.0 = 0.40 mol so mass
Mol O = = 0.30 mol
16 = 0.04 × 58.5 = 23.4 g
iii Simplest ratio = 2 As to 3 O so empirical
formula is As2O3 35.4
b i Moles HCl = 0.2 × = 7.08 × 10−3 mol
1000
c Empirical formula mass = (2 × 74.9) +
(3 × 16.0) = 197.8 7.08 × 10 −3
ii Moles barium hydroxide =
2
Molar mass = 395.6 = 2. = 3.54 × 10−3 mol (from the stoichiometry)
empirical formula mass 197.8
3.54 × 10 −3 mol
So molecular formula is As4O6 iii Concentration =
0.02 dm3
2 × 74.9 = 0.177 mol dm−3
d × 100 = 65.2%
(2 × 74.9) + (5 × 16.0 ) c i mol HCl =
20
× 1.5 = 0.03 mol
1000
Exercise 3.5 from stoichiometry, mol Fe needed
= 0.03 / 2 = 0.015 mol
80
a A. Moles of gas = = 3.30 × 10−3
24000 actual number of mol of Fe = 0.9/55.8
B. Mass = mol × Mr = 3.3 × 10 × 34−3 = 0.016 (so Fe in excess)
= 0.112 g ii limiting reactant
C. Volume in dm3 = mol × 24 = 0.125 × 24
= 3.0 dm3 Exercise 3.7
mass 8 a i Ba(NO3)2(aq) + Na2SO4(aq) →
D. Mol = = = 0.125 mol BaSO4(s) + 2NaNO3(aq)
Mr 64.1
E. Volume in dm3 = mol × 24 = 0.150 × 24 ii Ba2+(aq) + SO42−(aq) → BaSO4(s)
= 3.6 dm3 = 3600 cm3
iii Sodium ions and nitrate ions
F. Mass = mol × Mr = 0.150 × 32.0 = 4.80 g
b Mole ratio is 2 moles of HCl reacting with 1
b i 20 cm3 mole of iron oxide to make 1 mole of iron(II)
chloride
ii 40 cm3 (because 60 cm3 total − 20 cm3
oxygen remaining) FeOx + 2HCl → FeCl2 + H2O
iii NO2 (because the stoichiometry is so x must be 1 for the equation to balance.
2 volumes NO to 1 volume O2 to FeO(s) + 2HCl(aq) → FeCl2(aq) + H2O(l)
2 volumes of NO2)
iv 2NO + O2 → 2NO2

c Balanced equation: CaCO3(s) + 2HCl(aq) → e i C2H535Cl = 64; C2H537Cl = 66

CaCl2(aq) + CO2(g) + H2O(l)
ii The C2H535Cl is about three times higher
So ionic equation is: CaCO3(s) + 2H (aq) → +
than the C2H537Cl peak because the ratio
Ca2+(aq) + CO2(g) + H2O(l) of 35Cl : 37Cl is 3 : 1.
iii Two:
Exercise 3.8
35
ClC2H537Cl = [M+2] peak
mass of isotope / fragment
a charge on isotope / fragment 37
ClC2H535Cl = [M+2] peak (same mass as
b 4
35
ClC2H537Cl)
c 88
Sr
37
ClC2H537Cl = [M+4] peak
d 84
Sr 8771.02 ÷ 100 = 87.71
e 84 × 0.56 = 47.04
86 × 9.86 = 847.96 Exam-style questions
87 × 7.02 = 610.74 Question 1
88 × 82.56 = 7265.28 = 72.7
100 a Idea of suitable apparatus, e.g. burette and
volumetric pipette. [1]
Exercise 3.9
Add suitable acid-base indicator to the acid in
a i 43 the flask. [1]
ii 77 Add sodium hydroxide into the acid until the
iii 64 / 66 indicator changes colour. [1]
iv 17 Repeat titration and take the best concurrent

readings (to within 0.1 cm3) for the
v 45 average titre. [1]
b i [C3H7]+ b Moles of malic acid = 3.60 = 2.687 ×
134
ii [CH2]+ 10−2 mol [1]
iii [OCH3]+ / [CH2OH]+ From the stoichiometric equation,
iv +
[C2H5] / [CHO] +
Moles of NaOH = 2 × 2.687 × 10−2 mol
= 5.374 × 10−2 mol NaOH [1]
v [C6H5CH2]+
mol 5.374 × 10 −2
vi [C2H4]+ / [CNH2]+ Volume (dm3) = =
concentration 0.125
c i 27 = [C2H3]+; 29 = [C2H5]+; 31 = [OCH3]+ /
= 4.30 × 10−1 dm3 [1]
[CH2OH]+; 45 = [C2H5O]+ /
[COOH]+; 46 = [C2H5OH]+ Correct number of significant figures [1]
ii [C2H5OH]+ is the molecular ion so 29 Note that you do not have to use the 20 cm3
= [C2H5]+; 45 is [C2H5O]+ volume of water in the calculation.
0.0125 × 25
(not COOH) and 31 is [CH2OH]+ (not c Mol hydroxide =
OCH3) 1000
iii The relative molecular mass = 3.125 × 10−4 mol [1]
d n = 100 × 3.8 = 7 carbon atoms Mol HCl = 0.05 × 12.5

1.10 4.93
49.3 1000
= 6.25 × 10−4 mol [1]

Stoichiometric ratio is 2 mol HCl to 1 mol Question 3

of metal hydroxide [1]
a 54 × 5.84 = 315.36
X(OH)2 + 2HCl → XCl2 + 2H2O [1]
56 × 91.68 = 5134.08
[Total: 12]
57 × 2.17 = 123.69
Question 2 58 × 0.31 = 17.98
a Number of specified particles (atoms, ions, 5591.11 ÷ 100 = 55.9
molecules or electrons) in a mole of
those particles [1] Multiplying isotopic masses by relative
abundance [1]
0.0011
b Mol CO2 = = 2.50 × 10−5 mol [1] Correct working of multiplications [1]
44
Mol oxygen atoms = 2 × 2.50 × 10−5 Correct answer to 3 significant figures [1]
= 5.00 × 10−5 mol [1]
b Mass of iron in 1 mole of limonite = 111.6 [1]
Number of atoms = 5.00 × 10−5 × 6.02 × 1023
Molar mass of limonite = 177.6 [1]
= 3.01 × 1019 [1]
111.6 × 100 = 62.8 % [1]
c CxHy + O2 → CO2 + H2O 177.6
14 cm3 84 cm3 56 cm3
c i Mol Fe2O3 = 798 = 5 mol [1]
Mol ratio 1 mol 6 mol 4 mol [1] 159.6
Mol of carbon per mol of butene = Mol of iron = 2 × mol Fe2O3 = 10 mol [1]
4 so C4Hy [1] Mass of iron = 10 × 55.8 = 558 g [1]
Mol oxygen atoms remaining (for ii Moles CO2 = 3 × mol Fe2O3 = 15 mol [1]
combination with H in water) = 12 − 8 = 4 [1]
15 × 24 = 360 dm3 [1]
so 4H2O and formula for butene is C4H8. [1]
d mol FeS2 = 60 = 0.5 mol [1]
d i Mol C = 37.25 = 3.1 mol 55.8 + 2 ( 32.1)
12
mol Fe2O3 expected if 100% conversion
Mol H = 7.75 = 7.75 mol = 0.5 / 2 = 0.25 mol [1]
1.0
26.6
mol Fe2O3 = = 0.1667 mol [1]
Mol Cl = 55.0 = 1.55 mol (1 mark for 2 (55.8 ) + 3 (16 )
35.5
division by atomic masses) [1] 0.1667
% yield = × 100 = 66.7 % [1]
0.25
Dividing by smallest number (1.55)
gives 2 C, 5 H, 1 Cl. [1] e 3Fe + 4H2O → Fe3O4 + 4H2
Empirical formula is C2H5Cl. [1] Correct formulae [1]
ii The relative molecular mass [1] Correct balance [1]
e The formula showing the number of each f Fe(s) + Cu2+(aq) → Fe2+(aq) + Cu(s)
type of atom in a compound. [1]
Correct symbols [1]
[Total: 13]
Correct balance and state symbols [1]
[Total: 19]

may be different.
Workbook answers
Chapter 4
Exercise 4.1
a i − b i ii
Cl P Cl N N
2+
F
Cl
Mg
−
iii iv
F H Br S
Cl Cl
ii
+
v vi O
Na O C O H C
− 2−
+
O
Li Cl O H
+
Na vii H viii
F F F
H N B F F S F
b An ionic bond is the strong force of F F F
electrostatic attraction between positive and H
negative ions in a crystal lattice. The charge on
the ions is spread out in all directions. It is not
like a covalent bond where the bonding is in Exercise 4.3
one direction between two particular atoms. a i R = 107°
c Metals conduct electricity because the ii S = 109.5°
delocalised electrons are able to move
throughout the structure between the positive iii T = 120°
metal ions. Many metals are strong and hard
iv U = 109.5°, V = 104.5°
because the metal ions are held together by
the strong electrostatic forces of attraction b i O ii +
between the ions and the delocalised electrons. H 104.5° H O
H H
107°
Exercise 4.2 H
H H V - shaped Triangular pyramidal

a H H
H N H H C C O H C C iii Cl Be Cl iv O C O
H H H H H 180°
ammonia ethanol ethene 180°
Linear Linear
H
109.5°
v P
vi
C N H
H
Cl Cl 107° Cl H 107° H
Tetrahedral around C atom.
Triangular pyramidal
Pyramidal around the N atom
vii viii H +
H H 109.5°
H
107°
H
V - shaped Triangular pyramidal
iii Cl iv O C O
CAMBRIDGE
Be INTERNATIONAL
Cl AS & A LEVEL CHEMISTRY: WORKBOOK
180°
180°
Linear Linear
H e i Water is hydrogen bonded and pentane

109.5°
v P
vi has id-id forces between molecules.
C N H
H Hydrogen bonding is stronger than id-id
Cl Cl 107° Cl H 107° H
forces so more energy is required to break
Tetrahedral around C atom. the bonds between water molecules than
Triangular pyramidal
Pyramidal around the N atom
between molecules of pentane.
vii viii H + ii Pentane has a longer hydrocarbon chain
H H 109.5°
and more electrons than butane. So
C C 120° (Allow 117–120°) N
H pentane has more contact areas for id-id
H H H
H forces and therefore has a higher boiling
Planar with each H−C−H being
trigonal planar
point (high enough for it to be a liquid).
Tetrahedral
iii CH3NH2 is hydrogen bonded but CH3Cl
ix has permanent dipole forces. Hydrogen
I I bonds are stronger than permanent dipole
Ga forces so more energy is required to break
120° the bonds between CH3NH2 molecules
than between molecules of CH3Cl.
I
Trigonal planar
Exercise 4.5
Exercise 4.4 a i A covalent bond in which both the
electrons in the bond come from the same
a fluorine > oxygen> nitrogen > chlorine > atom
hydrogen
ii The power of an atom to draw the pair of
b i electrons in a covalent bond toward itself
H ± H b i Electronegativity increases across a period.

H + − F
The positive charge in the nucleus increases
across a period. So there is a greater
attraction for the electrons in the covalent
ii Fluorine is more electronegative than bond as you go across a period. The outer
hydrogen, so it pulls the bonding electrons electrons are in the same electron shell so
closer towards it and this end of the they are roughly the same distance from
molecule is slightly more negative than the the nucleus so this factor has less effect.
hydrogen end The amount of shielding is about the same.
c i Permanent dipole-dipole forces ii Chlorine is more electronegative than
bromine. The electrons in the bond are
ii Hydrogen bonding
attracted more to the Cl. A dipole is
iii Instantaneous dipole-induced dipole forces formed with the Cl end of the molecule
slightly more negative than the Br end.
iv Permanent dipole-dipole forces
iii Br─Cl is a polar molecule and so can
v Permanent dipole-dipole forces (not attack a centre of positive charge easily.
hydrogen bonding because the Br is not
electronegative enough) c The difference between the electronegativity
H Br
of the Mg and Cl is large, so magnesium
chloride is ionic. The difference between the
d i C ii C
Br Br electronegativity of the C and Cl is small, so
H Cl+
δ Br carbon tetrachloride is covalent.
Cl −
δ
None d i The distance between the two nuclei of
iii iv the atoms which make up the bond.
δ− Cl Br
δ+ N − + ii Bond lengths increase as the size of the
δ δ
H H
halogen atom increases (down the group).
H

As you go down the group the group the

outer electrons of the halogen atoms are Exam-style questions
further from the nucleus and there is more
shielding. These two factors have a greater Question 1
effect than the effect of increasing nuclear
charge. a The boiling points increase as the molecules
get larger / increase in molar mass. [1]
e i B (id-id forces) → D (permanent dipole)
→ A (H-bonding) → C (ionic) The higher the molar mass, the more electrons
there are [1]
ii They both vary considerably in strength.
(The bonding in sodium is not very strong so the intermolecular forces are greater /
and neither is the covalent I─I bond. The greater van der Waals’ forces with increasing
bonding in iron is very strong and so is mass / size of molecules [1]
the bonding in H─F)
so it is more difficult to break the weak forces
between the molecules. [1]
Exercise 4.6
b Methane has the lowest boiling point because
a i A = sigma, B = pi, C = sp3, D = sp2 there are only instantaneous dipole-induced
ii The clouds of electrons have approximately dipole attractive forces between the molecules.
the same electron density close to each [1]
other, so they repel each other equally. Ammonia, water and hydrogen fluoride all
b i The p orbitals join to form a ring above and have hydrogen bonding. [1]
a ring below the plane of the carbon atoms. The hydrogen bonding in ammonia is
ii The electrons arising from the p orbitals weakest [1]
are able to move around the rings. because nitrogen is less electronegative than
iii Benzene is a molecule, so although the either oxygen or fluorine. [1]
delocalised electrons can move within Water has a higher boiling point than
the molecule, they cannot move between hydrogen fluoride because it can form
molecules. (on average) two hydrogen bonds per
iv The rings of p electrons can combine so molecule. [1]
that the electrons move over each layer of Fluorine can only form (on average) one
the graphite. hydrogen bond per molecule. [1]
c The covalent bonds are weaker in oxygen c
compared with nitrogen / the bond energy
of the double bond in oxygen is less than O
the bond energy of the triple bond in
nitrogen. So the bonds in oxygen are more H H
easily broken.
Bonding pair of electrons between each O
d The electron density of the pi bond in ethene and H [1]
is more exposed to attacking reagents than the
sigma bonds Two lone pairs on the oxygen [1]
e CH3CH2CH2Cl is a polar molecule because d i Lone pair–lone pair repulsion is greater
the Cl is slightly electronegative. So this than lone pair–bond pair repulsion. [1]
molecule leaves the carbon slightly positive
and therefore open to attack by other reagents. Idea of the lone pair–lone pair repulsion
CH3CH2CH3 is non-polar so there are no pushing the OH bonds closer together /
dipoles to allow attack by other molecules. into V-shaped position. [1]
ii 104.5 [1]

iii Hydrogen attached to very electronegative c H H

atom [1]
H N H N
such as N, O or F [1]
H H
bonded to lone pair on another very
electronegative atom [1] Two ammonia molecules with intermolecular
bond between N and H [1]
(extreme) form of permanent-dipole
permanent dipole forces [1] Lone pairs shown on nitrogen which is
hydrogen bonded [1]
e H
δ+ N----H−N in line (approximately 180°) [1]
δ− C
Cl H d i 2NH3(aq) + H2SO4(aq) → (NH4)2SO4(aq)
H
Correct formulae [1]
Tetrahedral structure [1] correct balance [1]
dipole in correct direction (towards the Cl) [1] state symbols [1]
f The dipoles cancel each other / the centre of ii Salts have ionic bonding. [1]
positive and negative charge in the molecule
is the same. [1] Ionic bonds are strong / takes a high
temperature to break ionic bond [1]
[Total: 22]
Ammonia is a molecule. [1]
Question 2 Weak forces of attraction between
a Any five of: molecules / hydrogen bonding between
molecules [1]
Polymer C has the lowest value because the 2+ 2−
side chains are non-polar. e
Only temporary dipole-induced dipole forces Mg O

between the chains.
Polymer A has more bulky side chains so the
chains are further from each other than in Correct electron configuration [1]
polymers B and C / there are fewer contact
points in A than in B and C. Correct charges [1]
Polymers A and B have polar side chains. [Total: 19]
Nitrogen is more electronegative than Cl
Question 3
so greater forces of attraction between the
chains in polymer A than in polymer B. [5] a i
b − O I O
C N O
Correct electron configuration [1] Structure completely correct [3]

Correct charge shown [1] If 3 marks not scored allow correct
bonding around double bonded
oxygen atoms
ALLOW lone pair / correct structure
around the single bonded oxygen

ii Lone pair–bond pair repulsion greater

than bond pair–bond pair repulsion [1] b i H C C H [1]
Idea of the lone pair–lone pair ii linear [1]

repulsion pushing the O─I bonds
180° [1]
closer together [1]
c i The triple bond is formed from two π
iii ALLOW values between 98 and 104° [1] bonds / pi bonds [1]
b iodine has more electrons / iodine has and one σ bond /sigma bond. [1]
bigger molecule [1]
The two π bonds are at right angles to
so id-id forces are greater [1] each other / at right angles to the long
c Hydrogen fluoride is hydrogen bonded. [1] axis of the molecule. [1]
Hydrogen iodide has permanent dipole The H─C bond is a σ bond /sigma
bonds. [1] bond. [1]
Sigma bonds formed by end-on overlap.
Hydrogen bonding is stronger than
[1]
permanent dipoles. [1]
ii sp carbon hybrid (with 1s of H) [1]
d 1-iodopropane has greater contact area /
2-iodopropane has less contact area [1] [Total: 14]
because the chains can get closer in
1-iodopropane / chains cannot get as close
for 2-iodopropane / 2-iodopropane has side
chain sticking out. [1]
Van der Waals’ forces / intermolecular forces
greater for 1-iodopropane / less for
2-iodopropane. [1]
e Co-ordinate bond / dative covalent bond [1]
Idea of completing octet of electrons around
the aluminium [1]
[Total: 16]
Question 4
a i the average energy needed to break a
specific covalent bond [1]
averaged from a variety of molecules in
the gaseous state. [1]
ii The electron pairs in a double bond repel
each other. [1]
One of the electrons pairs forms a pi-bond
which is more easily broken (or has a
higher energy) / the electron pair in one of
the bonds have more energy so are more
easily separated. [1]
iii Allow values between 700 and 876 (actual
value 838) [1]

may be different.
Workbook answers
Chapter 5
Exercise 5.1
a
Substance State at 25 °C and Proximity Arrangement Motion
1 atm pressure
bromine liquid close together / irregular / random moving slowly / sliding
not far apart over each other
carbon gas far apart irregular / random moving rapidly from
dioxide place to place
sulfur solid close together regularly arranged vibrating (around a
fixed position)
b i Giant; covalent; diamond; four; between each carbon and oxygen

tetrahedrally; high; atoms; strong; does atom. Carbon dioxide is a gas at room
not conduct temperature because the forces of
attraction between the molecules are weak.
ii Carbon dioxide has a simple molecular
structure. It has strong covalent bonding
Exercise 5.2
a A is ionic, B is giant molecular / giant covalent, C is metal
b
Structure A Structure B Structure C
type of particles present positive and negative atoms of Si and O metal ions and
in the diagram ions / anions and cations delocalised electrons
melting point high high (generally) high
electrical conductivity does not conduct does not conduct conducts
of solid
conductivity when conducts does not conduct conducts
molten
c 1 with D; 2 with C; 3 with B; 4 with E; Metals conduct electricity because the

5 with A delocalised electrons (are free to) move (when
voltage applied).
d Metal structure is formed by outer shell
electrons / valence electrons of metal atom Metals are malleable because the attractive
being lost forming delocalised electrons / sea forces between the metal ions and the
of electrons between the layers of metal ions. delocalised electrons are overcome (when a
force is applied)
causing the layers to slide over each other.

When the force is removed, attractive forces b i C60 is a simple molecule. There are weak
are reformed between the metal ions and attractive forces / van der Waals’ forces
delocalised electrons. between the molecules. So not much
heat energy is needed to overcome these
Exercise 5.3 attractive forces.
a pV = nRT so p = nRT/V Diamond is a giant molecular / giant

covalent structure. The forces between all
100 °C = 373 K, V in dm3 = 0.25 dm3 the atoms are strong. So a lot of energy
is needed to overcome these attractive
Substituting in the equation p = 0.2 × 8.31 ×
forces.
373 / 0.25 / 1000 = 2.48 kPa
ii Both C60 and benzene are non-polar. A
b i The temperature of the vapour = 120 + 273
non-polar solvent generally dissolves a
= 393 K
non-polar solute / idea of like dissolves
The mass of L vaporised = 10.71 − 10.54 like (in terms of polarity). Water is a polar
= 0.17 g molecule so does not dissolve C60.
The volume of vapour in the gas syringe iii Similarity: both contain rings of 6 carbon
in m3 = 69.0 − 4.0 = 65.0 cm3 atoms / arrangement of carbon atoms is
hexagonal.
= 6.5 × 10−5 m3
Difference: graphene is a single sheet /
pv
ii n= layer but graphite has many layers
RT (attracted to each other by weak
n = 1.0 × 10 × 6.5 × 10 = 2.0 × 10 −3 mol
5 −5
iii intermolecular / van der Waals’ forces).
8.31 × 393
iv M r = mass or 0.17 −3 = 85
moles 2.0 × 10
Exercise 5.5
a Gas molecules are in continuous movement.
v • Having 4 cm3 air - no effect because
They collide with each other and with the walls
the volume is being measured by the
of the container. The pressure is due to the
difference at the same temperature and
force of the collisions over a particular area.
pressure
b When the oxygen in the syringe is heated at
• Loss of liquid - lower volume of gas
constant pressure its volume increases. This
than expected so relative molecular
is because the oxygen molecules move faster
mass higher than expected (because
at a higher temperature and collide with each
Mr is inversely proportional to V
mRT other with a greater frequency. They also hit
(in M r = )) the walls of the container with greater force. If
pv the pressure is to remain constant, the greater
• Temperature too high - higher than
force of the molecules on the walls of the
expected (1) because temperature is
syringe pushes the plunger out and the volume
proportional to the relative molecular
of the gas increases.
mRT
mass (in M r = )
pv c In an ideal gas the particle volume is zero and
there are no intermolecular attractive forces.
Exercise 5.4 d B
a Graphite is an allotrope of carbon. The The higher the pressure, the smaller the
carbon atoms in graphite are arranged in volume. At higher pressure the molecules are
layers. The carbon atoms are arranged in (on average) closer / distance between the
hexagons. Graphite has a high electrical molecules is (on average) smaller. Idea of
conductivity. This is because some of the concave downwards curve because pressure is
electrons are delocalised and are able to move inversely proportional to volume.
when a voltage is applied. Graphite has weak
van der Waals’ forces between the layers. e The volume of the molecules is negligible / is
very small / can be ignored.

The forces of attraction and repulsion C is simple molecular [1] weak forces / van der
between the molecules can be ignored / are Waals’ forces
negligible.
between molecules. [1]
No (kinetic) energy is lost when molecules
collide / the collisions are elastic. Covalent bonding within the molecules [1]
f The kinetic theory assumes that the molecules D is giant molecular / giant covalent structure
behave as hard spheres with no attractive [1] bonding is covalent. [1]
forces between them. At high pressures or low NOTE: giant covalent = 2 marks
temperatures the molecules are closer together.
So there are attractive forces between the [Total: 18]
molecules which tend to reduce the volume
more than the ideal gas laws would suggest. Question 2
The kinetic theory also assumes that the
molecules do not have a volume, so this also a Boron nitride rings are not planar / rings are
must be taken into account. bent / boron atoms are not in
the same plane as the nitrogen atoms / in
graphene the rings are planar [1]
Exam-style questions b i It has a lot of strong (covalent) bonds /

all the bonds are strong. [1]
Question 1 ii Some of the electrons are delocalised /
a i Different forms of the same element [1] some of the electrons are mobile. [1]
ii Regular arrangement of particles c Weak forces between the layers / sheets [1]
(atoms/ions or molecules) in Layers slide over each other [1] Must be
three dimensions) [1] reference to layers or sheets not atoms.
b Titanium has regular arrangement of positive d Any five of: (1 mark each)
ions / cations / metal ions [1]
• C60 is a simple molecule
Surrounded by delocalised electrons /
surrounded by mobile electrons [1] • Weak bonds / van der Waals’ forces
between these molecules
Strong forces of attraction between positive
ions and delocalised electrons / it takes a lot • Not much energy required to overcome
of energy to overcome the forces of attraction these forces
between the positive ions and delocalised
• Polymer has a greater surface area /
electrons [1]
greater contact area
Diamond has a giant molecular structure /
• Total forces between polymer ‘tubes’
giant covalent structure [1]
greater than for C60 molecules
All the atoms are strongly bonded / it takes
• More energy needed to overcome the
a lot of energy to break the bonds [1]
attractive forces between the polymer
c i Positive and negative ions / anions and chains
cations [1]
[Total: 10]
Idea of alternating positive and negative
ions in every direction [1] Question 3
ii When molten the ions can move. [1] a i Regular arrangement [1]
Ions only vibrate in solid. ALLOW: in three dimensions [1]
cannot move in solid. [1]
ii Solubility: insoluble [1]
d A is ionic (structure and bonding). [1]
Electrical conductivity: does not
B is metallic (structure and bonding). [1] conduct [1]

b The higher the temperature, the greater the nRT

kinetic energy of the molecules [1] d V= (or implication of this from
P
Molecules collide with (the walls of the working) [1]
container with) more force (per second) [1]
pv V = 0.400 × 8.31 ×5 313 = 5.20 × 10 −3 m 3 [1]
c i n= (or implication of this from 2.00 × 10
RT
working) [1] = 5.20 dm3
Correct temperature (363) and volume [Total: 14]

8.5 × 10−5 m3 [1]
n = 1.1 × 10 × 8.5 × 10 = 3.1 × 10 −3 mol

5 −5
8.31 × 363
[1]
ii M r = mass or 0.22 −3 (1) = 71 [1]
moles 3.1 × 10

may be different.
Workbook answers
Chapter 6
a An enthalpy change is the exchange of heat a i Standard enthalpy change of
energy between a chemical reaction mixture neutralisation is the enthalpy change
and its surroundings at constant pressure. when one mole of water is formed by the
The symbol for enthalpy change is ∆H. If reaction of an acid / alkali with an alkali /
heat is absorbed from the surroundings the acid under standard conditions. (last gas
reaction is endothermic. If heat is released to dependent on what put in previous gap).
the surroundings the reaction is exothermic. In
ii Standard enthalpy change of combustion
comparing enthalpy changes we use standard
is the enthalpy change when one mole of a
conditions. These are a pressure of 101 kilopascals,
substance is burnt in excess oxygen under
a temperature of 298 kelvin with the reactants
standard conditions.
and products in their normal physical state
under these conditions. iii Standard enthalpy change of reaction is
the enthalpy change when the amounts
b i
shown in the equation react to give
Enthalpy, H/kJ mol–1 products under standard conditions.
b 1 with D; 2 with E; 3 with B; 4 with A; 5 with C
Mg(s) + CuSO4(aq) EA
Hreactants
c i C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)
∆Hr ∆H⦵c[C3H8(g)]
–531 kJ mol–1
MgSO4(aq) + Cu(s)
Hproducts ii OH−(aq) + H+(aq) → H2O(l)∆H⦵n[OH−aq]
Reaction pathway iii MgCO3(s) → MgO(s) + CO2(g)

∆H⦵r [MgCO3(s)]
ii Exothermic because the reactants have 1
more energy than the products / enthalpy iv 2Na(s) + 2 O2(g) → Na2O(s) ∆H⦵f [Na2O(s)]
change negative d iii needs a constant input of energy.
c Enthalpy, H/kJ mol–1
e Standard conditions are a temperature of 298 K
and a pressure of 101 kPa.
Hproducts
EA
2NaNO2(s) + O2(g)
Exercise 6.3
a Put known volume / amount of water in the
∆Hr + 218 kJ mol–1
can. Weigh the spirit burner with the fuel in it
2NaNO3(s)
Hreactants (and cap on). Measure the temperature of the
water before lighting the spirit burner. Light
Reaction pathway
the spirit burner and let it heat up the water.
Keep the water stirred. After water has reached
a suitable temperature, blow out the spirit burner
and put the cap on it. Record the temperature of
the water. Reweigh the spirit burner.

b i Mass of fuel burned = 92.33 − 92.19 Exercise 6.5

= 0.14 g
a i ∆Hr
ii Temperature change = 35.2 − 20.5 Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g)
= 14.7 °C
iii mass of water × specific heat capacity ∆H1 ∆H2
× temperature rise
80 × 4.18 × 14.7 = (−)4915.7 J 2Fe(s) + 3C(graphite) + 3O2(g)
iv C6H13OH = (6 × 12) + (14 × 1) + 16 = 102
102
v (−)4915.7 × 0.14 = 3581438.5 J = ii ∆H⦵1 = ∆H⦵f[Fe2 O3(s)] + 3 × ∆H⦵f [CO(g)]
(−)3581 kJ mol−1 = (−824.2) + 3 × (−110.5)
c Heat losses from the walls of the can / from = −1155.7 kJ

the water surfaces / from the flame ∆H⦵2 = 3 × ∆H⦵f[CO2(g)] = 3 × (−393.5)
d C6H13OH(l) + 9O2(g) → 6CO2(g) + 7H2O(l) = −1180.5 kJ
∆H⦵c[C6H13OH(g)] = −3581 kJ mol−1 ∆H⦵1 + ∆H⦵r = ∆H⦵2

So ∆H⦵r = ∆H⦵2 − ∆H⦵1
Exercise 6.4
= −1180.5 − (−1155.7) = −24.8 kJ mol−1
a The energy released in forming the bonds in the
products is greater than the energy absorbed b ∆Hr
when the bonds in the reactants are broken. C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(I)
b i Bonds broken Bonds formed /

∆H1 ∆H2
/ kJ kJ
4 × (C−H) = 4 × 2 × (C═O) = 2 ×
3C(graphite) + 4H2(g) + 5O2(g)
410 = 1640 kJ 805 = 1610 kJ
2 × (O═O) = 2 × 4 × (O−H) = 4 ×
∆H⦵1 = ∆H⦵f[C3H8(g)] = −104.5 kJ
496 = 992 kJ 465 = 1860 kJ
Total = 2632 kJ Total = 3470 kJ ∆H⦵2 = 3 × ∆H⦵f[CO2(g)] + 4 × ∆H⦵f [H2O(l)]
= (3 × −393.5) + (4 × −285.8) = −2323.7 kJ
ii Enthalpy change = +2632 − 3470 = ∆H⦵1 + ∆H⦵r = ∆H⦵2
−838 kJ mol−1
So ∆H⦵r = ∆H⦵2 − ∆H⦵1
c
Bonds broken / kJ Bonds formed / kJ
= −2323.7 − (−104.5) = −2219.2 kJ mol−1
1 × (C═C) = 1 × 612 4 × (C═O) = 4 × 805
= 612 kJ = 3220 kJ c i ∆Hf
4C(graphite) + 5H2(g) (+6 12 O2) C4H10(g) (+6 12 O2)
4 × (C−H) = 4 × 410 4 × (O−H) = 4 × 465

4 × ∆H c [C(graphite)]
= 1640 kJ = 1860 kJ ∆Hc [C4H10(g)]
5 × ∆Hc [H2(g)]
3 × (O═O) = 3 × 496 4CO2(g) + 5H2O(I) (+6 12 O2)

= 1488 kJ
Total = 3740 kJ Total = 5080 kJ ii ∆H⦵ left arrow = 4 × ∆H⦵c [C(graphite)] +
5 × ∆H⦵c[H2(g)]
Enthalpy change = + 3740 − 5080
= −1340 kJ mol−1 = (4 × −393.5) + (5 × −285.8)
= −3003.0 kJ
∆H⦵ right arrow = ∆H⦵c[C4H10(g)]
= −2876.5 kJ

4 × ∆H⦵c [C(graphite)] + 5 × ∆H⦵c[H2(g)] = ∆H⦵r = ∆H⦵f [Ca(OH)2(s)] − (∆H⦵f [CaO(s)]

∆H⦵f [C4H10(g)] + ∆H⦵c [C4H10(g)] + ∆H⦵f[H2O(l)])
So ∆H⦵f [C4H10(g)] = 4 × ∆H⦵c [C(graphite)] or
+ 5 × ∆H⦵c [H2(g)] − ∆H⦵c [C4H10(g)]
∆H⦵r = −986.1 − (−635.1 − 285.8) [1]
= −3003.0 − (−2876.5) = −126.5 kJ mol −1
−65.2 kJ mol−1 [1]
iii It is the reverse reaction, the products and
reactants being in the same state. d Enthalpy change of solution of calcium
hydroxide [1]
Exercise 6.6 e i
3Ca(s) + Fe2O3(s) 2Fe(s) + 3CaO(s)
a Mg(NO3)2(aq) + Na2CO3(aq) →
MgCO3(s) + 2NaNO3(aq)
∆Hf [Fe2O3(s)] ∆Hf [CaO(s)]
b i Insulate the beaker / put a lid on the
beaker / stir the mixture with the 3Ca(s) + 2Fe(s) + 1 12 O2(g)
thermometer (so that there are no ‘hot
spots’ and the reaction takes place as
quickly as possible). Correct enthalpy cycle with elements at
bottom [1]
ii Volume of solution = 20 cm3 + 20 cm3
= 40 cm3 Arrows in correct directions [1]
Temperature rise = 23.2 − 18.9 = 4.3 °C ii Enthalpy
mass of solution × specific heat capacity ×

temperature rise EA
Ca(s) + Fe2O3(s)
40 × 4.18 × 4.3 = (−)718.96 J
∆Hr = –1081.1 kJ mol–1
iii The specific heat capacity of the solution
is the same as that of water. 2Fe(s) + 3CaO(s)
iv Moles magnesium nitrate 20.0 × 1.0 =

1000 Reaction pathway
0.02 mol (−)718.96 × 1 = 35 948 J =
0.02
(−)36.0 kJ mol−1 Axes labelled correctly [1]
Reactants on left and products on right [1]
Exam-style questions Reactants energy level above the
product [1]
Question 1 Enthalpy change shown with downward
pointing arrow and labelled [1]
a The reaction is exothermic [1]
Activation energy shown and labelled [1]
The heat liberated is conducted through the
aluminium to heat the soup [1] [Total: 15]
b i It may exert a pressure on the inside of Question 2
the can [1]
a i Energy needed to break one mole of
ii There is a space above the calcium bonds between two atoms [1]
oxide for it to expand [1]
of a specified gaseous molecule [1]
c Indication of correct use of Hess’s Law, e.g.
∆H⦵f [CaO(s)] + ∆H⦵f [H2O(l)] + ∆H⦵r
= ∆H⦵f [Ca(OH)2(s)] [1]
Correct rearrangement:

ii Exact bond energies are for particular ∆H⦵r = ∆H⦵at[C(graphite)] + (4 × ∆H⦵at

bonds in ethanol / exact bond energy
2
[ 1 Cl2(g)]) − ∆H⦵1
depends on the ‘environment’ of the
bond [1] (If two marks not awarded, 1 mark for 4 ×
average bond energies are taken from the ∆H⦵at[ 21 Cl2(g)])
same bonds in a variety of compounds /
do not take account of the ‘environment’ ∆H⦵r = +716.7 + (4 × 121.7) − (−129.6)
of the bonds [1] = 1333.1 kJ [1]
iii Br2(g) → 2Br(g) (1 mark for correct For 1 C─Cl bond, 1333.1 ÷ 4
formulae and balance, 1 mark for state = 333.3 kJ mol−1 [1]
symbols) [2] [Total: 17]
b Bond energy of reactants = +435.9 +
243.4 = 679.3 kJ [1] Question 3
Bond energy of product = 2 × 432 a Enthalpy change when one mole of water [1]
= 864.0 kJ [1]
is formed when an acid reacts with an
Enthalpy change = +679.3 − 864.0 alkali under standard conditions [1]
= −184.7 kJ [1]
b Add measured volume of acid to measured
c 2H(g) + 2Cl(g) volume of alkali [1]
Known concentrations of acid and alkali [1]
Carry out reaction in insulated vessel [1]
Energy
H2(g) + Cl2(g) Measure temperature of acid and alkali

∆Hr before mixing and the maximum temperature
2HCl(g) reached after mixing [1]
Reaction pathway Stir reaction mixture [1]

c Volume of mixture is 75 cm3 [1]
Reactants on left and product on right with
product level below the reactant level [1] Energy change = m × c × ∆T = 75 × 4.18
× 8.9 = 2790.15 J [1]
Arrows in correct directions for bond breaking
and bond making [1] 50
Moles of NaOH = 1.0 × 1000 = 0.05 mol [1]
Arrow showing enthalpy change correct and
labelled [1] Enthalpy change per mole 2790.15 × 1.0
0.05
= 55.8 kJ mol−1 [1]
d Absorbed, because energy is released in the
reaction of chlorine with hydrogen / absorbed d i It is difficult to measure the temperature
because it is the reverse of the reaction when of solids accurately during a reaction if
chlorine and hydrogen combine [1] the reaction requires heating to start it.[1]
e Use of Hess’s Law, e.g. ii Enthalpy change of formation of
copper(II) oxide [1]
∆H⦵1 + ∆H⦵r = ∆H⦵at [C(graphite)] + 4 × ∆H⦵at
1 Cu(s) + 1 O2(g) → CuO(s) [1]
[ 2 Cl2(g)] [2] 2

[Total: 14]

may be different.
Workbook answers
Chapter 7
a i The sum of the oxidation numbers in a a i +3 to 0 reduction
compound is zero.
ii −1 to 0 oxidation
ii The sum of the oxidation numbers in an
ion is equal to the charge on the ion. iii −3 to +5 oxidation
iii The oxidation number of fluorine is −1. iv +1 to +2 oxidation
iv The oxidation number of oxygen is −2 v +3 to +5 oxidation

except in peroxides where it is −1. vi +6 to −2 reduction
v The total oxidation number of the sulfur b i Reduction
and the 4 oxygen atoms in SO42− is −2.
ii Oxidation
b The sum of the oxidation numbers of all the
atoms in Fe2O3 is zero. iii Oxidation
Each O atom has an oxidation number of −2. iv Reduction
The oxidation number for 3 O atoms is −6. v Reduction
The oxidation number for 2 Fe atoms is +6. c i Ni → Ni2+ + 2e−
So each Fe atom has an oxidation number ii HNO2 + H2O → NO3− + 3H+ + 2e−
of +3. iii Te + 2H2O → TeO2 + 4H+ + 4e−
c The sum of the oxidation numbers of all the iv Fe3+ + e− → Fe2+
atoms in the NO3− ion is −1.
v MnO4− + 8H+ + 5e− → Mn2+ + 4H2O
Each O atom has an oxidation number of −2.
The oxidation number for 3 O atoms is −6. Exercise 7.3
The oxidation number for the N atom is +5 a Oxidising agents gain electrons and get reduced.
(N + (+6) = −1). b A reducing agent decreases the oxidation
d i +3 number of another atom by losing / donating
electrons. The reducing agent gets oxidised.
ii −1
c i Bromine: it increases the oxidation
iii +6 number of iodine from −1 to 0.
iv +5 ii Copper oxide: it increases the oxidation
number of the nitrogen from −3 to 0.
v +7
iii Sulfuric acid: it increases the oxidation
vi +5
number of I from −1 to 0.
vii +4

d i Iodide ion: It decreases the oxidation Exercise 7.5

number of oxygen from −1 to −2.
a i iron(II) carbonate
ii Bromide ion: it decreases the oxidation
number of chlorine from 0 to −1. ii manganese(IV) oxide
iii Hydrogen sulfide: it decreases the iii iodine(V) chloride

oxidation number of iodine from 0 to −1. iv sodium bromate(V)
Exercise 7.4 v chromium(III) hydroxide

vi potassium manganate(VI)
a A chemical reaction in which there is a
simultaneous oxidation and reduction b Deduce the formula for these compounds
to include the oxidation number as Roman
b i Ag+ + e− → Ag
numerals.
ii 2
i KClO4
iii Zn + 2Ag+ → Zn2+ + 2Ag
ii AuCl3•2H2O
c i Cl2 + 2Fe2+ → 2Cl− + 2Fe3+
iii NaIO3
ii 6H+ + 2Al → 3H2 + 2Al3+
iv SnCl4
iii 2IO3 + 10I + 12H → 6I2 + 6H2O
− − +
v KClO
iv 2Hg2+ + 2Cr2+ → Hg22+ + 2Cr3+
vi NH4VO3
d i MnO4− + Cr2+ + H+ → Mn2+ + Cr3+ + H2O
+7 +2 +2 +3
Exam-style questions
ii Mn from +7 to +2 = −5
Cr from +2 to +3 = +1 Question 1
iii MnO4 + 5Cr + H →
− 2+ +
a i 0 [1]
Mn2+ + 5Cr3+ + H2O
ii +2 [1]
iv MnO4− + 5Cr2+ + 8H+ →
Mn2+ + 5Cr3+ + H2O b Ba + 2H2O → Ba(OH)2 + H2
v MnO4− + 5Cr2+ + 8H+ → Correct symbols [1]

Mn2+ + 5Cr3+ + 4H2O correct balance [1]
e i 2Cu → Cu + Cu
+ 2+
c i Ba → Ba2+ + 2e− [1]
ii 2I− + 2Fe3+ → I2 + 2Fe2+ ii 2H2O + 2e → 2OH + H2
− −
[1]
iii Fe2O3 + 3CO → 2Fe + 3CO2 iii Equation ii / 2H2O + 2e− → 2OH− + H2
iv IO3− + 5Fe 2+ + 6H+ → 1 I2 + 5Fe3+ + 3H2O (no mark alone) because electrons are
2 being gained. [1]
v 3CuO + 2NH3 → 3Cu + N2 + 3H2O
d i Fe2+ because the oxidation number of
vi 2Fe3+ + H2S → 2Fe2+ + 2H+ + S oxygen decreases from −1 to −2 / because
the oxidation number of Fe2+ is increasing
vii 2MnO42− + Cl2 → 2MnO4− + 2Cl−
/because the Fe2+ has lost electrons [1]
viii 3MnO42− + 4H+ → 2MnO4− + MnO2 + 2H2O
ii 2H+ + H2O2 + 2e− → 2H2O
f i A simultaneous reduction and oxidation
of the same species in a chemical reaction
correct balance with electrons [1]
ii reactions e i and e viii

e i +2 to +4 = +2 [1] Question 3

ii −1 to −2 = −1 [1] a i −2 [1]
iii H2O2 + Mn + 2OH → MnO2 + 2H2O
2+ −
ii 0 [1]
Correct formulae [1] iii Sulfur because it increases in oxidation
correct balance [1] number [1]
[Total: 14] b Hydrogen sulfide because it has decreased

the oxidation number of iodine atoms [1]
Question 2 c i Oxidation number change of 2 I atoms
is 2 × +5 , so −10 needed [1]
a i +5 [1]
ii I2O5 + 5H2S → I2 + S + 5H2O [1]
ii +3 [1]
d 2I− → I2 + 2e− oxidation of iodide ions [1]
iii N (in NaNO3) gains electron(s) and
oxygen (in NaNO3) loses electron(s) to Oxidation of iodide ions because the iodine
form O2 [1] increases in oxidation number from −1 to 0
in I2 [1]
Oxidation number of nitrogen decreases
and oxidation number of (some of the) H2O2 + 2H+ + 2e− → 2H2O [1]
oxygen increases [1]
Reduction of hydrogen peroxide because
Idea of oxidation and reduction the O in the hydrogen peroxide has decreased
happening simultaneously [1] in oxidation number from 0 to −2 (in O
in water) [1]
iv Sodium nitrate(III) (But with nitrates
and sulfates, nitrate and nitrite and [Total: 10]
sulfate and sulfite are often preferred) [1]
b i −1 to 0 = +1 [1]
ii +3 to +2 = −1 [1]
iii The oxidation numbers are balanced /
+1 balances −1 [1]
iv NO2− because it increases the oxidation
number of the iodine in iodide / it gets
reduced / it takes electrons from the
iodide ions [1]
c i +7 to +2 = −5 [1]
ii +3 to +5 = +2 [1]
iii 2MnO4− + 5NO2− + 6H+ → 2Mn2+ + 5NO2−
+ 3H2O
correct balance [1]
[Total: 14]

may be different.
Workbook answers
Chapter 8
Exercise 8.1
a 1 with B; 2 with A; 3 with F; 4 with E; 5 with iii Position of equilibrium moves to the left
C; 6 with D to reduce the increase in concentration.
b i Position of equilibrium moves to iv Position of equilibrium moves to the left
the right to reduce the increase in so concentration of reactant is increased.
concentration.
d i Cl2 + ICl ⇌ ICl3
ii Position of equilibrium moves to the left
to reduce the increase in concentration. ii The yellow solid changes to a brown
liquid as the chlorine escapes.
iii Position of equilibrium moves to the left
in the direction of greater number of iii The equilibrium is shifted to the left to
molecules / moles. increase the concentration of chlorine.
iv Position of equilibrium moves to the left iv The reaction is shifted to the right to
to reduce the increase in temperature due reduce the concentration of added chlorine.
to exothermic reaction. e When any of the conditions affecting the
v Position of equilibrium moves to the position of equilibrium are changed, e.g.
right (because ammonia is removed) pressure, concentration (or temperature) or
so concentration of ammonia to be temperature (or concentration), the position
increased. of equilibrium moves to oppose / counteract
the change.
c i No effect because there is an equal
number of gaseous molecules / moles on Exercise 8.2
each side of the equation.
a An equilibrium expression links the
ii No effect. A catalyst does not affect the concentration of reactants and products to the
position of equilibrium, only the rate of stoichiometric equation. Under stated conditions
reaction. the value calculated from the equilibrium
expression is called the equilibrium constant.
b C and D

c
Chemical equation Equilibrium expression Units
Br2(g) + H2(g) ⇌ 2HBr(g) none
[HBr ]
2
Kc =
[Br2 ][H2 ]
N2(g) + 3H2(g) ⇌ 2NH3(g) dm6 mol−2
[ NH3 ]
2
Kc =
[ N 2 ][H2 ]
3
CaCO3(s) ⇌ CaO(s) + CO2(g) K c = [CO2 ] mol dm−3
2NO2(g) ⇌ 2NO(g) + O2(g) mol dm−3

[ NO] [O2 ]
2
Kc =
[NO2 ]2
3Fe(s) + 4H2O(g) ⇌ Fe3O4(s) + 4H2(g) [H2 ]4 none

Kc =
[H2O]4
Cu(s) + 2Ag+(aq) ⇌ Cu2+(aq) + 2Ag(s) [Cu 2+ ] dm3 mol−1

Kc =
[ Ag ]
2
2CrO42−(aq) + 2H+(aq) ⇌ Cr2O72−(aq) + H2O(aq) [Cr2O7 2− ] [ H2O] dm6 mol−2

Kc =
[CrO42− ]2 [H+ ]2
d Chemical equation Equilibrium expression Units

2NO2(g) ⇌ 2NO(g) + O2(g) 2 × p
pNO O2
Pa (or atm)
Kp =
pNO
2
2
2SO2(g) + O2(g) ⇌ 2SO3(g) pSO

2 Pa−1 (or atm−1)
Kp = 3
pSO2 × pO2
2
2HI(g) ⇌ I2(g) + H2(g) pI2 × pH2 no units

Kp =
pHI
2
PCl5(g) ⇌ PCl3(g) + Cl2(g) pCl3 × pCl2 Pa (or atm)

Kp =
pCl5
3Fe(s) + 4H2O(g) ⇌ Fe3O4(s) + 4H2(g) pH42 none

Kp =
pH4 2O
Exercise 8.3
a i nitric acid c i 9–12
ii sulfuric acid ii 0–1
iii potassium hydroxide iii 13–14
iv ammonia iv 4–6
b i CH3COOH v 7
ii HCl d i 2NaOH + H2SO4 → Na2SO4 + 2H2O
iii NaOH ii HNO3 + NH3 → NH4NO3

iii 3KOH + H3PO4 → K3PO4 + 3H2O iii Acid is NH4+, base is H2O
iv Ba(OH)2 + 2HCl → BaCl2 + 2H2O iv Base is NH2OH, acid is H2O
e i sodium sulfate v Acid is H2SO4, base is H2O
ii ammonium nitrate vi Acid is H2SO4, base is HNO3
iii potassium phosphate c HCl, H2SO4 and HNO3
iv barium chloride d i HSiO3− is conjugate with SiO32− and H2O
is conjugate with H3O+
f i Add universal indicator to the solution.
Compare the colour of the indicator to ii HCO2H is conjugate with HCO2− and
the colour on the pH colour chart. H2O is conjugate with H3O+
ii blue / purple • orange / yellow iii CH3NHCH2NH3+ is conjugate with
CH3NHCH2NH2 and H2O is conjugate
Exercise 8.4 with H3O+
a 1 with C; 2 with G; 3 with E; 4 with F; 5 with iv NH2OH is conjugate with NH3OH+ and
A; 6 with D; 7 with B H2O is conjugate with OH−
b i Acid is HCl, base is H2O e D
ii Base is CH3NH2, acid is H2O
8.4f Chemical equation Equilibrium expression Units

C2H5CO2H(aq) ⇌ C2H5CO2 (aq) + H (aq)
− +
[C 2H5CO2− ] [H+ ] mol dm−3
K=
[C 2H5CO2H]
N2H4(aq) + H2O(l) ⇌ N2H5+ (aq) + OH−(aq) [ N 2H5+ ] [OH− ] none
K=
[ N 2 H 4 ] [H 2 O]
H2O2(aq) ⇌ HO2−(aq) + H+(aq) [HO2− ] [H+ ] mol dm−3
K=
[ H 2 O2 ]
Pb(OH)2(s) ⇌ PbOH+(aq) + OH−(aq) K = [PbOH+] [OH−] mol2 dm−6
HPO42− (aq) ⇌ PO43−(aq)+ H+(aq) [ PO43− ] [H+ ] mol dm−3

K=
[HPO42− ]
Exercise 8.5 ii Moles of ethanoic acid at equilibrium =

(1.00 × 10−3) − (7.84 × 10−4)
[HI]
2
= 2.16 × 10−4 mol
a i Kc =
[I2 ][H2 ] iii Concentration of pentene at equilibrium
(2.52 × 10−2 )
2
= 7.025 mol dm−3
ii = 46.4(no units)
(1.14 × 10−2 )( 0.12 × 10−2 ) iv Concentration of ethanoic acid at
iii The equilibrium concentrations on the top equilibrium = 2.70 mol dm−3
and bottom of the equilibrium expression [CH3CO2C5H11 ]
cancel. v Kc =
[C5H10 ] [CH3CO2H]
b i Moles of pentene at equilibrium = (6.40 ×
(7.84 × 10 −4 )
10−3) − (7.84 × 10−4) = 5.62 × 10−3 mol vi = 646 dm3 mol −1
(5.62 × 10−3 ) × (2.16 × 10−4 )

Exercise 8.6 Adding excess acid to this indicator shifts the

equilibrium to the left and the indicator turns
a number of moles of one particular gas in yellow. The colour of the indicator depends
mixture total number of moles of all gases in on the relative concentrations of the ionised
mixture and unionised forms.
OR b i There is little change in pH (high pH /
The molar proportion of one gas in a mixture pH10) at first / until about 17 cm3 of acid
of gases has been added. The pH then decreases
more rapidly and at 20 cm3 there is a
b i 5.0 mol sudden drop from pH 8 to pH 1.5. The
1.0 pH then decreases less rapidly as more
ii N2 = 5.0 × 40 = 8 atm
acid is added and remains steady at pH 1.
3.5
iii H2 = 5.0 × 40 = 28 atm ii 20 cm3
c i Bromocresol green. The change in colour
Ar = 0.5 × 40 = 4 atm
5.0 corresponds to the sudden change in pH.
c i mol He = 0.15, mol CH4 = 0.40, ii Because the change in colour does not
mol O2 = 0.30 correspond to the sudden change in pH.
total number of moles = 0.85 It will not change colour fully until past
mol fraction = 0.40/0.85 = 0.47 the equivalence point / point where equal
numbers of moles of acid and alkali have
ii Mol He = 0.15, mol CH4 = 0.40, reacted.
mol O2 = 0.30
d i 14
Total number of moles = 0.85
0.40 12
Partial pressure of CH4 = 0.85 × 200
pH of flask contents
= 94 atm 10
d i Total number of moles = 1.02 8

7
0.96 6
Partial pressure of NO2 = 1.02 × 2 × 104
= 1.88 × 104 Pa 4
0.04 2
Partial pressure of NO = 1.02 × 2 × 104
0
= 7.84 × 102 Pa 0 2 4 6 8 10 12 14 16
0.02 Volume of weak acid added to strong base/cm3
Partial pressure of O2 = 1.02 × 2 × 104
Note that the equivalence point is 10 cm3
= 3.92 × 102 Pa because there are twice as many moles
pNO
2 of ethanoic acid as there are moles
ii Kp = 2
of potassium hydroxide. The starting
pNO
2 × pO 2
point is pH 13 because that is the pH of
(1.88 × 10 4 )2 0.1 mol dm−3 potassium hydroxide.
iii = 1.47 Pa −1
(7.84 × 10 2 )2 × (3.92 × 102 )
ii 14
Exercise 8.7 12
pH of flask contents
10
a An acid-base indicator changes colour over a
narrow pH range. These indicators are usually 8
7
weak acids in which the acid, HIn, and its 6
−
conjugate base, In , have different colours.
For example: 4
+ − 2
HIn ⇌ H + In
0
yellow violet 0 2 4 6 8 10 12 14 16
Volume of acid added to strong base/cm3

Note that the equivalence point is 10 cm3 Question 2

because there are twice as many moles
of H+ ions which react in sulfuric acid a i Position of equilibrium moves to
as there are moles of sodium hydroxide. the left [1]
The starting point is pH is 12 because
To oppose the removal of sulfur so
that is the pH of 0.01 mol dm−3 potassium
that equilibrium is restored / idea of le
hydroxide. The final pH is slightly above
Chatelier’s principle [1]
pH 2 because the concentration of H+
ions in the excess acid is (slightly less ii Position of equilibrium moves to the
than) 0.02 mol dm−3. right. [1]
e Thymolphthalein Because if there is a decrease in
temperature, the reaction goes in the
direction of more heat being produced.
Exam-style questions ALLOW: because the reaction is exothermic
[1]
Question 1 iii Position of equilibrium moves to
a Any two different ways (1 mark each), e.g. the right [1]
increase concentration of hydrogen (or carbon
Moves in the direction of fewer moles /
monoxide or remove methane) / increase the
molecules to counteract the pressure
pressure / decrease the temperature. [2]
increase [1]
b i Products are being converted to reactants
b K=
[H2S ]2 [1]
at the same time as reactants are being
converted to products [1] [H ]2 [S2 ]
The concentration of reactants and c i dm3 mol−1 [1]
( 0.442)
2
products remains constant under specified
ii 9.40 × 105 =
( 0.234) × [S2 ]
2
conditions / rate of forward and back
reaction is the same [1]
[S2] =
( 0.442 )2 × (9.40 × 105)
ii No matter is lost to the surroundings or ( 0.234)2
gained from the surroundings [1]
= 3.80 × 10−6 (dm3 mol−1) Correct
c No effect / only increases the rate of answer [3]
reaction [1]
If these not scored, 1 mark for correct
pCH3OH substitution in equation, 1 mark for correct
d i Kp = [1] rearrangement of equation.
pH22 × pCO
pSO2
ii (9.92 × 101)/(6.67 × 104)2 × (3.33 × 104) d i Kp = 3
[1]
2
pSO × pO2
= 6.7 × 10−13 Pa−2 2
Correct numbers inserted, correct (80100)2

answer, correct unit (1 mark each) [3] ii Kp = (10100)2 × (68800)
16.8 = 9.14 × 10−4 Pa−1 All correct
e Partial pressure of hydrogen = 7.2 + 16.8 × [3]
5.00 × 104 = 3.50 × 104 Pa Correct answer [2] If not then 1 mark for correct substitution
but if not scored allow 1 mark for correct including the squares, 1 mark for correct
16.8 unit.
mole fraction, i.e. 7.2 + 16.8
[Total: 12]

e i Position of equilibrium moves to the right Question 4

/ moves in direction of more products [1]
a CH3COOH + OH− → CH3COO− + H2O [1]
Fewer moles / molecules of gaseous
products (in stoichiometric equation) b i Phenolphthalein / other suitable
than reactants [1] indicator [1]
ii High pressure dangerous / more corrosive ii Its colour range does not coincide
at higher pressures / higher pressures with the sudden change of pH [1]
more expensive [1]
c
Reaction is already far to the right [1]
9
iii Higher temperature favours the
8
endothermic reaction (which is to the
left) so yield less [1] 7
6
At lower temperatures rate of reaction
5
is too slow. [1] pH
4
f Fe catalyst [1] 3
450 °C (allow ±20 °C) [1] 2
200 atm pressure (allow ±20 atm / 2000 kPa) [1] 1

0
[Total: 24] Volume of base
Question 3 Axes labelled and one or more pH values

given [1]
a Ethanoic acid partially ionises /
dissociates in water [1] Curve typical ‘S’ shape with sudden rise
in pH [1]
Nitric acid ionises / dissociates
completely in water [1] Midpoint of curve clearly below pH 7 /
curve levels of at pH 9 to 11 and starts at
[CH3CO2− ] [H+ ] pH 0 to 3 [1]
b i Kc =
[CH3CO2H]
[Total: 6]
[CH3CO2− ] [H3O+ ]
ALLOW: CH CO H H O [1]
[ 3 2 ][ 2 ]
ii It is present in great excess [1]
so its concentration is effectively
constant. [1]
c Nitric acid has a higher concentration of
hydrogen ions than ethanoic acid [1]
so more collisions per second compared
with ethanoic acid (or reverse argument). [1]
ALLOW: nitric acid is an oxidising acid for
1 mark
d i (0 to +2) = +2 [1]
ii (+5 to −3) = −8 [1]
e H + OH → H2O
+ −
[1]
[Total: 10]

may be different.
Workbook answers
Chapter 9
Exercise 9.1
a i B and C e Particles are closer together / more particles
per unit volume. Number of effective
ii A: the molecules do not have enough collisions increases.
energy to react when they collide / the
molecules have less energy than the
activation energy.
Exercise 9.2
C: the molecules have not collided in the a CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) +
correct orientation. H2O(l)
iii The molecules have energy greater than or b i

equal to the activation energy and collide
with the correct orientation. Time 0 20 40 60 80 100 120 140
/s
iv effective collisions Mass 0.00 0.10 0.20 0.28 0.34 0.39 0.425 0.45
b i Activation energy is the minimum energy CO2
that colliding particles must have in order /g
to react. The symbol for activation energy Table continued with the other values.
is EA.
ii 60
ii
enthalpy H/kJ mol−1
B
50
EA
Mass of CO2 released / g
reactants
40
∆Hr
products
30
reaction pathway 20
iii Exothermic because the reactants have

10
more energy than the products.
iv The activation energy ‘hump’ is lower. 0
0 50 100 150 200 250 300 350
c A reaction will speed up if the frequency of Time / s
effective collisions increases and the proportion iii The one at 160 s
of particles with energy greater than the
activation energy increases. iv 1st 20 seconds:
rise = 0.1 g / 20 s = 5 × 10 − 3 gs −1
d The 0.8 mol dm−3 hydrochloric acid is more run
concentrated. It has more hydrogen ions per
unit volume than the 0.4 mol dm−3 acid. So the 20−40 seconds:
frequency of effective collisions is greater. rise = 0.2 − 0.1 g = 5 × 10 − 3 gs −1
run 40 − 20 s

v The graph begins to curve / the line is not c i 20°C: Ek = 3 × 8.31 × 293 = 3652.25 units
2
straight.
30°C: Ek = 3 × 8.31 × 303 = 3776.90 units
vi Take a tangent to the curve. 2
ii The % increase in kinetic energy is only
vii rise = 0.60 − 0.20 g, run = 215−0 s = 215 s 3.4% which is far less than the doubling
gradient (rise / run) = 1.86 × 10−3 gs−1 of rate every 10 °C.
c i 0.53 g so moles = 0.53 = 0.012 mol d When the sample is heated, the mean energy
44
ii From the equation: 2 mol HCl form 1 mol of the molecules increases. There is a wider
CO2. So moles HCl = 0.012 × 2 spread of energy values. A greater proportion
= 0.024 mol of the molecules exceed the activation energy
compared with the proportion at a lower
Volume (dm3) = temperature.
mol
concentration (in mol dm − 3 ) Exercise 9.4
= 0.024 = 0.6 dm 3 /60 cm 3 a The activation energy for the catalysed
0.40
iii 0.012 mol × 24 = 0.288 dm / 288 cm
3 3 reaction is lower. So there is a greater
proportion of molecules with energy values
iv Yes: because mass of gas is very small / air above the activation energy.
current can affect the balance / decimal
places b i Reaction proceeds by a different route
with lower activation energy.
OR
ii
No: because the graduations on a gas
syringe are thicker lines and only read
to nearest 2 cm3. Larger volumes being E+P
read so less % error / syringe plunger
EA for the
Enthalpy
constantly moving so more difficult to uncatalysed

∆Hr
read accurately. reaction
E+S
d See line B in answers to (b)(ii) above.
EA for the catalysed
Exercise 9.3 reaction
a i A few molecules have small amount of Progress of reaction

energy, a large number of molecules have
energies near the average, a very small c i In homogeneous catalysis the reactants,
number of molecules have very high energy. products and catalyst are all in the same
phase; in heterogeneous catalysis the
ii Activation energy. The minimum energy
catalyst is in a different phase from the
required by molecules to react when they
reactants and products.
collide.
ii Equation 1: heterogeneous
iii The proportion of molecules with energies
Equation 2: heterogeneous
equal to and above the activation energy.
Equation 3: homogeneous
b i Average kinetic energy of the molecules
increases (slightly).
ii Frequency of collisions increases.
iii Reaction rate increases.

above products and to the left of

Exam-style questions the products [1]
Question 1 Correct activation energy for catalysed

reaction [1]
a i Decreases rate (no mark on own but if
Correct activation energy for uncatalysed
not correct max. 1 for question) Idea
reaction [1]
that particles have less kinetic energy on
average [1] [Total: 17]
Lower proportion of reactant particles has
energy greater than activation energy [1] Question 2
ii Increases rate (no mark on own but if not a Heterogeneous, because the catalyst is in
correct max. 1 for question) a different phase from the reactants and
products / because the catalysts are solid and
Increasing the pressure forces particles the reactants and products are not. [1]
closer together [1]
b Catalyst lowers the activation energy. [1]
Frequency of effective collisions
increases [1] Greater proportion of reactant molecules
has energy above the activation energy [1]
iii Increases rate (no mark on own but if not
correct max. 1 for question) for catalysed reaction. [1]
Adding a catalyst lowers the c Decrease in pressure causes molecules to

activation energy [1] move further apart. [1]
Greater proportion of particles has energy Frequency of effective collisions is reduced. [1]
above the activation energy [1]
d
b Add known mass of catalyst to hydrogen
peroxide. [1] C3H6 + H2
Enthalpy
Record volume of gas in burette [1] C3H8 EA ∆Hf
at particular times. [1]

Repeat with same mass of different catalyst. [1]
Same volume and mass of hydrogen
peroxide. [1] Progress of reaction
All other conditions / named conditions kept
Axes labelled [1]
constant. [1]
Reactants and products labelled [1]
c
EA uncatalysed Reactants above and to the left of the
reaction products [1]
2H2O2
Enthalpy
Correct activation energy [1]

EA catalysed
reaction Arrow for enthalpy change in the upward
2H2O + O2 direction and labelled [1]
[Total: 11]
Progress of reaction
Axes labelled [1]

Reactants and products labelled [1]

Question 3 b i Rate decreases [1]
a i Increases rate (no mark on own but if not gradient decreases with time / gradient
correct max. 1 for question) gets shallower with time [1]
16 cm 3
(1) = 0.8 cm 3s −1
More particles per unit volume at higher ii 20 s [1]
concentration / particles 16 cm 3
closer together [1] (1) = 0.8 cm 3s −1 [1]
20 s
Greater frequency of effective iii 0.25 mol dm−3 [1]
collisions. [1] The magnesium is in excess so the
ii Increases rate (no mark on own but if not acid is the limiting reagent. [1]
correct max. 1 for question). The volume of hydrogen produced
Magnesium powder has a greater surface is half that of B, so the moles
area for the same mass [1] and (for the same volume) the
concentration is half that for B. [1]
More magnesium ions / atoms exposed for
the hydrogen ions to collide with [1] iv The increased gradient reflects the
increased rate of reaction / increase in
iii Increases rate (no mark on own but if not temperature increases reaction rate [1]
correct max. 1 for question).
The final volume is the same because
idea that particles have more kinetic there are the same number of moles of
energy on average [1] acid / the acid is the limiting reagent [1]
Greater proportion of reactant [Total: 15]
particles has energy greater than
activation energy [1]

may be different.
Workbook answers
Chapter 10
Exercise 10.1
a 1 with C; 2 with F; 3 with A; 4 with D; 5 with to break the strong metallic bonds between
B; 6 with E the ions and delocalised electrons. S has no
delocalised electrons so does not conduct. Al
b Sodium chloride dissolves in water to form has delocalised electrons which move through
a neutral solution because the polar water the whole structure between the ions when a
molecules surround the positive and negative voltage is applied.
ions and separate them. Aluminium chloride is
hydrolysed by water and the solution becomes
acidic. Chlorides of silicon, phosphorus and
Exercise 10.2
sulfur react with water. The gas, hydrogen a i There is a general increase in ionisation
chloride, is released, some of which dissolves in energy across the period. This is because
water and reacts to form an acidic solution. successive atoms have one more proton
c i PCl5 + 4H2O → H3PO4 + 5HCl in their nucleus so there is an increased
nuclear charge. The outer electrons are
ii SO3 + H2O → H2SO4 in the same principal quantum shell
and there is no significant difference in
iii Mg(OH)2 + 2HCl → MgCl2 + 2H2O
shielding. So the attractive effect of the
iv SiO2 + 2NaOH → Na2SiO3 + H2O increased nuclear charge on the electrons
makes it more difficult to remove an outer
v 2Na + 2H2O → 2NaOH + H2 electron from an atom across the period.
vi Al2O3 + 3H2SO4 → Al2(SO4)3 + 3H2O ii The additional electron in aluminium
vii SiCl4 + 2H2O → SiO2 + 4HCl goes into a p orbital which is, on average,
slightly further from the nucleus and has
viii 2P + 5Cl2 → 2PCl5 slightly more shielding. These effects
overcome the effect of the increased
ix 4Al + 3O2 → 2Al2O3
nuclear charge. In sulfur, the added
d i sodium oxide pH 13–14 magnesium oxide electron goes into an orbital so that its
pH 9–11 spin opposes that of the electron already
in the orbital. This gives the outer
ii Sodium oxide reacts to form sodium electrons additional stability so an outer
hydroxide which is very soluble so the electron is less easily removed.
concentration of OH− ions is high.
Magnesium oxide reacts to form magnesium iii K: value should be slightly less than Na
hydroxide which is not very soluble so the (actual value = 419 kJ mol−1)
concentration of OH− ions is lower.
Ca: value should be slightly less than Mg but
iii MgO + H2O → Mg(OH)2 greater than K (actual value = 590 kJ mol−1)
e S is a simple molecule with weak b Across a period, the number of protons
intermolecular forces. Only low temperature is (positive charges) increases. So the nuclear
needed to separate the molecules. Al is a giant charge also increases. The number of electrons
metallic structure. High temperatures needed (negative charges) also increases across a

period. Each electron added to the atom between the ions and the electrons so
of successive elements goes into the same making it more difficult to overcome
principal quantum shell. So the shielding of these.
outer shell electrons by inner shell electrons
does not increase significantly. Across a iii Covalent giant structure (giant molecular
period, the greater attractive force between structure). Takes a very high temperature
the nucleus and the outer electrons pulls them / a lot of energy to break all the bonds in
closer to the nucleus. the lattice.
c From sodium to silicon, the ionic radius c Ne: element before Na so about the same
decreases for similar reasons detailed for the level as argon. ALLOW: 5−100 K (actual
atomic radius (part b). The outer electrons value 25 K)
are in the second quantum shell because the K: next element after Ar value should be
ions are formed by loss of the outer electrons nearer to that of Na but slightly lower.
and so the ionic radii are smaller than the ALLOW: 250−400 K (actual value 336 K)
corresponding atomic radii. The values for
phosphide to chloride are much higher because Ca: next element after K so should be higher
the outer electrons are in the next quantum than potassium. ALLOW: 900−1300 K (actual
shell (the third). So the outer electrons are value 1112 K)
further from the nucleus and the attraction to d i They are metals so have delocalised
the nucleus is much less. The values decrease electrons which are responsible for the
from phosphide to chloride for similar reasons transfer of charge throughout the whole
detailed for the atomic radius (part b). structure.
d i Group 1 ii Each aluminium atom can provide 3
ii Decreases from Group 1 to Group 13 or electrons to the ‘sea’ of delocalised
14 and then increases to a maximum. electrons in the metallic structure. A
sodium atom can only provide 1 electron.
iii The atomic radius decreases gradually
across a period but the atomic volume iii It has a simple molecular structure so there
decreases then increases. are no delocalised electrons (or mobile ions).
iv The atomic volume depends on how the e i The ratio of chlorine to other element
atoms are packed in the structure, whether increases to a maximum in Group 14 or
they are packed so that there is a lot of 15 and then decreases.
space between some of the atoms or ii CCl4, SiCl4, NCl3, PCl5
whether they are packed more efficiently.
iii P = +5, S = +4
v It increases (compare similar points on
the curve, e.g. Li with Na with K). f i If the difference in electronegativity
between the ‘atoms’ is relatively large e.g.
Exercise 10.3 1.0, the structure is ionic. If the difference
in electronegativity between the ‘atoms’
a It increases to a maximum (at Si) and then is relatively small e.g. 0.5, the structure
decreases to very low values. is covalent (although there is some ionic
character in PCl5).
b i They have molecular structures with only
weak forces of attraction (van der Waals’ ii Magnesium and chloride ions are
forces) between the molecules. stabilised by water molecules (ion-dipole
bonding) in solution and do not react. In
ii Each aluminium atom can provide
PCl5 the Cl is more electronegative than
3 electrons to the ‘sea’ of delocalised
the P. So P is δ+ and a highly polar water
electrons in the metallic structure. A
molecule (O δ−)can attack the P) and
sodium atom can only provide 1 electron.
hydrolyse the molecule.
A greater number of delocalised electrons
and a higher ionic charge (3+ for Al) mean
that there are greater forces of attraction

Exercise 10.4 d High melting point → giant structure.

Alkaline oxide → group 1 or 2.
a i There is a regular pattern in the melting
points, e.g. in the d-block the melting Neutral solution of chloride → group 1 or 2.
points rise to high values then fall again / Chloride XCl2 → group 2.
there is a peak for the Group 14 element. 3rd highest ionisation energy in Group →
ii Element X is silicon and Y is germanium. period 4 (since 1st in group is period 2 and 1st
They have giant structures of covalent ionisation energies decrease down the group.
bonds. It takes a lot of energy / high So X is Ca.
temperature to break all these bonds.
iii Element with atomic number 15
(phosphorus) is in group 15 and is a
simple molecule. There are only weak
forces of attraction between the molecules
Question 1
so it does not take much energy / relatively a i Mass of atoms [1]
low temperature required to overcome
these forces. size of atoms [1]
iv They rise from high values to very high the way the atoms are packed together [1]
values then fall again. ii The mass of the atoms increases as the
v They are noble gases / Group 18. There are number of protons and neutrons
only very weak forces of attraction between increases [1]
their atoms (because the van der Waals’ the atomic radius / volume decreases
forces are only between single atoms). So from sodium to aluminium [1]
not much energy / only low temperature is
required to overcome these forces. so ratio of mass / volume decreases. [1]
b i ALLOW: between 500 and 1200 °C b i Na2O(l)s) + H2O(l) → 2NaOH(aq)
(actual value is 931 °C)
ii Conductor (the elements are more
correct balance [1]
metallic down the group)
correct state symbols [1]
iii 1.8
ii Amphoteric [1]
iv (Weakly) acidic
iii Al2O3 + 2NaOH + 3H2O → 2NaAl(OH)4
v The covalent bonding gets weaker as the
atoms get larger because there is less force Correct formulae [1]
of attraction between the nucleus and the
bonding electrons. correct balance [1]
vi They are metals and so do not form c Any six of:

covalent bonds. Melting point of sodium, magnesium and
c i Gets more negative aluminium oxides are high because
they are giant ionic structures.
ii It has a higher nuclear charge than the
atoms of the elements before it. So it is more Increase in melting point from sodium to
likely to attract an electron and fill the outer aluminium reflects the increased electrostatic
p-electron shell to make it stable. forces between the ions because of the
increased charges on the ions.
iii The outer shell electrons are further from
the nucleus, so attractive forces between Silicon dioxide has a high melting point
the positive nuclear charge and an because it is a giant covalent structure.
incoming electron is less.

It takes a lot of energy / high temperatures Phosphorus and sulfur do not conduct
to break the electrostatic forces or covalent because they are molecular and do
bonds in a giant structure. not have delocalised electrons. [4]
Phosphorus and sulfur oxides have low ii Any value between 10−11 and 10−22
melting points because they are simple (actual value is 10−17 S m−1) [1]
molecules.
b i The energy needed to remove 1 mole of
With weak intermolecular forces / van der electrons from 1 mole of atoms of an
Waals’ forces between the molecules element [1]
It does not take much energy / low in the gaseous state to form 1 mole of
temperature to overcome these forces of gaseous ions. [1]
attraction. [6]
ii Argon [1]
d i In Period 2 there is a gradual increase
with increase in atomic number Greatest nuclear charge in the period [1]
up to Group 15 then decrease to The last (8th) electron added goes into the
fluorine oxide. [1] same principal quantum shell as the
In Period 3 there is a gradual increase atoms of others elements in the same
from Group 1 to 17. [1] period [1]
ii Nitrogen: N2O5 [1] so the shielding is approximately

the same [1]
Silicon: SiO2 [1]
so there is the greatest force of attraction
Chlorine: Cl2O7 [1] between the nucleus and the outer
electrons. [1]
iii Maximum oxidation number increases
across a period [1] c i 2Mg + O2 → 2MgO [1]
Number of outer shell electrons / valency ii Electronegativity difference large
electrons forming bonds is the same as between Mg and O so ionic. [1]
the (maximum) oxidation number [1]
Electronegativity difference small
Example: Al3+ OxNo +3, SO3 OxNo between S and O so covalent. [1]
of S +6. [1]
iii MgO reacts to form Mg(OH)2 [1]
[Total: 26]
O2− ion behaves as a base / O2− ion accepts
H+ from water molecule. [1]
Question 2
SO3 reacts to form H2SO4 [1]
a i Any four of:
In SO3 the O is more electronegative than
Sodium, magnesium and aluminium the S. So S is δ+ [1]
are metals
Highly polar water molecule (O δ−)
so have delocalised electrons which flow can attack the S (and hydrolyse the
through the structure when a voltage is molecule). [1]
applied.
d i Covalent [1]
Conductivity increases from sodium to
aluminium because there are more ii As4O10 ALLOW: As2O5 [1]
electrons to conduct.
iii Acid hydrolysis / forms an acid / forms
Silicon does not conduct very well / is a arsenic acid [1]
semiconductor since it is a giant
[Total: 23]
covalent structure and does not have
delocalised electrons / a few electrons
can jump from place to place.

Question 3 c i Any five of:
a i Across a period the nuclear charge Melting points of sodium, magnesium

increases. [1] chlorides are high because they are
giant ionic structures.
Each electron added to the atom of
successive elements goes into the It takes a high temperature / lot of energy
same principal quantum shell [1] to break these strong attractive forces.
so the shielding of outer shell electrons by Decrease in melting point from sodium
inner shell electrons does to aluminium reflects the decreased
not increase significantly. [1] ionic bonding / greater proportion of
covalent bonding in aluminium chloride
So across a period, the greater attractive / aluminium chloride without water is
force between the nucleus and the covalently bonded.
outer electrons pulls them closer to the
nucleus. [1] Chlorides of silicon, phosphorus and
sulfur have low melting points because
ii The outer electrons in the magnesium ions they are simple molecules
are in the second quantum shell [1]
(because the two outer electrons of the with weak intermolecular forces / van der
magnesium atom have been lost). Waals’ forces between the molecules
The sulfide ion has a greater ionic radius It does not take much energy / low
because the outer electrons are temperature to overcome these forces
in the third quantum shell. [1] of attraction. [5]
so the attraction to the nucleus is much ii The melting point of aluminium chloride
less than for magnesium. [1] is not measured at r.t.p. ALLOW:
phosphorus chloride sublimes so its
b i Ease of hydrolysis increases across melting point cannot be measured. [1]
Period 3. [1]
iii Sodium chloride dissolves in water [1]
ii SiCl4(l) + 2H2O(l) → SiO2(s) + 4HCl(g)
so its pH is the pH of water. [1]
Magnesium chloride undergoes a small
correct balance [1] amount of hydrolysis in water [1]
correct state symbols [1] So sufficient hydrogen ions formed to
lower the pH. [1]
iii 2Al + 3Cl2 → Al2Cl6 Correct formulae [1]
[Total: 23]
correct balance [1]

may be different.
Workbook answers
Chapter 11
a i 2Ca + O2 → 2CaO a i ALLOW 660−710 °C (actual = about
700 °C)
ii Mg + 2HCl → MgCl2 + H2
ii ALLOW 4−6 g cm−3 (actual about
iii Mg + H2SO4 → MgSO4 + H2 5.0 g cm−3)
iv Ba + 2H2O → Ba(OH)2 + H2 iii ALLOW 0.97 to 1.04 (actual 1.0)
b i CaCO3 heat CaO + CO2 iv ALLOW 0.18 to 0.21 (actual = 0.197 nm)
ii CaCO3 + 2HCl → CaCl2 + CO2 + H2O b Down the group density decreases to
iii Ca(OH)2 + 2HNO3 → Ca(NO3)2 + 2H2O minimum at calcium, then increases.
iv CaO + H2O → Ca(OH)2 c Magnesium
c i MgO(s) + 2HCl(aq) → d Down the group solubility of the hydroxides

MgCl2(aq) + H2O(l) increases.
ii Ba(OH)2(aq) + H2SO4(aq) → e Strontium hydroxide is more soluble than

BaSO4(s) + 2H2O(l) magnesium hydroxide.
So strontium hydroxide has higher
Exercise 11.2 concentration of hydroxide ions in solution
than magnesium hydroxide.
a 1 with D; 2 with G; 3 with A; 4 with F; 5 with The higher the concentration of hydroxide
C; 6 with B; 7 with E ions, the higher the pH.
b i 2Ca(NO3)2 → 2CaO + 4NO2 + O2 f Down the group solubility of the sulfates
decreases.
ii BaCO3 + 2HNO3 → Ba(NO3)2 + CO2 +
H2O
Exercise 11.4
iii 2Sr + O2 → 2SrO
a i Down the group, there is an increase in
iv MgCO3 heat MgO + CO2 reactivity.
c i SrCO3(s) heat SrO(s) + CO2(g) ii 2Mg(s) + O2(g) → 2MgO(s)
ii 2Mg(NO3)2•6H2O(s) → 2MgO(s) + iii Litmus will turn blue due to alkaline pH.
4NO2(g) + O2(g) + 6H2O(l) The magnesium oxide reacts with water
to form magnesium hydroxide, which is
iii SrCO3(s) + 2HCl(aq) → SrCl2(aq) + slightly alkaline.
CO2(g) + H2O(l)
iv 2Sr(s) + H2O(l) → Sr(OH)2(aq)

b i Constant heating is required (which iii 2Ba + O2 → 2BaO [1]

means energy is absorbed).
iv Oxidation and reduction occur in the
ii same equation / together [1]
∆Hr
MgCO3(s) MgO(s) + CO2(g) Oxidation number of Ba increases from
0 in Ba to +2 in Ba2+ ion in BaO [1]
∆Hf [MgCO3(s)] ∆Hf [MgO(s)]
∆Hf [CO2(g)] Oxidation number of O decreases from 0
1
in O2 to −2 in O2− ion in BaO [1]
Mg(s) + C(graphite) + 12 O2(g)
b i Ionic radius increases [1]
iii −1095.8 + ∆H⦵r = −601.7 − 393.5 ii 1s22s22p63s23p6 [1]
So ∆H⦵r = −601.7 − 393.5 + 1095.8
[Total: 13]
= + 100.6 kJ mol−1
iv Strontium carbonate decomposes Question 2
less readily because, as you go down
the group, the temperature at which a i Solubility of hydroxides increases [1]
decomposition occurs gets higher. down the group [1]
c i 2Ca(NO3)2 → 2CaO + 4NO2 + O2 ii Calcium hydroxide is more soluble than
ii Brown fumes of nitrogen dioxide magnesium hydroxide [1]
d i Group 2 nitrates are more difficult so calcium hydroxide has higher

to decompose / decompose at higher concentration of hydroxide ions in
temperatures as you go down the group. solution than magnesium hydroxide. [1]
Calcium hydroxide decomposes at a lower The higher the concentration of hydroxide
temperature than barium hydroxide and ions, the higher the pH. [1]
calcium is higher in the group, which is
the same pattern. b The solubility of the hydroxides increases
down the group [1]
ii ALLOW between 770 and 1300 °C.
c Molar mass of calcium hydroxide = 74.1 [1]
iii Sr(OH)2 heat SrO + H2O
mass = moles × molar mass
= (1.50 × 10−3) × 74.1 = 0.111 g
Exam-style questions (in 100 g water) [1]

In 500 cm3 water = 0.556 g [1]
Question 1
d Solubility decreases down the group [1]
a i Sr+(g) → Sr2+(g) + e−
Correct reactants and products [1] e i Barium sulfate [1]
state symbols [1] because it is insoluble in water / its

solubility in water is very low [1]
ii Going down the group the ionisation
energies decrease [1] ii Ba2+(aq) + SO42−(aq) → BaSO4(s)
because the outer electrons are in electron Correct reactants and products [1]
shells further from the nucleus [1]
state symbols [1]
so there is less attraction between the
outer electrons and the nucleus [1] f i BaCO3(s) + H2SO4(aq) → BaSO4(s) +
CO2(g) + H2O(l)
and more shielding of outer electrons
by electrons in inner shells. [1] Correct reactants and products [1]
So the two outer electrons are more easily state symbols [1]
transferred to the oxygen atom going
down the group. [1]

ii Barium sulfate is insoluble in water [1] c 2Sr(NO3)2(s) → 2SrO(s) + 4NO2(g) + O2(g)

so forms a layer round the outside of Correct formulae [1]
the barium carbonate particles [1]
correct balance [1]
(so the sulfuric acid cannot reach the
barium carbonate) correct state symbols [1]
[Total: 13] d Oxidation and reduction occur in the same

equation / together. [1]
Question 3 Oxidation number of Sr increases from 0 in Sr
to +2 in Sr2+ ion in Sr3N2 [1]
a O2− + H2O → 2OH− [1]
Oxidation number of N decreases from 0 in
b Molar mass of strontium oxide = 103.6 g and N2 to −3 in N3− ion in Sr3N2 [1]
molar mass of strontium nitrate = 211.6 g [1]
41.4 e i Because the outer electrons in strontium
Moles of SrO = 103.6 = 0.400 mol [1] are in electron shells further from the
Mass strontium nitrate = 0.400 × 211.6 nucleus [1]
= 84.6 g [1] ii 1s22s22p63s23p63d104s24p65s2 [1]
iii Sr → Sr2+ + 2e− [1]
[Total: 13]

may be different.
Workbook answers
Chapter 12
Exercise 12.1
a 1 with C; 2 with A; 3 with E; 4 with F; 5 with ii Hydrogen chloride is denser than air.
D; 6 with B
iii White fumes of hydrogen chloride would
b hydrogen iodide < hydrogen bromide < be seen at the mouth of the measuring
hydrogen chloride < hydrogen fluoride cylinder (due to reaction with water
vapour in the air).
c 2HI(g) ⇌ H2(g) + I2(g)
d i 2HI + H2SO4 → I2 + SO2 + 2H2O
Exercise 12.2 ii 6HI + H2SO4 → 3I2 + S + 4H2O
a The suspected halide is dissolved in dilute iii 8HI + H2SO4 → 4I2 + H2S + 4H2O
nitric acid. A few drops of aqueous
silver nitrate are added. If chloride ions are e i I from −1 to 0; S from +6 to +4
present a white coloured precipitate is formed
ii I from −1 to 0; S from + 6 to 0
which goes grey / violet in the presence of
light. The precipitate dissolves in dilute iii I from −1 to 0; S from +6 to −2
ammonia solution. If a bromide is present
a cream coloured precipitate is seen which f Brown solution (aqueous iodine), purple
dissolves in concentrated ammonia solution. fumes (iodine vapour), black solid (iodine),
smell of rotten eggs (hydrogen sulfide)
b i AgNO3(aq) + KI(aq) →
AgI(s) + KNO3(aq) g Sulfuric acid reacts with NaCl to produce
NaHSO4 and HCl. The bond energy H─Cl
ii Ag+(aq) + I−(aq) → AgI(s) is relatively high so HCl can only undergo
thermal decomposition at very high
c i Carry out the experiment in a fume
temperatures.
cupboard. Place sodium chloride in the
flask and sulfuric acid in the dropping Sulfuric acid reacts with NaI to produce
funnel. Remove the stopper from the NaHSO4 and HI. The bond energy H─I is
dropping funnel and open the tap so that low high so HI readily undergoes thermal
the sulfuric acid drips slowly onto the decomposition to produce iodine and sulfur
sodium chloride. Close tap when sufficient dioxide. Iodide ions are good reducing agents
sulfuric acid has been added. and so SO2 can be reduced to S and further
to H2S.

Exercise 12.3
a
Halogen Halide Reaction or no Colour of the aqueous Colour of the
reaction mixture after the hexane layer
addition
Cl2(aq) NaBr(aq) reaction orange dark orange
I2(aq) KCl(aq) no reaction brown (colour of I2(aq)) purple
Br2(aq) KI(aq) reaction brown purple
Cl2(aq) LiBr(aq) reaction orange dark orange
Br2(aq) MgCl2(aq) no reaction orange (of bromine) dark orange
Cl2(aq) NaI(aq) reaction brown purple
b i Chlorine because it is better at accepting e i Because they are measured at different

electrons from another reactant than the temperatures and density varies slightly
others in the table. with temperature.
ii Iodide because it is better at donating ii The particles in a liquid are packed close
electrons to another reactant than the together and so the mass divided by the
others in the table. volume of the atoms can still be compared.
The comparison with iodine may be less
c i Cl2(aq) + 2KI(aq) → I2(aq) + 2KCl(aq) valid because the packing will be different.
ii Br2(aq) + 2NaAt(aq) → At2(aq) + f H2(g) + Cl2(g) → 2HCl(g)
2NaBr(aq)
iii Cl2(aq) + MgBr2(aq) → Br2(aq) + Exercise 12.5
MgCl2(aq)
a i Mg(s) + Cl2(g) → MgCl2(s)
d i Br2(aq) + 2KI(aq) → I2(aq) + 2KBr(aq)
ii Mg has been oxidised because its
ii Cl2(aq) + 2NaBr(aq) → Br2(aq) + oxidation number has increased from
2NaCl(aq) 0 to +2.
Chlorine has been reduced because its
Exercise 12.4 oxidation number has decreased from
a i ALLOW: 200−450 °C (actual = 337 °C) 0 to −1.
ii ALLOW: 0.5−1.54 g cm−3 b i chlorine = 0; sodium chloride = −1;

(actual = 1.54 g cm−3) sodium chlorate(I) = +1
iii Grey black / black ii The chlorine has been reduced to chloride
ions (oxidation number change 0 to −1)
b Colour gets darker going down the group. and it has also been oxidised to Cl in
c Liquid, because −4 °C is above the melting chlorate (oxidation number change 0
point but lower than the boiling point. to +1).
d Less volatile down the group because the iii Cl2 + 2OH− → Cl− + ClO− + H2O
boiling points are increasing down the group. 1
iv 2 Cl2 + 2OH → ClO + H2O + e
− − −
(oxidation because loss of electrons)

1
2 Cl2 + e → Cl (reduction because of
− −
gain of electrons by Cl)

c i To kill bacteria / to kill microbes of nitrogen / has decreased its oxidation

number. [1]
ii The chlorine has been reduced to chloride
ions (oxidation number change 0 to −1) e i Add nitric acid and aqueous silver
and it has also been oxidised to Cl in nitrate [1]
chlorate (oxidation number change 0
White precipitate formed [1]
to +1).
ii Precipitate dissolves [1]
d H2(g) + Cl2(g) → 2HCl(g)
[Total: 19]
Exam-style questions Question 2

Question 1 a chlorination kills (harmful) bacteria [1]
Cl2 + H2O ⇌ HClO + HCl [1]
a i Gas because −32 °C is above the boiling
point of chlorine. [1] Hypochlorous acid and chlorine are strong
oxidising agents [1]
ii ALLOW: −250 to −150 °C (actual value
= −220 °C) [1] b i Oxidation number of Cl in sodium
chloride = −1 [1]
iii Less volatile down the group / less volatile
with greater relative molecular mass [1] Oxidation number of Cl in sodium
chlorate(V) = +5 [1]
id-id forces. instantaneous dipole-induced
dipole forces [1] ii Chlorine has been reduced to
chloride ions (oxidation number change
These forces increase as the number of
0 to −1) [1]
electrons in the molecules increases [1]
Chlorine has been oxidised to Cl in
Number of electrons in the halogens
chlorate(V) (oxidation number change
increases as the molar mass of the
0 to +5) [1]
molecules increases [1]
It is disproportionation because the
b 1s22s22p63s23p63d104s24p5 [1]
chlorine has been both oxidised and
c Halogens are better oxidising agents, the reduced at the same time. [1]
higher they are in the group / less good
iii Cl2(aq) + 6OH−(aq) → 5Cl−(aq) +
oxidising agents down the group. [1]
ClO3−(aq) + 3H2O(l) [1]
The higher in the group, the smaller the bond
c i Cl2(aq) + 2KI(aq) → I2(aq) + 2KCl(aq)
length / the smaller the atoms [1]
Correct formulae and balance [1]
and the greater the pull of the nuclei on
electrons from other atoms. [1] correct state symbols [1]
So electrons more easily gained [1] ii Colourless (ALLOW: very light green)
to brown [1]
d i 3NH3 + 3Cl2 → NCl3 + 3HCl
Aqueous iodine is brown [1]
iii Shake the mixture with hexane then allow
correct balance [1]
the layers to settle. [1]
ii Oxidation number of nitrogen increases
Colour in the hexane layer is purple. [1]
from −3 to + 3. [1]
d i Hydrogen iodide [1]
Oxidation number of chlorine changes
from 0 to −1. [1] Oxidation number of S decreases / goes
from +6 to 0 OR oxidation number
Chlorine is oxidising agent because it has
of I increases / goes from −1 to 0 [1]
increased the oxidation number

ii +6 to −2 [1] d i Cl2 + 2KBr → Br2 + 2KCl [1]

iii 1 mark each for any three of: ii Add nitric acid and aqueous silver
nitrate [1]
Black solid / yellow solid / purple vapour /
brown solution / bad egg smell [3] Cream precipitate formed [1]
[Total: 21] iii Precipitate dissolves [1]
because a complex ion is formed [1]
Question 3
which is soluble in the solution. [1]
a i Chlorine reacts faster than bromine with
hydrogen. [1] e i Manganese(IV) oxide [1]
Hydrogen reacts explosively with chlorine Increases the oxidation number of iodine
in sunlight. [1] from −1 to 0 [1]
ii I− + e− → 1 I + e− [1]
Bromine reacts on heating. [1] 2 2
b i No effect [1] Oxidation because of loss of electrons
from I− / increase in oxidation number
ii Position of equilibrium shifted to the left / of I from −1 to 0 [1]
concentration of HI lowered / reaction
shifted in favour of the reactants [1] MnO2 + 4H+ + 2e− → Mn2+ + 2H2O [1]
iii Position of equilibrium shifted to the right / Reduction because gain of electrons by
concentration of HI increased / reaction Mn / decrease in oxidation number
shifted in favour of the product [1] of Mn from +4 to +2 [1]
c The atoms get larger as the atomic number is [Total: 21]

increased / down the group. [1]
The attraction between the nuclei of the
atoms and the electrons in the covalent bond
decrease (as the atoms get bigger). [1]
The energy needed to break the bond
decreases / bond energy gets smaller
(down the group). [1]

may be different.
Workbook answers
Chapter 13
a Nitrate fertilisers dissolve in rainwater and are a i
then leached into lakes and rivers. The nitrates
N N
promote the excessive growth of water plants,
especially algae. The algae spread across the
surface of the water and block out the light so
that the water plants cannot grow. The plants ii It has a triple bond with very high bond
are decomposed by aerobic bacteria, which energy.
multiply and use up the dissolved oxygen b i Lone pairs
in the water. Fish and other water creatures
cannot survive without oxygen and they die. ii 107° because lone pair─bond pair
This process taking place in streams and rivers repulsion is greater than bond pair─bond
leading to the death of plants and animals is pair repulsion. So the bond angle closes
called eutrophication. up compared with 4 bonding pairs to
minimise repulsive forces of electron pairs.
b i Removal of crop plants depletes the
soil of nitrogen so there is not sufficient iii 109.5° There are no lone pairs so there are
nitrogen in the soil after several years for only bond pair─bond pair repulsions so
plants to grow well. Plants need nitrogen the bonds move to minimise these electron
to grow / plants need nitrogen to make pair repulsions.
proteins. c i Ammonia is less dense than air.
ii The products are ammonia which is a ii Damp red litmus placed at the mouth of
weak base and HCl which is a strong the tube turns blue.
acid. So there are more hydrogen ions
than hydroxide ions (from ammonia) in iii To dry the ammonia (since water vapour
solution. will also be formed).
iii Lone pair of electrons on ammonia iv It will react with the ammonia to form
accepts hydrogen ion from water. ammonium sulfate.
Hydroxide ion formed.
v Displacement of ammonia
iv 2NH4Cl + Ca(OH)2 → CaCl2 + 2NH3 +
vi Neutralisation (of ammonia): the reaction
2H2O
of an acid with an alkali.
v Calcium carbonate
Displacement (of ammonia): The
replacement of one group by another.
In this case hydroxide ions in calcium
hydroxide have been displaced by
chloride ions.

Thermal decomposition: The ammonium g i By combination of nitrogen with oxygen

chloride would break down when heated at the high temperature within the engine.
to form ammonia and hydrogen chloride.
ii 4CO + 2NO2 → 4CO2 + N2
d i NH3 + H3PO4 → (NH4)3PO4
h i NO2 reacts with SO2 to form SO3 and NO.
ii Heat the solution to evaporate the water. The NO is then oxidised by atmospheric
Melt the solid formed and then spray it in oxygen to reform NO2. The NO2 acts as a
a tower through which air is blown. catalyst since it is reformed and can then
oxidise further molecules of SO2.
iii To provide extra nutrients / extra nitrogen,
phosphorus and /or potassium to the soil, ii NO2 is in the same phase (gas phase) as
to replace nutrients taken up by previous the SO2 and the products.
crops. These elements increase the growth
of (crop) plants and therefore increase i i Reduced growth (because of increased
food production. leaching of nutrients from the soil);
increased likelihood of disease (due to
e Nitric acid decomposition of the waxy covering on
the surface of leaves); leaf burn (especially
Exercise 13.3 in conifers); reduction in ability to absorb
material through the roots, etc.
a In the mornings the concentration of nitrogen
dioxide increases. After midday there is a ii Corrosion of metals; erosion of mortar;
slight decrease but there is a general increase erosion of carbonate building materials
from mid-afternoon until early evening. There (limestone / chalk, etc.).
is a decrease in concentration from the late
evening to early morning (except for day 3).
b Increasing amount of traffic producing
nitrogen dioxide, e.g. diesel vehicles.
Question 1
c i 2NO + O2 → 2NO2
a i Line A because towns are more likely to
ii NO2 + O2 → NO + O3 have more traffic. [1]
iii The NO formed in the second reaction Idea of nitrogen dioxide being produced
can react with more oxygen in the air to by car engines /high temperature furnaces
form more nitrogen dioxide so the reaction in industry. [1]
continues in the presence of oxygen.
ii Winds blow the nitrogen dioxide from
d i Nitrogen dioxide is brown. The other areas where concentration is
concentration of the nitrogen dioxide higher [1]
increases during the day.
iii 400 ×× 10
400 10−6
−6 g(1) moles NO
g moles NO2 2 [1]
ii The amount of ozone will gradually
400 × 10 −6
increase during the day as the = or 8.7 × 10 −6 mol [1]
concentration of nitrogen dioxide 46
increases (see reaction (c)(ii)). 8.7 × 10 −6
In 1 dm 3 = mol
e Day 3. Temperatures are usually lower at 1000
night so the amount of nitrogen dioxide in the = 8.7 × 10 −9 mol dm −3 [1]
atmosphere during the night falls in the first b High temperature caused by (electric
two days. discharge) of lightning [1]
f Nitrogen reacts with oxygen in the presence causes nitrogen to combine with oxygen to
of lightning. The lightning produces high form NO / nitric oxide. [1]
enough temperatures for the reaction to occur.
Nitrogen(II) oxide / nitric oxide is formed. This Nitric oxide reacts with oxygen to form
reacts with oxygen to form nitrogen dioxide. nitrogen dioxide. [1]
N2 + O2 → 2NO / 2NO + O2 → 2NO2 [1]

c 4CO + 2NO2 → 4CO2 + N2 c i 4NH3 + 5O2 → 4NO + 6H2O [1]

Correct formulae [1] ii for fertilisers [1]
correct balance [1] iii NO oxidised to NO2 in atmosphere [1]
d i N in NO has oxidation number +2; N in NO2 reacts with rainwater to form nitric
N2 has oxidation number +4 / oxidation acid [1]
number change is −2. [1]
iv acts as a catalyst [1]
C in CO has oxidation number +2; C in
CO2 has oxidation number +4 / oxidation in oxidation of sulfur dioxide to sulfur
number change is +2. [1] trioxide [1]
Decrease in oxidation number is reduction d Reaction of nitrogen with oxygen [1]

and increase in oxidation number is in presence of high electric discharge from
oxidation. [1] lightening [1]
ii Heterogeneous catalysis [1] e free radical [1]
The catalyst is a solid and the reactants f i sunlight / ultraviolet light [1]
are gases / the catalyst is in a different
phase to the reactants. [1] ii peroxyacetyl nitrate / PAN [1]
e i It has very strong bonds / its bond energy [Total: 18]

is very high [1]
Question 3
It needs a high temperature / lot of energy
to break these bonds in order to react [1] a i N in NH4+ has OxNo −3; N in NO2− has
OxNo +3 / oxidation number change
ii is +6. [1]
N N O in O2 has OxNo 0; O in H2O has OxNo
−2 / oxidation number change is −2. [1]
3 pairs of bonding electrons [1] Decrease in oxidation number is reduction

and increase in oxidation number is
the 2 lone pairs [1] oxidation. [1]
[Total: 21] ii + [1]
H
Question 2 H N H
a i (NH4)2SO4 + 2NaOH → 2NH3 + Na2SO4 H
+ 2H2O
Correct formulae [1] iii 2NO2− + O2 → 2NO3− Correct species [1]
Correct balance [1] balanced [1]
ii Displacement [1] iv Idea of run off / ions moving into deeper
soil / ions going to where plant roots
b i Incompletely ionised in solution / cannot reach them [1]
incompletely dissociated in solution [1]
b Nitrogen has very strong bonds / its bond
ii Lone pair on ammonium ion accepts energy is very high. [1]
proton / H+ ion [1]
It needs a high temperature / lot of energy to
from water [1] break these bonds in order to react. [1]
Hydroxide ion / OH− formed which is c Ammonia is a proton acceptor / ammonia is
responsible for alkalinity [1] taking H+ ions from the acid. [1]

2 × 14 × 100 = 35% is more economical to spread it /

d [2]
80 ammonium nitrate has greater % nitrogen.[1]
(If 2 marks not scored, 1 mark for correct
f NH4+ + OH− → NH3 + H2O [1]
molar mass of NH4NO3 (80))
[Total: 15]
e i Potassium nitrate is less soluble in water
so not so much is leached away. [1]
ii Ammonium nitrate is more soluble in
water so plants can absorb it more readily /
ammonium nitrate has a lower density so it

may be different.
Workbook answers
Chapter 14
Exercise 14.1
a 1 with C; 2 with A; 3 with G; 4 with B; 5 with d i O H ii
H H H O H
H; 6 with D; 7 with E; 8 with F
H C C C H H C C C H
b i Hexane H H H H
H C H
ii Propanol H
iii But-1-ene iii iv

H H H O H H H O
iv Pentanal H C C C O C H H C C C C
H H H H H H H
v 1-bromopentane
vi Propanone Exercise 14.2
vii Propanoic acid
a i Addition
viii Heptane
ii Oxidation
ix butan-1-ol
iii Hydrolysis
x Pent-1-ene
iv Substitution
xi Methanal
v Elimination
xii pentanenitrile
vi Reduction
xiii pentylamine
vii Substitution
c S 2-methylbutane
viii Condensation
T Butan-2-ol
b i In heterolytic fission a covalent bond
U 1,2-dibromoethene breaks so that two free radicals are
formed.
V Hex-2-ene
ii In homolytic fission a covalent bond
W 3-ethyl-3methylhexane breaks so that one of the atoms in the
X 2,2-dibromobutane bond accepts both the bonding electrons.
iii A nucleophile is a species which donates
/ gives a pair of electrons to an electron-
deficient atom.
iv An electrophile is a species with a positive
or partially positive charge which accepts
a pair of electrons from another species.

v A carbocation is an organic ion which has e R is electrophilic addition. Bromine is adding

a carbon atom which is positively charged. across the double bond of ethene so it is an
addition reaction (no other product formed).
vi radical, unpaired It is electrophilic because the electrophile is
c i Termination the positively polarised end of the bromine
molecule which attacks the double bond of
ii Initiation the ethene. The bromine accepts accept a pair
iii Propagation of electrons from the double bond.
d i B S is nucleophilic substitution. It is substitution

because the OH replaces the Br. It is
ii D nucleophilic because the nucleophile is the OH-
ion which donates donates a pair of electrons to
the positively charged area of the carbocation.
Exercise 14.3
a Type of Compound
formula Butane But-2-ene Propan-2-ol Propanone
displayed H H H H H H H H H H H OH
formula H C C C C H H C C C C H H C C CH H CCCH
H H H H H H H H H H
HO H
condensed CH3CH2CH2CH3 CH3CH=CHCH3 CH3CH(OH)CH3 CH3COCH3
structural
formula
molecular C4H10 C4H8 C3H8O C3H6O
formula
skeletal OH O
formula
empirical C2H5 CH2 C3H8O C3H6O
formula
b i L = C2Cl4 M = C2H8N2 N = C4H6O5 O = C9H11NO2

ii L = CCl2 M = CH4N N = C4H6O5 O = C9H11NO2
c Cl Cl OH
Cl
Cl Cl
Y Z


a Structural isomers are compounds with a i A group of organic compounds having the
the same molecular formula but different same functional group, the same general
structural formulae. formula and similar chemical properties.
b i H H H ii An atom or group of atoms in an organic
H C C C H molecule that determines the characteristic
reactions of a homologous series
H O HH
b i CnH2n+2
ii H
H H
ii CnH2n+1OH / CnH2n+2O
H C C C
O
c C6H14O
H H
H d i There is a general increase in density as
iii H C H the number of carbon atoms increases.
H H H H H H
H C C C C H and H C C C H ii Ethanol has a density which is lower than
expected from the trend / methanol has a
H H H H H higher density.
H C H H C H
H H iii allow values between 0.61 and 066
(inclusive)
c i H
H H H iv There is a general increase in boiling point
C Br as the number of carbon atoms increases.
H C H C H H
C C v Butane ALLOW: values between 250 and
C C H
Br C H 290 K (actual = 272.6 K) Pentan-1-ol
Br Br ALLOW: values between 400 and 420 K
H H
cis-2,3-dibromobut-2-ene trans-2,3-dibromobut-2-ene (actual = 411.1 K).
vi CH3CH2 is ethyl, CH3 is methyl
ii Cis/trans isomerism / geometrical
isomerism
Exercise 14.6
d i Br C3H7
a The structural formula of methane is CH4.The
structural formula of ethane is CH3CH3.
C C
Cl H i H H H
H C2H5
CH3 CH3
C C C
H H
ii C atom in centre of molecule (attached to H H
H H H
4 different groups)
methane ethane
e H H H H
HOOC C COOH HOOC C H ii 109.5°. There are only bonding pairs of
electrons so the repulsions between these
C C C C bonding pairs are the same, leading to the
H H H COOH minimum repulsion which corresponds to
the tetrahedral bond angle.
cis-cyclopropane trans-cyclopropane
1,2-dicarboxylic acid 1,2-dicarboxylic acid b σ bonds are single bonds formed by the
hybridisation of the s orbitals of the hydrogen
isomers of cyclopropane dicarboxylic acid atoms with the p orbitals of the carbon atom
forming sp2 hybrid orbitals. Then π bond
is formed by the sideways overlap of the
remaining p orbitals from the carbon atoms

to form a bond which has its electron density c i Substitution [1]

above and below the plane of the C and H
atoms and at right angles to this plane. ii Elimination / dehydration [1]
c All the bonds in butane are single bonds. d CH3CH2CH2CH2OH + 2[O] →

There is free rotation of the atoms about CH3CH2CH2COOH + H2O
single bonds and so there are no isomers with Correct reactants and products [1]
fixed positions of the atoms. But-2-ene has a
double bond. There is no free rotation around balance [1]
a double bond, so two possible geometric e H
isomers are possible.
C
d The repulsion between lone pairs of electrons
and bond pairs of electrons is greater than HO CH3
C2H5
the repulsion between two bonding pairs of
electrons. So the bond angle is less than the
Groups attached correctly to central c atom[1]
tetrahedral bond angle to minimise repulsive
forces between the electron clouds. use of wedge and dashed line [1]
e There are 4 sp3 hybrid orbitals of the same f i OH [1]

shape. The electron density in each of these is
exactly the same. The areas of electron density
arrange themselves so the electron repulsions ii Carbon atom attached to the OH [1]
are minimised. This is the tetrahedral
structure. the bond angle is 109.5°. This carbon has 4 different groups
bonded to it [1]
[Total: 16]
Question 2
Question 1 a CH3CH2CH2Cl [1]
a i C H O b i (Chlorine) free radical [1]
47.4 10.5 42.1
ii Homolytic [1]
12.0 1.00 16.0
(1 for correct division) c Carbocation [1]
3.95 10.5 2.63 d i Nucleophile [1]

2.63 2.63 2.63 It donates a pair of electrons to a
1.50 3.99 1.00 positive / partially positive ion [1]
(1 for dividing by smallest number) ii It shows the direction of movement
of the electron pair [1]
3 8 2 = C3H8O2
(1 for simplest ratio and formula) [3] iii Alcohol(s) [1]
ii Empirical formula mass = (12 × 3) + (8 × 1) + iv 2-methylpropan-2-ol [1]
(16 × 2) = 76 e (Nucleophilic) substitution [1]
This is also the molecular mass. Indication of [Total: 10]
working required. [1]
b Any 3 of: CH3CH2CH2CH2OH
CH3CH2CHOHCH3
(CH3)3COH
CH3CH(CH3)CH2OH ALLOW: displayed
formulae [3]

Question 3 b i Each C atom forms three sigma-bonds [1]
a i and ii with two hydrogen atoms and the other

carbon [1]
O O
remaining carbon electrons form pi-bond
C C C C (1 mark each) (by sideways overlap of p orbitals) [1]
H
pi-bond electron density above and below
[2] the plane of the C and H atoms [1]
b i CnH2n+1CHO [1] Leads to planar arrangement of

ethene [1]
ii H H H O [1]
So H─C─H bond angle about 120° (allow
H C C C C 117-120°) to minimise repulsions [1]
H H H H
ii electrophilic [1]
c i Reduction [1]
addition [1]
Addition of hydrogen [1]
c i CH3 Cl [1]
ii Propan-1-ol [1]
C C
d i Hydration [1]
Cl CH3
ii Propene [1]
iii Alkene(s) [1] ii CH3 Cl [1]
[Total: 10] C C
Question 4 CH3 Cl
a i Cl2 → 2Cl• [1] iii The C─C bond can rotate freely [1]
ii methyl free radical [1] So there is no fixed positions for the

groups attached to the C atoms [1]
iii propagation [1]
[Total: 16]
iv CH3• + CH3• → C2H6 or CH3• + Cl• →
CH3Cl [1]

may be different.
Workbook answers
Chapter 15
Exercise 15.1
a The top of the fractionating column is at a iii They have a double bond, one of which
lower temperature than the bottom. Petroleum can break and add other atoms. The
enters the column at the bottom in both the activation energy for this is relatively
gaseous state and liquid state. The more volatile low compared with the activation energy
hydrocarbons with lower relative molecular required to break a single bond in an
masses rise up the column further than the alkane.
less volatile hydrocarbons. The hydrocarbons
condense at different levels in the column as the iv High temperature and zeolite catalyst
temperature falls and are collected as liquids. v The alkane might undergo combustion.
The most volatile hydrocarbons are alkanes
with very short carbon chains (methane, vi C─C bonds
ethane, propane and butane). These leave the c i C12H26 → C7H16 + C5H10
top of the fractionating column as gases.
ii C18H38 → C6H12 + C8H18 + C4H8
b i To provide more alkanes for which
demand is greater than supply / to produce iii C10H22 → C3H6 + C7H16
more petrol / to produce more diesel
iv C3H8 → C3H6 + H2
ii They are used to make other chemicals /
they are used to make plastics.
Exercise 15.2
Hydrocarbon Displayed formula Structural formula Skeletal formula
butane H H H H CH3CH2CH2CH3
C4H10 H C C C C H
H H H H
ethene H H CH2=CH2
C=C
C2H4 H H
but-2-ene H H CH3CH=CHCH3
C4H8 H C C C C H
H H H H
(Continued)

Hydrocarbon Displayed formula Structural formula Skeletal formula

cyclopentane C5H10 H HH CH2
H C CH2 CH2
C C
H H CH2 CH2
C C
H
H HH
buta-1-3-diene C4H6 H H CH3=CHCH=CH2

C C C C
H H H H
Exercise 15.3 d The first step is homolytic fission.

Cl2 → 2Cl•
a i No reaction. Alkanes are unreactive apart
from combustion and reaction with free The second step (propagation step) is attack of
radicals. the chlorine free radical on ethane.
ii Hexane burns / blue flame / slightly smoky C2H6 + Cl• → C2H5• + HCl
flame. Combustion reaction. Alkanes
burn with blue flame in excess air or C2H5• can react further and regenerate a
smoky flame when air not in excess. chlorine free radical.
iii No reaction. Ultraviolet light needed to C2H5• + Cl2 → C2H5Cl + Cl•

form chlorine free radicals with enough In excess chlorine this can continue until
energy to react with alkanes. all the hydrogen atoms are substituted by
iv Two layers, the top one of which is chlorine.
(purple) coloured. No reaction but The reaction can be terminated when free
aqueous solution is immiscible with water radicals combine.
so two layers formed. Iodine is more
soluble in organic solvent so the colour For example:
migrates here. C2H5• + Cl• → C2H5Cl
v Green colour of chlorine disappears. C2H5• + C2H5• → C4H10
Ultraviolet light forms chlorine free
radicals which have enough energy to e combustion/burning; ultraviolet
react with alkanes.
Exercise 15.4
b i C6H14 + 9 1 O2 → 6CO2 + 7H2O (or
2
doubled) a 1 with C; 2 with E; 3 with D; 4 with A; 5 with
F; 6 with B
ii C3H8 + 5O2 → 3CO2 + 4H2O
b i Pent-2-ene
iii C10H22 + 15 1 O2 → 10CO2 + 11H2O (or
2
doubled) ii Methylpropene
iii Hept-2-ene
c i C4H10 + 4 1 O2 → 4CO + 5H2O (or doubled)
2
c i CH3CH2CH═CH2 + HBr →
ii C7H16 + 7 1 O2 → 7CO + 8H2O (or
2 CH3CH2CHBrCH2Br
doubled)
ii CH3CH═CHC2H5 + 4[O]
iii C12H26 + 12 1 O2 → 12CO + 13H2O (or
2 hot
CH3COOH + C2H5COOH
doubled) concentrated
KMnO4

iii CH2═CHCH2CH═CH2 + 2H2 So the charge density on the carbocation /

Ni
C+ ion is reduced. The greater the
CH3CH2CH2CH2CH3
reduction in charge on the C+ ion /
iv CH2═CH2 + H2O CH3CH2OH carbocation, the more stable the C+ ion /
conc H3PO4 carbocation.
v CH3CH═CHCH3 + H2O + [O]
dilute cold The secondary carbocation is more stable
KMnO4
because it has more alkyl groups attached.
CH3CH(OH)CH(OH)CH3
d Add aqueous bromine. Unsaturated Exercise 15.6
hydrocarbon: orange aqueous bromine turns
colourless. Saturated hydrocarbon: orange a i CH3 H
aqueous bromine remains orange.
C C
OR
Add aqueous acidified KMnO4. Unsaturated H H n
hydrocarbon: purple aqueous KMnO4 turns
colourless. Saturated hydrocarbon: purple ii C6H5 H
aqueous KMnO4 remains purple.
C C
Exercise 15.5
H H n
a i The high electron density in the ethene
double bond repels the bonding electrons iii F F
in the bromine and pushes them towards
the further bromine atom making the Br C C
atom nearest the ethene δ+.
F F n
ii H H
b A is CH3CH2CH=CH2; B is CH3CH=CHCH3
C C
c i The C─C bonds are not reactive.
H H
There are few / no bacteria / organisms
δ+
Br
which can break the C─C bonds in
δ−
Br hydrocarbons.
iii Heterolytic because one of the bromine ii Block watercourses / rivers / drains
atoms takes both electrons of the electron (leading to flooding); litter / eyesore; gets
pair. into animals’ or birds’ gullets and chokes
them; takes up space in landfill sites.
iv Carbocation
iii Poisonous fumes released; carbon dioxide
v H H (greenhouse gas) released which causes
enhanced global warming; acidic gases, e.g.
H C C H HCl, released which contribute to acid rain.
+
Br
Br− Exercise 15.7
a Disturbs the balance between respiration
vi The carbocation. It is accepting a pair of and photosynthesis which are approximately
electrons. balanced. A small increase in concentration
b i 1-chlorobutane, CH3CH2CH2CH2Cl. of atmospheric carbon dioxide can cause a
significant increase in global warming.
ii CH3CH2C+HCH3 ALLOW: displayed
formula b Water vapour condenses easily to form liquid
which does not get high into the atmosphere.
iii Alkyl groups have a positive inductive
effect / alkyl groups push electrons away c Melting of polar ice caps; causing sea level rise;
from themselves. desertification; more extreme weather patterns

d C5H12 + 8O2 → 5CO2 + 6H2O b i H [1]

e Carcinogenic means cancer-causing. H C H
Particulates, VOCs. H H
f 2NO + 2CO → N2 + 2CO2 H C C C H
g We use the characteristic wavelength of H Br H

the infrared radiation absorbed by the
ii Alkyl groups have a positive inductive
pollutant molecules to identify the molecule.
effect / alkyl groups push electrons away
The intensity of the absorbed radiation at
from themselves. [1]
characteristic wavelength gives us a measure
of the concentration of each pollutant. So the charge density on the carbocation /
C+ ion is reduced. [1]
h i breathing difficulties / asthma / heart
attacks irritates lungs / irritates throat / The greater the reduction in charge on
irritates eyes / nose the C+ ion / carbocation, the more stable
the C+ ion / carbocation. [1]
ii catalyst; in oxidation of sulfur dioxide to
sulfur trioxide The tertiary carbocation is more stable
because it has more alkyl groups
attached. [1]
Exam-style questions iii CH3 H
Question 1 C C
H H H H CH3 H n
a H C C O H H C C H (1 mark each) Basic structure without double bond [1]
H H H H square brackets, n, and continuation
A B bonds [1]
b i Steam, phosphoric acid, high c does not decompose / does not break down [1]
temperature / 330 °C (1 mark each) [3] fills landfill / blocks drains / harms animals
ii Hydrogen and high temperature [1] when they ingest it [1]
nickel catalyst [1] [Total: 13]
iii Cold dilute acidified [1] Question 3

potassium manganate(VII) [1] a H
H C H
iv Hot concentrated [1] H H H H H H H H H H H
H C C C C C H H C C C C H H C C C H
potassium manganate(VII) [1]
H H H H H H H H H H
H C H H C H
[Total: 11] H H
(1 mark each) [3]

Question 2
b i Free radical [1]
a i (CH3)2CO [1]
substitution [1]
(C2H5)2CO [1]
ii Oxidation [1] ii Cl2 → 2Cl• [1]
iii Ketones [1] iii Excess chlorine (and continued UV

light) [1]

iv Any two free radicals combining (1 mark Ethane has no effect / bromine remains
each), e.g. orange. [1]
Cl• + Cl• → Cl2; OR
C5H11• + C5H11• → C10H22;
React with acidified KMnO4 [1]
C5H10Cl• + Cl• → C5H10Cl2 [2]
Ethene turns KMnO4 (from purple)
c i C11H22 [1]
colourless [1]
ii heat [1]
Ethane has no effect / KMnO4 remains
aluminium oxide catalyst / zeolite purple [1]
catalyst [1]
b H H [1]
[Total: 12]
C C
Question 4 H H
a C5H12 + 5 1 O2 → 5CO + 6H2O (or doubled) ethene

2
Reactants and products [1] c Sigma bonds between H and C and one of the
C─C bonds [1]
balance [1]
Makes C and H in one plane [1]
b Carbon monoxide is poisonous [1]
Pi bond formed by overlap of remaining p
c i Nitrogen combines with oxygen [1] orbital of C atoms [1]
Under conditions of high temperature Is above and below the plane of the C and H
and pressure [1] atoms [1]
ii 2NO2 + 4CO → N2 + 4CO2 d i H H
Reactants and products [1] C C
balance [1] H H
δ+
Br
d i Carbon dioxide is a greenhouse gas [1]
δ−
Br
Carbon dioxide absorbs infrared
radiation [1] Correct polarisation of the bromine
So traps heat in the atmosphere [1] molecule [1]
So temperature of the atmosphere curly arrow showing movement of

increases [1] electron pair in bromine [1]
ii Any two effects (1 mark each), e.g. curly arrow showing movement of
melting of polar ice caps / electron pair from ethene to δ+Br atom [1]
sea level rise / desertification / more ii Cl− ion from sodium chloride has lone
extreme weather patterns [2] pair of electrons [1]
[Total: 13] Acts as a nucleophile / can attack the
positive carbon atom [1]
Question 5
Br− ion formed from attack of bromine
a React with aqueous bromine. [1] molecule on ethene [1]
Ethene turns aqueous bromine (from orange) Also acts as a nucleophile / can attack
colourless. [1] positive carbon atoms [1]

e HCl is polar molecule [1] This stabilises the secondary carbocation [1]
HCl is an electrophile [1] More than the primary carbocation [1]
electrons withdrawn from one of C=C So Cl− (from HCl) attracted to the secondary
bonds by δ+ end of HCl [1] carbocation [1]
CH3 group has positive inductive effect [1] [Total: 22]

may be different.
Workbook answers
Chapter 16
Exercise 16.1
a Halogenoalkane Structural formula Displayed formula Skeletal formula
I-iodobutane CH3CH2CH2CH2I HH H H I
H C C C C I
HH H H
2-chloro-2- (CH3)2CCICH3 H Cl H Cl
methylpropane H C C C H
H H
H C H
H
3-bromopentane CH3CH2CHBrCH2CH3 H H Br H H
H C C C C C H Br
H H H H H
b H H ii HH
δ− δ+
C C H3N: Br C C H
CH3 CF3 CF3 CH3 HH
Cl Cl
iii The ammonia molecule. Because it
c 1 with D; 2 with C; 3 with A; 4 with E; 5
donates an electron pair to a centre of
with B
partial positive charge.
d When iodoethane is refluxed with aqueous
iv An intermediate / transition state
sodium hydroxide, the hydroxide ion acts as
a nucleophile and substitutes the iodine atom. v The Br−C bond breaks and the NH3−C
The reaction is also called a hydrolysis reaction bond forms.
which means ‘breakdown’ by water. Hydrolysis
with sodium hydroxide is faster than hydrolysis vi It has a positive charge on the nitrogen
with water because the negatively charged which is not stabilised very much by the
hydroxide ion is a more effective nucleophile. alkyl group.
The hydrolysis of chloroethane is slower than vii A hydrogen ion is lost from the NH3+
the hydrolysis of iodoethane because the C−Cl group.
bond is stronger than the C−I bond.
viii S = substitiution, N = nucleophilic, 2 =
Exercise 16.2 two molecules involved in the slow step.
a i Bromine is more electronegative than b i CH3

δ+ δ−
carbon so it tends to draw the electrons in H3C C Cl
the Br−C bond towards it.
CH3

ii Carbocation d Add alcoholic silver nitrate solution to the

reaction mixture. White precipitate indicates
iii The OH− ion because it donates a pair of presence of chloride ions.
electrons to the + charged ion.
e i CH3CH2CH2CH2Br + NaOH →
iv S = substitiution, N = nucleophilic, 1 = CH3CH2CH=CH2 + NaBr + H2O
one molecule involved in the slow step
ii CH3CH2CH2CH2Br + KCN →
Exercise 16.3 CH3CH2CH2CH2CN + KBr
a They are unreactive because of their strong iii CH3CHClCH3 + NaOH →

bonds which are not likely to be hydrolysed CH3CH(OH)CH3 + NaCl
under the aqueous conditions in the body iv CH3CH2Cl + NH3 →
b Aerosol propellants, solvents and refrigerants CH3CH2NH2 + HCl
c Easily vaporised / has a low boiling point Exercise 16.5

d The Sun a i CH3CH2CH2OH + SOCl2 →
e By diffusion CH3CH2CH2Cl + SO2 + HCl
f Ultraviolet radiation causes fission of C─Cl ii 3CH3CH2OH + PBr3 →

bonds to produce chlorine free radicals which 3CH3CH2Br + H3PO3
are very reactive and can react further by a iii CH3CH(OH)CH3 + HCl →
series of chain reactions. CH3CH(Cl)CH3 + H2O
g i Cl• + O3 → ClO• + O2 iv CH3CH2CH2OH + PCl5 →
ii ClO• + O3 → Cl• + 2O2 CH3CH2CH2Cl + POCl3 + HCl
uv light
h i The propagation step involves the v CH3CH2CH3 + Cl2
formation of more chlorine free radicals CH3CH2CH2Cl + HCl
so that the process starts over again. b Reaction v. It is a free radical reaction. More
ii By free radicals combining (termination chlorine free radicals can react to substitute
step) more hydrogen atoms. So a variety of
products can be formed.
Exercise 16.4 c Action of concentrated sulfuric or phosphoric
acids on potassium chloride.
a R secondary, S primary, T secondary,
U tertiary d i Secondary.
b i CH3CH2Br + NaOH → CH3CH2OH + NaBr ii type: addition; mechanism: electrophilic
ii CH3CH2I + NH3 → CH3CH2NH2 + HI
iii CH3CH2Cl + NaOH → CH2=CH2 + NaCl
+ H2O
iv CH3CHClCH3 + NaOH → Question 1
CH3CH(OH)CH3 + NaCl
a H [1]
v CH3CH2CH2Cl + KCN → H C H
CH3CH2 CH2CN + KCl H H
vi C6H5CH2Br + KCN → H C C C H
C6H5CH2CN + KBr H Br H
vii CH3CH2CH2Br + NaOH → b i The OH group replaces the Br atom. [1]
CH2=CHCH3 + NaBr + H2O
ii An electron pair is donated to a centre of
c In b i nucleophilic substitution; in b iii positive charge. [1]
elimination

c Add nitric acid until the solution is neutralised e tertiary carbocations have greater stability
/ acidic. [1] than primary carbocations [1]
Add aqueous silver nitrate. [1] Because the more alkyl groups that are
attached to a carbocation, the greater is the
Cream precipitate indicates bromide is positive inductive effect on reducing the
present. [1] charge on the carbocation [1]
d Alkyl groups have a positive inductive effect / The C─Hal bond is more easily broken
alkyl groups (without the help of a nucleophile) [1]
push electrons away from themselves. [1] For a primary carbocation the C─Hal bond
So the charge density on the carbocation / bond is less easily broken / has a higher
C+ ion is reduced. [1] activation energy [1]
The greater the reduction in charge on the So the nucleophile is needed to assist the
C+ ion / carbocation, the more stable bond breaking [1]
the C+ ion / carbocation. [1] [Total: 17]
The tertiary carbocation is more stable
because it has more alkyl groups attached. [1] Question 3
So the first stage in the reaction for tertiary a i CH3CH2I + CN− → CH3CH2CN + I− [1]
halogenoalkane is the self-ionisation
of the halogenoalkane. [1] ii An additional carbon atom is being added
to the chain / the carbon chain is being
[Total: 11] lengthened. [1]
b −
Question 2
a CH3CH2CH2CH2I + NaOH → C N
CH3CH2CH2CH2OH + NaI [1]
b The C─I bond in the halogenoalkane is [1]
polar [1]
c It has a pair of electrons which are donated to
because I is more electronegative than C [1] an atom with a positive or partial
so the C has a partial positive charge. [1] positive charge. [1]
d −
OH− ion is a nucleophile. [1]
H H H H
δ+ δ− I
A lone pair of electrons on the hydroxide ion H C C I :CN− H C C
is donated to the CN
H H H H
partially positive carbon atom. [1]
Polarisation of C−I bond [1]
c The C─Cl bond energy is greater than
the C─I bond energy. [1] arrow [1]
It needs a higher activation energy to start the intermediate [1]
reaction in the chloroalkane. [1]
e S = substitiution [1]
d i CH3CH2CH2CH2I + OH− →
CH3CH2CH = CH2 + H2O + I− [1] N = nucleophilic [1]
ii Elimination [1] 2 = two molecules involved in the

slow step. [1]
iii Hydroxide ion is acting as a base [1]
[Total: 10]
by accepting a proton from the
halogenoalkane. [1]

may be different.
Workbook answers
Chapter 17
Exercise 17.1
Al2O3, heat
a A = primary; B = tertiary; C = secondary; iii CH3CH(OH)CH3
D = secondary; E = tertiary CH3CH═CH2 + H2O
Al O , heat
b A is propan-1-ol; B is 2-methypropan-2-ol; iv CH3CH2CH2CH2CH2OH 2 3
C is butan-2-ol; D is pentan-2-ol; E is CH3CH2CH2CH═CH2 + H2O

2-methylbutan-2-ol
c i C3H7OH + 4 1 O2 → 3CO2 + 4H2O
2
c Primary alcohols: Potassium dichromate(VI)
turns from orange to green. The ii C4H9OH + 4O2 → 4CO + 5H2O
product distilled off is an aldehyde. On iii C6H11OH + 8 1 O2 → 6CO2 + 6H2O
further oxidation a carboxylic acid is 2
formed. Secondary alcohols: Potassium d C because C contains the CH3CH(OH)─
dichromate(VI) turns from orange to green. group
The product is a ketone. On further oxidation
no reaction occurs. Exercise 17.3
Tertiary alcohols: Potassium dichromate(VI) a i By reaction of sodium / potassium
stays orange. No reaction takes place. bromide with concentrated sulfuric acid.
d i acidified potassium manganate(VII) ii 1-bromopropane is insoluble in water /
immiscible with water and is denser than
ii purple to colourless
water.
e i CH3CH2CH2OH + [O] →
iii The oxygen atom is more electronegative
CH3CH2CHO + H2O
than the carbon atoms. So the oxygen has
ii CH3CH(OH)CH3 + [O] → a slight negative charge and the carbon
CH3COCH3 + H2O atom has a slight positive charge.
iii CH3CH2CHO + [O] → CH3CH2COOH iv δ+ δ−

H—Br
iv CH3CH(OH)CH2CH(OH)CH2CH3 + 2[O]
→ CH3COCH2COCH2CH3 + 2H2O v The δ+ end of the hydrogen bromide
attacks the partially negative oxygen atom.
Exercise 17.2 vi CH3CH2CH2OH + HBr →
a 1 with F; 2 with D; 3 with A; 4 with B; CH3CH2CH2Br + H2O
5 with C; 6 with E b C4H9OH + PCl5 → C4H9Cl + POCl3 + HCl
b i 2C3H7OH + 2Li → 2C3H7O Li + H2 − +
c i 3C2H5OH + PI3 → 3C2H5I + H3PO3
ii 2CH3OH + Ca → (CH3O )2 Ca + H2
− 2+
ii 3C4H9OH + PBr3 → 3C4H9Br + H3PO3
d CH3CH2CH2OH + SOCl2 →
CH3CH2CH2Cl + SO2 + HCl


a i CH3CH2CH2CH2CH2COOH a i Ethyl butanoate
ii HCOOH ii Propyl hexanoate
iii HOOCCOOH iii Methyl pentanoate
b i Concentrated acidified potassium b i Butyl methanoate
dichromate(VI), reflux
ii Pentyl ethanoate
ii CH3CH2CH2CH2OH + 2[O] →
iii Propyl butanoate
CH3CH2CH2COOH + H2O
c i It is a catalyst
iii A bond in the carbon chain would have
to be broken to accommodate the extra ii CH3COOC3H7 + H2O ⇌
oxygen atom. This would lead to the chain CH3COOH + C3H7OH
breaking.
d i HCOOC3H7 + NaOH →
c i CnH2n+1CN HCOO−Na+ + C3H7OH
ii The breakdown of a substance by water ii CH3COOCH3 + NaOH →
(usually involving H+ or OH− as a catalyst). CH3COO−Na+ + CH3OH
d i CH3CN + HCl + 2H2O → iii CH3CH2COOC4H9 + NaOH →
CH3COOH + NH4Cl CH3CH2COO−Na+ + C4H9OH
ii CH3CH2CH2CH2CN + HCl + 2H2O → Exercise 17.7
CH3CH2CH2CH2COOH + NH4Cl
a i CH2=CH2(g) + H2O(g) → CH3CH2OH
iii CH3CH2CN + H+ + 2H2O →
CH3CH2COOH + NH4+ ii CH3CH2CH2COOCH3 + NaOH →
CH3CH2CH2COO−Na+ + CH3OH
e i ethanenitrile
iii CH3CH2Cl + NaOH →
ii pentanenitrile CH3CH2OH + NaCl
Exercise 17.5 iv CH3CH2COOH + 2[H] →
CH3CH2CH2OH + H2O
a i It only partly dissociates in solution / it
ionises only partially in solution. v CH3COCH3 + 2[H] → CH3CH(OH)CH3
ii CH3CH2COOH + H2O ⇌ vi CH3CH2COOCH2CH3 + H2O →
CH3CH2COO− + H3O+ CH3CH2CH2COOH + CH3OH
b i CH3COOH + KOH → b i addition
CH3COO−K+ + H2O
ii hydrolysis
ii 2CH3CH2CH2COOH + Mg →
(CH3CH2CH2COO−)2Mg2+ + H2 iii hydrolysis / substitution
iii 2C6H5COOH + Na2CO3 → iv reduction

2C6H5COO− Na+ + CO2 + H2O v reduction
c i Potassium ethanoate vi hydrolysis
ii magnesium butanoate. c i CH2=CH2 + [O] + H2O → CH2(OH)CH2(OH)
d i CH3COOH + 4[H] → CH3CH2OH + H2O ii CH3CH2CHO + 2[H] → CH3CH2CH2OH
ii CH3CH2COOH + 4[H] → iii CH3COOCH2CH2CH3 + NaOH →
CH3CH2CH2OH + H2O CH3COO−Na+ + CH3CH2CH2OH
iii HOOCCH2CH2COOH + 8[H] → iv CH3CH2COOH + 4[H] →
HOCH2CH2CH2CH2OH + 2H2O CH3CH2CH2OH + H2O

Water has no alkyl group so negative

Exam-style questions charge on oxygen not increased as much
(so it is more acidic / more likely to donate
Question 1 a proton) [1]
a Heat with acidified potassium (also the effect of the side chain on
dichromate(VI) [1] hydration makes it harder for RO− to be
stabilised)
Propan-1-ol turns potassium dichromate
from orange to green [1] [Total: 19]
No reaction with 2-methylpropan-2-ol /
dichromate remains orange [1]
Question 2
b Acidified potassium dichromate [1] a i Ethanoic acid donates a proton to
water. [1]
High concentration of dichromate and acid [1]
The ethanoate ion is relatively stable
Reflux [1] in water. [1]
c H H O Ethanol is hardly acidic (ALLOW: not
H C C C acidic) / the ethoxide ion is less stable
in water. [1]
H H O H [1]
ii Sodium hydroxide reacts with ethanoic
d i Add methanol to mixture of propanoic
acid [1]
acid and sulfuric acid in flask. [1]
to form sodium ethanoate and water. [1]
Reflux. [1]
Ethanol does not react with sodium
Neutralise the acid with sodium
hydroxide [1]
carbonate. [1]
b i 2C2H5OH + 2Na → 2C2H5O−Na+ + H2
Distil and collect ester as distillate. [1]
ii CH3CH2COOH + CH3OH ⇌
CH3CH2COOCH3 + H2O [1] balance [1]
iii Methyl propanoate [1] 2CH3COOH + 2Na →
2CH3COO−Na+ + H2
e i It is behaving as an acid because it is
donating a H+ ion to the NH2 group [1] Correct formulae [1]
ii The inductive effect is greater when more balance [1]
alkyl groups are attached to the C next to
the O [1] ii Bubbles / effervescence [1]
When there are more electron donating c i C2H5OH + PCl5 →

groups it increases the negative charge on C2H5Cl + POCl3 + HCl [1]
the O atom [1] ii HCl released as white fumes [1]
More charge means less stability (compared iii CH3COOH + PCl5 →
with the unionised molecule) [1] CH3COCl + POCl3 + HCl [1]
−
So the RO ion is less likely to form / ROH d CH3COOH + 4[H] → CH3CH2OH + H2O [1]
form less likely to donate a proton [1]
[Total: 15]

Question 3 c Phosphorus(V) chloride / phosphorus

pentachloride [1]
a Step 1: Bubble ethene through concentrated
hydrochloric acid / React ethene d Butan-1-ol absorbed into ceramic wool in
with hydrogen chloride [1] bottom of a test tube [1]
At room temperature and Butan-1-ol is heated to form the vapour [1]
pressure [1] Butan-1-ol vapour passed over heated
Step 2: Add dilute sodium hydroxide [1] aluminium oxide [1]
Reflux / heat [1] Butene collected (in inverted test tube) over
water [1]
Step 3: Add concentrated acidic potassium
dichromate [1] e i CH3CH(OH)CH2CH3 [1]
Reflux [1] ii yellow precipitate [1]
b i CH3CH2CH2OH + HCl → the isomer contains the

CH3CH2CH2Cl + H2O [1] CH3CH(OH)─ group [1]
ii It is accepting a hydrogen ion from the [Total: 18]

hydrogen chloride. [1]
iii Suitable metal chloride, e.g. sodium
chloride [1]
Concentrated sulfuric acid [1]

may be different.
Workbook answers
Chapter 18
Exercise 18.1
a i Methanal gently with Fehling’s solution, the colour
changes from blue to orange (precipitate).
ii Hexan-3-one
Propanal is oxidised to propanoic acid.
iii Butanal Copper(II) ions are reduced to copper(I) ions
b i CH3CH2COCH3 When a ketone is heated with Tollen’s reagent

there is no reaction / no silver mirror
ii CH3CH2CH2CH2CHO
b i A solution of 2,4-DNPH is added to a
iii CH3COCH2COCH3 carbonyl compound. An orange coloured
c i Acidified potassium dichromate(VI) precipitate of a dinitrophenylhydrazone is
formed. The precipitate is purified by
ii Cr2O72− and Cr3+ recrystallisation and the melting point is
iii It distils off before the alcohol measured. Each dinitrophenylhydrazone
derivative of an aldehyde or ketone has a
iv If refluxed it would be oxidised further to characteristic melting point which can be
propanoic acid compared with known data book values.
v Propanone c Two (larger) molecules join together and a
small molecule is eliminated
vi Ketones cannot be further oxidised to
carboxylic acids / very strong d i There are two compounds with a melting
oxidation would break the carbon chain. point of 126 °C so X is either butanal or
propanone.
d i CH3COCH2CH3 + 2[H] →
CH3CH(OH)CH2CH3 ii Heat with Tollen’s reagent. Butanal
will react to form a silver mirror but
ii CH3CH2CHO + 2[H] →
propanone will not. OR, heat with
CH3CH2CH2OH
Fehling’s solution. Butanal will react
iii CH3COCH2COCH2CH3 + 4 [H] → to form an orange-red precipitate but
CH3CH(OH)CH2CH(OH)CH2CH3 propanone will not react.
e i Butan-2-ol
Exercise 18.3
ii Propan-1-ol
a i Oxygen is more electronegative than
iii Hexan-2,4-diol carbon. So the electron density in the
bond is attracted to the oxygen more than
Exercise 18.2 the carbon.
a When propanal is warmed gently with Tollen’s ii C2H5

δ+ δ−
reagent the colour changes from C=O
colourless to a silver mirror. Propanal is H
oxidised to propanoic acid. Silver ions are
:CN−
reduced to silver. When propanal is warmed

iii CN− ion because it donates a lone pair of pattern of their infrared spectrum.
electrons to an electron-deficient area of The spectrum shows the percentage absorbance
a molecule (which has a partial positive (vertical axis) and wavenumber (horizontal axis).
charge). Wavenumber is the reciprocal of the wavelength.
iv An intermediate b Ethanol: Broad strong peak at 3200−3600
indicates hydrogen bonding of O─H in an
v From ionisation of hydrogen cyanide / alcohol. Peak near 1300−1400 may indicate
from the acid used to make the hydrogen C─O bond in alcohol.
cyanide (by reaction with sodium cyanide)
Ethanoic acid: Broad less strong peak between
vi The pair of electrons on the oxygen forms 2500−3200 indicates hydrogen bonding
a bond with the hydrogen ion. of O─H in carboxylic acid. Strong peak near
b i OH ii OH 1600 may indicate C═O bond.
CH3 C CN CH3 C C N
CH3 H Exam-style questions
iii OH Question 1
CH3CH2CH2 C CN
a i CH3CH2CH2CH2OH + [O] →
CH3 CH3CH2CH2CHO + H2O [1]
ii Butanal [1]
Exercise 18.4 iii From orange [1]
a i butanone; to green [1]
ii ethanal; iv To prevent further oxidation / to prevent
butanoic acid from forming [1]
iii pentane-2,4-dione;
b i Add Tollen’s reagent to the carbonyl
v propan-2-ol
compound in a test tube and warm
b i Substitution gently. [1]
ii RCOCI3 If a silver mirror forms on the side of
the tube, the unknown is an aldehyde. [1]
iii Hydrolysis
If no silver mirror forms the unknown
iv Triiodomethane is a ketone. [1]
v Sodium propanoate ii (Aqueous) silver nitrate and (excess)
c The alkaline iodine oxidises a CH3C(OH) ammonia [1]
group to a CH3CO group which does give a iii Ag+ + e− → Ag [1]
positive test.
c i CH3CH2COCH3 + 2[H] →
Exercise 18.5 CH3CH2CH(OH)CH3 [1]
a The bonds in organic compounds vibrate by ii Butan-2-ol [1]

stretching, bending and twisting. They have iii yellow precipitate is triiodomethane [1]
a natural frequency at which they vibrate.
When molecules absorb infrared radiation CHI3 [1]
that corresponds to these natural frequencies,
other product is sodium propanoate [1]
it stimulates larger vibrations and energy
is absorbed. This frequency is called the CH3CH2CO2 Na − +
[1]
resonance frequency. Each type of bond absorbs
infrared radiation at a characteristic range of (allow error carried forward from part ii)
frequencies. We can identify different functional [Total: 16]
groups from the absorbance

Question 2 Warm the mixture [1]
a i Sodium cyanide / potassium cyanide / Yellow precipitate with pentan-2-one [1]

other suitable cyanide of a reactive No precipitate / no reaction with pentan-
metal [1] 3-one [1]
ii The cyanide ion has a pair of electrons b Add 2,4-DNPH to the carbonyl compound
which it donates to an electron-deficient and filter the
area on the organic molecule. [1]
precipitate [1]
iii CH3
δ+ δ−
C=O Recrystallise to get pure sample [1]
CH3 Take the melting point [1]
:CN−
Compare the melting point with table of data
for dinitrophenylhydrazones [1]
Any five of: [5]
c Two species add together [1]
• Stating that propanone is a polar
molecule And a small molecule is eliminated [1]
• Correct polarisation of C═O bond d i 0
• Electron pair on cyanide ion

Absorbance/%
• Curly arrow going from CN (electron

pair) to carbonyl carbon 50
• Curly arrow going from C═O bond to

C═O oxygen
• Bond forming from CN to C of C═O 100
4000 3000 2000 1000
iv From dissociation of HCN [1] Wave number/cm−1
from acid added to the cyanide [1] Correct labelling of x-axis [1]
v i OH Correct labelling of y-axis [1]
CH3 C CN Sharp and deep peak at 3000 cm−1 [1]
CH3 [1] Sharp and weak peak at 1600 cm−1 [1]
b About 1700 [1] ii Peak at 1600 cm−1 is due to a C═C
C═O [1] bond [1]
in aldehyde or ketone [1] Peak at 2900 cm−1 is due to a C─H bond [1]
[Total: 13] In an alkene [1]

[Total: 18]
Question 3
a i CH3CH2CH2COCH3 [1]
ii Add alkaline solution of iodine [1]

may be different.
Workbook answers
Chapter 19
Exercise 19.1
a 1 with E; 2 with C; 3 with A; 4 with F; 5 with b 2Na+(g) + S2−(g)
D; 6 with G; 7 with B EA2
2Na+(g) + S(g) + 2e−
b Lattice energy is the enthalpy change when one
EA1 2Na+(g) + S−(g) + e−
mole of an ionic compound is formed from its ∆Hat
2Na+(g) + S(s) + 2e−
gaseous ions under standard conditions.
∆Hlatt
First electron affinity is the enthalpy change 2IE1
when one mole of electrons is added to one 2Na(g) + S(s)
mole of gaseous atoms to form one mole
2∆Hat
of gaseous ions with a charge of 1− under 2Na(s) + S(s)
standard conditions.
∆Hf Na2S(s)
c mole; gaseous; element; standard
d i negative; less; first c ∆H⦵latt + sum of the other values, ∆H⦵x
= ∆H⦵f [Na2 S]
ii attraction; positively; charge; electron;
energy; force; radius; decreases ∆H⦵x = 2∆H⦵ at[Na] + 2IE1⦵[Na] + ∆H⦵ at[S] +
EA1[S] + EA2⦵[S]
e i Al+(g) → Al2+(g) + e−
∆H⦵x = 2(107.3) + 2(496) + 278.5 + −200.4 + 640
ii N2−(g) + e− → N3−(g) = +1924.7 kJ mol−1
iii Mg(s) + S(s) + 2O2(g) → MgSO4(s) ∆H⦵latt + ∆H⦵x = ∆H⦵f
iv 2K+(g) + O2−(g) → K2O(s) ∆H⦵latt = ∆H⦵f − ∆H⦵x
Exercise 19.2 = −364.8 − 1924.7 = −2289.5 kJ mol−1
a d As the size of the cation increases from Li

Ca2+(g) + 2Br(g) + 2e−
to Rb, the lattice energy decreases (gets less
2∆Hat Ca2+(g) + Br2(I) + 2e− exothermic).
2EA1 Ca2+(g) + 2Br−(g)
As the size of the anion increases from oxide
to sulfide, the lattice energy decreases (gets less
IE2 exothermic).
Ca+(g) + Br2(I) + e−
∆H Latt
IE1
Ca(g) + Br2(I)
∆Hat Ca(s) + Br2(I)
∆Hf CaBr2(s)


a absorbed; one; solid; dilute, mole; gas(eous); a Mg2+ because it has the highest charge density
dilute (charge to radius ratio).
b ∆Hlatt b S2− because the polarisability of an anion
Mg2+(g) + 2I−(g) MgI2(s) increases with increased size and increased
charge.
∆Hhyd[Mg2+]
∆Hsol c The magnesium ion is small and has a
+
2∆Hhyd[I−]
relatively high charge.
Therefore, its (positive) charge density is high.
Mg (aq) + 2I (aq)
2+ − The nitrate ion is a large ion and its outer
electrons are attracted to the small highly
charged magnesium ion. This distorts the
c Mg2+(g) + 2I–(g) shape of the nitrate ion.
d i Magnesium
∆HLatt [MgI2(s)]
∆H [Mg2+(g)]
hyd
ii Magnesium
+
iii Magnesium nitrate
2∆H [I–(g)]
hyd
MgI2(s) iv Nitrogen dioxide and oxygen
∆H
sol
MgI2(aq) Exam-style questions
d i The larger the cation, the smaller the Question 1
value of ΔH⦵hyd (the sulfate ion is the
same in both). a The enthalpy change when one mole of an
ionic compound is formed from its gaseous
ii It decreases as the size of the cation ions under standard conditions.
decreases. Idea of one mole of compound being formed
iii Lattice energy is inversely proportional from its ions [1]
to the size of the ions. The sulfate ion (Ions) are gaseous and standard
contributes a larger part to the lattice conditions apply [1]
energy because it is much larger than the
cation. Therefore, the decrease in lattice b As the size of the cation increases, the lattice
energy is small. The hydration energy is energy decreases (gets less exothermic) [1]
more dependent on the size of the cation As the size increases, the charge density of
because the hydration energy of sulfate is the cation decreases. This results in weaker
smaller because it is a larger ion. electrostatic forces between the ions. [1]
iv The more exothermic or less endothermic As the charge on the cation increases,
the value of ∆H⦵r, the more likely is the the lattice energy increases (gets more
process to take place. The ∆H⦵sol value exothermic). [1]
for calcium sulfate is less endothermic
than the ∆H⦵sol for strontium sulfate, so As the charge increases, the charge density
calcium sulfate is more likely to have a also increases.
higher solubility.
This results in stronger electrostatic forces
between the ions. [1]

c ∆Hlatt Question 2
K+(g) + I−(g) KI(s)
a ∆Hr
1
Mg(NO3)2(s) MgO(s) + 2NO2(g) + O (g)
2 2
∆H
at
[K(s)]
+ ∆H [KI(S)]
f
∆Hf (Sum of) ∆Hf
1
∆H [ I2(s)]
at 2
+ Mg(s) + N2(g) + 3O2(g)
1
∆H
ion
[K(g)] K(s) + I (s)
2 2
+ 2 marks for all boxes correct, but 1 mark if

EA1[I(g)]
two correct [2]
Arrows in correct direction [1]
2 marks for all boxes correct but 1 mark if two
correct [2] b ∆H⦵f[Mg(NO3)2 ] + ∆H⦵r = ∆H⦵ f[MgO]
+ 2∆H⦵f [NO2]
Arrows in correct direction [1]
−790.7 + ∆H⦵r = −601.7
d ∆H⦵latt + sum of the other values, ∆H⦵x + 2(33.20)
= ∆H⦵f [KI]
= −535.3

∆H⦵x = ∆H⦵ at[K] + IE1⦵ [K] + ∆H⦵ at[ 1 I2 ]
2
+ EA1⦵ [1] ∆H⦵r = ∆H⦵f [MgO] + 2∆H⦵f[NO2]
− ∆H⦵f[Mg(NO3)2]
∆H⦵x = (89.20) + (419.0) + 106.8 + −295.4 =
+319.6 kJ mol−1 = −535.3 − (−790.7) = +255.4 kJ mol−1
∆H⦵latt + ∆H⦵x = ∆H⦵f Correct value of ∆H⦵f[MgO] + 2∆H⦵f[NO2]

(or indication of this) [1]
∆H⦵latt = ∆H⦵f − ∆H⦵x
Idea of ∆H⦵f[Mg(NO3)2] + ∆H⦵r
= −327.9 − 319.6 = −647.5 kJ mol−1 = ∆H⦵f[MgO] + 2∆H⦵f[NO2] [1]
⦵
Correct value of ∆H x (or indication that all Correct answer from calculation done
these values are added) [1] correctly [1]
Idea of ∆H⦵latt + ∆H⦵x = ∆H⦵f or ∆H⦵latt = Correct number of significant figures +
∆H⦵f − ∆H⦵x [1] units [1]
Correct answer from the calculation done c The ease of decomposition decreases down
correctly [1] the group / increases up the group [1]
Correct number of significant figures + Because the values get more endothermic
units [1] down the group [1]
e An electron is being added to a negative d i The distortion of the electron cloud of a
ion. [1] (large) ion [1]
An input of energy is needed to overcome by a smaller / more highly charged ion [1]
the repulsive forces of two negative / like
charges [1] ii The size of the cation [1]
[Total: 15] The charge on the cation [1]

iii The larger the cation, the less easy it is
to decompose the nitrate [1]
[Total: 14]

Question 3 ii ∆H⦵hyd [Na+] + ∆H⦵hyd [Br−] = ∆H⦵latt

[NaBr] + ∆H⦵sol[NaBr] [1]
a V shaped water molecule with bond angle of
−390 − 337 = −742 + ∆H⦵sol[NaBr]
104.5 (see answer to Exercise 4.3(b)(i)) [1]
[1]
Arrow drawn in the direction relatively ∆H sol[NaBr] = (−390 − 337) + 742
⦵
smaller between the hydrogen atoms with = +15 kJ mol−1 [1]
the head towards the oxygen /δ− on O atoms
and δ+ between the H atoms [1] iii The enthalpy change when one mole of a
solid dissolves in a solvent [1]
b i H H [1]
H to form a very dilute / infinitely dilute
O
H O H solution under standard conditions. [1]
H Na+ O e So both the lattice energy and hydration
O H
O energy of Mg(OH)2 are greater than those
H H H of Ba(OH)2 because Mg2+ ion smaller than
Ba2+ ion [1]
Note: The oxygen of the water molecules
must be pointing towards the ion. The difference between the lattice energies of
Mg(OH)2 and Ba(OH)2 is relatively larger / the
ii Ion-dipole bonding [1] difference between the hydration energies of
c When forces are formed between the water Mg(OH)2 and Ba(OH)2 is relatively smaller [1]
and the ions, energy is given out. [1] enthalpy change of solution = enthalpy
When forces between ions in the ionic giant change of hydration − lattice energy [1]
structure are broken energy is absorbed. [1] So the enthalpy change of solution of
Energy change is exothermic / not too Ba(OH)2 is less positive (or more negative)
endothermic. [1] than the enthalpy change of solution of
Mg(OH)2 [1]
d i
Less positive / more negative enthalpy change
∆Hlatt
Na (g) +
+
Br−(g) NaBr(s)
of solution means greater solubility
(of Ba(OH)2) [1]
[Total: 20]
∆Hhyd ∆Hsol
Na+(aq) + Br–(aq)
2 marks for all boxes correct but 1

mark if two correct [2]
Arrows in correct direction and enthalpy
changes correctly labelled [1]

may be different.
Workbook answers
Chapter 20
Exercise 20.1
a i The right hand electrode because it is ii Anode: oxygen because the solution is
negative. very dilute so the water is electrolysed / a
mixture of chlorine and oxygen because
ii Anions are negatively charged. The anode
Cl− is not very far below OH− in the
is positively charged. Opposite charges
discharge series.
attract.
Cathode: hydrogen because it is low in
iii The ions are not free to move from place
the discharge series / H+ accepts electrons
to place / the ions only vibrate / the ions
more readily.
are fixed in a lattice.
iii Anode: oxygen because it is below SO42−
iv They conduct electricity; they do not react
in the discharge series / OH− from water is
with the electrolyte.
being electrolysed.
v From the anode to the positive pole of the
Cathode: hydrogen because H+ is the only
cell from the negative pole of the cell to
positive ion.
the cathode.
iv Anode: oxygen because water / OH− from
vi The outer shell electrons from the metal
water is being electrolysed / OH− below
atoms are free to move throughout the
SO42− in discharge series.
whole structure / the delocalised electrons
move throughout the structure. Cathode: copper because it is low / below
H+ in the discharge series.
b i Mg + 2e → Mg (reduction)
2+ −
v Anode: chlorine because it is below OH−

2Cl− → Cl2 + 2e− (oxidation)
in the discharge series.
ii Zn2+ + 2e− → Zn (reduction)
Cathode: hydrogen because H+ is the only
2O → O2 + 4e (oxidation)
2− −
positive ion.
iii Al3+ + 3e− → Al (reduction) vi Anode: oxygen because water / OH− from
water is being electrolysed.
2O2− → O2 + 4e− (oxidation)
Cathode: silver because it is low / below
iv Ca2+ + 2e− → Ca (reduction)
H+ in the discharge / reactivity series.
2Br − → Br2 + 2e− (oxidation)
v Li+ + e− → Li (reduction)
Exercise 20.2
2I− → I2 + 2e− (oxidation) a i 0.200 × 96 500 = 19 300 C
c i Anode: chlorine because it is below OH− ii 3 × 96 500 = 289 500 C to deposit 1 mol
in the discharge series. of Al
Cathode: hydrogen because it is below So 5 × 289 500 = 1 447 500 C to deposit

sodium in the discharge series / H+ accepts 5 mol
electrons more readily.

iii 2 × 96 500 = 193 000 C to deposit 1 mol Since the Ag+ ion has a single charge, the
of Pb charge on a mole of electrons (F) is
So 0.400 × 193 000 = 77 200 C to deposit 410.4
4.2632 × 10 −3 = 96 265.7 C mol
−1
0.4 mol
L = 96265.7
1.6 × 10 −19 = 6.009 × 10
23
b i Step 1: charge transferred = 3 × 10 × 60
= 1800 C
d Electrolyse solution of copper sulfate between
Step 2: number of coulombs to deposit copper electrodes for a known amount of
1 mol Cu = 2 × 96 500 time (40 min) keeping current constant.
= 193 000 C Determine the increase in mass of the cathode
step1 (or decrease in mass of anode). Calculate
Step 3: moles Cu deposited =
step2 the number of moles of copper deposited.
= 9.326 × 10−3 mol
Determine the increase in mass of the cathode
Step 4: mass of copper deposited (or decrease in mass of anode). Calculate
= 9.326 × 10−3 × 63.5 = 0.59 g quantity of electricity passed in coulombs by
Q = It (t in seconds). Calculate the quantity of
ii Charge transferred = 0.90 × 10 × 60 electricity passed to deposit 1 mole of copper.
= 540 C Divide this by 2 to get the value of F (because
Number of coulombs to deposit 1 mol Ag for every mole of copper deposited, 2 moles of
= 1 × 96 500 = 96 500 C electrons are required (Cu2+ + 2e− → Cu).
Moles Ag deposited = 540 Exercise 20.3

96500
= 5.596 × 10−3 mol
a i Co(s) → Co2+(aq) + 2e−
Mass of Ag deposited
= 5.596 × 10−3 × 107.9 = 0.60 g Pb2+(aq) + 2e− → Pb(s)
iii Charge transferred = 0.50 × 30 × 60 ii Zn(s) → Zn2+(aq) + 2e−
= 900 C
Cu2+(aq) + 2e− → Cu(s)
Number of coulombs to deposit 1 mol Pb
iii Al(s) → Al3+(aq) + 3e−
= 2 × 96 500 = 193 000 C
Ag+(aq) + e− → Ag(s)
iv Moles Pb deposited = 900
193000
= 4.663 × 10−3 mol iv Mg(s) → Mg2+(aq) + 2e−
Mass of lead deposited Sn2+(aq) + 2e− → Sn(s)
= 4.663 × 10−3 × 207.2 = 0.97 g
b i Zn(s) → Zn2+(aq) + 2e−
v Charge transferred = 0.15 × 20 × 60
= 180 C Cu2+(aq) + 2e− → Cu(s)
Number of coulombs to release 1 mol O2 ii Zn(s) → Zn2+(aq) + 2e− is oxidation (loss

= 4 × 96 500 = 386 000 C of e−)
(Multiply by 4 because each O atom has a Cu2+(aq) + 2e− → Cu(s) is reduction (gain
charge of −2) of e−)
Moles O2 = 180 = 4.663 × 10−4 mol iii Reduction always takes place at a cathode.
386000
1 mol O2 occupies 24.0 dm3 at r.t.p. iv The electrons move from the electrode
where the electron density is higher (the
So volume of O2 = 4.663 × 10−4 × 24 dm3 zinc) to where it is lower (the copper).
= 0.011 dm3 / 11 cm3
v To maintain electrical contact between
c Charge transferred = 0.07600 × 90 × 60 = the solutions so a complete circuit is
410.4 C obtained.
Moles Ag = 0.4600 = 4.2632 × 10−3 mol
107.9

c i The voltage increases because silver is Exercise 20.5

lower in the reactivity series than copper.
a i H+ ions are easier to reduce than Zn2+ ions
ii The voltage increases because magnesium as they have a more positive value of E⦵.
is higher in the reactivity series than zinc.
ii H+ ions
iii The voltage decreases because tin is lower
in the reactivity series than zinc. iii 2H+(aq) + Zn(s) ⇌ H2(g) + Zn2+(aq)
iv The voltage decreases because iron is b i Cl2(aq)
higher in the reactivity series than copper.
Cl2(aq) + 2Fe2+(aq) ⇌ 2Cl−(aq) + 2Fe3+(aq)
v There will be no voltage because the
ii MnO4−(aq)
electrodes are the same.
MnO4−(aq) + 8H+(aq) + 5Fe2+(aq) ⇌
Exercise 20.4 Mn2+(aq) + 4H2O(l) + 5Fe3+(aq)
a i Hydrogen gas at a pressure of iii Pb2+(aq)

approximately 101 kPa
Pb2+(aq) + 2Cr2+(aq) ⇌ Pb(s) + 2Cr3+(aq)
ii H+ ion concentration of 1.00 mol dm−3
iv Br2(aq)
iii Electrode is Pt
Br2(aq) + 2I−(aq) ⇌ 2Br−(aq) + I2(aq)
iv Temperature is 298 K
c i 1.36 − 0.8 = 0.56 V (Ag electrode is
v The voltage of a standard hydrogen negative pole)
electrode is 0 V
ii −0.76 − (−0.13) = −0.63 V (Zn electrode is
b H+(aq) + e− ⇌ 1 H2 negative pole)
2
c The more negative (or less positive) the iii 0.8 − 0.54 = 0.26 V (Iodine electrode is
electrode potential, the more difficult it is negative pole)
to reduce the ions on the left hand side of
iv −0.25 − 1.47 = −1.72 V (Ni electrode is
the equation. So the metal on the right is a
negative pole)
relatively good reducing agent. The ions on
the left hand side are relatively good oxidising d i Potassium manganate(VII) to Mn2+ ions,
agents. E⦵ = +1.52 V Fluorine to fluoride ions,
E⦵ = +2.87 V
d i Zinc
So Fluoride ions to fluorine E⦵
ii Zinc
= −2.87 V + 1.52 − 2.87 = −1.35 V
iii Copper (reaction not feasible)
iv Copper ii Ni2+ to Ni, E⦵ = −0.25 V
e i V2+(aq) So Ni to Ni2+, E⦵ = + 0.25 V
ii Cl2(aq) Fe3+ to Fe2+, E⦵ = +0.77 V
iii Chlorine is better at releasing electrons Fe3+ to Fe, E⦵ = −0.04 V + 0.25 + 0.77 =
than iodine / iodide is better at accepting +1.02 V (reaction feasible)
electrons than bromide.
+0.25 − 0.04 = + 0.21 V (reaction feasible)
iv Bromine is better at releasing electrons
iii Mn2+ to Mn, E⦵ = −1.18 V
than iodine / iodide is better at accepting
electrons than bromide so the reaction Iodine to iodide, E⦵ = +0.54 V
will be the reaction of bromine with
iodide ions. So iodide to iodine, E⦵ = −0.54 V −1.18 +
(−0.54) = 1.72 V (reaction not feasible)

Exercise 20.6
a i Shifts the equilibrium to the right, so the
value of E⦵ is less negative than −0.76 V. Question 1
ii Shifts the equilibrium to the left, so the a O2− → 1 O2 + 2e− (or doubled) [1]
2
value of E⦵ is more negative than −0.76 V.
b 56 cm3 O2 = 56 = 2.333 × 10−3 mol [1]
iii Greater concentration of Cr2+ ions shifts 24000
the equilibrium to the left, so the value of Charge = 4 × 96 500 × 2.333 × 10−3 mol
E⦵ is more negative than −0.41 V. = 900.5 C (2)
iv No effect, because the concentrations of Multiplying by 4 for 4e− required for each
the ions are the same / the changes cancel O2 molecule [1]
each other out.
Rest of calculation correct [1]
b R is the gas constant = 8.314 J K−1 mol−1
c Charge = 2.6 × 10 × 60 = 1560 C [1]
E is the electrode potential under non-standard
conditions Charge required for 1 mole = 3 × 96 500
= 289 500 C [1]
F is the Faraday constant in coulombs per mole
(96 500 C mol−1) Moles Al = 1560 = 5.3886 × 10−3 mol [1]
289500
log10 is the logarithm to the base 10 Mass Al = 5.3886 × 10−3 × 27 = 0.15 g [1]
c i The reduced form is the metal whose d The ions cannot move from place to place /
concentration, being a solid, does not the ions only vibrate / the ions are fixed in a
change. lattice [1]
ii E = −0.76 + 0.059 log10(2.0) e i Hydrogen [1]

2
Hydrogen is more readily discharged
= −0.75 V (to 2 significant figures) than zinc /
Exercise 20.7 hydrogen accepts electrons more readily

than zinc [1]
a i H2(g) → 2H+(aq) + 2e−
ii Oxygen comes from OH− ions in water [1]
ii 4H (aq) + O2(g) + 4e → 2H2O(l)
+ −
Cl− ions are close to OH− ions in the
iii 2H2(g) + O2(g) → 2H2O(l) discharge series / reactivity series so
some Cl2 formed [1]
The only product is water which is not a
pollutant. [Total: 13]
iv The electron flow is from the negative Question 2

(hydrogen electrode) to the positive
(oxygen) electrode. The E⦵ value for the a The standard electrode potential of a
hydrogen electrode is more negative. half cell [1]
v Zero because it is acting as a standard when measured against a standard
hydrogen electrode. hydrogen electrode [1]
b i NiO2 + 2H2O + 2e− → Ni(OH)2 + 2OH− b To maintain electrical connection between the
half-cells / so that there is a complete electrical
This has a more positive E⦵ value so circuit. [1]
proceeds in the forward direction.
Filter paper / inert support / named inert
ii 1.30 V support [1]
iii Cd + NiO2 + 2H2O → Ni(OH)2 + Cd(OH)2 Soaked in saturated potassium nitrate [1]
iv Ni(OH)2 + Cd(OH)2 → Cd + NiO2 + 2H2O

c 1.00 mol dm−3 zinc ions [1] b Electrons flow from − to + electrode in
the wires. [1]
298°C and 101 kPa [1]
Electrons more easily released at the negative
d H+ ions at concentration of 1.00 mol dm−3 [1]
electrode (or by copper) / copper more easily
Pt coated with Pt black [1] oxidised than iron(II) [1]
H2 gas passed over Pt at 105 Pa [1] c 0.77 − 0.34 = 0.43 V [1]
e Zn(s) + 2H+(aq) → H2(g) + Zn2+(aq) d Cu + 2Fe3+ → Cu2+ + 2Fe2+
Correct formulae [1] Correct formulae [1]
balance and state symbols [1] balance [1]
f i 1.52 − (−0.76) = 2.28 V [1] e E = 0.34 + 0.059 log10 (0.15) = 0.32 V [2]
2
ii Electrode potential of Zn / Zn ion cell will 1 mark for error carried forward using
get less negative [1] incorrect number of electrons
since the equilibrium is pushed to the f i The likelihood of a reaction occurring
right / in favour of the reductant. [1] when two or more substances are added
together. [1]
So difference between the electrode
potential of the half-cells decreases. [1] ii PbO2 is a better oxidising agent since E⦵
more positive / PbO2 more likely to accept
[Total: 16] electrons since E⦵ more positive [1]
Question 3 I− better reducing agent since E⦵ less

positive / I− better reducing agent since
a more likely to release electrons [1]
voltmeter
I2 weaker oxidising agent and PbO2
copper
weaker reducing agent so reaction not
rod feasible [1]
salt bridge
E⦵cell suggested reaction is +0.54 −
(1.47) = −0.93 V [1]
Negative value of E⦵cell suggested reaction
platinum not feasible [1]
298K [Total: 19]
Cu2+, 1.00 mol dm−3 Fe3+, 1.00 mol dm−3
Fe2+, 1.00 mol dm−3
Two half-cells connected to a (high resistance)

voltmeter labelled V or voltmeter [1]
Salt bridge labelled [1]
Negative and positive electrodes labelled
correctly / Cu negative and Pt positive [1]
Cu dipping into solution of Cu2+ ions or
suitable soluble Cu salt [1]
Pt electrode dipping into solution of Fe3+ and
Fe2+ ions or suitable soluble
iron(II) and iron(III) salts [1]
All solutions 1.00 mol dm−3 [1]

may be different.
Workbook answers
Chapter 21
a i A proton donor / H+ ion donor a 1 with C; 2 with A; 3 with F; 4 with E; 5 with B;
6 with D
ii ionised / dissociated; solution
iii weak; dissociated / ionised; strong; it is b i The ionic product for water
completely dissociated / ionised in water ii The dissociation constant for a weak acid
b Ethanoic acid is a weak acid and hydrochloric iii Solubility product
acid is a strong acid; there is a lower
concentration of H+ ions in ethanoic iv Partition coefficient
acid/ higher concentration of H+ ions in c i 1.7 ii 0.9 iii 4.2
hydrochloric acid; the collision frequency of
the H+ ions with magnesium in ethanoic acid d i 6.31 × 10−11 mol dm−3
is lower / the collision frequency of the H+ ions
ii 3.98 × 10−7 mol dm−3
with magnesium in hydrochloric acid is higher.
c i acid HNO3; base H2O iii 0.0126 mol dm−3
ii acid H2O; base NH3 e i Kw = [H+(aq)][OH−(aq)]
iii acid CH3OH; base NH2− so [H+(aq)] =

Kw −14
iv acid H2O; base NH2OH = 1.00 × 10
[OH − (aq)] 6.40 × 10 −3
v acid H2SO4; base H2O
= 1.56 × 10−12 mol dm−3
vi acid H2SO4; base HIO3
So pH = 11.8
d i NH3 base; NH4+ conjugate acid
ii Kw = [H+(aq)][OH−(aq)]
H2O acid; OH− conjugate base
so [H+(aq)] =
ii H2O base; H3O+ conjugate acid
Kw
= 1.00 × 10 −4
−14
CH3COOH acid; CH3COO− conjugate base [OH − (aq)] 3.00 × 10
iii H2O base; H3O+ conjugate acid = 3.33 × 10−11 mol dm−3
CH3NHCH2NH3+ acid; So pH = 10.5
CH3NHCH2NH2 conjugate base
iii [H+(aq)] (from pH)
iv H2O base; H3O+ conjugate acid = 3.16 × 10−13 mol dm−3
HSiO3− acid; SiO32− conjugate base Kw = [H+(aq)][OH−(aq)]
v H2O base; H3O+ conjugate acid so [OH−(aq)] =
Kw −14
HCO2H acid; HCO2− conjugate base = 1.00 × 10 −13
[O H (aq)] 3.16 × 10
−
vi NH2OH base; NH3OH+ conjugate acid
H2O acid; OH− conjugate base = 0.032 mol dm−3

Exercise 21.3
a
Chemical equation Equilibrium expression Units
Fe2+(aq) + 2OH−(aq) ⇌ Fe(OH)2(s) Ksp = [Fe2+(aq)] [OH−(aq)]2 mol3 dm−9
Sn2+(aq) + CO32−(aq) ⇌ SnCO3(s) Ksp = [Sn2+(aq)] [CO32−(aq)] mol2 dm−6
2Ag+(aq) + CrO42−(aq) ⇌ Ag2CrO4(s) Ksp = [Ag+(aq)]2 [CrO42−(aq)] mol3 dm−9
3Ag+(aq) + PO43−(aq) ⇌ Ag3PO4(s) Ksp = [Ag+(aq)]3 [PO43−(aq)] mol4 dm−12
Cr3+(aq) + 3OH−(aq) ⇌ Cr(OH)3(s) Ksp = [Cr3+(aq)] [OH−(aq)]3 mol4 dm−12
2Ag+(aq) + S2−(aq) ⇌ Ag2S(s) Ksp = [Ag+(aq)]2 [S2−(aq)] mol3 dm−9
b i Ksp = [Ag+(aq)]2[S2−(aq)] [Sr2+(aq)] × [CO32−(aq)] = (0.50 × 10−4) ×

(4.0 × 10−6) = 2.0 ×10−10 mol2 dm−6
= (2 × 5.25 × 10−17)2 × (5.25 × 10−17)
Remember: there are 2 Ag+ ions per This value is greater than the solubility
mole Ag2S product, so strontium carbonate will
precipitate.
= 5.79 × 10−49 mol3 dm−9
e Equation: Sr2+(aq) + SO42−(aq) ⇌ SrSO4(s)
ii Ksp = [Pb2+(aq)][SO42−(aq)]
Concentrations are divided by two because
= (1.48 × 10−6) × (1.48 × 10−6) each dilutes the other twofold.
= 2.18 × 10−12 mol2 dm−6 [Sr2+(aq)] = 2.5 × 10−7 mol dm−3
iii Ksp = [Ba (aq)][BrO3 (aq)]
2+ − 2
[SO42−(aq)] = 0.025 mol dm−3 (ignoring the
= (9.86 × 10 ) × (2 × 9.86 × 10 )
−5 −5 2 sulfate ions from the SrSO4)
Remember: there are 2BrO3− [Sr2+(aq)] × [SO42−(aq)] = (2.5 × 10−7) × (0.025)
ions per mole Ba(BrO3)2 = 6.25 × 10−9 mol2 dm−6
= 3.83 × 10−12 mol3 dm−9 This value is greater than the solubility
c i [Ba (aq)] = [SO4 (aq)]
2+ 2− product, so strontium carbonate will
precipitate.
So Ksp = [Ba2+(aq)]2
So [Ba2+(aq)] = KKspsp == 1.0 −10 Exercise 21.4

1.0 ××10
10 −10
= 1.0 × 10−5 mol dm−3 a i pH = −log[H+(aq)]. So [H+(aq)]
= 1.26 × 10−3 mol dm−3
ii [Cd2+(aq)] = [S2−(aq)]
+
Ka = [H (aq)] = (1.26 × 10 )
2 −3 2
So Ksp = [Cd2+(aq)]2 [HA(aq)] 0.1
So [Cd2+(aq)] = K ksp = −27
sp = 8.0
1.0 ×
× 10
10 −10 = 1.59 × 10−5 mol dm−3
= 8.9 × 10−14 mol dm−3
ii pH = −log[H+(aq)]. So [H+(aq)]
d Equation: Sr (aq) + CO3 (aq) ⇌ SrCO3(s)
2+ 2− = 5.13 × 10−8 mol dm−3
Concentrations are divided by two because [H + (aq)]2 (5.13 × 10 −8 ) 2

Ka = =
each dilutes the other twofold. [HA(aq)] 0.002
[Sr2+(aq)] = 0.50 × 10−4 mol dm−3 = 1.32 × 10−12 mol dm−3
[CO32−(aq)] = 4.0 × 10−6 mol dm−3

iii pH = −log[H+(aq)]. So [H+(aq)] c Addition of alkali shifts the equilibrium to

= 1.78 × 10−5 mol dm−3 the right, because hydrogen ions from the acid
combine with OH− ions from the alkali.
[H + (aq)] 2 (1.78 × 10 −5 ) 2
Ka = =
[HA(aq)] 0.005 The concentration of hydrogen ions does not
fall significantly because more butanoic acid
= 6.34 × 10−8 mol dm−3 ionises to maintain the equilibrium.
[H + (aq)]2 The concentration of C3H7COOH / butanoic
b i Ka =
[HA(aq)] acid does not fall significantly because it is
ii [H+(aq)]2 = Ka × [HA(aq)] present in relatively high concentration.
iii [H+(aq)]2 = (1.5 × 10−5) × 0.2 = 3.0 × 10−6 The concentration ratio [C3H7COO−] to
[C3H7COOH] does not change much so the
So [H+(aq)] =
( 3.0 × 10 −6 ) pH does not change significantly.
= 1.73 × 10−3 mol dm−3 [H + (aq)] [A − (aq)]
d Ka =
iv −log (1.73 × 10 ) = pH 2.76 / pH 2.8
−3 [HA(aq)]
c i [H+(aq)]2 = Ka × [HA(aq)] Rearranging: [H+(aq)] =

K a × [HA(aq)] 1.35 × 10−5 × 0.5
[H+(aq)]2 = (1.3 × 10−5) × 0.10 = 1.3 × 10−6 =
[A − (aq)] 0.4
So [H+(aq)] =
(1.3 × 10 −6 )
[H+(aq)] = 1.69 × 10−5 mol.
= 1.14 × 10−3 mol dm−3 So pH = 4.77 / 4.8
−log (1.14 × 10−3) = pH 2.94 / pH 2.9 e Convert pH to [H+(aq)] = 6.31 × 10−6 mol dm−3
ii [H+(aq)]2 = Ka × [HA(aq)] [H + (aq)] [A − (aq)]
Ka =
[H+(aq)]2 = (4.7 × 10−4) × 0.15 = 7.05 × 10−5 [HA(aq)]
So [H+(aq)] =
( 7.05 × 10 −5 ) Rearranging: [A−(aq)]
K a × [HA(aq)] (1.35 × 10 −5 ) × 1.00
= 8.40 × 10−3 mol dm−3 = =
[H + (aq)] (6.31 × 10 −6 )
−log (8.40 × 10−3) = pH 2.07 / pH 2.1 [A−(aq)] = 2.14 mol (since in 1 dm3)
Exercise 21.5 f Concentrations have to be calculated because

each solution dilutes the other.
a A solution which contains a conjugate acid-
base system that minimises change in pH on The total volume is 400 cm3.
addition of acid or alkali. [ethanoic acid] = 0.50 × 300
400
b In this buffer solution the conjugate base is = 0.375 mol dm−3
C3H7COO− / butanoate ion
100
[sodium ethanoate] = 0.80 ×
Addition of acid shifts the equilibrium to 400
the left because hydrogen ions from the acid = 0.20 mol dm−3
combine with C3H7COO− / butanoate ions [H + (aq)] [A − (aq)]
from the buffer solution. The concentration Ka = [HA(aq)]
of C3H7COO− / butanoate ions does not
fall significantly and the concentration of Rearranging: [H+(aq)]
C3H7COOH / butanoic acid does not rise
K a × [HA(aq)] (1.70 × 10 −5 ) × 0.375
significantly because the acid and base (salt) = =
[A − (aq)] (0.20)
are both in relatively high concentrations.
The concentration ratio [C3H7COO−] to [H+(aq)] = 3.19 × 10−5 mol. So pH = 4.5
[C3H7COOH] does not change much so the
pH does not change much / does not change g dissolved; hydrogencarbonate; hydrogen;
significantly. direction; excess; hydrogencarbonate;
concentrations; pH

Exercise 21.6 c i Rearranging: [H+(aq)]2 =

Ka × [HA(aq)] [1]
a i More soluble in CCl4
[H+(aq)]2 = (4.5 × 10−7) × 0.01
ii more soluble in C6H6 = 4.5 × 10−9 [1]
iii more soluble in water [H+(aq)] = ( 4.5 × 10 −9 ) = 6.71 × 10−5 [1]
b i Titrate with strong acid (hydrochloric or pH = 4.2 [1]
sulfuric).
ii The concentration of H2CO3 is the same
Using methyl orange indicator / methyl as the equilibrium concentration. [1]
red / bromophenol blue / indicator that
changes colour in acidic region. Justified by low value of Ka / % of
hydrogen which ionises is extremely low.
ii The gradient of the graph gives the value. [1]
e.g 1.57 − 0.63 ; Kpc = 23.5
0.05 − 0.01 The concentration of HCO3− equals
the concentration of H+ / water does
(The graph does not go through the origin not ionise. [1]
because some of the ammonia combines with
the copper(II) sulfate as a complex.) Justified by assumption that the ionisation
of water is so small compared with the
c The value of the partition coefficient ionisation of the acid. [1]
(much greater than 1) shows that iodine is
much more soluble in CCl4 than in water. [Total: 13]
Iodine is a non-polar molecule. It dissolves
well in CCl4 because this molecule has no Question 2
overall polarity. New instantaneous dipole-
induced dipole attractions can be formed a The equilibrium shifts slightly to the right [1]
between iodine and CCl4.This is because
because OH− ions remove H+ ions. [1]
the strength of the instantaneous dipole-
induced dipole forces in both molecules Butanoic acid ionises to maintain
are similar. Water is a polar molecule equilibrium. [1]
which is hydrogen-bonded. The strength of
The concentrations of butanoic acid and
hydrogen bonds is much greater than the
butanoate ions do not change much. [1]
strength of instantaneous dipole-induced
dipole forces. So the iodine molecules So pH does not increase much / remains
cannot penetrate the structure of the water (fairly) constant. [1]
very easily (the reaction would be highly
exothermic). b [butanoic acid] = 0.2 × 50 = 0.05 mol dm−3
200
[sodium butanoate] = 0.4 × 150
200
Exam-style questions = 0.30 mol dm−3
(1 mark for both correct) [1]
Question 1
[K a × [HA(aq)]
a i It donates hydrogen ions [1] Rearranging: [H+(aq)] = [1]
[A − (aq)]
to water / the base [1]
(1.50 × 10 −5 ) × 0.05
[H+(aq)] =
ii H2CO3 (acid) and HCO3− (base) [1] 0.3
= 2.5 × 10−6 mol dm−3 [1]
H2O (base) and H3O+ (acid) [1]
pH = 5.6 [1]
[H + (aq)] [A − (aq)] [H + (aq)] 2
b Ka = or Ka = [1]
[HA(aq)] [HA(aq)] c Hydrogen ions produced could lower
the pH of the blood [1]

which could disrupt enyme function / body Question 4

function [1]
a i Ksp = [Mg2+(aq)] [CO32−(aq)] [1]
HCO3− ions combine with H+ ions to remove
them. [1] mol dm
2 −6
[1]
CO2 + H2O ⇌ HCO3− + H+ [1] ii Ksp = [Mg2+(aq)]2 [1]
[Total: 13]
[Mg2+(aq)] = k sp = 1.0 × 10 −5 [1]
Question 3 3.2 × 10−3 mol dm−3 [1]

a CH3COOH + OH− → CH3COO− + H2O [1] b i Ksp = [Ag+(aq)]2[CO32−(aq)] [1]
b pH 4.8 from graph [1] mol3 dm9 [1]
[H+(aq)] = 1.58 × 10−5 mol dm−3 [1] ii [Ag+(aq)] = 2 × 1.2 × 10−5
= 2.4 × 10−5 mol dm−3 [1]
Kw
c [H+(aq)] = [1]
[OH− (aq)] Ksp = (2.4 × 10−5)2 × 1.2 × 10−5 [1]
(1.00 × 10 −14 ) Ksp = 6.9 × 10−15 [1]
= = 5 × 10−13 mol dm−3 [1]
0.02
mol3 dm−9 [1]
d i Phenolphthalein / other suitable
indicator [1] c i Reduction in the solubility of a
dissolved salt [1]
ii Its colour range does not coincide with
the sudden change of pH. [1] by adding a solution containing an ion in
common [1]
e Make a concentrated solution of sodium
ethanoate by dissolving in water / make a ii Some of the precipitate may dissolve
1 mol dm−3 (or greater) solution of sodium in water. [1]
ethanoate by dissolving in water [1]
Washing with sulfuric acid reduces the
Make a concentrated solution of ethanoic possibility of the precipitate dissolving /
acid by dissolving in water / make a 1 mol dm−3 sulfate both in sulfuric acid and barium
(or greater) solution of ethanoic acid by sulfate causes common ion effect [1]
dissolving in water. [1]
d Concentrations are divided by two because
Use a pH meter to find the pH of both each dilutes the other twofold.
solutions [1]
[Ca2+(aq)] = 0.005 mol dm−3
Slowly add a solution of one to a fixed volume
of the other (with stirring) until the required [SO42−(aq)] = 0.01 mol dm−3 (1 mark if
pH is reached [1] both correct) [1]
[Total: 11] [Ca2+(aq)] × [SO42−(aq)] = 0.005 × 0.01 =
5.0 × 10−5 mol2 dm−6 [1]
This value is greater than the solubility
product, so calcium sulfate will precipitate. [1]
[Total: 18]

may be different.
Workbook answers
Chapter 22
Exercise 22.1
a i 0.004 × 1000 = 0.02 mol dm−3 d i The power to which the concentration of
200
a reactant is raised in the rate equation.
0.02 = 1.1 × 10−5 mol dm3 s−1 e.g. [X]2 is second order
30 × 60
80 × 1000 = 6.67 × 10−2 mol dm−3 ii Graph should show approximately
ii
24000 50 proportional relationship.
6.67 × 10 −2 = 5.6 × 10−4 mol dm3 s−1 iii First order. Idea of some variability in the
2 × 60
data so more tangents should be taken to
iii 3 g propanol = 3 = 0.0517 mol in get wider spread of data.
58
250 cm3 = 0.207 mol dm−3 iv Deduce the time when the concentration
0.207 = 2.3 × 10−4 mol dm3 s−1 drops to half its original value, then to a
15 × 60 quarter of its original value, then to one-
eighth.
b i Measure increase in electrical conductivity
/ take samples of solution for analysis of v When [H2O2] = 7.75 time = 800 s
H+ ion concentration by titrating with (approximately) When [H2O2] = 3.875 time
sodium hydroxide = 16500 s (approximately) (2nd half-life
= 850 s). So the half-life is more or less
ii Measure increase in pressure (in closed constant. So the reaction is first order
reaction vessel) due to increasing moles
of gas. vi 8.66 / 8.7 × 10−4 (s−1)
iii Colorimetry: measure colour change e i An equation showing the relationship

at appropriate wavelength either of between the rate constant and the
decrease in dichromate orange or increase concentration of those reactants that
in copper or chromium ion colours / affect the rate reaction.
decrease in electrical conductivity (H+ ion
ii rate = k[H2O2]
more conductive than others).
iv Increase in volume of oxygen produced Exercise 22.2
using gas syringe.
a order; rate constant; rate; concentrations;
v Take samples of solution for analysis of OH− concentration
ion concentration by titrating with acid.
b i Left hand graph:
c i Intial rate 15.5 = 0.0148 mol dm−3 s−1;
1050 y-axis − concentration of reactant
500 s 13.0 = 0.00765 mol dm−3 s−1; (in mol dm−3)
1700
x-axis − time (in s)
1000 s 12.0 = 0.00462 mol dm−3 s−1
2600 Right hand graph:
ii The rate decreases as the concentration
decreases. y-axis − rate of reaction (in mol dm−3 s−1)

x-axis − concentration of reactant Exercise 22.3

(in mol dm−3)
a Rate equation Overall order Units of k
ii Zero order = A and D
of reaction
First order = B and F
Rate =
2nd dm3 mol−1 s−1
Second order = C and E k[HCOOCH3][H+]
c Rate =
Details of reaction Rate Overall 1st s−1
k[H2O2]
equation order of
reaction Rate =
0 mol dm−3 s−1
k[NH3]0
rate proportional to rate 2nd
concentration of I2 and = k[H2][I2] order Rate =
1st s−1
concentration of H2 k[N2O]
rate proportional to rate 2nd Rate =
4th dm9 mol3 s−1
the square of the = k[NO2]2 order k[BrO3−][Br −][H+]2
concentration of NO2 Rate =
2nd dm3 mol−1 s−1
rate proportional to rate = 3rd k[NO2]2
concentration of I2 k[I2][O2]2 order
and the square of the b i Hydrogen: (compare the 2nd and 4th lines
concentration of O2 of data to keep NO constant). Doubling
concentration doubles rate. So first order
rate proportional to rate = 2nd
with respect to hydrogen.
concentration of HI k[HI][H2O2] order
and concentration of NO: (compare the first three lines of
H2O2 data to keep H2 constant). Doubling
rate independent on rate = k 0 order concentration increases rate × 4. So
the concentration of second order with respect to NO.
any of the reactants ii Rate = k[H2][NO]2
d i Zero order reaction: Successive half-lives iii 2.4 × 10−6 = k (1.0 × 10−6) × (1.25 × 10−2)2
decrease with time. First order reaction:
k = 1.92 × 104 dm6 mol2 s−1
Successive half-lives are constant. Second
order reaction: Successive half-lives c i First order because rate is proportional to
increase with time. concentration.
ii For A, the first half-life is 10 s (6.4 to 3.2), ii Take any rate and corresponding
the second half-life is 10 s (3.2 to 1.6). concentration, e.g
Half-life is constant so it is first order. For
B, the first half-life is somewhere between 0.2 mol dm−3 and 0.0075 mol dm−3 s−1
20–30 s (6.4 to 3.2), the second half-life is 0.0075 = k (0.2) So k = 0.0375 s−1
somewhere between 30–40 s (3.2 to 1.6).
Half-life decreases so it is zero order. iii Rate = k[H2O2][catalyst]
e i A temperature rise of 10°C approximately iv Graph of concentration against time

doubles the rate of reaction. shows a gentle curve downwards as in
line B in figure in Exercise 22.1 part (a).
ii As the temperature increases the rate
constant also increases as the rate of d i Graph should show a gentle downward curve
reaction increases. as in line B in figure in Exercise 22.1 part (a).
ii First half-life is from 100% to 50% =
54 × 103 s
Second half-life is from 50% to 25% =
(108 − 54) × 103 s = 54 × 103 s Half-life is
constant so order of reaction is first order.

0.693 = 1.28 × 10−5 s−1 b i S2O82−(aq) + 2Fe2+(aq) + 2I−(aq) →

iii
54 × 10 3 2SO42− (aq) + 2Fe3+ (aq) + I2(aq)
iv Because the % cyclopropane is ii The Fe2+ ions are being reformed.
proportional to concentration. They are the same at the end as at the
beginning.
Exercise 22.4 iii Homogeneous
a i Rate = k[C2H5Br][OH ] −
iv The iodide ions get oxidised first and the
ii CH3CH2(OH)Br− Fe3+ ions get reduced to Fe2+. The Fe2+
ions then react with the S2O82−(aq) to form
iii The slow step has two species, C2H5Br and sulfate ion and Fe3+ ions.
OH− colliding.
v uncatalysed
These two species appear in the rate equation. reaction
iv Nucleophile. It is negatively charged and

attacks the C atom attached to the Br catalysed
Enthalpy change
atom. This C atom has a δ+ charge. reaction
S2O82− + 2I−
b i The sodium hydroxide
Fe3+ → Fe2+
ii Rate = k[CH3COCH3][OH−] reaction 1
Fe2+ → Fe3+
(CH3COCH3 and OH− both appear in the reaction 2 2SO42– + I2
rate determining step)
iii Electrophile. It attacks an area of negative
charge. Progress of reaction
c i Rate = k[RSO4−]
ii Water is in excess so its concentration is Exam-style questions
effectively constant.
iii Since the concentration of water is
Question 1
constant, only the sulfate is involved in a Measure the volume of gas / carbon dioxide
the slow (rate determining) step and this given of using a gas syringe. [1]
appears alone in the rate equation.
Volume of gas increases with time. [1]
Exercise 22.5 Some carbon dioxide may dissolve in the
a i Mixture of nitrogen oxides / NO + NO2 reaction mixture. [1]
ii CO is poisonous and NO2 causes acid rain ALLOW: Measure volume of gas in upturned
/ catalyst for oxidation of sulfur dioxide / measuring cylinder full of water in trough full
NOx associated with photochemical smog / of water for the first marking point.
ALLOW: its a greenhouse gas / potentiates Measure the electrical conductivity (no marks)
asthma / increase risk of heart attacks
The conductivity decreases with time. [1]
iii D, F, E, A, C, G, B
Other substances in the mixture, e.g. + ions
iv The molecules of NOx and CO would not
have not been taken into account. [1]
be able to move away from the surface of
the catalyst / the molecules would be too b i C2O42− Second order [1]
strongly bonded to allow bonds to form
between NOx and CO. (Compare the first two lines of data.
Doubling concentration increases rate by 4.)
v The molecules of NOx and CO would
diffuse away from the surface before they HgCl2 first order [1]
could react. (Compare the lines of data 1 and 3.
vi Desorption Doubling concentration doubles the rate.)

ii rate = k[C2O42−]2[ HgCl2] [1] Titrate with standard acid using an

indicator. [1]
iii Correct substitution, e.g. 4.3 × 10−4 =
k(0.11)2 × (0.0418) [1] ALLOW: back titration for marks 2 and
3, i.e.
Answer: 0.85 [1]
– add excess acid of known concentration;
Unit: dm6 mol−2 s−1 [1]
– titrate with standard sodium hydroxide
[Total: 11] using indicator.
Question 2 ii Rate = k[(CH3)3CBr] [1]
a Catalyst [1] iii (CH3)3CBr spontaneously ionises [1]

to form (CH3)3C+ [1]
b Reaction rate changes when temperature
changes. [1] This is the slow step corresponding to
(CH3)3CBr being
c Points correct [1]
first order in rate equation. [1]
Curved line joining all points [1]
OH− ion reacts with (CH3)3C+ [1]
d Rates: 0 = 0.046; 0.036; 0.027; 0.017
This is the fast step. [1]
(2 marks if all within ± 0.005; 1 mark if 2 are
within ± 0.005) [Total: 17]
e First order [1] Question 4

The rates are (roughly) proportional to the a uncatalysed
concentrations [1]
reaction
f The concentration of water is not known [1]
Enthalpy change
The experiment has not been done varying the C2H4 + H2

concentration of HCl [1]
[Total: 10] catalysed
reaction
C2H6
Question 3
a i 2nd order [1]
ii 4th order [1]
Progress of reaction
b dm9 mol−3 s−1 [1]
Axes labelled and reactants on left and
c Slow step involves HBr and HBrO3 [1] product on right with product level
[HBr] depends on the concentration of below reactant level. [1]
Br− and H+ [1] Energy hump of uncatalysed reaction higher
[HBrO3] depends on the concentration than catalysed, and labelled. [1]
of H+ and BrO3− [1] Energy hump of catalysed reaction lower than
−
One mole of each of Br and BrO3 − uncatalysed, and labelled. [1]
involved. [1] b Lower the activation energy. [1]
+
Two moles of H involved. [1] Mechanism is different / provides an
d i Take small portions of the reaction alternative route. [1]
mixture at various time intervals. [1] (Second mark dependent on the first mark
Quench them [1]; ALLOW: cool them being correct)
immediately.

c C2H4 and H2 diffuse to the catalyst surface. [1] Idea of desorption / bonds between atoms
on surface and ethane broken and ethene
C2H4 and H2 adsorbed on the catalyst diffuses from the surface. [1]
surface / C2H4 and H2 form bonds with
atoms on the catalyst surface. [1] d i Nitrogen dioxide is reformed / nitrogen
dioxide is not used up. [1]
Adsorbed molecules of C2H4 and H2 which are
close together start to form bonds. [1] ii Homogeneous [1]
Bonds between C2H6 and the surface atoms The catalyst and the reactants are both
are weakened. [1] in the same phase. [1]
[Total: 13]

may be different.
Workbook answers
Chapter 23
Exercise 23.1
a A spontaneous change is a change that, once is possible. So HBr has a higher entropy. The
started, will carry on until it is finished. Cl in HCl is also more electronegative than
Examples are diffusion, or the reaction of Br, so the dipole– dipole forces are stronger,
sodium with water. Spontaneous reactions leading to a more ordered structure.
happen because statistics tell us that there is
a greater likelihood of the particles having CH4 (methane) and C3H8 (propane) are both
more ways of arranging their energy. In a gases but methane has fewer atoms and
spontaneous reaction, the entropy increases. electrons and so has more order than propane,
Entropy is a measure of the randomness or which has a higher entropy.
disorder. The greater the randomness, the
greater is the entropy. The total entropy takes Exercise 23.2
into account the system (the reactants and
a i The left. It has two types of molecule and
products) and the surroundings (everything
seems to have more disorder.
else around the reactants and products).
The system is more stable when it is more ii The left (reactant) square
disordered. The entropy is also greater when
there are more ways of arranging the energy. iii Higher, because it is a more complex
molecule.
b System: magnesium and hydrochloric acid.
iv The reactants have greater entropy
Surroundings: test tube, thermometer, because there are more molecules and two
air, water in the hydrochloric acid (rest of types of molecule.
solution).
v The entropy will decrease.
c 1 with E; 2 with D; 3 with A; 4 with B; 5 with C
vi The reaction is not likely to be spontaneous
d H2O (water) and C2H5OH (ethanol) are both (feasible) at room temperature considering
liquids but water has a greater amount of the system alone because the entropy
hydrogen bonding which means more order. change of the system is negative.
So it has a lower entropy. In addition, ethanol
has a greater variety of atoms and more b i The reactants are likely to have higher
atoms, both of which contribute to a larger entropy because chlorine is a gas and has
entropy. a high entropy. NaCl and Na are solids
and have low entropy. There are also two
NaCl and NaClO3 are both solids. NaClO3 has different substances on the left.
more atoms and a greater variety of atoms. So
it has a higher entropy. Br2 liquid has a lower ii Greater entropy on the left because the
entropy than the vapour because there is more iron(II) chloride and sodium hydroxide
order in a liquid and there are fewer ways of are both aqueous and the ions are free to
arranging the energy in a liquid than a vapour move. The iron(II) hydroxide on the right
where there are more quanta of energy. is solid so it has low entropy. This makes
it likely that the products have lower
HCl and HBr are both gases but HBr has entropy.
more electrons, so a greater degree of disorder

iii Oxygen gas is released which has high v Mg(NO3)2(s) → MgO(s) + 2NO2(g)
entropy and there are three molecules
on the right and only two on the left. It + 1 O2(g)
2
is likely that the products have greater 164.0 26.9 + (2 × 240.0) + 1 (205)
entropy. 2
∆S = +445.4 J K−1 mol−1
iv There are two gas molecules on the left
and only one on the right, so it is likely Exercise 23.3
that there is greater entropy on the left.
a i The equilibrium will be over to the left.
v There is one molecule of solid on the left
but three on the right, two of which are ii There is exact equilibrium.
gases with high entropy. So it is likely that
iii The reaction is unlikely to occur.
there is greater entropy on the right.
iv The equilibrium is to the right.
c Ice has very low entropy because the particles
are in fixed positions and only vibrate. b i C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l)
The particles are highly ordered. As the ∆Hr = −1367.3 kJ mol−1
temperature of the solid is increased there is a
small increase in entropy because the particles 160.7 (3 × 205) (2 × 213.6) (3 × 69.9)
vibrate more. The entropy increases to a ∆Ssystem = −138.8 J K−1 mol−1
greater extent on melting because the water
molecules begin to move randomly. ΔG = ΔH⦵ − TΔSsystem = −1 367 300 −
(298 × −138.8) = −1326 kJ mol−1
There is still some hydrogen bonding in the
liquid so the particles do not move completely ii SrCO3(s) → SrO(s) + CO2(g)
randomly. The entropy of the liquid water ΔHr = + 1418.6 kJ mol−1
increases slowly as temperature increases as
97.1 54.4 213.6
more and more hydrogen bonds are broken
and the particles move faster and faster. The ΔSsystem = + 170.9 J K−1 mol−1
energy is more spread out with increase in
temperature so the entropy increases. At the ΔG = ΔH⦵ − TΔSsystem = +1418600 −
boiling point, the entropy increase is very (298 × +170.9) = +1367.7 kJ mol−1
large because the attractive forces between the
iii 3Mg(s) + Fe2O3(s) → 3MgO(s) + 2Fe(s)
water molecules are broken and a vapour is
ΔHr = −980.9 kJ mol−1
formed where the molecules move freely and
randomly (very high entropy). (3 × 32.7) 87.4 (3 × 26.9) (2 × 27.3)
d i 2SO2(g) + O2(g) → 2SO3(g) ΔSsystem = −50.2 J K mol−1

−1
(2 × 248.1) + 205 (2 × 95.6) ΔG = ΔH⦵ − TΔSsystem = −980 900 −

∆S = −510 J K−1 mol−1 (298 × −50.2) = −965.9 kJ mol−1
ii H2O(g) + C(graphite) → H2(g) + CO(g) c i ∆Gr
Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g)
188.7 + 5.7 130.6 + 197.6
∆S = +133.8 J K−1 mol−1
∆G1 ∆G2
iii B2O3(s) + 3Mg(s) → 2B(s) + 3MgO(s)
2Fe(s) + 3C(s) + 3O2(g)
54.0 + (3 × 32.7) (2 × 5.9) + (3 × 26.9)
∆S = −59.6 J K−1 mol−1
ii Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)
iv SiO2(s) + 4HF(g) → SiF4(g) + 2H2O(l)
−742.2 (3 × − 137.2) 0 (3 × −394.4)
41.8 + (4 × 173.7) 282.4 + (2 × 69.9)
∆S = −314.4 JK−1 mol−1 ΔG = −29.4 kJ mol−1
iii It is spontaneous (feasible) since ΔG is
negative.

d i SiO2(s) + 4HF(g) → SiF4(g) + 2H2O(l) for the extraction of aluminium by

carbon. A lower temperature is required
−856.7 (4 × −273.2) − 1572.7 (2 × −69.9) for the zinc extraction so less energy is
ΔG = +237 kJ mol−1 required (in the extraction of zinc by
reduction with carbon, carbon burns
ii SrCO3(s) → SrO(s) + CO2(g) to carbon monoxide which is a better
−1140.4 −561.9 −394.4 reducing agent)
ΔG = +184.1 kJ mol−1 e i The value of ΔH ⦵ is small and positive.

The entropy change is large and positive
since a solid (low entropy) is being
Exercise 23.4 converted to a gas and liquid (high
a i ΔS ⦵system = ΣS ⦵products − ΣS ⦵reactants = entropy). In the equation
239.2 − 49.3 = +189.9 J mol−1 K−1 ΔG ⦵ = ΔH ⦵ − TΔS ⦵, the large positive
value of TΔS ⦵ (large negative value
ΔH ⦵ = −110.5 − (−348.3) = of −TΔS ⦵) may be greater than the small
+ 237.8 kJ mol−1 = + 237 800 J mol−1 positive value of ΔH ⦵ so ΔG ⦵ is negative
ΔG ⦵ = + 237 800 − (298 × 189.9) = and the reaction is feasible.
+ 181 209.8 J mol−1 = + 181.2 kJ mol−1 ii The value of ΔH ⦵ is large and negative.
ii ΔS ⦵system = + 21.8 J mol−1 K−1 The entropy change is small and negative.
In the equation ΔG ⦵ = ΔH ⦵ −TΔS ⦵, the
ΔH⦵ = +318 700 J mol−1
large negative value of ΔH ⦵ is much
ΔG ⦵ = +312.2 kJ mol−1 greater than the small value of TΔS ⦵
iii ΔS ⦵system = + 160.4 J mol−1 K−1 so ΔG ⦵ s negative and the reaction is
feasible.
ΔH ⦵ = +178 300 J mol−1
ΔG ⦵ = +103.5 kJ mol−1 iii The value of ΔH ⦵ is large and positive.
The entropy change is large and positive
iv ΔS ⦵system = −407.5 J mol−1 K−1 since a solid (low entropy) is being
ΔH ⦵ = − 583 200 J mol−1 converted to a gas and liquid (high
entropy). In the equation
ΔG ⦵ = −461.8 kJ mol−1
ΔG ⦵ = ΔH ⦵ −TΔS ⦵, the large positive
v ΔS ⦵system = + 581.4 J mol−1 K−1 value of TΔS ⦵ is unlikely compensate
ΔH ⦵ = +1344 200 J mol−1 large positive value of ΔH ⦵ because the
ΔG ⦵ = +1287.2 kJ mol−1 relative value of ΔH ⦵ (kJ mol−1) is larger
than the relative value of ΔS ⦵ (only in
b reaction iv (sulfur dioxide + oxygen forming J mol−1 K−1) so ΔG ⦵ positive and the
sulfur trioxide) because the value of ΔG ⦵ is reaction is not feasible.
negative.
f i E ⦵cell = + 0.15 V ΔG ⦵ = −nFE ⦵cell
c i Rearranging the equation to find T with = −2 × 96 500 × 0.15 = −28 950 J mol−1
ΔG ⦵ at 0 for the reaction to just become (−29.0 kJ mol−1). ΔG ⦵ is negative so
feasible. reaction is feasible.
ΔH ⦵ 237 800 ii E ⦵cell = −0.43 V ΔG ⦵ = −nFE ⦵cell
= T = 1252 K
ΔS ⦵system 189.9 = −2 × (96 500 × −0.43)
= + 82 990 J mol−1 (+ 83 kJ mol−1).
ii ΔH ⦵ 1344 200 ΔG ⦵ is positive so reaction is not feasible.
= T = 2312 K
ΔS ⦵system 581.4
iii E ⦵cell = + 0.26 V ΔG ⦵ = −nFE ⦵cell
d i the values assume that the enthalpy = −2 × 96 500 × 0.26 = −50 180 J mol−1
change and the entropy change do not (−50.2 kJ mol−1). ΔG ⦵ is negative so
vary with temperature (in fact they do). reaction is feasible.
ii It would take too much energy to
maintain the high temperatures required

Top line of Hess cycle correct [1]

Exam-style questions Rest of cycle correct with arrows in
Question 1 correct direction [1]
ii ∆G ⦵r = 2 × ∆G ⦵f[CO(g)] − ∆G ⦵f[TiO2 (s)]
a The number of possible arrangements of the
particles and their energy in a given system.[1] = (2 × −137.2) − (−884.5) [1]
b Sodium has low entropy because it is a solid. [1] ∆G ⦵
= +610.1 kJ mol
−1
[2]
r
Aqueous sodium hydroxide has a higher iii No it is not spontaneous because ∆G ⦵r is

entropy than water because there are positive. [1]
more particles. [1]
b Use of Gibbs equation:
Hydrogen has high entropy because it is a gas.[1] ΔG ⦵ = ΔH ⦵ −TΔS ⦵ [1]
The products have higher entropy than the At lower temperatures value of −TΔS ⦵ is not
reactants. [1] large enough to overcome the positive enthalpy
change of the reaction (and the value of ΔG ⦵
The higher the entropy, the greater the
still positive so the reaction is not feasible) [1]
stability of the system. [1]
At higher temperatures the increased value
c i Use of ΣSproducts − ΣSreactants
of T mean that the value of −TΔS ⦵ is large
= (33.2 + 213.6) − (42.6 + 197.6) [1] enough to overcome the positive enthalpy
= + 6.6 J mol−1 K−1 [1] change of the reaction so the value of ΔG ⦵
ii Use of Hess’s Law ∆H ⦵r negative so reaction is feasible. [1]
= (−393.5) − (−110.5 + −157.3) [1] c i E⦵ = −0.09 V [1]
cell
= −125.7 kJ mol−1 [1]
Use of ΔG ⦵ = −nFE ⦵
cell
[1]
iii Use of Gibbs equation: ΔG ⦵
= ΔH ⦵ −TΔS ⦵ [1] −2 × 96 500 × (−0.09) = + 17 370 J mol−1
(+ 17.4 kJ mol−1) [1]
conversion of kJ to joules for ΔH ⦵
and 200 °C to 473K for T [1] ii Position of equilibrium so far over to the
left that the reaction is not feasible [1]
ΔG ⦵ = −125 700 − 473 (+6.6)
= −128 821.8 J mol−1 / −128.8 kJ mol−1 [1] Value of ΔG ⦵ positive (so not feasible) [1]
iv Reaction feasible because value of value of E ⦵
cell
negative (so not feasible) [1]
ΔG ⦵ is negative [1]
[Total: 15]
v The values of ΔH ⦵ or S ⦵ does not
change with temperature [1] Question 3
[Total: 15]
a 2Rb(s) + S(s) → Rb2S(s)
∆H ⦵r = + 360.7 kJ mol−1 (at 298 K)
Question 2
(2 × 76.8) + 32.6 → 134.0 [1]
a i
∆Ssystem = −52.2 J K−1 mol−1 [1]
∆Gr
TiO2(s) + 2C(g) Ti(s) + 2CO(g) b i Use of ΣSproducts − ΣSreactants
= (121.5 + 56.5) − (95.9) [1]
∆G1 ∆G2
= + 82.1 J mol−1 K−1 [1]
⦵ ⦵
Ti(s) + 2C(s) + O2(g) ii Use of Gibbs equation: ΔG = ΔH
−TΔS ⦵ [1]

conversion of kJ to joules for ΔH ⦵ and The entropy increase on going into

25 °C to 298 K for T [1] solution is large and positive/TΔS ⦵ is
large and positive. [1]
ΔG ⦵ = + 9 500 − 298 (+ 82.1) = −14 965.8 J
mol−1/−14.97 kJ mol−1 [1] This value is greater than the value of
ΔH ⦵ so ΔG ⦵ is negative. [1]
iii Solid rubidium chloride has a very low
entropy because there are few possible Negative value of ΔG ⦵ mean reaction is
arrangements of the particles/energy. [1] feasible. [1]
When in solution the particles move about [Total: 12]
randomly and there are many more ways
of arranging the particles so entropy
higher. [1]

may be different.
Workbook answers
Chapter 24
Exercise 24.1
a variable oxidation state; catalytic activity; have iii There is a greater stability in a half full d
coloured ions; form complex ions level than in a full 4s level.
b Melting point: iron = 1808 K; calcium = 1112 K iv Sc only forms Sc3+ ions, so there are no d
(transition elements have higher melting points) electrons present. Zn only forms Zn2+ ions,
so Zn2+ ions have a full 3d shell (not a d
Density: iron = 7.86 g cm−3; calcium shell deficient in (electrons)).
1.54 g cm−3 (transition elements have higher
densities) d i 1s22s22p63s23p63d6
Metallic radius: calcium = 0.197 nm; iron ii 1s22s22p63s23p63d3
= 0.126 nm (transition elements have lower
radius for the same Period) iii 1s22s22p63s23p63d7
Boiling point: calcium 1380 K; iron = 3023 K iv 1s22s22p63s23p63d10

(transition elements have higher boiling e i 1 with H; 2 with F; 3 with B; 4 with A; 5
points) with G; 6 with C; 7 with D; 8 with E
Ionic radius (X2+): iron = 0.061 nm; calcium = ii Colour in transition elements complexes
0.100 nm (transition elements have lower ionic is due to d-orbital splitting in the presence
radius for the same Period) of ligands. The chiral centre must have an
First ionisation energy: iron 759 kJ mol−1; unpaired d-electron for this to occur readily.
calcium = 590 kJ mol−1 (in the same period The colour is due to the energy absorbed
transition elements have higher first ionisation when a d-electron is excited from the lower
energy) to the higher split d-orbitals. A scandium
ion, Sc3+, has no d-orbitals so there is no
Electrical conductivity: calcium = 2.82 × colour. A zinc ion, Zn2+, has a complete
107 S m−1; iron = 9.04 × 106 S m−1 (many d-subshell and so an excited electron will
transition elements have lower conductivity) have to go into an energy sublevel which is
higher. This requires too much energy. So
c i Co = 1s22s22p63s23p63d74s2 zinc compounds are colourless.
Ni = 1s22s22p63s23p63d84s2
Exercise 24.2
Cu = 1s22s22p63s23p63d104s1
a i 3Cr3+ + 3e− → 3Cr2+
ii 3d
ii VO2+ + 2H+ + e− → V3+ + H2O
4s
iii 2Ni → 2Ni2+ + 4e−
3p iv Fe2+ → Fe3+ + e−
v MnO4− + 8H+ + 5e− → Mn2+ + 4H2O
3s
vi CrO42− + 4H2O + 3e− → Cr(OH)3 + 5OH−
As shown in diagram or with 4s above 3d

b i MnO4− + 8H+ + 5Fe2+ → d 4− 2−

CN
Mn2+ + 4H2O + 5Fe3+ NC CN + Cl Cl
Fe H3N Ag NH3 Pt
ii 2VO2+ + 4H+ + Ni → 2V3+ + 2H2O + Ni2+
NC CN CN Cl Cl
iii 2Cr2+ + Ni2+ → 2Cr3+ + Ni
iv Cu2+ + 2I− → I2 + Cu i ii iii
v 2MnO4− + 5C2O42− + 16H+ → e i Bidentate, because it has a lone pair of

2Mn2+ + 10CO2 + 8H2O electrons on each N atom which are able
to form dative covalent bonds with the
c i The more positive the value of E ⦵, the transition element ion.
easier it is for the oxidised form to accept
electrons. The Cr2O72− ions have a more ii en
positive value of E ⦵, so are better at Cl
accepting electrons than Fe3+. Fe3+ ions are
better at releasing electrons. Cr
ii Cr2O72−(aq) + 14H+(aq) + 6Fe2+(aq) → Cl

2Cr3+(aq) + 6Fe3+(aq) + 7H2O(l) en
iii Cr +6 to +3, Fe +2 to +3 iii Cl
iv If dichromate is used, both the colours
of the dichromate and the Cr3+ ions are
en Cr en
intense so it is difficult to see a distinct
end point (the end would be a ‘muddy’
colour which is not clear). Potassium
manganate is purple but Mn2+ ions are Cl
very pale pink (essentially colourless) and
f i Bidentate, because it has lone pairs of
iron(III) ions are very light yellow, so the
electrons on each O atom which are able
end point is more easily seen.
to form dative covalent bonds with the
d Any E ⦵ values less positive than 1.52 V will be transition element ion.
oxidised (Mn2+, I− and Cu).
ii Bidentate, because it has lone pairs of
electrons on the OH oxygen atom and the
Exercise 24.3 C─O− oxygen atom which are able to form
a i ion; lone; ligand dative covalent bonds with the transition
element ion.
ii complex; transition; ligands
iii Hexadentate because it has lone pairs
iii dative covalent; co-ordination of electrons on each C─O− oxygen atom
and on each N which are able to form
b i A = nitrile / cyanide B = chloride
dative covalent bonds with the transition
ii A = 4; B = 4 element ion.
iii A = square planar; B = tetrahedral g F more electronegative than O so there is a

dipole with the δ− end towards the 3 F atoms
iv A = +2; B = +2 and the δ+ end towards the H2O
v A = [Ni(CN)4]2−; B = [CoCl4]2−
vi A 90° B 109.5°
c i +2 ii +1 iii +3 iv +6 v +3

Exercise 24.4 c i Co-ordinate / dative covalent [1]
a i [[Co(NH3 )6 (aq)]2 + ][(H2O)(1) ]6 ii Lone pairs of electrons [1]

[[Co(H2O)6 (aq)]2 + ][NH3 (aq)]6 iii 90° [1]
no units
The structure shown is planar so this
ii [[CoCl 4 )2 − (aq)][(H2O)(l)]6 minimises electron-pair–electron-pair
[[Co(H2O)6 ]2 + (aq)][Cl − (aq)]4 repulsion. [1]
−6
mol dm
2
iv Cl NH3 [1]
iii [[Cu(EDTA)]2 − (aq)][H2 O(l)]6 Pt
[[Cu(H2 O)6 ]2 + (aq)][(EDTA)4− ]
mol5 dm−15 H3N Cl
[Total: 9]
b i Adding ammonia: goes from green to
light violet because the stability constant Question 2
of the ammonia complex is greater so the
equilibrium goes to the right. a Ligand: molecule / ion with (one or more) lone
pair of electrons forming bond with transition
Adding water: no effect because the edta element ion. [1]
complex has such a high Kstab value that
even if excess water is added, it will not Bidentate: (ligand) forming two bonds with a
shift the equilibrium significantly. transition element ion. [1]
Adding EDTA: goes from light violet The bonds are co-ordinate / dative covalent.[1]
to blue because the stability constant of
b i [Cu(H2O)6]2+(aq) + 2(en) ⇌
the EDTA complex is greater than the
[Cu(en)2(H2O)2]2+(aq) + 4H2O(l)
ammonia complex so the equilibrium goes
to the right. [Cu(en)2(H2O)2]2+(aq) correct [1]
ii [Ni(H2O)6]2+(aq) + 6NH3(aq) ⇌ Rest of equation correct [1]
[Ni(NH3)6]2+(aq) + 6H2O(aq)
ii [[Cu(en)2 (H2O)2 ]2 + (aq)][H2 O(l)]4 [1]
iii ALLOW: any value between 9 and 18. [[Cu(H2O)6 ]2 + (aq)][(en)]2
mol2 dm−6 [1]
Exam-style questions iii en because it has a higher stability
constant [1]
Question 1
[Total: 8]
a Any three of:
Pt has:
Question 3
a The more positive the value of E ⦵, the easier it
higher boiling or melting point
is for the oxidised form to accept electrons. [1]
smaller atomic or ionic radius
The Fe3+ ions have a more positive value than
higher density Zn2+ ions so more readily oxidised [1]
higher 1st ionisation energy Zn better at releasing electrons than Fe2+

so Zn reduces Fe3+ / so Fe3+ oxidises Zn [1]
lower electrical conductivity [3]
b i +3 [1]
ALLOW: reverse argument for Ba
ii octahedral [1]
b The ions have electron configuration with an
incomplete d electron shell [1]

c i 2Fe3+ + 2I− → 2Fe2+ + I2 iv Adding ammonia has no / little effect [1]

Correct formulae [1] because the edta complex has such a high
Kstab value that a small amount added will
correct balance [1]
not shift the equilibrium significantly. [1]
ii A complex is formed with the 2−
c Cl
F / FeF63− formed [1]
The stability constant of the complex /
F is greater than that with water [1]
Co
all the iron(III) ions are involved in
Cl
complex formation so cannot react
with iodine [1] Cl
Cl
d i KMnO4 is pink / magenta and ethanedioic
acid is colourless [1]
at the end point there is a slight Tetrahedral structure drawn with Co in
permanent pink colour [1] centre [1]
18.6 Rest of structure drawn correctly (wedges
ii moles of MnO4− = × 0.02
1000 and dashed lines) [1]
= 3.72 × 10 mol
−4
[1]
moles ethanedioic acid = 109.5° [1]
2.5 × 3.72 × 10−4 mol = 9.30 × 10−4 mol [1] d i atoms / orbitals are at the same energy
concentration of ethanedioic acid level [1]
1000
= 20 × 9.30 × 10−4 = 0.0465 mol dm−3 [1] ii see diagram TG 4d ii [1]
[Total: 15] iii tetrahedral: 3 orbitals higher energy, 2
orbitals lower energy [1]
Question 4 octahedral: 2 orbitals higher energy, 3
a i 1s 2s 2p 3s 3p 3d 4s
2 2 6 2 6 7 2
[1] orbitals lower energy [1]
ii 1s22s22p63s23p63d6 [1] iv electrons in d energy sub-level absorb light

energy of particular wavelength [1]
b i Adding ammonia: colour goes from pink
to green [1] and move to a higher d energy non-
degenerate sub-level [1]
because the stability constant of the
ammonia complex is greater so the wavelength / frequency of absorbed light
equilibrium shifted to the right. [1] depends on energy difference between
non-degenerate sub-levels, ∆E [1]
ii [Co(H2O)6]2+(aq) + 6NH3(aq) ⇌
[Co(NH3)6]2+(aq) + 6H2O(l) light of complementary wavelength /
frequency transmitted / reflected [1]
Correct structure of [Co(NH3)6]2+(aq) [1]
∆E depends on types of ligand attached to
rest of equation correct [1] central (transition element) ion / atom [1]
iii (Ligand) forming 6 bonds with a [Total: 22]
transition element ion [1]
The bonds are co-ordinate / dative
covalent [1]

may be different.
Workbook answers
Chapter 25
Exercise 25.1
a Each carbon atom in the benzene ring forms Exercise 25.2
sp2 hybrid orbitals, sharing one pair of
electrons with each of the two neighbouring a i δ+ δ−
carbon atoms and one pair with a hydrogen Br Br FeBr3 Br+ + [FeBr4]−
atom. These are sigma bonds. The remaining p
electron from each carbon atom contributes to ii Iron is electropositive and bromine in
a pi bond by sideways overlap of p type atomic iron(III) bromide is electronegative. The
orbitals. These form two rings of delocalised positive charge on the iron attracts the
electrons above and below the benzene ring. electrons in the Br−Br bond towards it.
To allow maximum overlap of electrons, the iii and iv
benzene ring must be planar. The bond angles
around each carbon atom are 120°. H Br Br
b The lengths of each carbon–carbon bond in

Br+ + + HBr
benzene are the same, the bond length being
intermediate between that of a C─C and C═C stage B stage C Product
bond in alkanes and alkenes.
Benzene does not react with bromine water, so v The attacking reagent is deficient in an
it does not have a C═C double bond. electron pair and receives an electron pair
from the electrons in the benzene ring. Br+
c i ii iii is the electrophile.
OH
CH3 CH2Cl
vi Aluminium chloride. AlCl3 is a polar
CH3 molecule with δ+ on the Al and δ− on the
Cl. The polar AlCl3 with draws electrons
NO2 from the bond in the Cl2 molecule so that
Cl+ and AlCl4− are formed. The Cl+ acts
iv v vi as an electrophile and is attracted to the pi
OH Br electrons in the benzene ring.
CH3
Br Br
vii 2-chloromethylbenzene and
4-chloromethylbenzene
NO2
Br C2H5 b i Sulfuric acid. It donates a hydrogen ion to
the nitric acid.
d i ii iii
H H ii NO2+ is deficient in an electron pair
H O H
H C C H
O
and receives an electron pair from the
H
O H C electrons in the benzene ring.
H C H H C N H C H
C C C C C C
H
iii H NO2
H
C C C C C C
H C H H C H H C C
H
H H H
H +

iv In the intermediate there are 4 pi bonding from the electrons in the benzene ring.
+
electrons and the positive charge on the CH2CH3 is the electrophile.
ring is spread over 5 atoms. The C─H
vi C3H7COCl
bond breaks heterolytically and both
electrons from this ond go to complete pi b i Type: substitution; mechanism: free radical
bonded system. The H+ ion is released.
ii Initiation by light splitting the chlorine
Exercise 25.3 molecule by homolytic fission to form two
Cl• free radicals.
a i and ii
H c i C6H5−CH3 + 3[O] → C6H5 −COOH + H2O
δ+ δ− +
H3C C Cl AlCl3 CH3CH2 + [AlCl4]−
ii Benzoic acid
H
Stage A CH2CH3 iii Alkaline solution of potassium
H CH2CH3
+
manganate(VII) then acidify
CH2CH3 + + [AlCl4]− + HCl + AlCl3
iv Reflux + alkaline conditions
Stage B Stage C Products
d i C6H5−CH3 + 3H2 → C6H11−CH3
iii Ethylbenzene
ii Methylcyclohexane
iv HCl and AlCl3
iii Catalyst
v The attacking reagent is deficient in an
electron pair and receives an electron pair iv 150 °C / high temperature
Exercise 25.4
a either add water to benzendiazonium chloride, warm / heat sodium hydroxide with chlorobenzene to
form sodium phenoxide then add acid
b
Reaction Reaction conditions Reaction conditions Comparison of extent of
benzene with phenol reaction
bromination liquid bromine bromine water; benzene: need excess Br2 to get
halogen carrier e.g. room temperature 2 Br atoms substituted phenol: 3
iron(III) bromide / Br atoms easily substituted
Fe + Bromine
nitration concentrated nitric dilute nitric acid; benzene: second substitution
and sulfuric acid; room temperature quite difficult phenol: second
reflux at 55 °C substitution relatively easy; third
substitution needs concentrated
acid
substitution of fuming sulfuric acid heat with H2SO4 at benzene: second substitution
SO3H group reflux for 8 hrs / a 100 °C difficult phenol: quite difficult to
long time substitute a second SO3H group
substitution of does not work NaNO2, H2SO4,
NO group because if heated (electrophile only
electrophile stable at low
decomposes temperatures)
c The −OH group in phenol is an activating partly donated to the carbon atom next to it.
group. This means that the reaction with The intermediate formed when an electrophile
electrophiles is much more rapid than with is substituted has partial positive charge in
benzene. The oxygen atom in the −OH group various parts of the ring. The reduction in the
in phenol has an electron pair that can be positive charge by the donation of electrons

means that the electron density in various

parts of the ring increases. This makes the aryl Exam-style questions
ring more open to attack by electron-deficient
electrophiles. Question 1
d i 2C6H5OH + 2Na → 2C6H5ONa + H2 a NO2+ [1]
ii C6H5OH + KOH → C6H5OK + H2O b Substitution [1]
iii C6H5O−Na+ + C10H7N≡N+ Cl− → Electrophilic [1]
C10H7N=NC6H4OH + NaCl
c The C−H bond breaks [1]
e i stronger, higher
heterolytically. [1]
ii p, oxygen, reduces, negative, more
Both electrons from this bond go to
iii delocalisation, ions complete pi bonded system / go into the
benzene ring. [1]
iv weaker, sodium carbonate
H+ ion is released [1]
d It makes the ring more reactive [1]
Exercise 25.5
to electrophiles [1]
a i ii iii
NH2 CH3 There is a higher electron density in the
COOH
NO2 benzene ring [1]
Cl e i Light [1]
Br Br
NO2 Methylbenzene should be boiling / hot [1]
iv ii Free radical [1]
Cl Cl
NO2 f Methyl benzene: add concentrated nitric acid
or
and concentrated sulfuric acid [1]
reflux [1]
NO2
2-nitromethylbenzene / 2-nitromethylbenzene
v vi vii [1]
OH CN CH2CH3
Br Br Cl Phenol: add dilute nitric acid [1]
Cl Cl room temperature [1]
Br Cl 2-nitromethylbenzene / 2-nitromethylbenzene
[1]
b i Oxygen is more electronegative than S.
So the molecule is dipolar with S being OR
δ+. The δ+ end of the molecule is electron
deficient so it can act as an electrophile. Phenol: add concentrated nitric acid [1]
ii An electron pair for the benzene ring is room temperature [1]

donated to form a bond between a carbon 2, 4, 6-trinitromethylbenzene [1]
atom and the S atom. A further movement
of an electron pair from one of the S═O [Total: 19]
bonds causes the O to ionise: C─SO2─O−
iii In the 3- (and 5-) positions.
c i chlorine, uv light, heat
ii free radical (substitution)

Question 2 d i alkaline solution / aqueous sodium

hydroxide [1]
a i C6H5OH + H2O ⇌ C6H5O− + H3O+ [2]
low temperature / ice bath / 5-10oC [1]
(1 mark if → instead of ⇌ / C6H5OH ⇌
C6H5O− + H+) ii [1]
N=N OH
ii It reduces the negative charge density on
the O− [1]
so hydrogen ion is not so readily accepted.
[1] [Total: 19]
−
No stabilisation in ethoxide ion / C2H5O
ion (so H+ ion easily recombines) [1] Question 3
iii 2C6H5OH + 2Na ⇌ 2C6H5O− + Na+ + H2 a The substitution [1]
Correct formulae [1] of an alkyl group into a compound. [1]
correct balance [1] b Substitution [1]
b i 2,4,6-tribromophenol [1] Electrophilic [1]
ii The −OH group is an activating group. [1] c Dry AlCl3 [1]
It causes the benzene ring in phenol to 2-chlorobutane [1]
have a greater electron density
Reflux (at 50 °C) [1]
(in certain places). [1]
d C10H14 [1]
So pair of electrons donated to
electrophile more readily. [1] e i C2H5COCl [1]
c i Br2 liquid [1] ii ketone [1]
Fe / FeBr3 / any suitable named halogen f i Ni catalyst [1]
carrier [1]
150 °C / high temperature [1]
ii Br+ [1]
ii Ethylcyclohexane [1]
Electrophile is deficient in electron
pair. [1] [Total: 13]
Electron pair moves from benzene ring to

form bond with Br. [1]

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CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: WORKBOOK

c i 13 protons, 13 electrons, 14 neutrons There are 3 electrons, which are negatively

1 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020

Question 2 c i Cobalt-59 because it has 32 neutrons

b Relative atomic mass depends on the iii Co3+ [1]

2 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020

1 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020

Question 1 b Argon [1]

2 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020

Question 3 correct spin [1]

a The energy needed to remove one electron  [Total: 18]

3 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020

iii nitrate ii Ratio of moles = Sn = 1, Cl = 2, SnCl4 = 1

iv carbonate iii Equation: Sn + 2Cl2 → SnCl4

1 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020

Exercise 3.4 Exercise 3.6

2 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020

c Balanced equation: CaCO3(s) + 2HCl(aq) → e i C2H535Cl = 64; C2H537Cl = 66

iv 17 Repeat titration and take the best concurrent

iii The relative molecular mass = 3.125 × 10−4 mol [1]

d n = 100 × 3.8 = 7 carbon atoms Mol HCl = 0.05 × 12.5

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Stoichiometric ratio is 2 mol HCl to 1 mol Question 3

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H H V - shaped Triangular pyramidal

V - shaped Triangular pyramidal

H e i Water is hydrogen bonded and pentane

H ± H b i Electronegativity increases across a period.

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As you go down the group the group the

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iii Hydrogen attached to very electronegative c H H

Only temporary dipole-induced dipole forces Mg O

Correct electron configuration  [1] Structure completely correct [3]

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ii Lone pair–bond pair repulsion greater

Idea of the lone pair–lone pair ii linear [1]

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b i Giant; covalent; diamond; four; between each carbon and oxygen

c 1 with D; 2 with C; 3 with B; 4 with E; Metals conduct electricity because the

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a pV = nRT so p = nRT/V Diamond is a giant molecular / giant

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Exam-style questions b i It has a lot of strong (covalent) bonds /

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b The higher the temperature, the greater the nRT

Correct temperature (363) and volume  [Total: 14]

n = 1.1 × 10 × 8.5 × 10 = 3.1 × 10 −3 mol 

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Reaction pathway iii MgCO3(s) → MgO(s) + CO2(g)

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b i Mass of fuel burned = 92.33 − 92.19 Exercise 6.5

c Heat losses from the walls of the can / from = −1155.7 kJ

∆H⦵c[C6H13OH(g)] = −3581 kJ mol−1 ∆H⦵1 + ∆H⦵r = ∆H⦵2

b i Bonds broken Bonds formed /

4 × (C−H) = 4 × 410 4 × (O−H) = 4 × 465

3 × (O═O) = 3 × 496 4CO2(g) + 5H2O(I) (+6 12 O2)

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4 × ∆H⦵c [C(graphite)] + 5 × ∆H⦵c[H2(g)] = ∆H⦵r = ∆H⦵f [Ca(OH)2(s)] − (∆H⦵f [CaO(s)]

mass of solution × specific heat capacity ×

iv Moles magnesium nitrate 20.0 × 1.0 =

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ii Exact bond energies are for particular ∆H⦵r = ∆H⦵at[C(graphite)] + (4 × ∆H⦵at

H2(g) + Cl2(g) Measure temperature of acid and alkali

AS & A Level Chemistry Workbook Answers

AS & A Level Chemistry Workbook Answers

b Relative atomic mass depends on the iii Co3+ [1]

Question 1 b Argon [1]

Question 3 correct spin [1]

a The energy needed to remove one electron [Total: 18]

iii The relative molecular mass = 3.125 × 10−4 mol [1]

Correct electron configuration [1] Structure completely correct [3]

Correct temperature (363) and volume [Total: 14]

n = 1.1 × 10 × 8.5 × 10 = 3.1 × 10 −3 mol

Reaction pathway Stir reaction mixture [1]

v MnO4− + 5Cr2+ + 8H+ → Correct symbols [1]

e i +2 to +4 = +2 [1] Question 3

[Total: 14] b Hydrogen sulfide because it has decreased

200 atm pressure (allow ±20 atm / 2000 kPa) [1] 1

Record volume of gas in burette [1] C3H8 EA ∆Hf

at particular times. [1]

Question 3 b i Rate decreases [1]

ii Nitrogen: N2O5 [1] so the shielding is approximately