CHEMISTRY FOR THE IB DIPLOMA: 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 7 a Properties that do not involve chemical
reactions, such as melting point, boiling
1 118 point, hardness, and density.
2 a Any metal or C or Si. b How something reacts in a
chemical reaction.
b Any of: He, Ne, Ar, Kr, Xe, Rn.
8 It contains only one chemical substance.
(Sulfur and phosphorus are not correct as,
strictly, these are S8 and P4.) 9 They are not chemically bonded to each other.
c Any of: H2, N2, O2, F2, Cl2, Br2, I2, 10 Elements: iron, chlorine gas.
possibly At2.
Mixtures: air, sodium chloride solution.
3 a He: atom
Compounds: water, sodium chloride crystals,
b O2: molecule carbon dioxide gas.
c H2O: molecule 11 homogeneous
d C: atom 12 heterogeneous
4 a He: element 13 When solids are mixed, it is impossible to
have a perfectly uniform mixture, as there are
b O2: element distinct particles of sodium chloride and sand.
c H2O: compound 14 Flour is not soluble, so there is more than
d C: element one phase.

5 In the way that everything is made of atoms, 15 physical processes

then it is true to say that elements are made 16 A 2
of atoms, but the statement suggests that an
element is made up of individual atoms and B 6
this is not true, as elements can also be made
C 4
of molecules such as oxygen, which contains
O2 molecules. D 1
Not all compounds are made of molecules, E 3
as lots of compounds have giant structures,
such as sodium chloride, which is ionic, or F 5
silicon dioxide, which has a covalent network G 7
structure. These giant structures are not
molecules.
6 The components in the alloy can be mixed in
varying proportions.

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Exercise 1.2
1 Description Solids Liquids Gases
diagram showing the
arrangement of
the particles

relative distance of touching/close touching/close not touching/far apart

the particles from together together
one another
relative energy of lowest higher than that highest
the particles of solids but lower
than gases
movement of particles particles only vibrate particles move freely particles move freely
in their fixed positions around within the around to fill the
liquid; they move container; they move
more slowly than in more quickly than in
a gas a liquid
relative force of strongest weaker than in solids weakest; ideal gases
attraction between are assumed to have
the particles no forces of attraction
between the particles

2 Movement of particles. As the particles in a 5 Kelvin

solid are unable to move, solids have a fixed
6 The lowest temperature possible.
shape. In liquids and gases, the particles can
move freely, so both liquids and gases can flow 7
Celsius scale Kelvin scale
and take up the shape of the container.
0 273
3 Relative force of attraction between the
particles. The weak forces of attraction 100 373
between the particles in a liquid keeps 40 313
the particles close together, and so, a –199 74
liquid occupies the bottom of a container.
946 1219
As there are no forces of attraction between
the particles in gases, gases occupy the whole –270 3
of a container rather than just the bottom 227 500
of it.
8 1 K = 1°C so temperature change is the same
4 a The particles in a solid cannot move in both kelvin and in °C.
unless an external force is applied; they
occupy a fixed position. The particles in Exercise 1.3
liquids and gases are in constant motion;
1 a No: the gas will contain particles with
although this is not visible, it can be
a range of different kinetic energies.
demonstrated, as liquids and gases can
The distribution is shown by a Maxwell–
both diffuse.
Boltzmann distribution curve.
b Powders flow because, strictly, a powder
b No: the speed of a particle is related
is a mixture of a solid (the tiny particles)
to its kinetic energy (kinetic energy
and a gas (normally air) between the 1
particles. When poured, the air flows, (KE) = mv2). As the particles have
2
carrying the tiny solid particles with it. different energies, then they must
have different speeds.

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2 a The average kinetic energy is the same for both gases, as the temperature is the same.
b Average speed of helium particles > average speed of nitrogen particles, as helium particles
1
have a lower mass and KE = mv2.
2
3 a increases
b increases
c Increases, as the maximum on a Boltzmann distribution curve moves to the right at
higher temperatures.
d Decreases, as the maximum on a Boltzmann distribution curve is lower at higher temperatures.

Exercise 1.4
1 Evaporation can happen at any temperature above the melting point.
2 Exothermic: condensing, freezing, deposition.
Endothermic: melting, evaporation, boiling, sublimation.
3 melting point
4 boiling point
5 a Change of state from solid to gas without passing through a liquid phase.
b deposition
6
Substance Melting Boiling State at State at State at
point/°C point/°C –50 °C 115 °C 245K
A 15 125 solid liquid solid
B 253 578 solid solid solid
C –83 78 liquid gas liquid
D –169 –87 gas gas gas

7 a i solid: E–F
ii liquid: C–D
iii gas: A–B
iv freezing: D–E
v condensing: B–C
vi melting point = 150 °C
vii boiling point = 220 °C
b As the temperature falls, the particles have less energy and move more slowly. As the substance
changes state, forces of attraction are formed between the particles. These forces of attraction
are strong enough to hold the particles together. The formation of these forces of attraction is
exothermic and heat energy is released. This heat energy maintains the temperature, so it no longer
falls but remains constant until the substance has all changed state.

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Exam-style questions 10 a filtration [1]

1 D b homogeneous [1]

2 D c I2 = (aq) [1]

3 C H2O = (l) [1]

4 A d Solvent extraction or use a

separating funnel. [1]
5 B
Shake with a suitable non-aqueous
6 D solvent. [1]
7 A Allow to stand then separate
the layers. [1]
8 D
11 a iii, iv, v, ii, i
9 a i liquid [1]
all correct  [3]
ii solid [1]
three correct  [2]
iii liquid [1]
two correct  [1]
b Cooling curve for ammonia
b A and C  [1]
0
–10 c They are pure. [1]
gas
Temperature/°C

–20
–30 condensing
–40
liquid
–50

Time

axis labelled  [1]

graph goes downward (i.e. a cooling
curve and not a heating curve) [1]
flat section  [1]
flat section at –33 °C [1]

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Chapter 2
Exercise 2.1
1
Sub-atomic particle Relative mass Relative charge Location of the particle in the atom
proton 1 +1 centre or nucleus
neutron 1 0 centre or nucleus
electron 5 × 10−4 −1 outside of the nucleus

2
Element Atomic number (Z) Mass number (A) Number of Number of Number of
protons neutrons electrons
phosphorus 15 31 15 16 15
strontium 38 88 38 50 38
lead 82 207 82 125 82
bromine 35 79 35 44 35
tungsten 74 183 74 109 74

3
Formula Atomic number (Z) Mass number (A) Number of Number of Number of
protons neutrons electrons
Na+ 11 23 11 12 10
O2− 8 16 8 8 10
Cu+ 29 64 29 35 28
Fe2+ 26 56 26 30 24
Ti2+ 22 46 22 24 20

Exercise 2.2 3
Nuclear Number Number Number
symbol of of of
1 Isotopes are atoms with the same number of
protons neutrons electrons
protons but different numbers of neutrons.
79
2 Isotopes are atoms with the same atomic 35 Br 35 44 35
number but a different mass number. 81
35 46 35
35 Br
81
35 Br− 35 46 36
64
29 Cu2+ 29 35 27
23
11 Na+ 11 12 10
19 −
9 F 9 10 10
16
8 O2− 8 8 10

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4 Electrons. Chemical properties depend on the number and arrangement of the electrons in an atom.
5 Weighted average means that the average is calculated to take into account the different abundances
(proportions) of each isotope in a sample.
(98.93 × 12) + (1.07 × 13)
6 a carbon = = 12.0107 = 12.01 (4 sig figs)
100
(0.3365 × 36) + (0.0632 × 38) + (99.6003 × 40)
b argon = = 39.99
100
7 Using the formula
relative atomic mass – mass number of lighter isotope
% of heavier isotope = × 100
difference in the mass numbers of two isotopes
35.45 − 35
× 100 = 22.5
37 − 35
so 35Cl = 77.5 % and 37Cl = 22.5 %.
8 a Peak A: 63Cu+ and peak B: 65Cu+
(63 × 5.2) + (65 × 2.3)
b Ar(Cu) = = 63.6
5.2 + 2.3

Exam-style questions
1 B b i All have the same number (8)
of protons and (8) electrons. [1]
2 A
They have different numbers
3 B of neutrons/16O has 8, 17O has
4 D 9 and 18O has 10. [1]

5 A ii isotopes [1]

6 A (99.76 × 16) + (0.04 × 17) + (0.20 × 18)

c
 100 [1]
7 C
8 A = 16.00 (2 decimal places) [1]
9 a mass number = number of protons 10 D
+ number of neutrons [1]
Relative atomic mass is the weighted
average mass [1] of the naturally
occurring isotopes an atom of
1
an element, relative to th the mass
12
of an atom of carbon-12. [1]

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Chapter 3
Exercise 3.1 4 A region of space in which there is a high
probability of finding an electron.
1 As wavelength increases, frequency decreases
5
(or the reverse).
Sub-level Number Maximum Maximum
2 As wavelength increases, energy decreases (or
of number of number of
the reverse).
orbitals electrons in electrons
3 violet each orbital in the
sub-level
Exercise 3.2 s 1 2 2
1 One which shows all possible wavelengths/ p 3 2 6
frequencies of light.
d 5 2 10
2 One in which only certain wavelengths/
frequencies of light are present. f 7 2 14

3 Emission spectra are unique to each element. 6 s<p<d

4 Heating it/doing a flame test. 7 a 1s2 2s2 2p6 3s2 3p5
5 Lines show that there are jumps/gaps between b [Ne] 3s2 3p5
energy levels. If an electron could have any
amount of energy, then a continuous spectrum 8 4s sub-level is of lower energy than 3d
would be produced. 9 a carbon: 1s2 2s2 2p2
6 An electron falling to different energy levels. b calcium: 1s2 2s2 2p6 3s2 3p6 4s2
7 Line at 410.2 nm: 6 2 c arsenic: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p3
Line at 434.0 nm: 5 2 d chromium: 1s2 2s2 2p6 3s2 3p6 4s1 3d5
Line at 486.1 nm: 4 2
10 copper
Line at 656.3 nm: 3 2
11 period number = highest occupied main
8 Lines get closer together as the gap between energy level
different energy levels is not equal.
12 s block, number of outer-shell electrons
9 a convergence = group number
b The point beyond which the electron can p block, number of outer-shell electrons
have any energy, and so, is free from the = group number – 10
influence of the nucleus.
d block, number of outer-shell electrons
= group number
Exercise 3.3
13 a A = s block
1 2n2
B = d block
2 1st = 2
C = p block
2nd = 8
D = f block
3rd = 18
b block = highest energy sub-level that
4th = 32 is filled
3 s, p, d and f 14 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p2
15 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5

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Exercise 3.4 13
1s 2s 2px 2py 2pz
1 Four (s, p, d and f). a
2 b
c

3 14 4s electrons are lost before 3d

15 a V: 1s2 2s2 2p6 3s2 3p6 4s2 3d2
V2+: 1s2 2s2 2p6 3s2 3p6 3d2
b Fe: 1s2 2s2 2p6 3s2 3p6 4s2 3d6
Fe2+: 1s2 2s2 2p6 3s2 3p6 3d6
c Cr: 1s2 2s2 2p6 3s2 3p6 4s1 3d5
Cr3+: 1s2 2s2 2p6 3s2 3p6 3d3
4 Orientated at 90° to each other.
d Cu: 1s2 2s2 2p6 3s2 3p6 4s1 3d10
5 five
Cu2+: 1s2 2s2 2p6 3s2 3p6 3d9
6 seven
7 Of equal energy. Exercise 3.5
8 Using upward and downward facing arrows. 1 The energy required to completely remove one
electron from each atom in a mole of gaseous
9 111 (One electron in each orbital, all having atoms to form a mole of gaseous ions each
the same spin/arrows point the same way.) with a +1 charge.
10 a Nitrogen 2 Cl(g) Cl+(g) + e−
b Sulfur 3 K+(g) K2+(g) + e−
c Titanium [Ar] 4 S5+(g) S6+(g) + e−
11 5 The second electron has to be removed from a
3d positive ion, which attracts a negatively charged
4s electron more strongly than a neutral atom does.
Once the first electron has been removed, the
3p 3p
remaining electrons experience less repulsion
3s 3s from each other. They are, therefore, attracted
2p 2p more strongly to the nucleus, and more energy
2s 2s is required to remove one of them.
1s 1s 6 a The ionisation energy can be calculated by
a phosphorus b copper determining the energy of the convergence
limit of the series which relates to
12 transitions to the energy level of the
1s 2s 2px 2py 2pz
outermost electron.
a hc 6.63 × 10–34 × 3.0 × 108
b  E = hv = =
b λ 589 × 10–9
c  = 3.38 × 10 J –19

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hc 6.63 × 10–34 × 3.0 × 108 4 A

c 
E = hv = =
50.4 × 10 λ –9
5 C
 = 3.95 × 10 J –18

therefore, for 1 mol of helium, 6 D

E = 3.95 × 10–18 × 6.02 × 1023 7 B
= 2376 kJ mol–1
8 D
7 The first two electrons are removed from the 3s
shell, whereas the third electron is removed from 9 A
the 2p shell. The 3s electrons are shielded from
10 B
the force of attraction of the nucleus by two full
shells of shielding electrons (1s and 2s/2p), and 11 a Electrons falling from a higher to
so, are relatively easy to remove, whereas the a lower energy level. [1]
third electron in the 2p shell is only shielded by
one inner (1s) shell, and so, is held much more b The different series represent
tightly. A significantly larger amount of energy transitions to different energy levels. [1]
is required, therefore, to remove it.
c 5
8
Log10 ionisation energy/kJ mol–1

2 electrons 4

3
8 electrons
Energy 2

4 electrons

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Number of ionisation energy 1

9 series of lines getting closer together

Log10 ionisation energy / kJ mol–1

at higher energy [1]

3 electrons
y-axis labelled energy [1]
lines labelled starting at lowest
7 electrons with n = 1 [1]
series of arrows pointing down from
different energy levels to the n = 1 level [1]
d Where the lines on an emission
0 1 2 3 4 5 6 7 8 9 10 spectrum become so close together
Number of ionisation energy as to be indistinguishable. [1]
10 The successive ionisation energies of transition e Ionisation energy [1]
elements are quite similar, as the outer-shell
electrons are in the same shell, so there are no 12 aluminium [1]
large jumps in the ionisation energies. The large jumps in the ionisation energies
indicate different energy levels. There are
Exam-style questions two large jumps, suggesting at least three
energy levels. [1]
1 D
The first three electrons removed are all in
2 D
the same energy level suggesting that the
3 C element is in Group 13. [1]

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Chapter 4
Exercise 4.1 b 0.250 mol
c 0.0666 mol
1 Masses are compared to 1⁄12 the mass of an
atom of carbon-12. d 0.0605 mol
2 a CO2 = 12.01 + (2 × 16.00) = 44.01 g mol−1 e 0.130 mol
b H2O2 = (2 × 1.01) + (2 × 16.00) 4 rearranging the formula to
= 34.02 g mol−1
m=n×M
c NaNO3 = 22.99 + 14.01 + (3 × 16.00)
= 85.00 g mol−1 (not 85) a m(NO2) = 0.10 × [14.01 + (2 × 16.00)]
= 4.6 g
d 132.17 g mol−1
b 359 g
e 46.08 g mol−1
c 563 g
f 170.47 g mol−1
d 7.3 g
g 192.14 g mol−1
e 6.4 g
Exercise 4.2 5 rearranging the formula to
1 a n, number of moles m
M=
n
m, mass
54.0
a M= = 216 g mol−1
M, molar mass 0.250
b n: mol b 120 g mol−1

m: g
Exercise 4.3
M: g mol −1
1 Avogadro’s constant is the number of particles
10.0 that there are atoms of carbon-12 in exactly
2 a n= = 0.435 mol
22.99 12 g of carbon-12.
0.5 × 1000 2 a N, the number of particles
b n= = 9 mol
22.99 + 35.45 NA, Avogadro’s constant
0.25
c n= n, number of moles
39.10 + 54.94 + (4 × 16.00)
b N: no units – it is simply a number
= 1.6 × 10−3 mol
NA: mol−1
d 68 mol
n: mol
e 0.0939 mol
3 a N(H2O) = 2.50 × 6.02 × 1023 = 1.51 × 1024
f 0.06 mol
1.00 64
3 a n(H2O) = = 0.05549 mol b n(O2) = = 2.0 mol
(2 × 1.01) + 16.00 2 × 16.00
as there are 2 H atoms per H2O molecules, N(O2) = 2.0 × 6.02 × 1023 = 1.2 × 1024
n(H) = 2 × 0.05549 = 0.111 mol c 2.4 × 1024 (each O2 molecule contains
2 O atoms)

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1.0 b 10.8 g
d n(SiO2) = = 0.0166 mol
28.09 + (2 × 16.00) c 12.1 g
There are 3 atoms (Si, O, O) in the formula,
6 Not all substances are made of molecules,
using N = n × NA some are made of atoms or have giant
structures, such as metal and ionic substances.
N = 3 × 0.0166 × 6.02 × 1023
= 3 × 1022 7 a CH
eM(CO2) = 12.01 + (2 × 16.00) b HO
= 44.01 g mol−1
c C2H5
mass of 1 mole
mass of 1 molecule = d CO2H
6.02 × 1023
44.01 e N2H4O3
=
6.02 × 1023
f C2H4O
= 7.31 × 10−23 g
8
f As 6 H in the formula Molecular Empirical Ratio,
formula formula molecular formula
n(H) = 6 × 0.040 mol = 0.24 mol
empirical formula
using m = n × M
H2O2 HO 2
m = 0.24 × 1.01 = 0.242 g a N2H4 NH2 2

Exercise 4.4 b C6H12O6 CH2O 6

c C5H10 CH2 5
2 × 55.85
1 %(Fe) = × 100 d C3H6O3 CH2O 3
(2 × 55.85) + (3 × 16.00)
= 69.9 %
9 a molar mass of P2O5 = approx. 142
69.9 (the accurate value is not required)
2 × 500 = 350 kg
100
M(molecular formula)
3 Mg = 27.74% ratio
M(empirical formula)
P = 23.56 %
molecular formula 283.88
= = =2
O = 48.69 % empirical formula 142
4 %(Mg in Mg3(PO4)2) = therefore, the molecular formula is
3 × 24.31 2 × empirical formula = P4O10
(3 × 24.31) + {2 × [30.97 + (4 × 16.00)]}
b C5H10
72.93
= 27.74% c C2H4O2
262.87
so mass of Mg = 0.277 g
12.01
5 a C in CH4 = = 0.7483
12.01 + (4 × 1.01)
mass (CH4) containing 10 g C
10.0
= = 13.4 g
0.7483

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10 a
Step Calcium Bromine
Percentage mass of each element 20.05 79.95

Divide the mass by the Ar of 20.05 79.95

the element = = 0.500 = = 1.000
40.08 79.90
Divide both values by the smaller =1 1.000
of the two = =2
0.5000
Consider both numbers. Are they This is a 1 : 2 ratio
in a simple whole number ratio?
A small amount of rounding is Therefore, the empirical formula is CaBr2
allowed here but not too much.

b Na2S2O3
c C2H7N
11 Using the same method as in question 10 gives M(molecular formula)
the empirical formula P2O3. Using the same b
M(empirical formula)
method as question 4a gives the molecular
formula P4O6 90.04
= =2
12.01 + (2 × 16.00) + 1.01
12 a mass of oxygen = 0.60 – 0.36 = 0.24 g
therefore, the molecular formula is
b Using the same method as question 5 C2H2O4
gives MgO.
13 a n(CO2) formed =
m
=
1.47
= 0.0334 Exercise 4.5
Mr 44.01
1 a 0.025 dm3
mass of carbon in 1.47 g of
b 0.100 dm3
CO2 = n × Ar(C) = 0.0334 × 12.01
= 0.401 g c 0.001 dm3
0.30 × 2 d 50 cm3
Similarly, n(hydrogen atoms) =
18.02
= 0.03329 e 15 cm3

Note: ×2, as there are two hydrogen atoms f 2.5 cm3

per molecule mass (g)
2 using C(g dm−3) =
mass of hydrogen in 0.30 g of volume (dm3)
H2O = 0.03329 × 1.01 = 0.033629 g 1
a C= = 5 g dm−3
Therefore, mass of oxygen in the 0.200
compound = 1.50 – (0.401 + 0.033629) C(g dm−3)
C(mol dm−3) =
= 1.0652 g M
The empirical formula can then be 5
=
calculated from these masses using the 39.10 + 16.00 + 1.01
same method as previously to give CHO2. = 0.09 mol dm−3

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mass (g) 6 a 0.1 mol dm3, as NaNO3 contains only 1

b C(g dm−3) = NO3− ion
volume (dm3)
= 1 g dm−3 b 1.0 mol dm3
C(g dm−3)
C(mol dm−3) = c 4.5 × 10−3 mol dm3
M
1 7 a 1 dm3 of solution will contain 0.1 mol
= of NaNO3, as NaNO3 contains 2 ions,
63.55 + (2 × 35.45) then number of moles of ions in
= 7.4 × 10−3 mol dm−3 total = 0.2 mol
mass (g) b 1.5 mol
c C(g dm−3) =
volume (dm ) 3
c 6.0 × 10−3 mol
14 × 10−3
= = 0.40 g dm−3 n m m
3.5 × 10−2 8 a C= , as n = then C =
V M M×V
C(g dm−3) 1.00
C(mol dm−3) =
M 24.31 + 32.07 + (4 × 16.00) + (7 × 18.02) × 0.100
0.40
= = 0.0406 mol dm−3
39.10 + 54.94 + (4 × 16.00)
= 2.5 × 10−3 mol dm−3 b 0.0160 mol dm−3

C(g dm−3) 9 The solution is being diluted by a factor of 4

3 using C(mol dm−3) =
M dilution factor
10.2 volume of diluted solution made
a =
207.20 + {2 × [14.01 + (3 × 16.00)]} volume of undiluted solution used
= 0.031 mol dm −3 so concentration of diluted solution will be
1
of the original concentration
b 0.048 mol dm−3 4
= 0.250 mol dm−3
c using C(g dm−3) = C(mol dm−3) × M
10 n(CuSO4) in 200 cm3 of the diluted
= 0.01 × (22.99 + 16.00 + 1.01) solution = V × C = 0.200 × 0.150
= 0.4 g dm−3 = 0.0300 mol
4 using n = C × V so volume of original solution required is
that which contains this number of
a n = 0.025 × 0.01 = 2.5 × 10−4 mol n 0.0300
moles = = = 120 cm3
b 5.2 × 10−4 mol C 0.250

c 2.5 × 10−6 mol Exercise 4.6

5 a n(MnCl2) = C × V = 1.5 × 0.01 1 a 200 cm3
= 0.015 mol b 200 cm3
m(MnCl2) = n × M = 0.015 × 125.84 c 100 cm3
= 1.9 g 2 a 50 cm3
b 0.083 g b 3.25 dm3
c 1.6 g c 200 cm3

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3 a 3 dm3 b m(anhydrous MgSO4) = 19.70 – 18.27

= 1.43 g
b H2S = 0 dm3
m(water of crystallisation) = 21.19 – 19.70
O2 = 4 dm3 (unreacted as O2 was in excess) = 1.49 g
H2O = 2 dm3 for both masses [1]
SO2 = 2 dm3 m
n(MgSO4) =
c 8 dm3 Mr

4 CH4 reacts with O2 in a 1 : 2 ratio 1.43

=
24.31 + 32.07 + (4 × 16.00)
25 cm3 of CH4 requires 50 cm3 of O2
= 0.119 mol [1]
so CH4 is in excess, and only 12.5 cm3 of m 1.49
it will react with the 25 cm3 of oxygen, n(H2O) = = = 0.0827 mol [1]
forming 12.5 cm3 of CO2. Mr 18.02
mol water 0.0827
Volume of gases at the end are 12.5 cm3 ratio = =7
unreacted CH4 + 12.5 cm3 CO2 = 25 cm3 of mol MgSO4 0.0119
gas in total formula = MgSO4•7H2O [1]
H2O is ignored because it is a liquid c Each mass value has an uncertainty of
±0.01 g; therefore, total uncertainty is
Exam-style questions ±0.02 g
0.02 × 100
1 B as a percentage = = 0.7 % [1]
2.92
2 C Similarly, percentage uncertainty
0.02 × 100
3 B of anhydrous salt = = 1.4 % [1]
1.43
4 B n 0.0119
d C= = = 0.0476 mol dm−3 [1]
5 D V 0.250
6 C e 2.92 g (the mass of hydrated
MgSO4•7H2O used) [1]
7 D
12 mass of carbon atoms in 0.999 g of CO2
8 A 12.01 × 0.999
= = 0.2726 g [1]
9 A 44.01
10 D mass of hydrogen atoms in 0.409 g of H2O

11 a Heating to constant mass means that (2 × 1.01) × 0.409

= = 0.04585 g [1]
the sample is heated, allowed to cool, 18.02
weighed, reheated, allowed to cool and mass of C and H in compound =
reweighed repeatedly until the mass 0.2726 + 0.04585 < 0.500
reading is constant. [1]
compound must contain oxygen of mass
0.500 – (0.2726 + 0.04585) = 0.1816 g [1]

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To find the empirical formula:

Step Carbon Hydrogen Oxygen

Mass of each element / g 0.2726 0.04585 0.1816
Divide mass by Ar of each 0.2726 0.04585 0.1816
element = 0.0227 = 0.0454 = 0.01135 [1]
12.01 1.01 16.00
Divide each value by the smallest 0.0227 0.0454 1
of the values =2 =4 [1]
0.0113 0.0113
Consider both numbers. Are they This is a ratio of 2 : 4 : 1
in a simple whole number ratio? Therefore, the empirical formula is C2H4O [1]
To find the molecular formula:
M(C2H4O) = (2 × 12.01) + (4 × 1.01) + 16.00
= 44.06 g mol−1
molar mass of substance
as
molar mass of empirical formula
132.18
= =3
44.06
Therefore, molecular formula = C6H12O3 [1]

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Chapter 5
Exercise 5.1 Exercise 5.2
1 There is no change in the total kinetic energy 1 a P / Pa
when the particles collide.
2 Particles are in constant motion.
There are no intermolecular forces.
3 a less
b more
c less
4 a less 0
0 V / cm3
b more
b P / Pa
c less
5 helium (He is the smallest of all atoms)
6 a A: At high pressure, the volume of a real
gas is slightly larger than the volume
predicted by the ideal gas model because
the volume of the particles themselves
relative to the total volume of the gas
becomes more significant.
0
b B: At high pressure, the volume of 0 1/ V / cm–3
a real gas is slightly smaller than the
volume predicted by the ideal gas model c 1/ P Pa–1
because the forces of attraction between
the particles are stronger and hold the
particles closer together.
c B: At low temperatures, the volume of
a real gas is slightly smaller than the
volume predicted by the ideal gas model
because the forces of attraction between
the particles are stronger and hold the
particles closer together.
0
d A: For gases containing large molecules, 0 V / cm3
the volume of a real gas is slightly larger
than the volume predicted by the ideal gas d PV / cm3
model because the volume of the particles
themselves relative to the total volume of
the gas becomes more significant.
e B: For gases containing more polar
molecules, the volume of a real gas is
slightly smaller than the volume predicted
by the ideal gas model because the
forces of attraction between the particles
are stronger and hold the particles
0
closer together.
0 V/ Pa

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e PV / cm3 Pa b P / Pa

–273 0 T/ °C

0
Exercise 5.3
0 P/ Pa V1 V2
1 = as pressure is constant
T1 T2
2 a V / cm3
100 V2
=
330 250
100 × 250
V2 = = 75.8 cm3
330
P1 P2
2 = as volume is constant
T1 T2
200 P2
=
298 373
0 200 × 373
0 T/ K P2 = = 250 kPa
298
b V / cm3 P1V1 P2V2
3 =
T1 T2
100 × 200 150 × 400
=
273 T2
150 × 400 × 273
T2 = = 819 K
100 × 200
–273 0 T/ °C
= 546 °C
3 a P / Pa
P1V1 P2V2
4 =
T1 T2
125 × 250 62.5 × V
=
273 + 75 400
400 × 125 × 250
V2 = = 575 cm3
348 × 62.5
0 5 a 2.25 × 10−3 m3
0 T/ K
b 1.00 × 10−4 m3
c 500 cm3
d 75 000 cm3
e 34 dm3
f 0.250 dm3

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nRT V1 V2
6 P= 14 a = as P is the same at STP
V T1 T2
0.25 × 8.31 × 300 and SATP,
P= = 623 000 Pa
1 × 10 −3
22.7 V2
then = ,
PV 273 298
7 n=
RT 22.7 × 298
V2 = = 24.8 dm3
1.5 × 10 × 0.4
2
273
n= = 0.024 mol
831 × 298 150 × 10−3
b n= = 6.05 × 10−3 mol
mRT 24.8
8 P=
MV
2.4 × 8.31 × 298 Exam-style questions
P= = 135 000 Pa
44.01 × 1000 × 10−6
1 A
m 10
9 n(O2) = = = 0.3125 mol 2 B
M 32.00
3 C
m 40
n(He) = = = 10 mol 4 C
M 4.00
n(total) = 10 + 0.3125 = 10.3125 mol 5 B
nRT 6 D
using V =
P 7 A
10.3125 × 8.31 × 350 8 D
V= = 0.15 m3
200 × 103 9 C
mRT
10 Using M = 10 A
PV
11 a Avogadro’s law states that equal
73.07 × 8.31 × 323 volumes of ideal gases at the same
M= = 28 g mol −1
200 × 35.0 temperature and pressure will contain
the same number of molecules. [1]
2.45
11 a n= = 0.108 mol b It is assumed that the force of
22.7
attraction between the molecules
200 × 10−3 in an ideal gas is zero. [1]
b n= = 8.81 × 10−3 mol
22.7
It is also assumed that the volume
0.75 × 103 of the molecules is negligible
c n= = 33.0 mol
22.7 compared to the total volume of
the gas. [1]
12 a 34.1 dm−3
c Assume the formula of the compound
b 5.68 dm−3 is CxHy.
c 7.95 × 10−4 dm3 or 0.795 cm3 The equation for its combustion will be
m 2.50 as follows:
13 n = = = 0.0568 mol y
M 44.01 CxHy + excess oxygen xCO2 + H2O
2
as volume = n × molar volume total volume at start = 300 cm3
then volume = 0.0586 × 22.7 = 1.29 dm3 volume at the end = 200 cm3 (as the
volume is reduced by 100 cm3)

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This volume is composed of CO2 and In order for the equation to balance,
unreacted oxygen. the value of y must = 4 [1]
On treatment with NaOH, which removes Therefore, the formula of the
CO2, the volume is 100 cm3. compound is C2H4. [1]
Therefore, this remaining volume is excess C2H4(g) + 3O2(g) 2CO2(g) + 2H2O [1]
oxygen and only 150 cm3 of the original
oxygen react [1] and 100 cm3 of CO 2
are formed. [1]
From this, we can deduce the ratio of
C xHy to oxygen and CO2 in the equation
as 1 : 3 : 2. [1]
y
CxHy + ?O2 xCO2 + H2O
2
50 cm + 150 cm3 100 cm3
y
CxHy + 3O2 2CO2 + H2O
2

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Chapter 6
Exercise 6.1 4 a It gains an electron in its outer shell.
b –
1 positive
negative Cl + e– Cl
lose
gain
c Cl + e− Cl−
non-metallic
d 1s2 2s2 2p6 3s2 3p6
2 a Ionic bonding occurs between ions with
opposite charges. Atoms of an element e chloride
generally form ions with only one type 5 a Li+: 1s2
of charge, so atoms of an element will
not bond with each other ionically. b S2−: 1s2 2s2 2p6 3s2 3p6
Ionic bonding can only take place in c Be2+: 1s2
a substance made from two or more
d Mn2+: 1s2 2s2 2p6 3s2 3p6 3d5
different elements, and so, by definition,
can only occur in a compound. e Zn2+: 1s2 2s2 2p6 3s2 3p6 3d10
b i ionic
Exercise 6.2
ii not ionic
1 Atoms with 1, 2 or 3 outer-shell electrons
iii not ionic tend to form ions with a +1, +2 or +3 charge
iv not ionic so that the ion formed has the same electron
configuration as the previous noble gas.
v ionic Atoms with 5, 6 or 7 outer-shell electrons
vi not ionic tend to form ions with a −3, −2 or −1 charge
so that the ion formed has the same electron
3 a It loses an outer-shell electron. configuration as the next noble gas.
b +
2 For Groups 1 and 2, charge = group number,

Na Na + e– Groups 3–12, there is no particular

relationship to group number, as these atoms
can form ions with different charges,
Groups 13–17, charge = group number −10,
c Na Na+ + e−
Group 18, do not form ions.
d 1s2 2s2 2p6

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3
Group number 1 2 d-block elements 13 14 15 16 17 18
charge on ion +1 +2 form more than +3 tend not −3 −2 −1 do not
one ion to bond form ions
ionically

4 Using Roman numerals in brackets after the name of the element.

Exercise 6.3 5 a NaF

1 Electrons are transferred. b Na2O

2 + – c Na3N
d FeF2
Na Cl
e CuO

sodium ion chloride ion f Mg3N2

Na+ Cl –
3 g AlCl3
h Cr2O3
electron
transferred i AlN
Na
6 a NH4NO3
b Na2SO4
O c Mg(HCO3)2
d FeSO4
Na e Na3PO4
electron
transferred f Al(NO3)3
g Al2(SO4)3

+ h Cu3(PO4)2
2–
i (NH4)2CO3
2 Na O
Exercise 6.4
1 The electrostatic forces of attraction between
4 oppositely charged ions.
Name or formula Formula Formula
2 Regular repeating pattern.
of compound of the of the
cation anion 3 a Repeating pattern of Na+ ions and
Cl− ions arranged alternately in three
MgBr2 Mg2+ Br−
dimensions. Each Na+ ion is surrounded
Fe2O3 Fe3+ O2− by 6 Cl− ions, and each Cl− ion is
iron(III) hydroxide Fe3+ OH− surrounded by 6 Na+ ions.

potassium sulfate K+ SO42−

magnesium sulfide Mg2+ S2−
copper(II) carbonate Cu2+ CO32−
ammonium nitrate NH4+ NO3−

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b Exercise 6.6
CI–
1
Effect on lattice enthalpy
Na+
increasing decreases lattice enthalpy
anion radius
increasing decreases lattice enthalpy
cation radius
increasing increases lattice enthalpy
Exercise 6.5 anion charge

1 increasing increases lattice enthalpy

Usually have Electrostatic forces of
cation charge
high melting and attraction are strong
boiling points and exerted in all
2 a NaBr, as the radius of Na+ < K+, so the
directions through the
distance between the ions is lower, and the
3D lattice
forces of attraction are stronger in NaBr
Usually have Electrostatic forces of than in KBr.
low volatility attraction are strong
b KF, as the radius of F− < Cl−, so the
and exerted in all
distance between the ions is lower, and the
directions through the
forces of attraction are stronger in KF than
3D lattice
in KCl.
Do not conduct Ions are held in a
c MgCl2, as Mg2+ has a higher charge
electricity fixed lattice and cannot
than Na+, so the forces of attraction are
when solid move
stronger in MgCl2 than in NaCl.
Conduct Ions are free to move
electricity when d CaO, as O2− has a higher charge than Cl−,
molten or so the forces of attraction are stronger in
dissolved CaO than in CaCl2.
3 a NaBr
2 Ion–dipole forces of attraction are formed b KF
between polar solvents and the charged ions
of an ionic compound. The energy released c MgCl2 (although, in reality, NaCl is
by this process is often enough to overcome higher!)
the energy required to separate the ions in d CaO
the lattice. Ionic substances are not usually
soluble in non-polar solvents, as the forces of Exam-style questions
attraction between an ion and a non-polar
molecule (London forces) are much weaker 1 C
than ion–dipole forces, so the electrostatic 2 B
forces of attraction between the oppositely
charged ions in the lattice are not overcome. 3 C
4 B Group 17 (seventeen – not seven) ions tend
3 Ions move through the solution. The positive
to have –1 charge
ions move towards the negative electrode (to
the right in Figure 6.1) and the negative ions 5 A
towards the positive electrode (to the left in
6 C
Figure 6.1) because opposite charges attract
each other. 7 B
8 D
9 D
10 A

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11 a K2O, CaO, Al2O3 [3]

b
electrons
transferred
Al O

electrons
transferred
Al O

3+ 3+ 2– 2– 2–

Al Al O O O

correct dot/cross diagrams [1] b high melting/boiling points [1]

square brackets and correct charges [1] low volatility [1]
correct number of ions indicated [1]
poor electrical conductors when solid [1]
12 a Repeating pattern of Mg2+ ions and
O2− ions. [1] good electrical conductors when
dissolved or molten [1]
soluble in water/polar solvents [1]
2+ 2– 2+ 2–
insoluble in non-polar solvents [1]
2–
2 +
2–
2+
 [max 4 marks]
2+ 2– 2+ 2– c radius of ions [1]

2– 2+ 2– 2+
charge on ions [1]
d very high melting point [1]
Ions alternately arranged. [1]
3D arrangement [1]
2+ and 2− charged ions [1]
Marks can be gained from a
labelled diagram.
No diagram scores max 3 marks

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Chapter 7
Exercise 7.1 6 The more shared pairs of electrons there are
between the atoms, the greater the electrostatic
1 a force of attraction between the positive nuclei
F F
and the shared pairs of electrons, and so, the
b stronger and shorter the bonds. Triple bonds
H O O H
have three shared pairs, double bonds two
c H N H shared pairs and single bonds one shared pair of
electrons.
H
7 Both electrons in the shared pair originate
d H from the same atom in a coordination bond.
H C H
8 a H +
H

2 a H N H
O O
H
b N N
b +
c O C O
H O H
d H H
C C H
H H
3 a c C O
–
H O d H F

H N B F
b 2–
O
H F
C
O O
e –
O

c – O N
H O O O
C

O Exercise 7.2
1 The valence-shell electron-pair repulsion
4 a Cl Cl c Cl Cl (VSEPR) theory suggests that electron
B Al
domains will orientate themselves to minimise
Cl Cl the repulsion between them, and so, will be
as far away from each other as possible in
b Cl Be Cl space. It also suggests that lone pair–lone pair
5 The more bonds between two atoms (single/ repulsion is greater than lone pair–bonding
double/triple) then the shorter and stronger pair repulsion, which is greater than bonding
the bonds. Triple bonds are stronger and pair–bonding pair repulsion.
shorter than double bonds, which are shorter
and stronger than single bonds.

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2
Number of electron domains Shape Bond angle
2 linear 180°
3 trigonal planar 120°
4 tetrahedral 109.5°

Exercise 7.3
1 Strongest, non-bonding/non-bonding > non-bonding/bonding > bonding/bonding, weakest
2 Any example that has a lone pair of electrons, such as NH3 or H2O.
3 Species Lewis structure Sketch showing the shape Bond angle Name of the shape
H2S H S H S 104° bent
H H

PCl3 Cl P Cl P 107° pyramidal

Cl Cl Cl
Cl

CCl4 Cl Cl 109.5° tetrahedral

Cl C Cl
C
Cl
Cl
Cl Cl
NH2− – – 104° bent
H N H N
H H

Exercise 7.4
1 Double bonds have a higher electron density. A double bond is made of four electrons, rather than
two in a single bond, and so, repulsion is greater.
2
Species Lewis structure Sketch showing the shape Bond angle Name of the shape
NO2− – – 118° bent
O N O N
O O

CS2 S C S S C S 180° linear

NO3− – – 120° trigonal planar

O O

N O N O

O O

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Exercises 7.5 and 7.6 7 hydrogen bonding > dipole–dipole >

London forces
1 Group 18 elements (noble gases) do not
readily form compounds. 8 Ion–dipole and hydrogen bonds are much
stronger than the types of intermolecular
2 F F = P H < O Cl < C Br = C H forces that are classed as van der Waals forces.
= H S < C Cl < N H = P Cl < O H
3 a non-polar Exercise 7.8
b non-polar 1 The stronger the intermolecular forces, the
higher the melting/boiling points, as more
c polar energy/higher temperatures is required to
overcome the stronger forces of attraction
d polar
between the molecules.
e non-polar
2 a Melting/boiling points increase as
molecular mass increases, as a higher
Exercise 7.7 molecular mass means there are more
1 At any given moment, the electrons in a electrons in the molecule. The more
molecule are unevenly distributed, and so, electrons, the larger the temporary dipoles
the molecule will have an instantaneous and, hence, the induced dipoles. This leads
temporary dipole. This temporary dipole will to stronger forces of attraction between
induce an opposite dipole in a neighbouring the molecules, and so, more energy is
atom or molecule. There is a force of required to separate them.
attraction between the opposite dipoles.
b London forces are very weak, so liquids
2 a H Cl with only London forces tend to have
very low boiling points. The stronger
b Difference in electronegativities between the London forces, the higher the
H and Cl is the largest. boiling point.
3 a No, as both C6H12 and Br2 are non-polar. c Hydrogen bonding is the strongest
b Yes, C8H18 is non-polar and CH3Cl type of intermolecular force, so more
is polar. energy/higher temperature is required
to overcome the forces of attraction.
c Yes, Br2 is non-polar and HBr is polar.
3 The halogens are non-polar, and there are
4 H only very weak London forces between
δ+
H O the molecules. The strength of these forces
δ–
H O δ– depends on the number of electrons in
the molecules. As the number of electrons
H
increases down the group, the size of the
5 Substances can form hydrogen bonds if they temporary dipole–induced dipole increases,
contain a hydrogen atom attached to a very and so, melting points increase down
electronegative atom, such as nitrogen, oxygen the group.
or fluorine. These hydrogen atoms form a
dipole–dipole interaction with a lone pair of 4 a I2: The London forces in I2 are stronger
electrons on the nitrogen, oxygen or fluorine than in Br2, as I2 has a higher relative
atom of a neighbouring molecule, which is molecular mass, and so, has more
stronger than other dipole–dipole interactions electrons than Br2.
and is known as a hydrogen bond.
b CH3OCH3: There are stronger
6 a yes dipole–dipole forces between the
CH3COCH3 molecules, as these are polar,
b no whereas C4H10 is non-polar with weaker
c yes London forces between the molecules.

d yes

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c H2O: There are hydrogen bonds between 4 Si and SiO2 have a structure most like that
H2O molecules, which are stronger than of diamond.
the weak dipole–dipole and London
forces between H2S molecules. 5 Diamond does not conduct electricity, as the
electrons are localised between the carbon
atoms, and so, are not able to move when a
Exercise 7.9 potential difference is applied. In graphite,
1 a No, as C4H8 does not contain an H each atom has one electron in a p orbital
attached to N, O or F. that is perpendicular to the plane of the
carbon atoms. These p orbitals overlap with
b Yes, as H of the OH group in CH3OH each other, forming a delocalised system.
can form hydrogen bonds with water. The electrons can move freely through
c No, as there are no H, N, O or F atoms. these delocalised orbitals when a potential
difference is applied.
d Yes, as H of H2O can form hydrogen
bonds to the lone pair of electrons on the 6 Graphite and diamond have giant structures
C O of propanone. Note that propanone with a large number of strong covalent bonds
cannot form hydrogen bonds with other between the carbon atoms, which would need
propanone molecules. to be broken on melting. Buckminsterfullerene
has a molecular structure and is made up of
2 Although the COOH group can form C60 molecules. In the solid, there are relatively
hydrogen bonds with water, the long weak intermolecular forces (London forces)
hydrocarbon chains prevent hydrogen bonding between these molecules, and so, only a
between the water molecules on either side. relatively small amount of energy is needed to
The hydrocarbon chain forms London forces overcome these, and so, C60 has a much lower
with other fatty acid molecules, and these melting point. The C C covalent bonds are
group together to form droplets. not broken.
3 a B4, as this is more soluble in the non-
polar mobile phase than in the stationary Exercises 7.11 and 7.12
phase (water in the cellulose fibres of
1 Period 3 onwards
the paper).
2 a Cl
b A2/B3
Cl Cl
c 0.8 – 0.9 P
Cl Cl
d i The order of the spots would be the
same, as the more polar substances
would be strongly adsorbed onto the b F
F F
surface of the silica plate.
S
ii adsorption F F
F
Exercise 7.10
3 a CO2
1 Allotropes are different forms of an element.
2 They have different physical and chemical
O(1) = 6 – ( ) 1
2
× 4 –4=0
properties.
3 a Buckminsterfullerene
C=4– ( )
1
2
×8 –0=0

b graphite O(2) = 6 – ( ) 1
2
×4 –4=0
c diamond
d graphene

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b CO32−
O=6– ( )
1
× 2 – 6 = –1

( )
2
1
C=4– ×8 –0=0
2
structure ii:
O(1) = 6 –( ) 1
2
×4 –4=0
N(1) = 5 – ( )
1
2
× 4 – 4 = –1

O(2) = 6 –( ) 1
× 2 – 6 = –1
2
N(2) = 5 – ( ) 1
2
× 8 – 0 = +1
O(3) = 6 –( ) 1
× 2 – 6 = –1
2
O=6– ( )
1
2
×4 –4=0
c CO
structure iii:
C=4– ( )1
× 6 – 2 = –1
2
N(1) = 5 – ( )
1
× 2 – 6 = –2
( )
2
1
O=6– × 6 – 2 = +1
2

4 a structure i:
N(2) = 5 – ( ) 1
2
× 8 – 0 = +1

S=6– ( ) 1
2
× 8 – 0 = +2 O=6– ( )
1
2
× 6 – 2 = +1

( )
O(1) = 6 –
1
2
× 2 – 6 = –1 Structures i and ii equally likely based on
their formal charges.

( )
O(2) = 6 –
1
2
×4 –4=0 5 a FC = –1 FC = +2 FC = –1
O Cl O
–
FC = 0 FC = 0 FC = 0
O Cl O
–

( )
O(3) = 6 –
1
2
× 2 – 6 = –1 O
FC = –1
O
FC = –1

structure ii: Right hand-structure is more likely.

( )
1 b – –
S=6– × 12 – 0 = 0 S C N S C N
2

O(1) = 6 – ( )
1
2
×4 –4=0
Left-hand structure FCs: S = 0, C = 0,
N = –1

O(2) = 6 – ( )
1
2
×4 –4=0
Right-hand structure FCs: S = –1, C = 0,
N=0

O(3) = 6 – ( )
1
2
×4 –4=0
Both structures are equally likely.

Exercise 7.13
Structure ii is the most likely structure of
1 a F
SO3, as formal charges are closer to zero. 90°
F
b structure i: P F
F 120°
N(1) = 5 – ( )
1
2
×6 –2=0
b
F

F 90°

N(2) = 5 – ( )
1
2
× 8 – 0 = +1
F
F
S
F
F
F

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c F 4
85° distorted T-shape
F I all atoms are in Name of Number Type and Bond
F the same plane hybrid of hybrid number of angle
orbital orbitals original atomic of the
d Cl 90° formed orbitals hybrid
Cl Cl orbitals
Br
Cl Cl sp 2 1 × s and 1 × p 180°
sp2 3 1 × s and 2 × p 120°
90°
sp3 4 1 × s and 3 × p 109.5°
e F
F 5 a sp3
F Sb 120°
90° b sp3
F
F c sp2
trigonal bipyramidal
d sp
f Cl 2–
Cl e sp2

Cl Pt Cl
90°
Exercise 7.15
Cl
Cl 1 a sigma
g – b sigma
Br
c sigma
I 180°
linear d pi
Br
e sigma

2 Figure 7.5a is more likely, as the lone pairs f sigma

are opposed to each other, so there will be
2 head-on/axial
less repulsion than if they were at 90°, as in
Figure 7.5b. sigma
3 Cl sigma
Cl
Te see-saw shape sideways/lateral
120°
Cl triple
88° Cl
90
Exercise 7.14 3
1 Number of orbitals does not change.
Number of Number of
2 Maximum number of electrons σ bonds π bonds
does not change.
H2O 2 0
3 Total energy is the same.
CO2 2 2
N2 1 2
HCN 2 2

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Exercise 7.16 7 The sharing of a pair of electrons between

three or more atoms.
1 a O
8 a Delocalisation can occur. The two π
O O
bonds are only one bond apart from each
other, and so, can overlap with each other.
b –
O H H
O N C C H
O H C C
H CH3
c 2–
O
b Delocalisation can occur. The p orbitals
O S O across all four atoms overlap with
one another.

O
2 O O O N
O O O O O

3 – –
c Delocalisation cannot occur. The two π
O O
O N O N bonds are at 90° to each other, and so,
O O do not overlap.

O C O
–
O
O N
d Delocalisation cannot occur. The two π
O
bonds are too far apart to overlap with
each other.
4 2– 2–
O O H H
C C H H
O S O O S O
H C C H
C
H

2– H
O
9 All the C C bonds are the same length.
O S O
All the C C bonds are of equal strength.
10 a C6H6 + 3H2 C6H12
5 a 1.5 (average of 1 double and 1 single bond)
b −360 kJ mol−1
4
b
3 c Less exothermic, which suggests that
benzene is more stable than expected.
4
c
3 11 Benzene reacts with bromine in a
substitution reaction:
6 Bond strength can be estimated to be the
average of O O and O O, 321 kJ mol−1 C6H6 + Br2 C6H5Br + HBr
(actual value approx. 364 kJ mol−1)
whereas molecules with C C bonds, such as
Bond length, 134.5 pm (actual value approx. alkenes, tend to undergo addition reactions.
1.28 pm)

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Exam-style questions 12 a Electron domains/pairs of electrons

around a central atom repel
1 B each other. [1]
2 A They orientate themselves to minimise
repulsion/be as far apart from each
3 D
other as possible. [1]
4 D 2–
b
S O
5 A O
O
6 C
must use 3D notation or describe as
7 D pyramidal [1]
8 A bond angle 107.5° [1]
9 C c i H2S has four electron domains,
10 B whereas SO2 has three electron
domains. [1]
11 a i C2H6 Ethane  [1]
H2S is based on a tetrahedral shape,

H H
H H whereas SO2 is based on a trigonal
H C C H H C C H planar shape. [1]
H H H2S bond angle 103 – 107°. [1]
H H
SO2 bond angle 116 – 119°. [1]
ii H
ii 
Both polar (due to the presence
H C O H
of lone pairs of electrons) [1]
H
d H2O can form intermolecular hydrogen
lone pairs on O must be shown [1] bonds, whereas there are only
dipole–dipole forces in H2S. [1]
iii H
13 a N O O  [2]
H C Cl N N
O O
O O
H NO2 N2O4
lone pairs on Cl must be shown [1]
b i sp3 [1]
Only penalise missing lone
pairs once. ii 103 – 108° [1]

b C2H6 London forces [1] c i coordination bond [1]

CH3OH hydrogen bonding [1] ii diagram a, P = 0, O = 0, Cl = 0 [1]

CH3Cl dipole–dipole forces [1] diagram b, P = +1, O = −1, Cl = 0 [1]

c CH3OH can form hydrogen bonds As the formal charges are closer
with water from the OH group whereas to zero for diagram a, this is the
CH3Cl cannot. [1] more likely structure. [1]

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d i P iii F –
F
Cl Cl 90°
107° Cl F P F

for shape [1] F F

for bond angle [1] for shape [1]

ii Cl
Cl for bond angle [1]
90°
Cl P 120° iv F +
Cl
Cl 109.5°
for shape [1] P
F
for bond angle [1] F F

for shape [1]

for bond angle [1]

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Chapter 8
Exercises 8.1–8.3 8 a The delocalised electrons move freely
through the structure under the influence
1 On the left, middle and towards the bottom. of an applied voltage.
2 a shiny b The delocalised electrons move more
quickly when heated and their free
b Electricity passes easily through the movement through the structure allows
substance/low resistivity. the kinetic energy to be transferred from
c Heat is transferred easily through electron to electron, and so, through the
the substance. whole material.

d Can be drawn into wires. c When a force is applied that distorts

the structure of the metal, the layers of
e Can be hammered into thin sheets. cations slide over each other and remain
3 Form positive ions/cations. held together by the delocalised electrons.

Tend to bond ionically with non-metals. 9 a Gold is unreactive, so it stays shiny.

Most form basic oxides. b Aluminium is strong and has a low

density. This reduces the weight of the
4 a The electrons are free to move between plane and allows it to fly.
the cations.
c Iron is malleable and can easily be pressed
b lattice of into shape.
electron metal ions
+ + + + + Exercise 8.3
+ + + + + 1 Melting points of transition metals are
generally higher than s and p block metals.
+ + + + +
2 4s and 3d electrons
+ + + + +
3 Although 3d electrons are delocalised, as
+ + + + + well as the 4s electrons, the actual number of
delocalised d electrons does not increase by
c The delocalised electrons are in constant one from element to element, particularly after
random motion and are free to move in manganese. The energy required to form ions
all directions. of charge greater than about 4+ is prohibitive.
5 cation size and cation charge 4 Electrical conductivities for first-row
6 Melting points decrease down the group, transition elements are lower than Na, Mg
as the ionic radii increases down the group. and Al (except for Cu). This suggests that
The electrostatic force of attraction between there are fewer delocalised electrons in the
the 2+ cations and the delocalised electrons transition metals.
decreases, as it is acting over a larger distance.
Exam-style questions
7 Melting points increase from Na to Mg to
Al, as the cation charge increases, and there 1 B
is an increase in the number of delocalised
electrons. The electrostatic forces of attraction 2 C
between the cations and the delocalised 3 A
electrons, therefore, increase. As the cation
radius also decreases from Na to Mg to Al, 4 D
then these forces of attraction are also acting
5 C
over a shorter distance.

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6 3D lattice [1] of cations [1] with 3+ charge b Increasing number of delocalised

[1] held by electrostatic force of attraction valence electrons from Na to Al. [1]
to delocalised [1] electrons. Marks can be
awarded for a labelled diagram. c Although both Sc and Al have three
valence electrons (Al = 3s2 3p1 and
7 a Delocalised electrons are free to move Sc = 4s2 3d1), the 3d valence electron
when a voltage is applied. [1] in Sc is not fully delocalised. [1]

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4 To some extent, as alloys have similar

Chapter 9 physical and chemical characteristics to their
components, such as being good conductors
Exercise 9.1 and malleable, but some properties are
different; stainless steel, for example, is
1 The ability of an atom in a covalent bond to resistant to corrosion whereas iron is not.
attract the shared pair of electrons towards itself.
5 It prevents the planes of ions sliding over
2 Average electronegativity and the difference one another.
between the electronegativities.
6 It often makes the alloy stronger and harder.
3 Pure ionic, pure covalent and pure
metallic substances Exercise 9.3
4 a ionic (average electronegativity of 2.45, 1 Strong, flexible, low density, unreactive,
electronegativity difference of 1.9) thermal insulator, electrical insulator,
b borderline metallic/covalent (difference properties can be easily modified.
of 0, average of 1.9) 2 Most are non-biodegradable; many are made
c borderline ionic/polar covalent (difference from crude oil, which is a non-renewable
of 1.8, average of 2.5) resource.

d covalent (difference of 0, average of 2.0) 3 Long-chain molecules formed by joining a

large number of smaller monomer molecules
e polar covalent (difference of 1.2, average together with covalent bonds.
of 2.8)
4 Intermolecular forces are relatively weak
f borderline ionic/polar covalent (difference compared to the strong covalent bonds in
of 1.6, average of 2.4) the cross-linked polymer. The cross-linked
polymer will probably be more rigid, stronger,
g ionic (difference of 1.7, average of 2.15) have a higher melting point and cannot
5 a A compound made of only two elements. be remoulded.

b They are not particularly useful for transition 5 a Longer chain lengths make stronger but
metals or their compounds, as these have less flexible polymers.
relatively high electronegativity values. b More branching increases flexibility and
They cannot distinguish between binary decreases strength.
compounds in different oxidation states, c More crystalline polymers are stronger
such as PbCl2 and PbCl4. but less flexible.
They cannot distinguish between different
d Plasticisers increase the flexibility of a
allotropes of an element.
polymer but reduce its strength.

Exercise 9.2 e The stronger the intermolecular forces,

the stronger and less flexible the polymer.
1 Compounds: elements are joined by chemical The strongest and least flexible will have
bonds and are in a fixed ratio. covalent bonds cross-linking the polymer
molecules, second hydrogen bonds, third
Mixtures: components are not chemically
dipole–dipole forces, the weakest/most
bonded and have variable composition.
flexible polymers will have only weak
2 They have variable composition. London forces.
3 A mixture where all the components are in the 6 Electrical conductivity: There are no charged
same phase and with a uniform composition. particles in the structure that are free to move;
(Mixtures of solids are usually considered polymers are covalently bonded molecules, so
heterogeneous but the mixing in alloys is the electrons are localised between atoms.
at the atomic level so they can be regarded
as homogeneous.)

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Thermal conductivity: There are only weak 6 carboxyl and amino

intermolecular forces between the polymer
chains, which means that kinetic energy is 7
not easily transferred through or between O H H H
H H
molecules. Electrons are all localised in bonds O
and H N C C N H
so are not free to move. C C C C C
HO OH H H H H
H H H
7 carbon–carbon double bond/alkene
8 none 8 The monomer would need to have both of the
functional groups required.
9 a
F F 9 H H
H O
C C N C C C
F H H H H O H

b F F 10 The breaking of a covalent bond by the

C C reaction with water.
F H
11 an enzyme
10 Cl CH3
Cl CH3
Exam-style questions
n C C C C
Cl H 1 A
Cl H n
2 D
poly(1,1-dichloropropene)
3 A
Exercise 9.4 4 B

1 Reaction in which two or more molecules 5 A

join together with the formation of a covalent
6 C
bond and the elimination of a small molecule
such as water. 7 C
2 O 8 B
O C 9 C

3 hydroxyl and carboxyl 10 D

(not alcohol and carboxylic acid, as these are 11 a alloy [1]

the names of the homologous series and not
b Cu and Zn atoms/ions are
the functional groups – see Chapter 11)
different sizes. [1]
4 O H O H
This prevents the planes of atoms/ions
HO C C C OH and H O C O H sliding over one another when a force
is applied. [1]
H H

5 O

N C

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c 13 a
180
n HO C C OH + n H2N NH2
160
O O
Relative ductility

140 H H
120 C C N N + 2n – 1 H2O
100 O O
n
80
formulas [1]
60
50 60 70 80 90 100 balanced correctly, accept 2n or 2n − 1
% copper for H2O [1]

correct axes [1] b It is able to form hydrogen bonds

between the amide links in
all points correctly plotted [1] different chains. [1]
two intersecting trend lines [1] c hydrolysis [1]
value read correctly from graph 14 a B2O3, 45% [1]
accept values between 72 and 74 % [1] Al2O3 60% [1]
12 a Ga2O3, In2O3 and Tl2O3, 50% [1]
Cl H

C C b i Al2O3 is most ionic – highest

melting point. [1]
H H n
Ga2O3, In2O3 and Tl2O3 should

b all have similar melting points. [1]
H H
B2O3 is most covalent – melting

C C point is lowest. [1]
H
ii None will conduct when solid. [1]
n Al2O3 is most ionic, so it is most

polystyrene likely to conduct when liquid;
c B2O3 is likely to have the lowest
H CH3 conductivity when liquid. [1]
C C

H C
O O CH3
n

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Chapter 10
Exercise 10.1 4 The strength of the forces of attraction
decreases down a group, as there is an increase
1 atomic number order in atomic radius due to the increase in the
number of electron shells.
2 bromine and mercury
5 Electronegativity is a measure of the extent to
3 vertical column which an atom in a covalent bond attracts the
4 horizontal row shared pair of electrons towards itself.
5 a metals and non-metals Electron affinity is the energy change when each
atom in one mole of gaseous atoms gains one
b metalloids electron to form an ion with a charge of −1.
6 s, p, d and f M(g) + e− M−(g)
Name relates to the highest energy sub-shell 6 The energy change when each atom in one
occupied by electrons. mole of gaseous atoms loses one electron to
7 a alkali metals form an ion with a charge of +1.

b halogens M(g) M+(g) + e−

c noble gases 7 a Atomic radius decreases;


the nuclear charge increases across a period,
d lanthanides
but the shielding stays constant (the number
e actinides of complete inner electron shells stays the
same) so the force of attraction between the
f transition metals
outer electrons and the nucleus increases,
8 hydrogen pulling the electrons closer to the nucleus,
and so, decreasing the atomic radius.
9 a Period 4, Group 15
b First ionisation energy increases
1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p3
(becomes more endothermic);
b Period 4, Group 11 the nuclear charge increases across a
1s2 2s2 2p6 3s2 3p6 3d10 4s1 period, but the shielding stays constant
(the number of complete inner electron
c Period 6, Group 6 shells stays the same) so the outermost
10 a carbon electron experiences a stronger force of
attraction towards the nucleus, and more
1s2 2s2 2p2 energy is required to remove it.
b potassium c Electronegativity increases;
1s 2s 2p 3s 3p 4s
2 2 6 2 6 1
the nuclear charge increases across a period,
c rhodium but the shielding stays constant (the number
of complete inner electron shells stays the
Exercise 10.2 same) and the atomic radius decreases, so
the force of attraction between the nucleus
1 Nuclear charge increases across a period and of an atom and a shared pair of electrons
down a group. in a covalent bond increases.

2 Shielding is constant across a period and 8 a Atomic radius increases; the force of
increases down a group. attraction between the positive nucleus and
outer-shell electrons decreases, as there
3 The strength of the forces of attraction are more shells of electrons. (The effect of
increase across a period as the nuclear charge the increase in nuclear charge is effectively
increases and shielding stays constant. cancelled out by the increase in the number
of complete shells of shielding electrons.)

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b First ionisation energy becomes less 4 a 4K(s) + O2(g) 2K2O(s)

endothermic down a group, as the
force of attraction between the positive b 2K(s) + Cl2(g) 2KCl(s)
nucleus and outer-shell electrons decreases, c 2K(s) + H2O(l) 2KOH(aq) + H2(g)
as there are more shells of electrons; these
forces are acting over a larger atomic 5 Reactivity increases down the group, as all the
radius, so the outer electron is held less reactions involve the formation of M+ ions.
strongly. (The effect of the increase in The energy required for this (first ionisation
nuclear charge is effectively cancelled energy) decreases down the group, as the
out by the increase in the number of outermost ns1 electron is further away from
complete shells of shielding electrons.) the attractive force of the positive nucleus, and
so, it is more easily lost.
c First electron affinity becomes less
exothermic down a group as the atomic Metallic character increases down the
radius increases; the force of attraction group, as the tendency to form a positive
between the positive nucleus and the ion increases as the first ionisation energy
electron being gained decreases and becomes less endothermic.
the electron is attracted less strongly. 6 Outer electrons are ns2 np5.
(The effect of the increase in nuclear
charge is effectively cancelled out by 7 The elements form diatomic molecules,
the increase in the number of complete X2, with a covalent bond between the two
shells of shielding electrons.) halogen atoms.
d Electronegativity decreases down a group There are weak London forces between the
as the atomic radii and the shielding molecules.
increases. Therefore the ability of the
8 There are only weak London forces between
nucleus to attract the shared electrons in a
the X2 molecules. The strength of these
covalent bond decreases.
forces increases down the group, as they
depend on the number of electrons that
Exercise 10.3 produce the temporary dipole. The number
1 Outer electron is ns1. of electrons increases down the group, and
so, the temporary dipole increases, requiring
2 metallic bonding increasingly more energy to overcome the
forces between the molecules.
3 Melting point decreases as the force of
attraction between the lattice of +1 charged 9 a A series of experiments can be used,
cations and the delocalised electrons decreases. mixing an aqueous solution of each
This decrease is due to the increased ionic halogen with a solution containing a
radius down the group. halide ion as indicated in the table.

Solution containing Solution containing Solution containing

chloride ions e.g. sodium bromide ions e.g. sodium iodide ions e.g. sodium
chloride(aq) (colourless) bromide(aq) (colourless) iodide(aq) (colourless)
chlorine solution solution turns orange; solution turns yellow/
(very pale green) Equation (1) brown; Equation (2)
bromine solution no observable change solution turns yellow/
(orange) brown; Equation (3)
iodine solution no observable change no observable change
(yellow/brown)

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Equation (1): which is lower than the value expected by

Cl2(aq) + 2Br−(aq) 2Cl−(aq) + Br2(aq) the dissolving of atmospheric CO2.
Equation (2): 3 The oxides of nitrogen and sulfur formed by
Cl2(aq) + 2I−(aq) 2Cl−(aq) + I2(aq) the burning of fossil fuels, which dissolve in
Equation (3): rain to give acidic solutions. Nitrogen oxides
Br2(aq) + 2I−(aq) 2Br−(aq) + I2(aq) are formed from the reaction of atmospheric
nitrogen and oxygen at the high temperatures
b redox = reduction/oxidation at which fossil fuels are burnt. Sulfur is found
Br2(aq) + 2I−(aq) 2Br−(aq) + I2(aq) as an impurity in fossil fuels.

Bromine is reduced, as it gains electrons: 4 Acid rain is harmful to trees/plants and

Br2 + 2e− 2Br− fish, as it changes the mineral composition
of soils and water courses either reducing
Iodide ions are oxidised, as electrons are the concentration of essential minerals or
lost: 2I− I2 + 2e− increasing the concentration of harmful ones.
10 a oxides of sodium and magnesium Acid rain also damages buildings and statues,
b aluminium oxide particularly those made from limestone
or marble.
c silicon, phosphorus, sulfur and
chlorine oxides
Exercise 10.5
11 a Na2O (s) + H2O(l) 2NaOH(aq)
1 a oxidation
alkaline
b reduction
b MgO(s) + H2O(l) 2Mg(OH)2(aq)
c reduction
alkaline
d oxidation
c CO – no reaction with water, not soluble
e reduction
d CO2(g) + H2O(l) H2CO3(aq)
f oxidation
acidic
g oxidation
e 2NO2(g) + H2O(l) HNO2(aq) + HNO3(g)
h reduction
acidic
2
f SO2(g) + H2O(l) H2SO3(aq) Substance Oxidation states
acidic KBr K: +1 Br: −1
g SO3(g) + H2O(l) H2SO4(aq) PCl5 P: +5 Cl: −1
acidic Fe2O3 Fe: +3 O: −2

Exercise 10.4 NaNO2 Na: +1 N: +3 O: −2

K2CrO4 K: +1 Cr: +6 O: −2
1 CO2 dissolves in water, forming the weak
acid H2CO3. This dissociates to form HCO3− H2 H: 0
and H+ ions. The H+ ions lower the pH of
the oceans. As corals, the exoskeletons and SO42− S: +6 O: −2
shells of many oceanic species are made from HCO3− H: +1 C: +4 O: −2
CaCO3, which reacts with H+ ions; these
species may find making shells, exoskeletons, NO3 −
N: +5 O: −2
etc. more difficult at lower pH.
2 All rain is naturally acidic due to dissolved
CO2, but this is not acid rain. Acid rain is
defined as rain with a pH lower than 5.6,

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3 a Li: +1, Al: +3, H: −1 6 There is a general increase in the first ionisation
energy, as there is a stronger force of attraction
b Na: +1, O: −1 between the outer-shell electrons and the
2 increasing number of protons, which is not offset
c C: −2 , H: +1
3 by any increase in shielding across a period.
4 a copper(I) iodide
7 The outer-shell electron in an aluminium
b vanadium(V) oxide atom is in the 3p sub-level. This is slightly
shielded by the 3s sub-level, and this shielding
c chromium(III) sulfate(VI)
effect slightly reduces the force of attraction
d ammonium vanadate(V) between the outer-shell electron and the
nucleus compared to the outer-shell electron
e potassium chromate(VI)
in the 3s sub-level of a magnesium atom.
f sodium nitrate(III)
Sulfur has 4 electrons in the 3p sub-level;
g scandium(III) sulfate(IV) two paired electrons with opposite spin in
one orbital and two unpaired electrons in
5 a FeO
separate orbitals. The paired electrons slightly
b NaClO repel each other, and this makes one of them
slightly easier to remove, so the first ionisation
c KBrO3 energy of sulfur is slightly lower than that
d FeSO4 of phosphorus, which has 3 singly occupied
unpaired electrons in its 3p sub-level.
e H2SO3
f KMnO4 Exercise 10.7
g Cr(NO3)3 1 An element with outer-shell electrons in a d
h N2O sub-shell.

i NO 2 An element that forms at least one stable ion

with a partially filled d sub-shell.
j NO2
3 exhibit variable oxidation states
Exercise 10.6 form coloured compounds

1 Nuclear charge increases down a group as elements and their compounds often act
the number of protons increases. as catalysts

2 Shielding increases down a group, as there form complex ions

are more complete inner shells of electrons. exhibit magnetic properties
3 Ionisation energies decrease down a group as 4 The only stable ion of zinc is Zn2+, which has
the number of shells of electrons increases. a full d sub-shell, and so, does not meet the
Therefore, the force of attraction between the definition of a transition metal.
nucleus and the outermost electron is weaker, and
so, less energy is required to remove an electron. 5 a Zn 1s2 2s2 2p6 3s2 3p6 4s2 3d10
b Sc 1s2 2s2 2p6 3s2 3p6 4s2 3d1
4 Nuclear charge increases across a period
(as the number of protons increases c Ti 1s2 2s2 2p6 3s2 3p6 4s2 3d2
sequentially by one from left to right).
d Cr 1s2 2s2 2p6 3s2 3p6 4s1 3d5
5 Shielding is constant, as there are the same
e Ni 1s2 2s2 2p6 3s2 3p6 4s2 3d8
number of complete inner shells of electrons
across a period. f Cu 1s2 2s2 2p6 3s2 3p6 4s1 3d10
g Fe3+ 1s2 2s2 2p6 3s2 3p6 3d5

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h Mn2+ 1s2 2s2 2p6 3s2 3p6 3d5 Exam-style questions

i V 1s 2s 2p 3s 3p 3d
3+ 2 2 6 2 6 2
1 B
j Co2+ 1s2 2s2 2p6 3s2 3p6 3d7
2 C
6 Transition elements exhibit variable
oxidation states because the difference 3 A
between successive ionisation energies is not 4 D
particularly large, and there is no large jump
between the 4s and 3d levels. 5 B
7 Coordination bond, with electrons donated 6 D
by the ligand to the central ion/atom.
7 D
8 the number of coordination bonds
8 A
9 L
9 B
L L
M M 10 D
L L L
L L 11 D
L 12 a Mg2+ has one fewer shell of electrons/two
L
fewer electrons [1] and the same nuclear
L M L charge/number of protons [1]. Electron–
L electron repulsion is lower (in Mg2+) [1], so
L the force of attraction between the positive
10 [Cr(SCN)6]3− nucleus and the outermost electrons is
increased and the radius is decreased [1].
11 a Ag: +1
b Metallic character is described as
b Fe: +3 the tendency to form cations [1].
c Pt: +2 Due to decreasing first ionisation energies
d Ni: +2 down the group [1] as the atomic radius
increases [1], metallic character rises.
12 d orbitals are often split into two groups
(3/2) with different energies. The energy c Group 18 elements do not form
gap corresponds to the visible part of the covalent bonds. [1]
electromagnetic spectrum. This wavelength
is absorbed as electrons jump from the lower 13 a Oxides change from basic to
to the higher energy level. The substance amphoteric to acidic. [1]
will appear the complementary colour Equation for a basic oxide forming
of the wavelengths absorbed. a salt or reaction with water [1]
13 green e.g.
14 The identity of the transition element.
Na2O + 2H+ 2Na+ + H2O
Its oxidation state.
Na2O + H2O 2NaOH
The identity of the ligands.
MgO + 2H+ Mg2+ + H2O
The coordination number of the complex.
MgO + H2O Mg(OH)2
The shape of the complex.
Equations for Al2O3
15 The greater the splitting of the d orbitals, the
larger the energy gap, and so, the shorter the Al2O3 + 6H+ 2Al3+ + 3H2O [1]
wavelength of light absorbed.
Al2O3 + 2OH− + 3H2O 2Al(OH)4− [1]

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Equation for an acidic oxide with 15 a [Cu(H2O)6]2+ + 4Cl− [CuCl4]2− + 6H2O

water or forming a salt [1]  [1]
e.g. SO2 + H2O H2SO3 b Green colour is due to a mixture of
both complexes. [1]
SO3 + H2O H2SO4
c H H
2+ 2–
SO3 + CaO CaSO4 H
O Cl
b First ionisation energies increase O H
H H
across Period 3. [1] O Cu O Cu Cl
H H
H O O 90° Cl
109.5°
Cl
As the number of protons/positive charge H
on nucleus increases [1], but the amount H H
of shielding/number of shells of electrons
stays the same [1], the force of attraction 3D diagrams [1 each]
between the outer electron and the all bond angles correct [1]
positive nucleus increases. [1]
oxidation states (+2) clearly indicated
c Metallic character decreases across but not by use of central Cu2+ [1]
Period 3 [1], as the bonding changes
from metallic to covalent [1] due to the d 
blue complex/[Cu(H2O)6]2+ absorbs
increasing first ionisation energies 585 – 647 nm [1]
across the period. [1] yellow/[CuCl4]2− absorbs 400 – 424 nm [1]
14 a Transition elements are those that form
at least one stable ion with a partially
filled d sub-shell. [1] Zinc only forms
one stable ion, Zn2+, which has a full
d sub-shell, and so, does not qualify
as a transition element. [1]
b i Transition metals exhibit variable
oxidation states, as there are no
large jumps in successive ionisation
energies [1], because the 3d and 4s
energy levels are close together. [1]
ii form complex ions
form coloured compounds
often act as catalysts
exhibit magnetic properties [max 3]
c Cu+ 1s2 2s2 2p6 3s2 3p6 3d10 [1]
Cu2+ 1s2 2s2 2p6 3s2 3p6 3d9 [1]
As Cu+ has a full d sub-shell, its
compounds are likely to be white,
whereas Cu2+ compounds are coloured/
Cu+ compounds will be diamagnetic, as
all the electrons are paired, whereas
Cu2+ will be paramagnetic. [1]

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Chapter 11
Exercise 11.1 5 a CH3CH2CH(OH)CH2CH3
b CH3CHC(CH3)2
1 a H H H H

H C C C C H
c CH3CH(NH2)CH(CH3)COOH

H H OH H 6 a C6H8O6

H O H b C3H4O3
b
c H H H
H C O C C H O
H H C C C C O
H
H O O HC C
c H Cl
H H O O H
C C H
H C C H d OH
O
H Cl HO O
2 a CH2BrCH2CH2OH
b CH3COCH2COOH H O O H

c CH3CHCH(CH2)3CH3 7 a molecular formula, C8H8O2

3 a empirical formula, C2H4O

H
b molecular formula, C12H16
C
H H empirical formula, C6H8
OH
b H H c molecular formula, C8H10O
C C empirical formula, C8H10O
H H
H H
c H H
Exercise 11.2
C C 1 a CnH2n+2
H H
b CnH2n
4 a
c CnH2n+2O or CnH2n+1OH
OH
2 They have the same functional group.
b Br
3 Each member of a homologous series differs
by a CH2 group, so there is a gradual change
in physical properties as the molar
O mass increases.
c
4 C C
5 hydroxyl, O H

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6 8 a carbonyl, bromo, alkoxy

Homologous Functional Name of
series group functional b hydroxyl, carbonyl, carboxyl
group
c alkoxy, amino, phenyl, ester, amido
alcohol O H hydroxyl
9 a Boiling points increase as the number of
aldehyde O carbonyl carbon atoms increases and the number
C of electrons increases, which increases the
H strength of the London forces between
the molecules.
alkane alkyl
b As the molar mass increases, the addition
alkene C C of just one extra CH2 unit becomes less
significant compared to the total molar mass,
alkyne C C and so, the boiling point increases by smaller
amide O amido increments leading to a non-linear change.
C 10 a A, C, B
NH2
b A, C, B
amine NH2 amino c A has the lowest boiling point, as it has only
NHR London forces, which are the weakest type
NR2 of intermolecular force, so A requires the
least amount of energy to overcome these.
carboxylic acid O carboxyl B and C can both form hydrogen bonds.
C Hydrogen bonds are stronger than London
O H forces, and so, B and C require more energy
to overcome these, and so, have higher
ester O ester boiling points than A. B has the highest
C boiling point, as B can form more hydrogen
O C bonds than C because B has more lone
pairs of electrons than C. B and C are both
ether C O C alkoxy soluble, as they can form hydrogen bonds
halogenoalkane F halogeno with water. A is non-polar, so it is insoluble.
Cl
Exercise 11.3
Br
I 1 a butane

ketone O carbonyl b 2-bromopropane

C c 3-methylpentane
C C d 2-methylbutanoic acid
e pentan-2-one
7 a CnH2n−2
f ethanal
b CnH2n+1X
g 3-methylbut-1-ene
c CnH2nO
h 3,4,4-trimethylpent-2-ene
d CnH2nO
i 4-chloro-3,4-dimethylhexan-2-ol
e CnH2nO2 j 2-bromo-3,4-dichloro-but-1-ene
f CnH2nO2 2 a H H H H H
H
C C C C C C H
H H H H H

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b 5
c CH3OCOCH2CH3 or CH3CH2COOCH3
or or or
d CH3

C
CH3 CH3 6 H H H
Br
H C C O C H
e O O O
or or H H H
O O O
7 H H
O
3 Saturated means that a molecule contains only
carbon–carbon single bonds. H C C C
H
Unsaturated means that there is at least one H H
carbon-carbon double bond.
8 O
4 alkenes and alkynes
H C O CH3
5 alcohols, halogenoalkanes and amines
9 The branched-chain isomer will have a lower
6 a saturated hydrocarbons: a and c
boiling point than the straight-chain isomer
b unsaturated hydrocarbons: g and h because there are fewer points of contact
between molecules, which means that the
c primary (chloro): j intermolecular London forces are weaker.
d secondary: (bromo) b and j, (chloro) j, 10 cis–trans isomerism occurs when there is
(hydroxyl) i restricted rotation in a molecule. This can
e tertiary (chloro) i be due to the presence of a C C or in a
cyclic molecule.
7 molecule d is a carboxylic acid
11 a no
molecule e is a ketone
b no
molecule f is an aldehyde
c yes
Exercise 11.4 d yes
1 12 a H H H

pentane 2-methylbutane 2,2-dimethylpropane H C C C C C H

H H H H H
2
but-1-ene but-2-ene b Cl

3 H H H H H H
Cl
H C C C H H C C C H
c Cl
Br H H H Br H
1-bromopropane 2-bromopropane Cl

4 OH OH OH 13 a cis-1,2-dimethylcyclobutane
OH b trans-4-bromopent-2-ene
c cis-2,2-dibromo-5-methylhex-3-ene
OH
OH

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14 non-superimposable mirror images; B, C, N, S, 3 a 3200–3600 cm−1 (strong/broad), O H

E, Z
2850–3090 cm−1 (strong), C H
15 It will be chiral if it contains a carbon atom
with four different groups attached to it. 1050–1410 cm−1 (strong), C O

16 a CH3 CH3 b 2850–3090 cm−1 (strong), C H

and 1620–1680 cm−1 (multiple weak), C C
C C
H OH HO H
CH2NH2 H2NCH2 c 2500–3000 cm−1 (strong/very broad), O H
2850–3090 cm−1 (strong), C H
b not chiral
1700–1750 cm−1 (strong), C O
c not chiral
d 2850–3090 cm−1 (strong), C H
d
1700–1750 cm−1 (strong), C O
C and C
H Br Br H 1050–1410 cm−1 (strong), C O
OH HO
4 a 3300–3500 cm−1 (2 medium bands), N H
17 enantiomers in primary amines
18 There is a plane of symmetry, so the mirror 2850–3090 cm−1 (strong), C H in alkanes,
images are superimposable. alkenes, arenes
plane of symmetry
b 1700–1750 cm−1 (strong), C O in
CH3 CH3 aldehydes and ketones (note, not an ester
or carboxylic acid due to the absence of a
H H
broad O H peak at 2500–3000 cm−1)
19 Molecules that are optically active rotate the 5 dipole moment
plane of polarisation of plane-polarised light.
6 a yes (bent-shaped molecule)
20 racemates or a racemic mixture
b no (no dipole)
21 Physical properties are the same, apart
from the direction that they rotate c yes (dipole)
plane-polarised light.
7 bending and stretching vibrations
Chemical properties may react differently
8 The amount of water vapour in the
when they react with other chiral molecules.
atmosphere is much higher than the amounts
of both carbon dioxide and methane, but its
Exercise 11.5 amount is only directly influenced to a small
1 If the characteristic vibration frequency of a extent by human activities.
bond matches with frequencies in the infrared 9 The fragmentation pattern is the pattern of
region of the electromagnetic spectrum, then peaks produced when the molecule breaks
infrared radiation will be absorbed causing into smaller pieces or fragments.
increased bond vibrations.
10 mass to charge ratio
2 It can be used to identify a molecule (by
comparing the signals in the fingerprint region 11 molecular ion peak
to a database of known substances). 12 a CH3+
b C2H3+ (e.g. H2C CH fragment)
c CH3CH2+

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13 peak at m/z = 60 is CH3CH2CH2OH+

peak at m/z = 59 is CH3CH2CH2O+
peak at m/z = 31 is CH2OH+
peak at m/z = 29 is CH3CH2+
14 peak at m/z = 110, CH3CH281Br+
peak at m/z = 108, CH3CH279Br+
peak at m/z = 95, CH281Br+
peak at m/z = 93, CH279Br+
peak at m/z = 81, 81Br+
peak at m/z = 79, 79Br+
peak at m/z = 29, CH3CH2+
peak at m/z = 15, CH3+
15 hydrogen atoms
16 radio-frequency range
17 a The number of different H environments.
b The ratio of the number of H atoms in each environment.
c The number of H atoms on adjacent atoms/neighbouring H atoms.
d The nature of each environment/functional group.
18 Used as a reference standard and given a chemical shift of 0 ppm.

19
Compound Number of Splitting pattern Ratio of Chemical shift /
signals integration trace ppm
propanone 1 singlet 9 2.2–2.7
1-chlorobutane 4 triplet 3 0.9–1.0
sextet 2 1.3–1.4
pentet 2 1.3–1.4
triplet 2 3.5–4.4
2-chlorobutane 4 triplet 3:2:1:3 0.9–1.0
pentet 1.3–1.4
pentet 3.5–4.4
doublet 1.3–1.4

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20 δ 1.0, 3H: CH3 9 C

triplet so adjacent to 2H 10 A

δ 2.0, 3H: CH3COO group 11 C

singlet so no adjacent H 12 C

δ 3.9–4.4, 2H CH2 O CO 13 a The boiling points of the alkanes

increase as the number of carbon
quartet, so three adjacent H atoms increases. [1]
molecule is CH3CH2OCOCH3, ethyl ethanoate This is because the presence of an extra
CH2 group increases the relative
21 a C5H8
molecular mass and the number of
b 1630 cm–1, C C bonds electrons in the molecule, so the
strength of the London forces increases.  [1]
2900 cm–1, C H bonds
b Although the increase in mass from
c molecular ion peak at m/z = 136, C10H16+ one member of the series to the next
other possible peaks at is regular, the size of the increase
becomes less significant as the total
15, due to CH3+ mass increases. [1]
41, due to C3H5 +
c London forces depend on the number of
electrons in a molecule/relative molecular
68, due to C5H8+
mass so compounds with similar
95, due to C7H11+ masses/numbers of electrons should
be compared. [1]
121, due to C9H13+
d for suitable choice/molecules with
d 8 similar molar mass. [1]
1
H e.g. butane (Mr = 58), bp 0 °C
H H
C non-polar with London forces [1]
8 H H 2
C chloroethane (Mr = 64.5), bp 12 °C,
H C C
polar with permanent dipole–dipole
H C C H
7 C 3 forces [1]
H H
C H 4 propan-1-ol (Mr = 60), bp 100 °C
H C C H with hydrogen bonds between
6 H the molecules [1]
H H 5
comparison of strength of the
intermolecular forces, London
Exam-style questions < dipole–dipole < hydrogen bonding [1]
1 B 14 a
2 C but-1-ene but-2-ene

3 A for each structure [1]

4 C for correct name [1]
5 A b alkenes [1]
6 D c H CH3  [1]
7 C C C

8 B H CH3

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d  [1]
or

e cyclobutane or methylcyclopropane [1]

15 a Optical isomers rotate the plane of
plane-polarised light in opposite
directions. [1]
A polarimeter is an instrument that
passes plane-polarised light through
a sample. [1]
A second polarising filter is rotated
such that its plane is perpendicular
to the plane of light coming through
the sample. [1]
The angle of rotation is then
measured. [1]
b
CH3 CH3

C C
H H
CH3CH2CH2 CH2CH3 CH3CH2 CH2CH2CH3

correct isomer drawn (3-methylhexane)[1]

correct drawings of both enantiomers [1]
c trans-1,2-dimethylcyclopropane [1]
H CH3 CH3 H
H H H H

H H
CH3 CH3

correct drawings of both enantiomers [1]

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Chapter 12
Exercise 12.1 6
Exothermic Endothermic
1 Temperature is a measure of the average a, d, e, g b, c, f, g
kinetic energy of the particles of a substance.
7 activation
2 K, kelvin energy
3 J, joule

potential energy
4 J mol−1 or kJ mol−1, joules (or kilojoules) Products
per mole
ΔH
5 a Both have the same amount of Reactants
chemical energy.
b Water, as it is at a higher temperature.
reaction coordinate
c Nickel, as it has a larger mass.
8
activation
Exercise 12.2 potential energy
energy

1 a During exothermic reactions, chemical Reactants

energy is converted into heat energy.
b During endothermic reactions, heat ΔH
energy is converted into chemical energy. Products

2 ΔH
reaction coordinate
3 ΔH measures the enthalpy change of the
chemical system. If the energy of the system
decreases (i.e. is negative), then the energy
Exercise 12.3
is transferred to the surroundings and the 1 Constant pressure of 100 kPa and all
temperature of the surroundings increases. substances in their standard state.
The enthalpy change measures the change in
the chemical system; the temperature change 2 ⦵
measures the change in the surroundings.
3 a +572 kJ mol−1
4 a true
b –286 kJ mol−1
b true
c +286 kJ mol−1
c true
d true
Exercise 12.4
Q
e false 1 Q = mcΔT, so c =
mΔT
5 a exothermic (combustion) 384
= = 0.384 J g−1 K−1
b endothermic (evaporation = bond 20.0 × 50.0
breaking, energy is required to overcome Q 2000
the forces between the molecules) 2 a ΔT = = = 4.78 K
mc 100 × 4.18
c exothermic (neutralisation) Q 2000
b ΔT = = = 83.3 K
mc 100 × 0.240
Q 7500
c ΔT = = = 83.3 K
mc 100 × 0.900

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3 a mass of water heated = 326.5 – 212.3 40.0

= 114.2 g n(NaOH) = × 1.00 = 0.0400 mol
1000
temperature change = 77.5 – 21.5 = 56.0 °C therefore, n(H2O) formed = 0.0400 mol,
as NaOH is the limiting reactant
using Q = mcΔT
–Q –2295
Q = 114.2 × 4.18 × 56.0 = 26 732 J ΔH = = = –57371 J mol–1
n 0.0400
mass of fuel used = 104.0 – 99.3 = 4.70 g = −57.4 kJ mol–1

relative molecular mass of C5H11OH = 88.17 6 Using Q = mcΔT

m 4.70 Q = (30.0+20.0) × 4.18 × 8.2 = 1714 J
using n = = = 0.0533 mol
M 88.17 2HCl + Ca(OH)2 CaCl2 + 2H2O
–Q –26732
enthalpy change = = 30.0
n 0.0533 n(HCl) = v × c = × 1.00 = 0.0300 mol
1000
= –501 kJ mol –1
20.0
b Copper is a good thermal conductor, so it n(Ca(OH)2) = × 1.00 = 0.0200 mol
1000
allows the heat energy from the flame to
therefore, n(H2O) formed = 0.0300 mol, as
be transferred to water.
HCl is the limiting reactant
c Heat losses to the surrounding air and the –Q –1714
copper can. ΔH = = = –57127 J mol–1
n 0.0300
Evaporation of the water. = −57.1 kJ mol–1
d Lagging or insulating the copper can. m 2.00
7 n= = = 0.0238 mol
Reducing evaporation by reducing the M 84.01
temperature/not heating for as long/ Q = −ΔH × n = −(+18000) × 0.0238
adding a lid.
= −428.5 J
e Data book values are quoted for the Q –428.5
complete combustion of a fuel; it is ΔT = = = –4.1 K
unlikely that this fuel has undergone mc 25.0 × 4.18
complete combustion. Data book The temperature would fall by 4.1 K
values are for the formation of H2O(l), (endothermic reaction).
but H2O(g) is probably formed in
8 Using Q = mcΔT
this reaction.
Q = 50.0 × 4.18 × 8.6 = 1797.4 J
Data book gives values under standard
conditions of 100 kPa and 298 K, which m 0.400
n(Zn) = = = 6.12 × 10−3 mol
may not have been the conditions of M 65.38
the experiment. n(AgNO3) = v × c = 0.050 × 0.200
4 Using Q = mcΔT = 0.0100 mol
Q = (20.0 + 20.0) × 4.18 × 6.8 = 1137 J as the ratio is 2 : 1, AgNO3 is the limiting
5 Using Q = mcΔT reactant

Q = (50.0 + 40.0) × 4.18 × 6.1 = 2295 J n(Zn) reacting = 0.00500 mol

–Q –1797.4
HCl + NaOH NaCl + H2O ΔH = = = –359480 J mol–1
50.0 n 0.00500
n(HCl) = v × c = × 1.00 = 0.0500 mol = −359 kJ mol–1
1000

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9 The calorimeter contains zinc nitrate solution, m 2.00

unreacted solid zinc and solid silver. All of these c n(Mg) = = = 0.0823 mol
M 24.31
substances will be at the same temperature, as
n(CuSO4) = v × c = 0.050 × 0.100
they will all have taken in some of the energy
released by the reaction. The mass of the metals = 0.00500 mol
is very small, and so, the value of mcΔT for these
metals can be ignored. for both calculations [1]

10 a systematic (heat loss always results in a Mg and CuSO4 react 1 : 1 then Mg
measured temperature change smaller is in excess and CuSO4 is the
than it would in the absence of heat losses) limiting reactant [1]
–Q –2403.5
b By taking the temperature at regular d ΔH = = = –480700 J mol–1
intervals before and after mixing the n 0.00500
reactant. A graph can then be plotted = −481 kJ mol–1 (460–502 kJ mol–1)
and extrapolated to estimate a more
accurate temperature change – hence for the value [1]
quantifiable. (Increasing insulation/using for the correct sign (units must  [1]
a lid, reduces the heat losses but does not be given)
make them quantifiable.)
e The value obtained from the graph
Exam-style questions attempts to correct for the heat losses
from the solution to the surroundings. [1]
1 C
f Although volume/moles of CuSO4
2 B has doubled, Mg is still in excess. [1]
3 C Twice the n(CuSO4) would produce
two times the amount of energy but
4 D
two times the volume of solution is
5 A being heated, and so, the overall [1]
temperature change is the same. [1]
6 C
7 C
8 a between 11 and 12 °C [1]
b using Q = mcΔT
Q = 50 × 4.18 × 11.5 = 2403.5 J
allow 2299–2508 J [1]

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Chapter 13
Exercise 13.1
1 Average bond enthalpy: a, b and e
Bond enthalpy: c and d (as these are diatomic molecules)
2 Average bond enthalpy values are values calculated from a range of molecules containing a particular
bond. Bond enthalpy refers to the energy required to break (one mole of) bonds in a diatomic molecule.
3 gaseous

Exercise 13.2
1 a H H H H
1
H C C C C H + 6 2O O 4O C O +5 O
H H
H H H H

3×C C ( Bonds
broken ) ( Bonds
formed ) 8×C O
10 × C H 10 × H O
1
6 2 ×O O

4C(g) + 10H(g) + 13O(g)

ΔH = ((3 × 346) + (10 × 414) + (6.5 × 498)) − ((8 × 804) + (10 × 463)) = –2647 kJ mol–1

Alternatively, use the following formula:
ΔHr = Σbonds broken − Σbonds formed
ΔHr = 8415 − 11063 = −2647 kJ mol–1
b Bond enthalpy values are average values deduced from across a range of molecules, and so,
are not entirely accurate.
Standard enthalpy of combustion refers to substances in their standard states. In this equation,
H2O(g) is formed, but the data book value will refer to H2O(l).
2 a H H
H H
H C C O H C C + O

H H H H H H

bonds broken = C C, 5 × C H, C O, O H
= 346 + (5 × 414) + 358 + 463 = 3237
bonds formed = C C, 4 × C H, 2 × O H
= 614 + (4 × 414) + (2 × 463) = 3196
ΔH = ΣΔHbroken − ΣΔHformed
ΔH = 3237 − 3196 = +41 kJ mol−1

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b H H
N N + O O N N + 2 O
H H H H
bonds broken = N N, 4 × N H, O O
= 158 + (4 × 391) + 498 = 2220
bonds formed = N N, 4 × O H
= 945 + (4 × 463) = 2797
ΔH = ΣΔHbroken − ΣΔHformed
ΔH = 2220 − 2797 = −577 kJ mol−1
c H H H H H
H
H C C C + Cl–Cl H C C C H

H H H Cl Cl
bonds broken = C C, C C, 6 × C H, Cl Cl
= 346 + 614 + (6 × 414) + 242 = 3686
bonds formed = 2 × C C, 6 × C H, 2 × C Cl
= (2 × 346) + (6 × 414) + (2 × 324) = 3824
ΔH = ΣΔHbroken − ΣΔHformed
ΔH = 3686 − 3824 = −138 kJ mol−1
3 H 6 ΔH = ΔH3 + ΔH1 − ΔH2
–114
C O + 2H H H C O H ΔH = −136 + (−99) − (−185)
H = −50 kJ mol−1
bonds broken = C O, 2 × H H
7 a C6H6 (l) + 3H2 (g) C6H12 (g)
= C O + (2 × 436) = C O + 872
+7 12 O2 (g) +1 12 O2 (g) +9O2 (g)
bonds formed = 3 × C H, C O, O H
–3268 3× –286 –3920
= (3 × 414) + 358 + 463 = 2063
ΔH = ΣΔHbroken − ΣΔHformed = −114 6CO2 + 6H2O (l)

−114 = (C O + 872) − 2063 b ΔH = −3268 + (3 × −286) − (−3920)

C O = −114 + 2063 − 872 = −206 kJ mol−1
= 1077 kJ mol−1 8 Mg (s) + Zn2+(aq) Mg2+(aq) + Zn(s)
4 ΔH = −(180) + 66 = −144 kJ mol−1 +2Ag+(aq) +2Ag+(aq)
5 Combining equation 2 with equation 1 gives
the equation –145 –85

4PCl5(g) 4PCl3(g) + 4Cl2(g)

Mg2+(aq) + 2Ag(s) + Zn2+(aq)
so ΔH2 + ΔH1 = ΔH × 4
ΔH = −145 − (−85)
= 3438 + (−2438) = 1000
= −60 kJ mol−1
1
so ΔH = × 1000
4
= +250 kJ mol−1

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9 N2 H4(l) + H2(g) 2NH3(g) + CH3OH(l) 4 ΔH = ΔH1 + ΔH2 − ΔH3

+CH3OH(l) ΔH = −1367 + (−874) − (−2238)

–46 –65 = −3 kJ mol−1
–37
Exercise 13.4
HCHO(g) + N2(g) + 3H2(g)
1
1 a 3C(s) + 4H2(g) + O2(g) C3H7OH(l)
ΔH = −37 + (−46) − (−65) 2

= −18 kJ mol−1 1
b Mg(s) + C(s) + 1 2 O2 MgCO3(s)
or
1 1
ΔH = ΔH1 + ΔH2 − ΔH3 c H (g)
2 2
+ 2
I2(s) HI(g)

ΔH = −37 + (−46) − (−65) 1

d H2(g) + 2
O2(g) H2O(l)
= −18 kJ mol −1

2 a
Exercise 13.3
CH3CH = CH2 (g) + HCl (g) CH3 CHClCH3 (g)
1 a CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

15 +20 –92 –145

b C5H10(g) + 2
O2(g) 5CO2(g) + 5H2O(l)
1 1
3C (s) + 3 H2 (g) +2 2 Cl2 (g)

9
c C3H7OH(l) + 2
O2(g) 3CO2(g) + 4H2O(l) ΔH = −(+20) − (−92) + (−145)
= −73 kJ mol−1
2 a 2C (s) + O2 (g) 2 CO (g)
b The arrows in the Hess cycle point away
2× –394 2× –283 from the elements, and so, the expression
is as follows:
2CO2 (g)
ΔH⦵ = ΣΔH⦵f(products) − ΣΔH⦵f(reactants)
ΔH = (2 × −394) − (2 × −283) 1
3 C6H6(l) + 7 2 O2(g) 6CO2(g) + 3H2O(l)
= −222 kJ mol −1

b Hess’s cycle has arrows pointing to using

the combustion products, CO2 in this ΔH⦵ = ΣΔH⦵f(products) − ΣΔH⦵f(reactants)
example, so the enthalpy of reaction can
be found using the following expression: ΔH = [(6 × −394) + (3 × −286)] − (+49)

ΔH = ΣΔH⦵c(reactants) = ΣΔH⦵c(products) = −3271 kJ mol−1

3 Using ΔH = ΣΔH⦵c(reactants) − 4 ΔH = −ΔH1 − ΔH2 + ΔH3 + ΔH4

ΣΔH⦵c(products)
ΔH = −(−278) − (−484) + (−479) + (−286)
ΔH = (−3800 + (−286) − (−3920)
= −3 kJ mol−1
= −166 kJ mol−1

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5 –2
C2H5OH (1) + SOCl2 (g) C2H5Cl (g) + SO2 (g) + HCl (g)

ΔHf (SOCl2) –297 –92

–278 –137

2 C (s) + 3H2 (g) +O2 (g) + 3 (s) + Cl2 (g)

ΔH = −ΔH1 − ΔHf(SOCl2) + ΔH2 + ΔH3 + ΔH4

−2 = −(−278) − ΔHf(SOCl2) + (−137) + (−92) + (−297)
ΔHf(SOCl2) = −(−278) + (−137) + (−92) + (−297) −(−2)
ΔHf(SOCl2) = −246 kJ mol−1

Exercise 13.5 B enthalpy of atomisation of oxygen

1
1 a Ca(g) Ca+(g) + e– or 2
bond enthalpy of oxygen

b Mn+(g) Mn2+(g) + e– C first ionisation energy of calcium

1 D second ionisation energy of calcium

c Li(s) + 2 F2(g) LiF(s)
E first electron affinity of oxygen
d O(g) + e− O–(g)
F second electron affinity of oxygen
e S−(g) + e− S2−(g)
G lattice enthalpy of CaO
f CaCl2(s) Ca2+(g) + 2Cl−(g)
1 H enthalpy of formation of CaO
g Br (l)
2 2
Br(g)
ΔHf = (+178) + (+249) + (+590) +
b 
h Na(s) Na(g) (+1145) + (–141) + (+753) − (+3401)
i Mg(s) Mg(g) = –627 kJ mol–1
j Cl2(g) 2Cl(g) c The value for MgO is more endothermic
2 a endothermic than CaO, which suggests that more
energy is required to separate the lattice
b endothermic into its gaseous ions, so the electrostatic
c exothermic forces of attraction between the ions in
MgO must be stronger than in CaO. This
d endothermic is because the radius of the Mg2+ ion is
smaller than the Ca2+ ion. Electrostatic
e either (although exothermic is more
forces of attraction are stronger over
common)
smaller distances.
f endothermic
g endothermic Exam-style questions
h endothermic 1 A

i endothermic 2 C

3 a A enthalpy of atomisation (or 3 B

sublimation) of calcium 4 D
5 D

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6 A
7 C
8 A
9 C
10 D
11 a H H
H
C C C H + 4 12 O O 3O C O +3 H O H
H H +4 ×O
1
2 O 6×C O

1×C C 6×O H
6×C H
1×C C
3C(g) + 6H(g) + 9O(g)

ΔH = (614) + (6 × 414) + (346) + (4.5 × 498) − (6 × 804) − (6 × 463)

= –1917 kJ mol–1 [3]
if any one sign is incorrect or multiples are missed [−1]
more than two mistakes [0]
b O O can be considered to only occur 14 a A, standard enthalpy of formation
in O2, so the bond enthalpy for the of C6H6 [1]
O O bond is not calculated using average
B, standard enthalpy of formation
values deduced from across a range of
of C6H5Cl [1]
different molecules. [1]
C, standard enthalpy of formation
12 a Hess’s law states that the energy change of HCl [1]
for a reaction is independent of the
route provided that the conditions b ΔHr = –(49) + (11) + (–92.3)
remain unchanged. [1] = –130.3 kJ mol–1 [2]
b ΔH = −175 − (−125) if any one sign is incorrect [−1]
= −50 kJ mol  −1
[1] more than one mistake [0]
1
13 a C6H5COOH(s) + 72 O2(g) 15 a 3C (s) + 3H2 (g) C3H6 (g)
7CO2(g) + 3H2O(l) + 32 O2 + 4 12 O2
+3O2 (g)
for formula [1] 3× –394 3× –286 –2058
for balancing [1]
3 CO2 (g) + 3H2O (l)
for state symbols [1]
for CO2 and H2O, ignoring balancing [1]
b Using ΔH⦵ = ΣΔH⦵f (products) −
ΣΔH⦵f (reactants) for cycle correctly balanced,
including O2 [1]
ΔH = (7 × −394) + (3 × −286) − (−385)
for arrows in correct directions [1]
= −3231 kJ mol−1
b enthalpy of formation of C3H6 [1]
all correct [2]
c ΔH = (3 × −394) + (3 × −286) − (−2058) [1]
for each error in sign or multiple [−1]
= 18 kJ mol−1 [1]

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16 a A: Mg(g) + Br2(l) b lattice enthalpy = –(–524) + (129) + (30) +

(193) + (738) + (1450) + (2 × –325)
B: enthalpy of vaporisation of bromine
= 2414 kJ mol–1  [3]
C: Br Br bond enthalpy or 2 × enthalpy
of atomisation of bromine if any one sign is incorrect or
multiples are missed [−1]
D: Mg(g) + 2Br(g)
more than two mistakes [0]
E: second ionisation energy of magnesium
c The larger the ionic radii, the less
F: Mg2+(g) + 2Br(g) + 2e– endothermic the lattice enthalpies. [1]
G: first electron affinity of bromine (×2) The higher the charges on the ions, the
H: lattice enthalpy of MgBr2 more endothermic the lattice enthalpies. [1]

I: enthalpy of formation of MgBr2

8 or 9 correct [4]
6 or 7 correct [3]
4 or 5 correct [2]
1, 2 or 3 correct [1]

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Chapter 14
Exercise 14.1 10 2C5H11OH + 5O2 10C + 12H2O
11 Complete combustion: blue flame
1 addition of oxygen
loss of hydrogen Incomplete combustion: yellow flame due to
the production of carbon particulates/soot.
loss of electrons
increase in oxidation state Exercise 14.2
2 loss of oxygen 1 A fuel formed from the remains of organisms
that lived millions of years ago.
gain of hydrogen
2 natural gas, coal, crude oil
gain of electrons
3 Carbon dioxide is a greenhouse gas and
decrease in oxidation state contributes towards global warming and
3 Oxidation and reduction always occur at the climate change.
same time.
There are only finite supplies of
4 non-renewable fuels, so these will
Oxidised Reduced
eventually run out.
a Na O2
4 a Coal is easiest to store because it is
b Li H2O a solid; gas is the most difficult, as it
takes up a large volume unless it is
c CO Fe2O3 compressed or liquified, which requires
d H2 C2H4 heavy cylinders/tankers to keep the gas
under pressure. There is a higher risk of
e NaBr Cl2 explosions with gas, as it ignites more
f Cu Ag+ easily than coal and oil.
b Gas is easiest to transport, as it is a gas;
5 a H2SO4 oil is also relatively easy, as, being a liquid,
it too can flow through pipelines. Coal is
b Fe3+ the most difficult to transport.
c CuO c Gas burns most cleanly, whereas coal
6 a Zn burns least cleanly, as a lot of incomplete
combustion tends to occur.
b Al
d Coal tends to contain more impurities,
c Cu such as sulfur, than oil or gas, and this
7 a C4H8 + 6O2 4CO2 + 4H2O causes acid rain.

b C10H22 + 15.5O2 10CO2 + 11H2O Coal production also produces large

heaps of spoil from mining, and coal
or mines are unsightly and cause a loss
of habitats.
2C10H22 + 31O2 20CO2 + 22H2O
Oil spills can cause significant pollution
c C3H7OH + 4.5O2 3CO2 + 4H2O
and environmental damage.
or 2C3H7OH + 9O2 6CO2 + 8H2O
e Coal releases the lowest amount of
8 Carbon, carbon monoxide and water. energy per gram and methane the most.
Crude oil is a mixture of compounds,
9 2C6H14 + 13O2 12CO + 14H2O so the amount of energy released will be
different for different types of crude oil.

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5 a i C + O2 CO2 ii n(CO2) released per mol of CH4 = 1

ii CH4 + 2O2 CO2 + 2H2O m(CO2) released per mol of

CH4 = 44.01g
iii 2C8H18 + 25O2 16CO2 + 18H2O
CO2 released per kJ
iv C2H5OH + 3O2 2CO2 + 3H2O
44.01
v 2H2 + O2 2H2O = = 0.0494 g kJ−1
891
n 1.00
b i n(C) = = = 0.0833 mol iii n(CO2) released per mol of C8H18 = 8
M 12.01
n(CO2) = n(C) = 0.0833 mol m(CO2) released per mol of C8H18=

8 × 44.01 g = 352 g
m(CO2) = n × M = 0.0833 × 44.01
CO2 released per kJ
= 3.66 g
352
n 1.00 = = 0.0644 g kJ−1
ii n(CH4) = = = 0.0623 mol 5470
M 16.05
iv 
n(CO2) released per mol of
n(CO2) = n(CH4) = 0.0623 mol C2H5OH = 2
m(CO2) = n × M = 0.0623 × 44.01 m(CO2) released per mol of

C2H5OH = 2 × 44.01 g = 88.02 g
= 2.74 g
n 1.00 CO2 released per kJ
iii n(C8H18) = = = 0.00875 mol
M 114.26 88.02
= = 0.0644 g kJ−1
n(CO2) = 8 × n(C8H18) = 8 × 0.00875 1367
v 0
= 0.0700 mol
m(CO2) = n × M = 0.0700 × 44.01 d Coal releases the least amount of energy
per gram of fuel, so it is not energy
= 3.08 g efficient.
n 1.00
iv n(C2H5OH) = = = 0.0217 mol It releases the most CO2 per gram of kJ of
M 46.08 energy produced. CO2 is a greenhouse gas,
n(CO2) = n(C) × 2 = 2 × 0.0217 mol which causes climate change.
= 0.0434 mol Coal tends to undergo incomplete
combustion, which releases particulates.
m(CO2) = n × M = 0.0434 × 44.01 These aggravate lung conditions.
= 1.91 g If the coal contains sulfur as an impurity,
v Combustion of hydrogen does not then it can potentially release sulfur
produce carbon dioxide. dioxide, which causes acid rain.

c i n(CO2) released per mol of C = 1 Exercises 14.3 and 14.4

m(CO2) released per mol of C = 44.01g
1 a A fuel produced from organic matter
44.01 obtained from plants.
CO2 released per kJ =
394 b solar energy
= 0.112 g kJ−1
wind power
tidal power
hydroelectric power

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c Advantages Exam-style questions

Biofuels are renewable; biodegradable; 1 C
can be produced locally; can be produced
from waste and, excluding their 2 D
production, they are carbon neutral.
3 C
Disadvantages
4 B
Large amounts of land would be
5 A
required to produce sufficient quantities
of biofuels to meet global demand; 6 a H, S, N, O (any one) [1]
this could lead to food shortages and
deforestation, which would destroy b i oil > coal > gas [1]
habitats. Biofuels release carbon dioxide ii coal > oil > gas [1]
when burnt. Combustion of biofuels such
as wood and charcoal often produces iii coal > gas > oil [1]
pollutants such as particulates/soot.
c Oil is more easily transported/stored. [1]
2 a H2(g) + 2OH–(aq) 2H2O(l) + 2e–
d Gas releases more energy per kg
1 than oil/gas releases less CO2 per kg
b O (g)
2 2
+ H2O(l) + 2e −
2OH (aq)
–

than oil. [1]

1
c H2(g) + 2 O2(g) H2O(l) e All fossil fuels produce CO2 during
combustion, [1]
3 a H2O
which is a greenhouse gas/contributes
b H2(g) 2H+(aq) + 2e– to climate change. [1]
1 7 a The trends in the two graphs show
c O (g)
2 2
+ 2H+(aq) + 2e− H2O(l)
similar patterns/there is a correlation
1 between the two sets of data. [1]
d H2(g) + 2 O2(g) H2O(l)
m 1000 × 103 b Increased combustion of fossil fuels
4 a n(CH4) = = = 62305 mol since industrialisation and increased
M 16.05
global population. [1]
n(H2) produced per mol CH4 = 4
c Any three from the following:
n(H2) produced = 4 × 62305
acidification of the oceans
= 249 200 mol
increased global temperatures
m(H2) = n × M = 249 200 × 2.02
melting of ice caps
= 503 400 g (503.4 kg)
loss of habitat for Arctic and
b mol H2 produced per 1 tonne of Antarctic species
CH4 = 249 200 mol
rising sea levels
energy released = 286 × 249 200
flooding of low-lying countries
= 71.3 × 106 J (71.3 MJ)
increased incidence of extreme
5 a Methanol is a liquid at room temperature, weather events
which makes it easier to store and transport.
changes in ability of crops to grow in
b anode: some areas
CH3OH(l) + H2O(l) CO2(g)
change in the distribution of pests
+ 6H+(aq) + 6e−
and diseases. [3]
cathode:
3
O (g)
2 2
+ 6H+(aq) + 6e− 3H2O(l)

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Chapter 15
Exercise 15.1 4 a using ΔG⦵ = ΔH⦵ − TΔS⦵
ΔG⦵ = −196 − (298 × 125 × 10−3)
1 a H2O(g)
= −233 kJ mol−1
b at 100 °C
As ΔG⦵ < 0, the reaction is spontaneous.
c at 100 kPa (there will be fewer collisions)
b using ΔS⦵ = ΣS⦵products − ΣS⦵reactants
d solution
ΔS⦵ = [(3 × 70) + (2 × 214)] −
2 a Positive, as a gas has been formed. [161 + (3 × 206)]
b Negative, as there are fewer moles of gas = −141 J K−1 mol−1
on the right-hand side (2 1). using ΔG⦵ = ΔH⦵ − TΔS⦵
c Negative, as the products contain fewer ΔG⦵ = −1367 − (298 × −141 × 10−3)
moles of solute (and include a solid) than = −1325 kJ mol−1
the reactants.
As ΔG⦵ < 0, the reaction is spontaneous.
3 using ΔS⦵ = ΣS⦵products − ΣS⦵reactants
c using ΔH⦵ = ΣΔHf⦵ products −
a ΔS⦵ = 5.7 − 2.4 = 3.3 J mol–1 ΣΔHf⦵ reactants
b ΔS⦵ = [214 + (2 × 70)] − [186 + (2 × 205)] ΔH⦵ = [−1131 + (−242) + (−394)] −
= –242 J mol–1 (2 × −951)
c ΔS⦵ = [(2 × 27) + 51] − [(2 × 28) + 87]   = +135 kJ mol−1
= –38 J mol–1
ΔS⦵ = ΣS⦵products − ΣS⦵reactants

Exercise 15.2 ΔS⦵ = (135 + 189 + 214) − (2 × 102)

= +334 J K−1 mol−1
1 ΔG⦵ = ΔH⦵ − TΔS⦵
using ΔG⦵ = ΔH⦵ − TΔS⦵
2 none (at this level – things get more
complicated if you continue to study ΔG⦵ = 135 − (298 × 334 × 10−3)
chemistry beyond IB) = +35.5 kJ mol−1

3 ΔG⦵ < 0 As ΔG⦵ > 0, the reaction is not spontaneous.

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5 ΔH⦵ ΔS⦵ ΔG⦵ Spontaneous?

positive positive negative at high temperatures only at high temperatures
positive negative positive at all temperatures never spontaneous
negative positive negative at all temperatures always spontaneous
negative negative negative at low temperatures only at low temperatures

6 Tipping point between a spontaneous and [N2][[H2]3 [2.0][1.5]3

non-spontaneous reaction is when ΔG⦵ 3 a Q= =
[NH3]2 [2.0]2
changes from negative to positive, that is,
= 1.6875
when ΔG⦵ = 0.
using ΔG = ΔG⦵ + RTlnQ
When ΔG⦵ = 0, then ΔH⦵ = TΔS⦵
ΔH ΔG = +33.2 × 103 + (8.31 × 350 × ln(1.69)
therefore, T =
ΔS = +34 722 J mol−1
ΔH 488.5 × 103
a = = 711 K = +34.7 kJ mol−1
ΔS 687
As ΔH⦵ is positive and ΔS⦵ is positive, the b As ΔG > 0, the forward reaction is not
reaction is spontaneous at temperatures spontaneous; equilibrium will shift to the left.
over 711 K.
4 a ΔG = ΔG⦵ + RTlnQ
ΔH
b T= 0 = ΔG⦵ + RTlnQ
ΔS
ΔH −176.5 × 103 ΔG⦵ = −RTlnQ
= = 618 K
ΔS −285.4 ΔG⦵ = −8.31 × 298 × ln(4)
As ΔH⦵ is negative and ΔS⦵ is = −3433 J mol−1
negative, the reaction is spontaneous at
b equilibrium constant
temperatures below 618 K.
5 a at equilibrium, ΔG = 0
c As ΔH⦵ is negative and ΔS⦵ is
positive, the reaction is spontaneous so ΔG⦵ = −RTlnQ = 7.5 × 103
at all temperatures. 7.5 × 103
lnQ = − = −1.81
8.31 × 500
Exercise 15.3 Q = e−1.81 = 0.16
1 Q>1 b at equilibrium, ΔG = 0
[NO2]2 [1.0]2
2 a Q= = = 0.4 so ΔG⦵ = −RTlnQ = −20.0 × 103
[N2O4]2 [2.5]
20.0 × 103
using ΔG = ΔG⦵ + RTlnQ lnQ = = 8.08
8.31 × 298
ΔG = −15 × 103 + [8.31 × 450 × ln(0.4)] Q = e8.08 = 3220
= −18 426 J mol −1
Exam-style questions
= −18.4 kJ mol−1
1 B
b As ΔG < 0, the forward reaction is
spontaneous; equilibrium will shift to 2 A
the right. 3 D
4 A

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5 B n 1.0
9 a [H2] = = = 0.50 mol dm−3 [1]
6 D volume 2.0
n 1.5
7 a X, melting [1] [I2] = = = 0.75 mol dm−3 [1]
volume 2.0
Y, boiling [1] n 2.5
[HI] = = = 1.25 mol dm−3 [1]
b A measure of the dispersal or distribution volume 2.0
of matter and/or energy in a system. [1]
[HI]2 [1.25]2
c entropy increases [1] b Q= =Q=
[H2][I2] [0.50][0.75]
d ΔG⦵ = ΔH⦵ − TΔS⦵
= 4.167 [1]
ΔH − ΔG 20000 −(−5500)
ΔS = =  [1]
T 298 c ΔG = ΔG⦵ + RTlnQ [1]
= 85.6 J K−1 mol−1 [1] ΔG = −
 23.2 × 103 + [8.31 × 500 ×
ln(4.167)]
8 a CuCO3(s) CuO(s) + CO2(g) [1]
ΔH = −17 270 J mol−1 or −17.3 kJ mol−1 [1]
b when ΔG⦵ = 0, T =
ΔS d As ΔG < 0, the forward reaction is
46.0 × 103 spontaneous and will continue to happen
=
153.5 (more than the backward reaction). [1]
= 300 K [1]
This increases the concentration of HI
reaction is spontaneous above 300 K [1] and decreases the concentrations of H2
and I2 in the equilibrium mixture. [1]

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Chapter 16
m 10.0
Exercise 16.1 6 a n= = = 0.435 mol
M 22.99
1 a 10 mol b M(Cu(NO3)2 = 63.55 + {2 × [14.01 + (3 ×
16.00)]}
b 600 molecules
= 187.57
c from 7 to 9
m = n × M = 0.300 × 187.57 = 56.3 g
d stays the same m 54.0
c M= = = 216 g mol−1
2 a 2Na + Cl2 2NaCl n 0.250
V 250 × 10−3
b N2 + 2O2 2NO2 d n= = = 0.0110 mol
22.7 22.7
c 2Li(s) + 2H2O(l) 2LiOH(aq) + H2(g)
e V = n × 22.7 = 0.25 × 22.7 = 5.68 dm3
d 2C2H6 + 7O2 4CO2 + 6H2O n 0.20
f C= = = 0.67 mol dm−3
e Fe2O3 + 3CO 2Fe + 3CO2 V 300 × 10−3
g n = V × C = 75 × 10−3 × 0.15 = 0.011 mol
f Cu + 4HNO3 Cu(NO3)2 + 2NO2 + 2H2O
m 2.50
3 a HCl(aq) and MgCl2(aq) h n= = = 0.0165 mol
151.92
M
b Mg(s) + 2H+(aq) + 2Cl−(aq) Mg2+(aq) n0.0165
+ 2Cl−(aq) + H2(g) C= = = 0.110 mol dm−3
V 150 × 10−3
c 2Cl−(aq) m 1.25
7 a n= = = 0.0157 mol
d Mg(s) + 2H (aq)
+
Mg (aq) + H2(g)
2+
M 79.55
e spectator ions b ratio n(CuO) : n(CO2) is 4:1
0.0157
4 a Cu(s) + 2Ag+(aq) + 2NO3−(aq) n(CO2) = = 3.93 × 10−3 mol
Cu2+(aq) + 2NO3−(aq) + 2Ag(s) 4
c m = n × M = 3.93 × 10−3 × 44.01
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)
= 0.173 g
b 
2H+(aq) + SO42−(aq) + 2Na+(aq) + 2OH−
m 2.50
(aq) 2Na+(aq) + SO42−(aq) + 2H2O(l) 8 n(CO2) = = = 0.0568 mol
M 44.01
H (aq) + OH (aq)
+ −
H2O(l)
ratio n(Mg) = 2 × n(CO2)
c Cu (aq) + SO4 (aq) + 2Na (aq) + CO3
2+ 2− + 2−
= 2 × 0.0568 = 0.1136 mol
(aq) CuCO3(s) + 2Na+(aq) + SO42−(aq)
m(Mg)= n × M = 0.1136 × 24.31
Cu2+(aq) + CO32−(aq) CuCO3(s)
= 2.76 g
d  e2+(aq) + SO42−(aq) + Ba2+(aq) + 2Cl−
F m 1000 × 103
(aq) Fe2+(aq) + 2Cl−(aq) + BaSO4(s) 9 n(Al) = = = 3.706 × 104 mol
M 26.98
SO42−(aq) + Ba2+(aq) BaSO4(s) 1
n(Al2O3) = × n(Al)
5 a 2H (aq) + CO3
+ 2−
H2O(l) + CO2(g) 2
1
b Sn4+(aq) + 2Cr2+(aq) Sn2+(aq) + = × 3.706 × 104 = 1.853 × 104 mol
2
2Cr3+(aq) m(Al2O3) = n × M = 1.853 × 104 × 101.96
c 2Fe3+(aq) + C2O42−(aq) 2Fe2+(aq) + = 1 889 548 g
2CO2(g)
= 1890 kg
d BrO3−(aq) + 6H+(aq) + 5Br−(aq)
3Br2(aq) + 3H2O(l) (Care needed with rounding – it is not 1889 kg.)

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m 1000 as n(HNO3) used > 0.0629, then Cu is the

10 n(Fe) = = = 17.91 mol limiting reactant
M 55.85
3 3 n(NO2)formed = 2 × n(Cu) = 2 × 0.0157
n(CO2) = × n(Fe) = × 17.91
2 2
= 0.0315 mol
= 26.86 mol
V(NO2)formed = n × molar gas volume at STP =
V(CO2) = n × 22.7 = 610 dm3 0.0315 × 22.7 = 0.715 dm3
m 0.25
11 n(CaCO3) = =
M 100.09 Exercise 16.2
= 2.50 × 10−3 mol m 3.0
1 a n(CaCO3) = = = 0.0300 mol
M 100.09
n(HCl) = 2 × n(CaCO3)
b n(CaO)theoretical = n(CaCO3) = 0.0300 mol
= 2 × 2.50 × 10−3 = 5.00 × 10−3 mol
n 5.00 × 10−3 m(CaO)theoretical = n × M
V(HCl) = = = 0.0200 dm3 or
C 0.250 = 0.0300 × 56.08 = 1.68 g
20.0 cm3
actual yield × 100
m 2.50 c % yield =
12 a n(Fe) = = = 0.0448 mol theoretical yield
M 55.85
1.5 × 100
m 2.50 = = 89 %
b n(S) = = = 0.0780 mol 1.68
M 32.07
m 10.0
2 n(C2H4) = = = 0.356 mol
c ratio Fe : S = 1:1, but, as n(Fe) < n(S), M 28.06
Fe is the limiting reactant
n(C2H5OH)theoretical = n(C2H4) = 0.356 mol
d n(FeS) = n(Fe) = 0.0448 mol
m(C2H5OH)theoretical = n × M
m(FeS) = n × M = 0.0448 × 87.92
= 0.356 × 46.08 = 16.4 g
= 3.94 g
actual yield × 100
m 1.00 % yield =
13 n(Al) = = = 0.037 mol theoretical yield
M 26.98 14.6 × 100
m 2.00 = = 89 %
n(I2) = = = 0.0079 mol 16.4
M 253.8 % yield = 88.9 %
n(I2) required to react with 0.037 mol
3 a n(Pb(NO3)2) = V × C
3
Al = 0.037 × = 0.056 mol
2 = 25.0 × 10−3 × 0.400 = 0.0100 mol
as n(I2) < 0.056 mol, then I2 is the limiting
reactant n(K2CrO4) = V × C

n(AlI3)formed = × n(I2)
2 = 75.0 × 10−3 × 0.250 = 0.01875 mol
3
2
= × 0.0079 = 0.00525 mol ratio = 1 : 1 and, as n(Pb(NO3)2) <
3 n(K2CrO4), then Pb(NO3)2 is the
m(AlI3) = n × M = 0.00525 × 407.68 limiting reactant
= 2.1 g n(PbCrO4)theoretical = 0.0100 mol
m 1.00
14 n(Cu) = = = 0.0157 mol m(PbCrO4)theoretical = n × M
M 63.55
n(HNO3) = 150 × 10−3 × 5.00 = 0.750 mol = 0.0100 × 323.2 = 3.232 g
n(HNO3) required = 4 × n(Cu)
= 4 × 0.0157 = 0.0629 mol

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actual yield × 100 4 a n(H2SO4) = V × C = 20.45 × 10−3 × 0.200

% yield =
theoretical yield = 4.09 × 10−3 mol
1.80 × 100
= = 55.7% b H2SO4 + 2NaOH Na2SO4 + 2H2O
3.232
c n(NaOH) = 2 × n(H2SO4)
b The precipitate may have been wet/not
dried properly. = 2 × 4.09 × 10−3 mol
using atom economy = = 8.18 × 10−3 mol

molar mass of desired product n 8.18 × 10−3

× 100 d C= = = 0.327 mol dm−3
theoretical yield V 25.00 × 10−3
82.16 × 100 5 n(Na2CO3) = V × C = 25 × 10-3 × 0.150
4 a atom economy = = 82.01%
100.18
= 3.75 × 10−3 mol
111.7 × 100
b atom economy = = 45.83% n(HCl) = 2 × 3.75 × 10−3 as react 1 : 2
243.73
= 7.50 × 10−3
26.04 × 100
c atom economy = = 26.00% n 7.50 × 10−3
100.14 V= = = 0.375 dm3
C 0.20
5 The higher the atom economy, the less waste
= 37.50 cm3
is produced that then needs to be disposed of
and is wasteful of raw materials. 6 n(citric acid) = V × C = 50 × 10−3 × 0.200
= 0.100 mol
6 The hazards associated with the substances
used. If the reactants, solvent or waste n(NaOH) = 3 × 0.100 as react 1 : 3
products are toxic, then their disposal could
harm the environment. = 0.300 mol
n 0.300
The energy required by the process. Unless the v= = = 0.120 dm3
c 0.250
energy is produced using green technologies,
then more energy is used, leading to higher = 120 cm3
carbon dioxide emissions, which then 7 a n(NaOH) = C × V
contribute to climate change.
= 0.100 × 19.85 × 10−3
Exercise 16.3 = 1.985 × 10−3 mol
n 0.10 1
1 a C= = = 1.0 mol dm−3 b n(oxalic acid) = × n(NaOH)
V 100 × 10−3 2
m 4.50 1
= × 1.985 × 10−3 = 9.925 × 10−4 mol
b n= = = 0.0157 mol 2
M 286.19
c 25 cm3 of solution was used from a total
n 0.0157
C= = = 0.0629 mol dm −3 volume of 250 cm3; therefore,
V 250 × 10−3
2 a n = V × C = 25.00 × 10−3 × 0.100 number of moles in total in the volumetric
flask = 9.925 × 10−4 × 10 = 9.925 × 10−3 mol
= 2.50 × 10−3 mol
d 
Mr(H2C2O4) = (2 × 1.01) + (2 × 12.01) +
b n = V × C = 50.00 × 10−3 × 0.025 (4 × 16.00) = 90.04
= 1.25 × 10−3 mol m = n × M = 9.925 × 10−3 × 90.04 = 0.894 g
n 0.025
3 V= = = 0.056 dm3 = 56 cm3 e mass of water of crystallisation =
C 0.45
total mass − mass that is H2C2O4
= 1.25 − 0.8936 = 0.3563 g
= 0.3563 g

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m 0.3563
f n(H2O) = = = 0.01977 mol f m(MgI2) = n × M
M 18.02
= 4.875 × 10−3 × 278.11
moles water 0.01977
g ratio of =
moles oxalic acid 9.925 × 10−3 = 1.356 g
1.356 × 100
=2 g % purity = = 90.4%
1.50
Hence, the formula is H2C2O4•2H2O. 10 n(S2O32−) = V × C
m 1.01 = 18.60 × 10−3 × 0.040
8 n(succinic acid)used = =
M 118.1
= 7.44 × 10−4 mol
= 8.55 × 10−3 mol in 250 cm3 of solution 1
n(I2) = 2
× n(S2O32−)
n 8.55 × 10 −3
[succinic acid] = = 1
v 0.250 = × 7.44 × 10-4
2
= 0.0342 mol dm−3 = 3.72 × 10−4 mol
n(succinic acid)titre = V × C Using the equation for the reaction of bleach
= 24.40 × 10 × 0.0342
−3 with iodide ions:

= 8.347 × 10−4 mol n(I−)reacting = 2 × n(I2)

n(NaOH) = V × C = 2 × 3.72 × 10−4

= 25.00 × 10−3 × 0.100 = 7.44 × 10−4 mol

1
= 2.50 × 10−3 mol n(NaOCl) = 2 n(I−) = 3.72 × 10−4 mol
n(sodium hydroxide) 2.50 × 10−3 n 3.72 × 10−4
ratio = =3 [NaOCl] = =
n(succinic acid) 8.347 × 10 −4
V 25.00 × 10−3
i.e. succinic acid is triprotic, H3A = 0.0149 mol dm−3
9 a n(S2O32−) = V × C
Exam-style questions
= 23.40 × 10−3 × 0.050
1 C
= 1.17 × 10−3 mol
1 2 D
b n(I2) = 2
× n(S2O32−)
3 D
1
= 2
× 1.17 × 10−3 4 D

= 5.85 × 10−4 mol 5 A

1
6 C
c n(I−) = 2
× 5.85 × 10−4
7 B
= 9.75 × 10 mol −4
8 A
d n(I−) in 250 cm3 = 10 × 9.75 × 10−4 9 C
= 9.75 × 10−3 mol 10 B
1 1
e n(MgI2) = 2
n(I−) = × 9.75 × 10 −3
11 a n(Na2CO3) = V × C
2
= 4.875 × 10 mol −3
= 50.0 × 10−3 × 0.100
= 5.00 × 10−3 mol

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n(M(NO3)2) = 50.0 × 10−3 × 0.200 13 a  eating to constant mass means that

H
the sample is heated, allowed to cool,
= 1.00 × 10−2 mol weighed, reheated, allowed to cool and
As the substances react 1 : 1, reweighed repeatedly until the mass
then Na2CO3 is limiting and reading is constant. [1]
M(NO3)2 is in excess. [1] This ensures that all of the water of
b n(MCO3) = n(Na2CO3) crystallisation is removed. [1]

= 5.00 × 10−3 mol [1] b m(MgSO4)anhyd = 19.70 − 18.27 = 1.43 g

m 0.74
c Mr = = m(H2O) = 21.19 − 19.70 = 1.49 g
n 5.00 × 10−3
= 148.00 [1] for both masses [1]
m 1.43
Mr(CO32−) = 12.01 + (3 × 16.00) n(MgSO4) = =
M 120.38
= 60.01 = 0.01188 mol [1]
1.49
Ar(M) = 148.00 − 60.01 = 87.99 [1] n(H2O) = = 0.08269 mol [1]
18.02
The Group 2 element with a relative
atomic mass closest to this value is n(H2O) 0.08269
ratio = =
strontium. [1] n(MgSO4) 0.01188
m 1000 × 10 3
formula = MgSO4•7H2O [1]
12 a n(SiO2) = = = 16642 mol[1]
M 60.09 c 
Uncertainty in mass of salts = ±0.02 g,
n(CaO required) = n(SiO2) as 1 : 1 as each mass was obtained by subtraction
in the equation = 16642 mol of the mass of the empty crucible from
the mass of the full crucible.
m(CaO) = n × M = 16 642 × 56.08
% uncertainty hydrated MgSO4
= 933 267 or 933.3 kg [1]
0.02 × 100
= = 0.7% [1]
b n(CaCO3) = n(CaO) = 16 642 mol 2.92
% uncertainty of anhydrous MgSO4
m(CaCO3) = n × M = 16 642 × 100.09
0.02 × 100
= 1 665 700 g [1] = 1.4% [1]
1.43
As limestone is only 95% CaCO3, then
1665700
m(limestone) =
0.95
= 1.753 × 10 g or 1753 kg
6
[1]

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Chapter 17
Exercises 17.1 and 17.2 4 a n(HCl) = 0.1 mol

1 a so n(CaCl2) formed = 0.05 mol

70 volume of solution = 0.1 dm3
0.05
so [CaCl2] = = 0.5 mol dm−3
60 0.1
b
50 A [CaCl2]

Concentration
volume CO2 /cm3

40

30 Answer b

20 Time

10 Exercise 17.3
1 If the collisions have insufficient energy.
0
0 50 100 150 200 250 300 If the particles are not correctly oriented.
Time/s
2 The minimum amount of energy that colliding
i at t = 0, gradient = 2.33 cm3 s−1 (approx)
species must have before a collision results
ii at t = 1, gradient = 0.18 cm3 s−1 (approx) in a chemical reaction.
iii at t = 2, gradient = 0.075 cm3 s−1 3 activation
(approx) energy
iv at t = 4, gradient = 0 cm3 s−1 (approx) Products
potential energy

change in volume 59
b rate = =
time 120 ∆H
= 0.49 cm3 s−1
c gradient = 0, line is horizontal Reactants

2 a 0 .0125 mol dm−3 s−1 (2 : 1 ratio of

S2O32− : I2 in the chemical equation) reaction coordinate
b 0 .0250 mol dm−3 s−1 (1 : 1 ratio of
S2O32− : I− in the chemical equation) Exercise 17.4
c 0.0125 mol dm s (2 : 1 ratio of
−3 −1

S2O32− : S4O62− in the chemical equation) 1 concentration of reactants

3 a and b pressure of a gas

surface area of solids
Concentration

temperature

[A]
the presence of a catalyst
[C] (part b)

[B] (part a)
Time

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2
Factors Effect on the Effect on the proportion of Effect on the
frequency of collisions successful collisions activation energy
changing the the higher the changing the concentration changing the
concentration concentration, the does not change the concentration does not
of a reactant more frequently the proportion of collisions change the minimum
particles collide that are successful amount of energy
required for a collision to
be successful
changing the the higher the changing the pressure changing the pressure
pressure of pressure, the more does not change the does not change the
a gas frequently the proportion of collisions that minimum amount of
particles collide are successful energy required for a
collision to be successful
changing the the higher the surface changing the surface changing the surface
surface area area, the more area does not change the area does not change
of a solid frequently the proportion of collisions that the minimum amount
particles collide are successful of energy required for a
collision to be successful
using a catalysts do not the addition of a catalyst the addition of a catalyst
catalyst change the frequency increases the proportion of lowers the minimum
of collisions collisions that are successful amount of energy needed
for the reaction, as it
provides an alternative
route with a lower
activation energy
changing the the higher the increasing the temperature changing the temperature
temperature temperature, the more increases the proportion of does not change the
frequently the particles collisions that are successful, minimum amount of
collide because their as a higher proportion of energy required for a
kinetic energy and the particles have energy collision to be successful
their average equal to or greater than the
speed increase activation energy

3 a The line should finish above the original line

at high energies; it may approach the x-axis
Number of particles

but must not be below the original line or

Higher temperature touch the x-axis.
The total area under both curves should be
approximately equal.
At the higher temperature, the average kinetic
Energy energy of the particles is higher as the curve is
higher. This means that a higher proportion of
The added line should start just above but not
the particles will have energy greater than or
below (0,0).
equal to the activation energy.
Its maximum should be lower and to the right
b Area under the curve represents the total
of the original line.
number of particles.

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4 Exercise 17.5
Fraction of particles

1 experimentally
Eacatalysed
2 a Rate constant; this is the proportionality
constant in an experimentally determined
Eauncatalysed
rate equation.
b Order of the reaction with respect to a
particular substance.
Kinetic energy
c Overall order of reaction.
A catalyst lowers the activation energy
of a reaction (by providing an alternative d Values of a and b are not affected by
pathway). The diagram shows that the area temperature. k increases when the
to the right of the line, representing Ea of the temperature increases.
catalysed reaction, is greater than that for the rate mol dm −3 s −1
uncatalysed reaction and, hence, a greater 3 a k= = = s −1
proportion of the particles have energy ≥ Ea
[A ] mol dm −3

in the catalysed reaction. b dm3 mol−1 s−1

5 a The frequency of successful collisions is c dm3 mol−1 s−1
greater at higher concentrations, as the
d dm6 mol−2 s−1
particles are closer together.
b The proportion of particles with 4 a Comparing experiments 1 and 2:
energy ≥ Ea is higher at higher [A] is constant, [B] doubles and the rate
temperatures, so a larger proportion of doubles; therefore, the order with respect
collisions are successful. There will also be to B is first.
an increase in the number of the collisions Comparing experiments 2 and 3:
per unit time. [B] is constant, [A] doubles and the rate
c At higher pressures, the particles are is unchanged; therefore, the order with
closer together, and so, there will be an respect to A is zero.
increase in the frequency of the collisions. The rate equation is rate = k[B]
d The smaller the particle size, the higher
Using the values for experiment 1:
the relative surface area of the solid.
This increases the number of collisions rate = k[B]
per unit time.
2=k×1
e A catalyst provides an alternative pathway
with a lower activation energy. If the so k = 2
activation energy is lower, then there will units: s–1
be a larger proportion of particles with
energy ≥ Ea, and so, a larger proportion of rate equation: rate = 2[B]
collisions will be successful.
b Comparing experiments 2 and 1:
6 [A] is constant, [B] doubles and the rate
increases by 22, so the order with respect
d f to B is second.
Potential energy

e Comparing experiments 1 and 3:

c
[B] is constant, [A] is three times and
a
the rate is three times, so the order with
respect to A is first.
g
b rate = k[A][B]2

Reaction coordinate

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Using the values for experiment 1: b

1.6 = k × 0.1 × 0.52

Concentration
k = 64 dm6 mol–2 s–1
rate equation: rate = 64[A][B]2
c  omparing experiments 1 and 2:
C
[G] and [J] are constant, [F] doubles and
the rate doubles, so the order with respect Time
to F is first.
Comparing experiments 1 and 3: c
[G] is constant, [F] increases by three
times, so, as the order with respect to F is

Concentration
first order, the rate would be expected to
increase from 3.0 to 9.0.
[J] doubles and the rate increases from
the expected 9.0 to 18 (i.e. two times);
therefore, the order with respect to J
is first. Time

Comparing experiments 3 and 4:

The halving of [F] and doubling of [J] d
cancel each other out, as both are first order.
1
[G] halves and the rate changes by 2 ;
2
Rate

therefore, the order with respect to G

is second.
rate = k[F][J][G]2
Concentration
Using the values for experiment 1:
3.0 × 10–2 = k × 0.2 × 0.5 × 0.102 e
k = 6.0 dm9 mol–3 s–1
rate equation: rate = 6.0[F][J][G]2
Rate

d catalyst
5 a
Concentration

Concentration

f
Rate

Time

Concentration

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Exercise 17.6
1 a  o that the concentration of methanoic acid is effectively constant, and the rate is only
S
affected by the change in the concentration of bromine.
b 0.0110
0.0100
0.0090
0.0080
[Bromine]/mol dm–3

0.0070
0.0060
0.0050
0.0040
0.0030
0.0020
0.0010
0.0000
0 50 100 150 200 250 300 350 400 450 500 550 600
Time/s
(i) (iii) (iv)
c i 200 s
ii half-life
iii 200 s
iv 200 s
v As the half-lives are constant, the reaction is first order with respect to bromine.
d i 0.0110
0.0100
0.0090
0.0080
[Bromine]/mol dm–3

0.0070
0.0060
0.0050
0.0040
0.0030
tangent at t = 480
0.0020
tangent at
0.0010 tangent at t = 0 t = 180
tangent at t = 90 tangent at t = 300
0.0000
0 50 100 150 200 250 300 350 400 450 500 550 600
Time/s
t = 0, gradient = 3.45
t = 90, gradient = 2.50
t = 180, gradient = 1.80
t = 300, gradient = 1.25
t = 480, gradient = 0.67

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ii approximate values b Half-lives increase if order > 1

Time / s [Br2] / Rate / ×10−5 c Half-lives decrease if order < 1

mol dm −3
mol dm−3 s−1 3 a  echanism 1, as the substances in the
M
0 0.0100 3.45 rate equation must match the substances
90 0.0073 2.50 in the rate-determining step of the
reaction. In mechanism 1, there are
180 0.0053 1.80 two of substance B colliding, and the
300 0.0036 1.21 rate equation shows that the rate is
480 0.0020 0.67 proportional to [B]2.
b intermediate
3.5
4 a 2NO2 + Br2 → 2NOOBr

3 b rate = k[NO2][Br2]
c rate = k[NO2]2[Br2]
2.5
5 a OCl–(aq) + I–(aq) → IO–(aq) + Cl–(aq)
Rate / × 10–5 mol dm–3 s–1

b step 2
2
c HOCl, OH– and IOH
1.5 d  ater is the solvent; its concentration can
W
be considered to be constant.
1 6 An elementary step is a step in a reaction that
involves the collision of two particles.
0.5 7 a 2 for both steps
b O3 + O → 2 O2
0
0 0.002 0.004 0.006 0.008 0.01 c rate = k[O][O3][Cl]
–3
[Br2]/mol dm d third order
Graph shows that rate is directly e intermediate
proportional to the concentration, so
the reaction is first order with respect f catalyst
to bromine. g
2 a Ea step 1
Ea step 2
Potential energy
Concentration of HI

Ea step 2 > Ea step 1

O3 + O + Cl

ClO + O2 + O
2O2 + Cl

Reaction coordinate
0
0 1st 2nd 3rd 8 a 3HBr + O2 → HOBr + Br2 + H2O
half-lives
Time
b step 1
c step 2 (highest activation energy)

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d 1: HBr + O2 → HOOBr c i  ate is proportional to k as rate = k

R
multiplied by various concentration
2: HBr + HOOBr → 2HOBr terms in the rate equation. The values
3: HBr + HOBr → Br2 + H2O of these concentration terms do not
change the gradient of the graph.
e rate = k[O2][HBr]2 The activation energy is determined
E
(rate equation for the second step is from the gradient of the graph = − a
as follows: R
ii A is determined from the intercept of
rate = k[HBr][HOOBr] the line with the y-axis. Although rate
is proportional to k, it does not equal
but HOOBr is formed in first step, so its
k. This means that the value of the
concentration depends on [HBr] and [O2].
intercept of a graph of ln rate would
So, [HOOBr] is substituted by [HBr][O2])
not be the same as that on a graph
which uses ln k.
Exercise 17.7
1 ln is the natural logarithm
Exam-style questions
1 B
k is the rate constant
2 C
A is the pre-exponential factor
3 A
T is the temperature in kelvin
4 A
Ea is the activation energy for the reaction
5 D
R is the universal gas constant
− Ea
6 D
2 using k = Ae RT
7 B
−35000
8.31 × 298
8 B
k = 12.5 e
9 A
k = 9.09 × 10 dm mol s
−6 3 –1 −1
10 D
3 A plot of T (K) on the x-axis and ln k on the
1
11 a  ollision theory states that, for a
C
y-axis will give a straight line with a gradient
reaction to occur, the particles
E
of − a . must collide  [1]
R with the correct orientation  [1]
The intercept with the y-axis = ln A.
and with energy equal to or greater
4 Rate is directly proportional to k at different than the activation energy of
temperatures, as long as the concentrations the reaction. [1]
of the reactants and the order of the reaction
b i rate increases [1]
is unchanged.
−Ea ii rate increases [1]
5 a gradient = –2550 =
8.31 iii rate decreases [1]
Ea = 21200 J mol–1
iv rate decreases [1]
ln A = 2.99
v rate increases [1]
A = 19.9 dm3 mol–1 s–1
12 a i initial rate = 5 cm3 min−1 [1]
b  mall values of A are found for
S
ii rate at t = 5 is 1.75 cm3 min−1 [1]
complicated molecules where the
orientation is more critical (for example, iii reaction is complete at t = 14 min
where steric hindrance may occur or in 25
biological processes). average rate =
14
= 1.8 cm3 min−1 [1]

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b 30 product line above that of the

Volume of oxygen produced/cm3 line b i reactants with labels [1]
25
profile lines with un-catalysed line
20 above the catalysed one [1]

15 activation energies correctly labelled [1]

line b ii
14 a 0.09
10
0.08
5 0.07

[Br–] / mol dm –3
0.06
0
0 5 10 15 20 25 0.05
Time/min 0.04

i Higher initial gradient. [1] 0.03

0.02
Reaches maximum volume sooner
0.01
and finishes at the same volume. [1]
0.00
0 1 2 3 4 5 6 7 8 9 10111213141516171819
ii Lower initial gradient. [1]
Time/min
Final volume of oxygen produced
[1] construction lines clearly drawn on the
at 21 cm3.
graph showing at least two half-lives [1]
13 a  substance that increases the
A
rate of a chemical reaction  [1] comment or label on the graph to state
by providing an alternative pathway that the half-life is constant (at 2.5 min) [1]
of lower activation energy  [1] statement linking constant half-life to
and is not consumed by the reaction. [1] first-order reaction [1]
b  or a reaction to happen, the
F b Second order with respect to H+.
particles must collide with the First order with respect to BrO3–.
correct orientation and have a
minimum amount of energy, for each order correctly deduced [1]
known as the activation energy. [1] c rate = k[Br–][BrO3–][H+]2 [1]
A catalyst works by providing an overall order = 4 [1]
alternative route, which has a lower
activation energy,  [1]
and so, a greater proportion of the
collisions are successful and lead
to products being formed. [1]
c without catalyst
Ea(u) = activation energy without catalyst
with catalyst
Ea(c) = activation energy with catalyst
products
Energy

ΔH
reactants

Reaction coordinate

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d using experiment 1: c step 1: H2 + ICl → HCl + HI [1]

rate = 4.6 × 10–5 step 2: ICl + HI → I2 + HCl [1]
= k × 0.025 × 0.020 × 0.0102 rate-determining step = step 1 [1]
k = 920 dm9 mol–3 s–1  ate-determining step must be consistent
R
with the rate equation. Two steps must
for substituting any one set of values be consistent with the overall equation.
into the rate equation [1]
d
for value (i.e. including ×10–5 in the
value for the rate) [1] step 1
step 2
for units [1] Ea1 HI(g) + HCl(g) + ICl(g) Ea2
e Decreasing the temperature lowers the

Energy
rate of reaction [1] H2(g) + 2ICl(g)
as the rate constant decreases. [1] –155 kJ mol –1

f A graph of ln k (y-axis) against 1 absolute temperature I2(g) + 2HCl(g)

(x-axis) would produce a straight-line
E Reaction coordinate
graph with gradient = − a where
R
R = gas constant. overall exothermic [1]

for stating correct axes [1] axes correctly labelled [1]

for showing how Ea is derived [1] two steps shown [1]

15 a second order [1] Ea of step 1 > Ea of step 2 [1]

b 
Rate of reaction

0
0
Concentration of HI

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Chapter 18
Exercise 18.1 2 There is a closed system.
Both forward and backward reactions
1 A closed system is one in which nothing can
are happening.
be added and nothing can escape; i.e. there is
no exchange of matter with the surroundings. Concentrations of all the substances present
are constant.
2 Dynamic: both the forward and backward
reactions are happening. Rates of forward and backward reactions
are equal.
Equilibrium: Rates of forward and backward
reactions are equal, so the concentrations of Equilibrium can be reached from either side.
all substances present remain constant. All substances are present in the mixture.
3 The rates of the forward and backward 3 a 
Equilibrium lies to the left.
reactions are equal.
b 
Equilibrium lies to the right.
4 constant
4 concentrations of the different substances

Exercise 18.2 temperature

1 a 
line A pressure of gaseous substances
5 Le Chatelier’s principle states that, if a system
b 
in a state of dynamic equilibrium is subject
to some change, then the position of the
A equilibrium will shift in order to minimise the
effect of that change.
6 a 
Equilibrium will move to the left, as
Concentration

Equilibrium increasing the temperature will favour the

endothermic direction to try to minimise
the effect of the change.
b 
Equilibrium will move to the right, as
increasing the temperature will favour the
B exothermic direction to try to minimise
the effect of the change.
0
0 c 
Equilibrium will move to the right, as
Time increasing the concentration of a reactant
will favour the forward direction to try to
c 
minimise the effect of the change.
forward reaction
d 
Equilibrium will move to the right,
Rate

as removing a product will favour the

forward direction to try to minimise the
reverse reaction effect of the change.
0 e 
Catalysts do not affect the position of
0 Time
equilibrium an equilibrium.
reached at
this time f 
Increasing the pressure will favour the
direction that has fewer moles of gas to
try to minimise the effect of the change.
7 a 
Equilibrium shifts right to move to the
side with fewer moles of gas (2 on left →
1 on right), and so, oppose the change.

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b 
Equilibrium shifts left to move to the side [CH3OH]
with fewer moles of gas (4 on right → 3 Equation 1: K1 =
[H2 ]2 [CO ]
2 on left), and so, oppose the change.
[H2 ]2 [CO ]
c 
No change as there are the same (2) moles Equation 2: K 2 =
of gas on both sides of the equation. [CH3OH]

d 
Equilibrium shifts left to move to the side 1
K1 =
with fewer moles of gas (1 on right → K2
0 on left), and so, oppose the change. 1
4 K= = 0.04
25
e 
The equilibrium will move to the left, 5 equilibrium lies to the left (as K << 1)
as there is one mole of gas on the right
compared to none on the left. 6 a 
no effect
8 Decreasing the concentration of a species will b 
affects K (increases K if the forward
cause the position of equilibrium to move reaction is endothermic and decreases K
such that the change is minimised; this means if the forward reaction is exothermic)
it will favour the direction that increases the
concentration of that species. c 
no effect

a 
shifts right d 
no effect

b 
shifts left e 
no effect

c 
shifts left 7 a 
As K is not affected by concentration,
if [C2H5OH] on top of the K expression
9 Alkali will react with the hydrogen ions decreases, then the equilibrium position
present according to the following equation: moves to the right to decrease the values
of [C2H4] and [H2O] on the bottom of the
H+(aq) + OH−(aq) → H2O(l) expression so that K remains constant.
This means the concentration of H+(aq) ions b 
K decreases when the temperature of an
will be decreased, and so, the equilibrium will exothermic reaction is increased, and so,
move to the right to increase the formation of the value of [C2H5OH] must decrease and
H+ ions, minimising the change. [C2H4] and [H2O] must increase, so the
Colour will become yellow. position of equilibrium will move to
the left.
Exercise 18.3 c 
K is not affected by pressure. If the
pressure is increased, then the values of all
[CH3OH]
1 K=
a  the concentrations will increase. As there
[H2 ]2 [CO ] are two concentration terms on the
[HI]2 bottom of the K expression, the bottom
K=
b  of the fraction is more affected than the
[H2 ][ I2 ]
top, so, in order for K to stay constant, the
⎡[ CoCl 4 ]2− ⎤ equilibrium position moves to the right to
K=
c  ⎣ ⎦ decrease the values of [C2H4] and [H2O]
⎡ ⎡Co ( H O ) ⎤2+ ⎤ ⎡Cl − ⎤ 4 and increase the value of [C2H5OH].
⎣⎢ ⎣ 2 6⎦ ⎦ ⎥⎣ ⎦
H2O is the solvent, so its concentration d 
K is not affected by the presence of a
can be considered to be constant. catalyst and, as the equilibrium is in a
closed system, there is no change in the
2 CH4(g) + H2O(g) ! CO(g) + 3H2(g) position of equilibrium.

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Exercise 18.4 e concentration at equilibrium C =

n
⎡ NH ] [ OH ⎤⎦
+ − v
K=⎣ 0.4
4
1 a
[ NH3 ] nitrogen =
2
= 0.2 mol dm−3

2.11 × 10 −3 × 2.11 × 10 −3 2.2

b K= hydrogen = = 1.1 mol dm−3
0.250 2
= 1.78 × 10−5 mol dm−3 1.2
ammonia = = 0.6 mol dm−3
K=
[ PCl ] 5
2
2 a
[ NH3 ]
2
⎡⎣ PCl ] [ Cl
3 2 ⎤⎦ f as K =
2 [ N ][H ]
2 2
3

b [PCl5] = = 0.667 mol dm3 0.62

3 then K =
1 0.2 × 1.13
[PCl3] = = 0.333 mol dm3
3
1.5 = 1.35 dm6 mol−2
[Cl2] = = 0.5 mol dm3
3 4 n([FeSCN]2+)formed = n(Fe3+)used
0.667
c K= = 4 mol−1 dm3 = n(SCN−)used = 0.020 mol
0.333 × 0.5
n 0.020
[ NH ] = = 0.04 mol dm−3
2
[[FeSCN]2+] =
3 a K= 3 v 0.50
[ N ][H ]
2 2
3
n(Fe3+)remaining = 0.050 − 0.020 = 0.030 mol
b 
As only 2.2 mol of hydrogen remain, 4 − 2.2 n 0.030
= 1.8 mol of H2 must have been used. [Fe3+] = = = 0.06 mol dm−3
v 0.50
c As nitrogen and hydrogen react in a n(SCN−)remaining = 0.030 − 0.020 = 0.010 mol
1 : 3 ratio, 0.6 mol of nitrogen must
have reacted and only 0.4 mol remains n 0.010
[SCN−] = = = 0.02 mol dm−3
at equilibrium. v 0.50

d If 0.6 mol of nitrogen reacts with 1.8 mol ⎡[FeSCN ]2+ ⎤
K = ⎣ 3+ ⎦
of hydrogen, then 1.2 mol of ammonia −
⎡⎣Fe ⎤⎦ ⎡⎣SCN ⎤⎦
must be formed.
0.04
= = 33.3 dm3 mol−1
0.06 × 0.02

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5 Ester + water → carboxylic + alcohol

acid
Number of moles initially 0.01 0.01 0 0
Amount of reactant reacting = x
Number of moles at equilibrium 0.01 − x 0.01 − x x x
Equilibrium concentrations, where 0.01 − x 0.01 − x x x
V = total volume of the mixture V V V V

K=
[acid ][alcohol ]
[ ester ][ water ]
As there are the same number of terms on the top and bottom of the expression, V will cancel,
n ( acid ) × n ( alcohol )
so K =
n ( ester ) × n ( water )
x2 x2
then K = = = 0.25
( 0.01− x )( 0.01− x ) ( 0.01− x )2
x
so = 0.25 = 0.5
( 0.01− x )
therefore x = 0.5 × (0.01 − x)
x = 0.005 − 0.5x
1.5x = 0.005
0.005
x= = 3.33 × 10−3
1.5
Therefore, the mixture contains 6.67 × 10−3 mol of both ester and water and 3.33 × 10−3 mol of both
carboxylic acid and alcohol.
(Note that, if K is very small,
then [reactant]eqm ≈ [reactant]initially.)
n 2.5
6 a 
[PCl5] = = = 1.25 mol dm−3
v 2
n 1.2
[PCl3] = = = 0.6 mol dm−3
v 2
n 0.2
[Cl2] = = = 0.1 mol dm−3
v 2

Q =
[ PCl5 ] = 1.25
[ 3 ][Cl2 ] 0.6 × 0.1
PCl
= 20.8 dm3 mol−1
b 
As Q < K, [PCl5] will increase and [PCl3] and [Cl2] will decrease. Reaction will move to the right
until Q = K.
7 As Q > K, in order for Q = K, the concentration of products must decrease and the concentration of
reactants increase. At equilibrium, therefore, there will be more reactants and fewer products than in the
original mixture.

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Exercise 18.5
1 a G G
Gibbs
energy of pure
reactants
G negative in
this direction GΘ for the
reaction

Gibbs
G negative in energy of pure
this direction products

G is a minimum
at equilibrium
composition of mixture equilibrium
pure reactants position pure products

b 
negative
c 
negative
Exam-style questions
1 C
d 
spontaneous in both directions
2 B
2 ΔG = −RT ln K
3 D
ΔG = −8.31 × 298 × ln(4.56)
a 
4 A
= −3760 J mol−1
5 C
As ΔG is negative and K is greater than
one, then the position of equilibrium is 6 B
closer to the products than the reactants
(to the right). 7 C

ΔG = −8.31 × 373 × ln(1.25 × 10−4)

b  8 A
= +27 900 J mol−1 9 D
As ΔG is positive and K is less than one, 10 D
the position of equilibrium is closer to the
reactants than the products (to the left). 11 a 
K=
[HCl ][HClO][1]
ΔG [Cl ]
2
3 As ΔG = −RT ln K, then ln K = −
RT b 
The equilibrium position will move
−7.5 × 1000
a  ln K = = −1.81 to the right.  [1]
8.31× 500
The value of the equilibrium
so K = 0.16 constant will stay the same.[1]
As the value of K < 1, the equilibrium lies c 
Products are acids/contain H+ ions/
to the left (there are more reactants than OH− reacts with H+/H+ + OH− → H2O[1]
products).
20.0 × 10 3 (This lowers the concentration of
b 
ln K = = 8.076 H+ so) equilibrium will move to
8.31 × 298
the right to try to minimise[1]
K = 3217 the effect of the change.[1]
As the value of K > 1, the equilibrium
lies to the right (there are more products
than reactants).

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12 Flask will contain more vapour and n 1.4

less liquid.[1] 14 [TiCl3]eqm = = = 0.70 mol dm−3[1]
V 2
As evaporation is endothermic (bond As 1.4 mol of TiCl3 are formed, 0.7 mol of
breaking), increasing the temperature[1] TiCl2 and 0.7 mol of TiCl4 must have been
favours the endothermic/evaporation used.
process.[1] n 2.5 − 0.70
[TiCl2]eqm = = = 0.90 mol dm−3[1]
[SO ] [1]
2
3 V 2
13 a 
K=
[SO ] [O ]
2
2
2
[TiCl4]eqm =
n 3.5 − 0.70
= = 1.4 mol dm−3[1]
b 
No effect on the position of equilibrium.[1] V 2
[TiCl 3 ]2
No effect on the equilibrium constant.[1] K= [1]
[ TiCl2 ][ TiCl 4 ]
c 
Increasing temperature:
0.70 2
K decreases[1] = = 0.389[1]
0.90 × 1.4
equilibrium position will shift left[1]
Increasing pressure:
no effect on K[1]
equilibrium shifts right[1]

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Chapter 19
Exercises 19.1 and 19.2 6 a 
sulfuric acid + calcium oxide/calcium
carbonate/calcium hydroxide
1 Name Formula Acid or b 
hydrochloric acid + ammonia/ammonium
base? carbonate/ammonium hydrogencarbonate
hydrochloric acid HCl acid
c 
propanoic acid + barium oxide/barium
barium hydroxide Ba(OH)2 base hydroxide/barium carbonate
potassium carbonate K2CO3 base 7 H+ + OH− → H2O
ammonia NH3 base
8 a 
hydrogen
ethylamine CH3NH2 base
b 
redox reaction
sulfuric acid H2SO4 acid
nitric acid HNO3 acid Exercise 19.3
magnesium oxide MgO base 1 Conjugate acid Conjugate base
ethanoic acid CH3COOH acid a HClO4 ClO4−
carbonic acid H2CO3 acid b H2SO4 HSO4−
potassium KHCO3 base c HCl Cl−
hydrogencarbonate
d HNO3 NO3−
2 A base is a substance that can neutralise an
e HNO2 NO2−
acid. An alkali is a soluble base that produces
OH− ions in solution. f H2S HS−

3 g HSO3− SO32−
Name Formula Name Formula of h H2PO4− HPO42−
of acid of acid of salt the anion i HCN CN−
in the salt
j NH4+ NH3
nitric acid HNO3 nitrate NO3−
k H2CO3 HCO3−
phosphoric H3PO4 phosphate PO43−
acid l HCO3− CO32−
benzoic acid C6H5COOH benzoate C6H5COO− m HPO42− PO43−
sulfuric acid H2SO4 sulfate SO42− n H2O OH−
hydrochloric HCl chloride Cl− o NH3 NH2−
acid
2 a 
H2SO4 (acid) and HSO4− (base)
4 a 
ammonium chloride
HNO3 (base) and H2NO3+ (acid)
b 
propylammonium chloride
b 
NH3 (base) and NH4+ (acid)
c 
phenylammonium chloride
H2O (acid) and OH− (base)
5 Mg(OH)2 + 2HNO3 → Mg(NO3)2 + 2H2O
a 
magnesium nitrate c 
HSO4− (acid) and SO42− (base)

CuCO3 + H2SO4 → CuSO4 + H2O

b  H2O (base) and H3O+ (acid)
copper sulfate
d 
H2PO4− (acid) and HPO42− (base)
NaHCO3 + CH3COOH →
c 
HCO3− (base) and H2CO3 (acid)
CH3COONa + H2O + CO2
sodium ethanoate

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3 HSO4− + H2O → H3O+ + SO42−

a  c 
They are opposites: weak acids have
relatively strong conjugate bases and
HSO4− + H2O → OH− + H2SO4
b  vice versa.

Exercise 19.4 Exercise 19.6

1 pH will increase by 2 1 H2O ! H+ + OH−
2 a 
pH = −log10(0.25) = 0.60 2 [H+] = 10−pH = 10−7.0 = 1 × 10−7 mol dm−3
b 
pH = 1.60 3 a 
[OH−] = 0.10 mol dm−3
c 
pH = 1.81 K 1 × 10 −14
[OH−] = w+ =
b 
[ H ] 4.65 × 10 −4
d 
pH = −0.30 [OH ] = 2.15 × 10−11 mol dm−3
−

3 a 
[H+] = 10−pH = 10−2.0 c 
[H+] = 10−2.52
[H ] = 0.0100 mol dm
+ −3 K 1 × 10 −14
[OH−] = w+ =
[H ] 10 −2.52
b 
[H+] = 3.16 × 10−5 mol dm−3 [OH ] = 3.31 × 10−12 mol dm−3
−

c 
[H+] = 1 × 10−7 mol dm−3 d 
[H+] = 10−8.67
d 
[H+] = 6.31 × 10−11 mol dm−3 K 1 × 10 −14
[OH−] = w+ =
[H ] 10 −8.67
Exercise 19.5 [OH−] = 4.68 × 10−6 mol dm−3

1 HNO3 → H+ + NO3− (full arrow essential) 4 a 

More dissociated, the value is >1 × 10−14,
so [H+][OH−] must be higher.
2 CH3COOH ! CH3COO− + H+ (! essential)
b 
Kw = [H+][OH−] = [H+]2 as [H+] = [OH−]
3 NH3 + H2O ! NH4+ + OH−
[H+]√31.3 × 10−14 = 5.59 × 10−7
4 Weak acids are only partially dissociated,
whereas a strong acid is fully dissociated. This pH = −log10[H+] = 6.25
means that [H+] will be lower for a weak acid c 
Water is still neutral as [H+] = [OH−].
and, hence, pH is higher.
5 A strong base must be more dilute than the Exercise 19.7
weak base.
1 a 
[H+] = 0.15 mol dm−3
6 a 
Strong acid will bubble more violently,
pH = −log10[0.15] = 0.82
and the magnesium ribbon will disappear
more quickly than in the weak acid. b 
[H+] = 2 × 0.025 = 0.050 mol dm−3
b 
The colour of the indicator in weak acid pH = −log10[0.050] = 1.30
will be more yellow/orange, whereas the
c 
[H+] = 0.075 mol dm−3
strong acid will be more red, as the pH of
the weak acid will be higher than the pH pH = −log10[0.075] = 1.12
of the stronger acid.
2 a 
[H+] = 10−pH = 10−3.4
c 
The conductivity reading for the weak
[H+] = 3.98 × 10−4 mol dm−3
acid will be lower than that of the
strong acid, as the weak acid is only b 
[H+] = 10−pH = 10−2.50
partially dissociated, and so, the total
[H+] = 3.16 × 10−3 mol dm−3
concentration of ions is lower.
c 
[H+] = 10−pH = 10−1.5 = 0.032 mol dm−3
7 a 
Left, as it is a weak acid, so it is only
partially dissociated. [H2SO4] = 0.5 × [H+] = 0.5 × 0.032
b 
C6H5COO− + H+ ! C6H5COOH [H2SO4] = 0.0158 mol dm−3
right

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Kw 1 × 10 −14 b 
n(OH−) = v × c = 10.0 × 10−3 × 0.20
3 a 
[H ] = +
− =
[OH ] 0.033 n(OH−) = 2.0 × 10−3 mol
[H ] = 3.03 × 10
+ −13
c 
H+ is in excess
pH = −log10[H+] = 12.52 n(H+) remaining = 5.0 × 10−4 mol
b 
[OH−] = 2 × 0.125 = 0.250 mol dm−3 n 5.0 × 10 −4
d 
[H+] = =
Kw 1 × 10 −14 total volume 35.0 × 10 −3
[H+] = − =
[OH ] 0.250 = 0.0143 mol dm−3
[H+] = 4.00 × 10−14 e 
pH = −log10[H+] = 1.85
pH = −log10[H+] = 13.40 4 a 
n(OH−) = v × c = 15.0 × 10−3 × 0.10
Kw 1 × 10 −14 n(OH−) = 1.5 × 10−3 mol
c 
[H+] = =
[OH − ] 1.54 × 10 −2
n(H+) = v × c = 10.0 × 10−3 × 0.25
[H ] = 6.50 × 10
+ −13
n(H+) = 2.5 × 10−3 mol
pH = −log10[H ] = 12.19 +
H+ is in excess
−14
Kw 1 × 10
4 a 
[OH−] = = n(H+) remaining = 1.0 × 10−3 mol
[H + ] 10 −10.50
n 1.0 × 10 −3
[OH−] = 3.16 × 10−4 mol dm−3 [H+] = = = 0.040 mol dm−3
v 25.0 × 10 −3
K 1 × 10 −14
[OH−] = w+ =
b  pH = −log10[H+] = 1.40
[H ] 10 −13.10
[OH−] = 0.126 mol dm−3 b 
n(H+) = v × c = 25.0 × 10−3 × 0.25
K 1 × 10 −14 n(H+) = 6.25 × 10−3 mol
[OH−] = w+ =
c 
[H ] 10 −9.80
n(OH−) = v × c = 10.0 × 10−3 × 0.50
[OH ] = 6.31 × 10−5 mol dm−3
−

n(OH−) = 5.0 × 10−3 mol

[Ba(OH)2] = 0.5 × [OH−]
H+ is in excess
[Ba(OH)2] = 0.5 × 6.31 × 10−5 mol dm−3
n(H+) remaining = 1.25 × 10−3 mol
[Ba(OH)2] = 3.15 × 10−5 mol dm−3 n 1.25 × 10 −3
[H+] = =
v 35.0 × 10 −3
Exercise 19.8
[H+] = 0.036 mol dm−3
1 The point when equal numbers of moles pH = −log10[H+] = 1.44
of H+ and OH− ions have reacted.
c 
n(H+) = 2 × n(H2SO4)
2
14 n(H+) = 2 × v × c = 2 × 20.0 × 10−3 × 0.10
13
12
11
n(H+) = 4.0 × 10−3 mol
10
9 n(OH−) = v × c = 25.0 × 10−3 × 0.25
8
7 n(OH−) = 6.25 × 10−3 mol
pH

6
5
4 OH− is in excess
3
2 pH = 1 n(OH−) remaining = 2.25 × 10−3 mol
1 tends towards pH 0.70 (the pH of 0.20 mol dm–3 HCl (aq))
0
0 10 20 30 40 50 [OH] = n/total volume (45 cm3)
volume of HCl at equivalence is at 12.5 cm3 = 2.25 × 10−3 / 0.045 = 0.05 mol dm−3
Volume of HCI added / cm3
Kw 1 × 10 −14
[H+] = − =
3 a 
n(H+) = v × c = 25.0 × 10−3 × 0.10 [OH ] 0.05
[H+] = 2 × 10−13
n(H+) = 2.5 × 10−3 mol
pH = −log10[H+] = 12.70

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d 
n(H+) = v × c = 15.0 × 10−3 × 0.10 2 a 
[OH−] = 10−pOH = 10−4.5
n(H+) = 1.5 × 10−3 mol [OH−] = 3.16 × 10−5 mol dm−3
n(OH−) = 2 × n(Ba(OH)2) Kw 1 × 10 −14
[H+] = − =
[OH ] 3.16 × 10 −5
n(OH−) = 2 × v × c = 2 × 10.0 × 10−3 × 0.10
[H+] = 3.16 × 10−10 mol dm−3
n(OH−) = 2.0 × 10−3 mol
b 
[OH−] = 10−pOH = 10−10.2
OH is in excess
−
[OH−] = 6.31 × 10−11 mol dm−3
n(OH ) remaining = 0.50 × 10 mol
− −3
Kw 1 × 10 −14
[H+] = − =
[OH] = n/total volume (25 cm ) 3
[OH ] 6.31 × 10 −11
= 0.50 × 10−3 / 0.025 = 0.02 mol dm−3
[H+] = 1.58 × 10−4 mol dm−3
Kw 1 × 10 −14
[H+] = − = c 
[OH−] = 10−pOH = 10−0.75
[OH ] 0.02
[H+] = 5 × 10−13 [OH−] = 0.18 mol dm−3
Kw 1 × 10 −14
pH = −log10[H+] = 12.30 [H+] = − =
[OH ] 0.18
Exercise 19.9 [H+] = 5.62 × 10−14 mol dm−3

1 a 
pOH = −log10[OH−] = 2 d 
[OH−] = 10−pOH = 10−2.30
Kw 1 × 10 −14 [OH−] = 5.01 × 10−3 mol dm−3
[H+] = =
[OH − ] 0.010 Kw 1 × 10 −14
[H+] = =
[H+] = 1.0 × 10−12 mol dm−3 [OH − ] 5.01 × 10 −3
pH = −log10[H+] = 12 [H+] = 2.00 × 10−12 mol dm−3

b 
pOH = −log10[OH−] = 0.38 3 a 
[OH−] = 2 × [Ba(OH)2]

Using an alternative method from the [OH−] = 2 × 0.25 = 0.50 mol dm−3
one in part a: pOH = −log10[OH−] = 0.30
as Kw = [H+][OH−] = 1 × 10−14 either use
then pKw = pH + pOH = 14 as Kw = [H+][OH−] = 1 × 10−14
so pH = 14 − pOH then pKw = pH + pOH = 14
pH = 13.62 so pH = 14 − pOH
c 
pOH = −log10[OH ] = −0.15 −
pH = 13.70
As Kw = [H ][OH ] = 1 × 10
+ − −14
or use
then pKw = pH + pOH = 14 Kw 1 × 10 −14
[H+] = − =
[OH ] 0.50
so pH = 14 − pOH
[H+] = 2 × 10−14 mol dm−3
pH = 14.15
pH = −log10[H+] = 13.70
d 
pOH = −log10[OH ] = 5.49 −

b 
[H+] = 0.90 mol dm−3
As Kw = [H ][OH ] = 1 × 10
+ − −14

pH = 0.046
then pKw = pH + pOH = 14
pOH = 14 − pH = 13.95
so pH = 14 − pOH
pH = 8.51

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Exercise 19.10 b C6H5NH2 + H2O ! C6H5NH3+ + OH−

[CH3COO− ][H + ] ⎡⎣C 6H5 NH3+ ⎤⎦ [OH − ]

1 a 
Ka = Kb =
[CH3COOH] [C6H5 NH2 ]
[C 6H5COO− ][H + ] c CH3NH2 + H2O ! CH3NH3+ + OH−
b 
Ka =
[C 6H5COOH] ⎡CH3 NH3+ ⎤⎦ [OH − ]
Kb = ⎣
⎡⎣CH3CH2COO ⎤⎦ [H − +
] [CH3NH2 ]
c 
Ka =
[CH3CH2COOH]
2 a pKb = −log10Kb = 4.34

2 Ethanoic acid, as it has a smaller value of Ka. b Kb = 10−pKb = 10−6.3 = 5.01 × 10−7

3 a 
pKa = −log10Ka = 2.07
[BH + ][OH− ]
c As Kb =
[B ]
b 
pKa = −log10Ka = 4.42
and [BH+] = [OH−]
c 
pKa = −log10Ka = 3.76
then [OH−] = K b × [B ]
4 a 
Ka = 10−pKa = 10−5.30
[OH−] =   3.50 × 10−3 × 0.0034
Ka = 5.01 × 10 mol dm −6 −3
[OH−] = 3.45 × 10−3 mol dm−3
b 
Ka = 10 −pKa
= 10 −4.98
pOH = −log10[OH−] = 2.46
Ka = 1.05 × 10 mol dm [BH + ][OH− ]
−5 −3

d As Kb =
c 
Ka = 10−pKa = 10−2.83 [B ]
Ka = 1.48 × 10−3 mol dm−3 and [BH+] = [OH−]

5 Phenylethanoic acid is stronger, as it has a then [OH−] = K b × [B ]

lower pKa value. [OH−] =   10−4.10 × 0.075
[H+ ][ A − ] [H ] + 2
[OH−] = 2.44 × 10−3 mol dm−3
6 Ka = =
[ HA ] [ HA ]
pOH = −log10[OH−] = 2.61
[H+] = K a × [HA ]
as pH = 14 − pOH
a 
[H+] =   (4.59 × 10−5 × 0.50)
pH = 14 − 2.61 = 11.39
[H+] = 4.80 × 10−3 mol dm−3
3 weakest: phenylamine
pH = −log10[H+] = 2.32
ammonia
b 
[H+] =   (10−2.59 × 0.010)
ethylamine
[H+] = 5.07 × 10−3 mol dm−3
strongest: diethylamine
pH = −log10[H+] = 2.30
c 
[H+] =   (10−3.16 × 0.25) Exercise 19.12
[H ] = 0.0132 mol dm
+ −3 K w 1.00 × 10 −14
1 a Ka = = = 6.17 × 10 −10 = 4.0 × 10 −10
K b 1.62 × 10 −5
pH = −log10[H+] = 1.88
= 4.0 × 10−10
Exercise 19.11 K w 1.00 × 10 −14
b Ka = = = 2.28 × 10 −11
1 a NH3 + H2O ! NH4+ + OH− K b 4.38 × 10 −4

⎡⎣ NH 4 + ⎤⎦ [OH − ] K w 1.00 × 10 −14

Kb = c Ka = = = 6.33 × 10 −5
[NH3 ] K b 1.58 × 10 −10

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2 pKa = pKw − pKb = 14 − pKb 4 a 

pH > 7, as it is the salt of a weak acid and
strong base
a pKa = 14 − 6.54 = 7.46
b 
pH < 7, as it is the salt of a weak base and
b pKa = 14 − 7.96 = 6.04 strong acid
c pKa = 14 − 3.74 = 10.26 c 
pH = 7, as it is the salt of a strong acid
K 1.00 × 10 −14 and strong base
3 a Ka = w = = 6.25 × 10 −8
K b 1.60 × 10 −7 5 a 
Using pKa + pKb = 14 for an acid–base
conjugate pair:
pKa = −log10(6.25 × 10−8) = 7.20
pKb = 14 − 4.87 = 9.13
b H2PO4−
Hydrolysis of a salt is given by the
4 a Convert all the values to the same format, following equation:
e.g. convert all to pKa:
CH3CH2COO− + H2O !
HCOOH: pKa = 3.74 CH3CH2COOH + OH−
NH4+: pKa = 9.25 CH3CH2COO− is acting as a base.
HCOO−: pKa = −log10(4.79 × 10−11) = 10.32 [OH− ]2
As Kb=
C2H5OH: pKa = 15.5 [B]

C6H5NH3+: pKa = 4.87 then [OH−] = K b × [B ]

Ranking these from strongest to weakest: [OH−] =   10−9.13 × 0.50

HCOOH > C6H5NH3+ > NH4+ > HCO3− > [OH−] = 1.93 × 10−5 mol dm−3
C2H5OH Kw 1 × 10 −14
As [H+] = − =
b Conjugate bases are HCOO−, C6H5NH2, [OH ] 1.93 × 10 −5
NH3, CO32−, C2H5O−
[H+] = 5.19 × 10−10
pH = −log10(5.19 × 10−10) = 9.28
Exercise 19.13
b 
Using pKa + pKb = 14 for an acid–base
1 a 
lithium hydroxide and ethanoic acid conjugate pair:
b 
ammonia and hydrochloric acid
pKb = 14 − 4.31 = 9.69
c 
sodium hydroxide and sulfuric acid
Hydrolysis of the salt is given by the
2 a 
strong acid following equation:
b 
strong acid C6H5CH2COO− + H2O !
C6H5CH2COOH + OH−
c 
strong base
C6H5CH2COO− is acting as a base.
d 
strong base
[OH − ]2
e 
weak base As Kb =
[B ]
f 
strong acid
then [OH−] = K b × [B ]
g 
weak acid
h weak base [OH−] =   10−9.69 × 0.125

3 CH3COO− + H2O ! CH3COOH + OH−

a  [OH−] = 5.05 × 10−6 mol dm−3
Kw 1 × 10 −14
HCO3− + H2O ! H2CO3 + OH−
b  As [H+] = =
[OH − ] 5.05 × 10 −6
NH3 + H2O ! NH4+ + OH−
c  [H ] = 1.98 × 10−9
+

CO32− + H2O ! HCO3− + OH−

d  pH = −log10(1.98 × 10−9) = 8.70

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c 
Using pKa + pKb = 14 for an acid–base b 14
conjugate pair:
pKa = 14 − 4.75 = 9.25

pH
NH4+ ! NH3 + H+ 7

So, NH4+ is acting as an acid.

[H + ]2
As Ka = 0
[ HA ] 0 10 20 30 40 50 60 70 80 90100
then [H+] = K a × [HA ] Volume of 0.250 mol dm –3
NH3 added/cm3
[H+] =   10−9.25 × 0.050
c 14
[H ] = 5.30 × 10 mol dm
+ −6 −3

pH = −log10(5.30 × 10−6) = 5.28

pH
d 
Using pKa + pKb = 14 for an acid–base 7
conjugate pair:
pKa = 14 − 3.34 = 10.66
0
CH3NH3+ ! CH3NH2 + H+ 0 10 20 30 40 50 60 70
So, CH3NH3+ is acting as an acid. Volume of 0.100 mol dm –3
CH3COOH added/cm3
[H + ]2
As Ka=
[HA ] 2 Ka: As pH = pKa when [A−] = [HA], which
then [H+] = K a × [HA ] is when half of the weak acid has been
neutralised. pKa can be found by using
[H+] =   10−11.66 × 0.040 construction lines to read the pH when half
the volume required to reach equivalence has
[H+] = 9.35 × 10−7 mol dm−3
been added from a weak acid/strong base
pH = −log10(2.96 × 10−7) = 6.03 titration curve.

6 a 
pH > 7
b 
pH > 7
pH ≅ 7
c  pH = pKa
pH

d 
pH < 7
e 
pH < 7
x x
Exercise 19.14 2
Volume of base added
1 a 14 x = volume at equivalence
x 1
2 = 2 neutralisation point
pKa = pH (y-axis value) at 2x
pH

7 Kb: similarly, pKb can be found by using

construction lines to read the pH when half
the volume required to reach equivalence has
been added from a weak base/strong acid
0
0 10 20 30 40 50 titration curve.
Volume of 0.100 mol dm –3
CH3COOH added/cm3

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4
pKb
Buffer region - contains
a mixture of a weak

pH
base and its salt
pH

Volume of weak base

x
2
x added to a strong acid
Volume of acid added
x = volume at equivalence
x 1
2 = 2 neutralisation point
pKb = pH (y-axis value) at 2x

pH
3 HIn(aq) ! H+(aq) + In−(aq) Buffer region - contains
a mixture of a weak acid
HIn is red and its salt
In− is yellow Volume of weak acid
added to a strong base
4 pKa = 8.8 (approx. midpoint of its range)
It would not be suitable for a titration between 5 An acidic buffer contains a relatively
HCl and NH3, as this is a strong acid/weak high concentration of a weak acid and its
base, so the indicator would not change conjugate base.
colour in the vertical section of the curve. The weak acid and its conjugate base are
in equilibrium:
Exercise 19.15
HA ! H+ + A−
1 An acidic buffer is an equilibrium mixture of
a weak acid HA, and its conjugate base, A−, On addition of a small amount of acid, the
which can be represented as follows: reservoir of A− ions react with the added acid;
the equilibrium shifts to the left to minimise
HA ! H+ + A− the effect of the increase in [H+].
There must be relatively high concentrations On addition of a small amount of base, the
of both of these species present. H+ ions react with the base according to the
2 A basic buffer is an equilibrium mixture of following equation:
a weak base, B, and its conjugate acid, BH+, H+ + OH− ! H2O
which can be represented as follows:
The equilibrium shifts to the right and HA
B + H2O ! BH+ + OH−
dissociates to replenish the H+ that has reacted
There must be relatively high concentrations with the added alkali, and so, minimise the
of both of these species present. effect of the increase in [OH−].
3 Either a salt of ethanoic acid, such as sodium 6 Diluting a buffer makes it less effective, as
ethanoate, approximately 0.100 mol, should there needs to be a large reservoir of the weak
be added or a strong alkali, such as sodium acid/base and its conjugate pair so that, when
hydroxide, to react with some of the ethanoic H+ or OH− ions are added to the buffer, the
acid and produce its salt; approximately change in concentrations is relatively small.
0.05 mol of NaOH should be added as
7 using pH = pKa + log10
[salt ]
approximately half of the ethanoic acid [acid ]
should be neutralised.
0.125
a 
pH = 4.76 + log10 = 4.46
0.252

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n m [NH4+] = 0.0615 mol dm−3

b 
[CH3COONa] = =
v M ×v [BH+ ][OH− ]
Kb =
0.350 [B]
=
82.04 × 100 × 10 −3 0.0615 × [OH − ]
Kb = 10−4.75 =
0.0385
= 0.0427 mol dm−3
[OH−] = 1.113 × 10−5
0.0427
pH = 4.76 + log10 = 4.39 pOH = −log10 [OH−] = 4.95
0.100
c 
n(CH3COOH) = v × c pH = 14 − pOH
n(CH3COOH) = 100 × 10−3 × 0.200
 pH = 9.05
= 0.0200 mol
n(NaOH) = v × c Exam-style questions
n(NaOH) = 30 × 10−3 × 0.400 = 0.0120 mol 1 D
CH3COOH is in excess, 0.008 mol of it 2 B
remains, so 0.0120 mol of CH3COO−
is formed. 3 A
n 0.008 4 B
[CH3COOH] = =
v 130 × 10 −3
5 C
[CH3COOH] = 0.0615 mol dm−3
6 B
n 0.0120
[CH3COO−] = = 7 D
v 130 × 10 −3
[CH3COO−] = 0.0923 mol dm−3 8 A
0.0923 9 C
pH = 4.76 + log10 0.0615 = 4.94
10 C

8 using pH = pKa + log10

[salt ] Cl2 + H2O → HCl + HClO[1]
11 a 
[acid ]
b i Strong acids are fully dissociated
log10
[salt ] = 4.20 − 3.98 = 0.22 into their ions, whereas in a[1]
[acid ] weak acid only a small proportion
[salt ] [salt ] of the molecules are dissociated
= 100.22 = 1.66 = into their ions.[1]
[acid ] 0.100
[salt] = 0.166 mol dm−3 in the buffer ii Any three experiments, for example:

[salt] originally used = 2 × 0.166 Add a small piece of magnesium

to both acids in separate test tubes. [1]
= 0.332 mol dm−3 (concentration of the salt Bubbles of hydrogen gas will be
was halved when it was mixed with the produced; the stronger acid will
acid solution) react more vigorously.[1]
9 For a basic buffer: Measure the conductivity of the
two acids. The conductivity[1]
NH3 + H2O ! NH4 + OH + −
of the stronger acid will be higher.[1]
n 25 × 10 −3 × 0.100
[NH3] = = Measure the pH of the two
v 65 × 10 −3 solutions. The stronger acid [1]
[NH3] = 0.0385 mol dm−3 will have a lower pH.[1]
n 40 × 10 −3 × 0.100
[NH4+] = =
v 65 × 10 −3

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Add a little sodium carbonate Kw at 87 °C = 34.0 × 10−14[1]

c 
to the two acids.  [1]
Kw = [H+][OH−]
The mixtures will fizz as bubbles
of carbon dioxide are produced; as [H+] = [OH−] then
the stronger acid will bubble Kw = [H+]2
more vigorously.[1]
[H+] =   34.0 × 10−14 = 5.83 × 10−7
HCl → H+ + Cl− [1] full arrow essential
c 
HClO ! H+ + ClO− [1] reversible sign pH = −log10(5.83 × 10−7) = 6.23[1]
essential
d 
Water is neutral as [H+] = [OH−].[1]
Conjugate bases are underlined[1] [H+ ][ A − ] [H + ]2
14 a 
using Ka = = [1]
d 
The strength of an acid depends on [ HA ] [ HA ]
how dissociated it is and is described [H+] = K a × [HA ] = 10 −4.84 × 0.200
by its Ka or pKa value.[1]
[H+] = 1.70 × 10−3 mol dm−3[1]
12 a 
Ba(OH)2 would have a higher pH [1];
as it contains twice the [OH−] pH = 2.77[1]
compared to KOH [1][2]
b i pH at equivalence >7, as strong
b 
[OH−] = 2 × 0.500 = 1.00 mol dm−3 base/weak acid titration[1]
Kw 1 × 10 −14 phenolphthalein/phenol red[1]
[H+] = =
[OH− ] 1.00
ii CH3CH(CH3)COO− ions
[H+] = 1.00 × 10−14[1] are hydrolysed.
pH = −log10[H+] = 14.00[1] CH3CH(CH3)COO− ions act as a base.
c 
CH3CH(CH3)COO− + H2O
0.050 mol dm–3 KOH, ! CH3CH(CH3)COOH + OH−
14 initial pH = 12.70
13
12 or A− + H2O ! HA + OH−
11
10
9 pKb of A− ions = 14 − pKa(HA)
8
7 pH at equivalence point = 7.0 pKb = 9.16[1]
pH

6
5
4
[ HA ][OH − ] [OH − ]2
Kb = = Kb =
3
2
[A ]−
0.100
1 tends towards pH = 1 (the pH of 0.100 mol dm HCI(aq))
[OH−] =   10−9.16 × 0.100
–3
0
0 5 10 15 20 25 30 35 40 45 50
volume of HCI Volume of HCI added / cm3 [OH−] = 8.32 × 10−6[1]
required for equivalence
pOH = −log10(8.32 × 10−6) = 5.08
pH starting around 13 and ending
around pH 1[1] pH = 14 − pOH = 14 − 5.08

midpoint of vertical section at pH 7[1] pH = 8.92[1]

equivalence point clearly at 10 cm3[1]

[H+ ][ A − ] [H + ]2
15 a 
using Ka = = [1]
[ HA ] [ HA ]
H2O ! H+ + OH−[1]
13 a 
[10 −4.51 ]2
b 
Kw = [H ][OH ][1] + − HX: Ka = = 9.55 × 10−9[1]
0.100
The graph shows that Kw increases [10 −5.78 ]2
as temperature increases, so the HY: Ka = = 2.75 × 10−11[1]
0.100
dissociation must be endothermic.[1]

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HX ! H+ + X−[1]
b  16 a 
A solution that resists a change in pH[1]
when a small amount of acid or alkali
Conjugate base is X−.[1] is added.[1]
Y− is stronger than X−.[1]
c 
b 
Buffer solution contains relatively high
d i Y− + H2O ! HY + OH−[1] concentrations of both C2H5NH2 and
C2H5NH3+.[1]
acts as a base as it accepts H+[1]
The following equilibrium is established:
ii Using Kw = Ka × Kb[1]
Kw 10 −14 C2H5NH2 + H2O ! C2H5NH3+ + OH−[1]
then Kb = =
K a 2.75 × 10 −11  n addition of OH−, the equilibrium
O
Kb = 3.64 × 10−4 moves left as C2H5NH3+ ions react with
added OH−, and so, resist the change/
pKb = 3.44[1] minimise the change in pH.[1]
Alternative method: 
On addition of H+, H+ reacts with OH−, [1]
using pKa + pKb = pKw[1] but there is sufficient C2H5NH2
present to react with H2O and shift
pKa = −log10(2.75 × 10−11) = 10.56 the equilibrium to the right, and so,
pKb = 14 − 10.56 = 3.44[1] resist the change in [OH−].[1]

iii Y− + H O ! HY + OH−
2

[ HY ][OH − ] [OH − ]2
so Kb = = [1]
[Y− ] 0.050
[OH−] = 3.64 ×10 −4 × 0.050
[OH−] = 4.27 × 10−3 mol dm−3[1]
pOH = 2.37
pH = 14 − pOH
pH = 14 − 2.37 = 11.63[1]

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Chapter 20
Exercise 20.1 4 a 
oxidised: iodine
oxidising agent: Fe3+
1 a 
0
b 
oxidised: magnesium
b 
C +4, O −2
oxidising agent: CO2
c 
H +1, Cl −1
c 
oxidised: sodium
d 
C −4, H +1
oxidising agent: H2O
e 
K +1, O −2, I +5
d 
oxidised: iron
f 
C −2, H +1, O −2
2 oxidising agent: MnO4−
Formula Name
CuSO4 copper(II) sulfate(VI) Exercise 20.2
NO2 nitrogen(IV) oxide
1 Ce4+ + 2e− → Ce2+ reduction
a 
VO3− vanadate(V) ion
V → V2+ + 2e− oxidation
b 
BrO− bromate(I) ion
CrO42− chromate(VI) H2 → 2H+ + 2e− oxidation
c 

3 a 
Zn 0, H +1, Zn2++2, H2 0 Cl2 + 2e− → 2Cl− reduction
d 

Zinc is oxidised; hydrogen ions are reduced. 2 a 

N: oxidation number changes from +5 to
+4 (reduction of 1)
b 
Mg 0
O: oxidation number remains −2
Fe3+ +3
NO3− + e− → NO2
b 
Mg2+ +2
NO3− + e− + 2H+ → NO2
c 
Fe +2
2+
NO3− + e− + 2H+ → NO2 + H2O
d 
Magnesium is oxidised; Fe ions
3+

are reduced. 3 SO2 + 2H2O → SO42− + 2e− + 4H+

a 

c 
C2H4: C −2, H +1 MnO4− + 8H+ + 5e− → Mn2+ + 4H2O
b 

H2: H 0 2BrO3− + 12H+ + 10e− → Br2 + 6H2O

c 

C2H6: C −3, H +1 2Cr3+ + 7H2O → Cr2O72− + 14H+ + 6e−

d 

H2 is oxidised; C2H4 is reduced. 4 Zn + 2VO2+ + 4H+ →

a 
Zn2+ + 2VO2+ + 2H2O
d 
Mg 0
2Cu2+ + 2I− → 2Cu+ + I2
b 
H2O: H +1 O −2
2IO3− + 12H+ + 10I− → 6I2 + 6H2O
c 
MgO: Mg +2, O −2
5H2O2 + 2MnO4− + 6H+ →
d 
H2 0 5O2 + 2Mn2+ + 8H2O
Mg is oxidised; H2O is reduced.

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5 Fe3+ + e− → Fe2+
a  Exercise 20.3
Zn → Zn + 2e
2+ −
1 a 
Yes. The elements nearer the top of the
2Fe + Zn → 2Fe + Zn
3+ 2+ 2+ activity series are oxidised most easily and
are, therefore, stronger reducing agents.
2H+ + 2e− → H2
b  Mg is above Zn (note not Zn2+), and so,
Mg → Mg2+ + 2e− Mg can reduce Zn2+ to Zn.

2H+ + Mg → Mg2+ + H2 b 
No. Bi is below H2, and so, cannot reduce
H+ ions to H2.
MnO4− + 5e− + 8H+ → Mn2+ + 4H2O
c 
c 
Yes. Al is above Fe, and so, can reduce the
Fe2+(aq) → Fe2+ + e− Fe3+ ions in Fe2O3 to Fe.

MnO4− + 5Fe− + 8H+ → d 
Yes. Sn is above Sb, and so, can reduce
Mn2+ + 5Fe3+ + 4H2O Sb3+ ions in Sb2O3 to Sb.
2S2O32− → S4O62− + 2e−
d  2 a 
Observation 1 tells us that the metal is
above hydrogen in the activity series.
I2 + 2e− → 2I−
Observation 2 tells us that the metal can
2S2O32− + I2 → S4O62− + 2I− reduce Ni ions to nickel, so the metal
must be above nickel.
6 a 
Br2 0
Observation 3 tells us that it cannot reduce
SO2: S +4, O −2 Cr3+, so the metal must be below chromium.
H2SO4: H +1, S +6, O −2 The metal could be cobalt, cadmium
HBr: H +1, Br −1 or iron.

S is oxidised (+4 to +6) b 

Place a small sample of the metal
into separate test tubes containing a
Br is reduced (0 to −1) soluble salt of each of the three possible
metals (for example, cobalt(II) nitrate,
SO2 + 2H2O → H2SO4 + 2e− + 2H+
b 
cadmium(II) nitrate and iron(II) nitrate).
Br2 + 2e− + 2H+ → 2HBr
c 
The unknown metal will displace a metal
d 
No multiplication is needed as both half- below it in the activity series; a deposit of
equations have two electrons. metal would form on the surface and the
solution may change colour. There will
Br2 + SO2 + 2H2O → H2SO4 + 2HBr
e  be no reaction with the solution of itself
7 a 
S is reduced from +6 to −2 (8e−) or with the solution of a metal above it in
the series.
I− is oxidised from −1 to 0
Say, for example, the unknown metal was
oxidation: 2I− → I2 + 2e− cadmium. A deposit of cobalt would form
on the surface of the cadmium in the test

reduction: H2SO4 + 8e− + 8H+ →
tube containing cobalt(II) nitrate, but
H2S + 4H2O
there would be no reaction in the other
Multiply the oxidation half-equation two test tubes.
by four to equal the number of
3 a 
Reactivity increases down these groups.
electrons in the reduction half-equation.
Combining the half-equations gives b 
Ionisation energies decrease down these
groups, as, although the nuclear charge
H2SO4 + 8H+ + 8I− → 4I2 + H2S + 4H2O
increases, so does the number of shielding
3C2O42− + Cr2O72− + 14H+ →
b  shells of electrons. The atomic radius
6CO2 + 2Cr3+ + 7H2O increases, and so, the force of attraction
between the outer-shell electron and the
2BrO3− + 10Br− + 12H+ → 6Br2 + 6H2O
c  nucleus decreases, meaning less energy is
required to overcome this attraction.

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Na(g) → Na+(g) + e−
c  3 a 
The salt bridge provides an electrical
connection between the two half-cells to
d 
The energy required to remove the outermost complete the circuit. It allows ions to flow
electron from each atom in one mole of into or out of the half-cells to balance the
gaseous atoms to form a mole of gaseous charges in the half-cells.
ions each with a +1 charge measured under
standard conditions of 100 kPa and at a cathode: Fe3+(aq) + e− → Fe2+(aq)
b 
stated temperature, often 298 K. anode: Zn(s) → Zn2+(aq) + 2e−
4 a 
fluorine c 
Cathode: the solution would slowly change
colour from pale orange to pale green.
i and ii only, as these equations involve the
b 
displacement of a less reactive halogen by Anode: the metal anode would get
a more reactive halogen. smaller as the zinc ions dissolve in the
solution. There would be no change
5 a 
Reaction would happen spontaneously in the colour of the solution, as zinc
so voltaic. nitrate is colourless.
b 
Reaction would happen spontaneously d
so voltaic.
e– –ve +ve
c 
Reaction would not happen anode ions ions cathode
–ve +ve
spontaneously so electrolytic.
salt bridge
d 
Reaction would not happen mixture of 1 mol dm–3 Fe2+
zinc
spontaneously so electrolytic. (aq) and 1 mol dm–3 Fe3+ (aq)
Zn2+ (aq)
1 mol dm–3 platinum electrode
Exercise 20.4
1 4 a 
phase boundary, e.g. solution–solid or
Voltaic cell Electrolytic
cell gas–solution
the name of the anode anode b 
salt bridge
electrode where
c 
copper (anode) and platinum (cathode)
oxidation occurs
anode: Cu(s) → Cu2+(aq) + 2e−
d 
the name of the cathode cathode cathode: Cr2O72−(aq) + 14H+(aq) + 6e− →
electrode where 2Cr3+(aq) + 7H2O(l)
reduction occurs
Cr2O72−(aq) + 14H+(aq) + 3Cu(s) →
e 
the sign of the negative positive 2Cr3+(aq) + 7H2O(l) + 3Cu2+(aq)
electrode where
oxidation occurs 5 Cu(s) | Cu2+(aq) Ag+(aq) | Ag(s)
a 

the sign of the positive negative Cu(s) | Cu2+(aq) H+(aq),

b 
electrode where NO3−(aq) | NO2(g) | Pt(s)
reduction occurs
Pt(s) | Mn2+(aq),MnO4−(aq),
c 
H+(aq) IO4−(aq),IO3−(aq) | Pt(s)
2 a 
Anode: the activity series lists metals
according to how easily they are oxidised. 6 B<A<C

b 
from the anode (negative) to the 7 a 
tin
cathode (positive) b 
tin
c 
copper
d 
from tin to copper

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Exercise 20.5 Disadvantages of rechargeable batteries:

Long period of down time whilst recharging,
1 Charge: the process of recharging a used
particularly for electric vehicles.
rechargeable battery by using an external power
supply to drive a non-spontaneous chemical They have a more finite lifespan.
reaction, and so, store chemical energy.
Discharge: the process of using the battery as Exercise 20.6
a voltaic cell.
1 a 
anode
2 anode
b 
Anode is positive; cathode is negative.
3 Oxidation always occurs at the anode during
c 
Ions must be free to move.
both charging and discharging.
d 
External circuit: electrons flow through the
4 Negative: discharging can be thought of
metal wires from the anode to the cathode.
as the same process as in a voltaic cell.
The substance at the anode is oxidised Electrolyte: the positive ions move towards
and gives up its electrons, making the the negative electrode, and the negative
anode negative. ions towards the positive electrode.
5 Positive: the external power source pulls electrons 2 a 
Anode: chlorine gas is liberated:
away from the anode, and the substance there
will lose electrons and be oxidised. 2Cl−(l) → Cl2(g) + 2e−

6 ions Cathode: copper is formed:

7 anode: PbSO4(s) + 2e− → Pb(s) + SO42−(aq)

a  Cu2+(l) + 2e− → Cu(l)

cathode: PbSO4(s) + 2H2O(l) → overall: CuCl2(l) → Cu(l) + Cl2(g)

PbO2(s) + 2e− + 4H+(aq) + SO42−(aq) b 
Anode: oxygen is liberated:
b 
sulfuric acid solution 2O2−(l) → O2(g) + 4e−
8 a 
They are oxidised to Li+. Cathode: zinc is formed:
Li → Li+ + e− Zn2+(l) + 2e− → Zn(l)
Co4+ + e− → Co3+
b  overall: 2ZnO(l) → 2Zn(l) + O2(g)
9 Advantages of fuel cells: c 
Anode: oxygen is liberated:
Fuel can be constantly supplied, so long 2O2−(l) → O2(g) + 4e−
periods of recharging are not required.
Cathode: manganese is formed:
Fuel cells have a better longevity than
rechargeable batteries. Mn4+(l) + 4e− → Mn(l)

Disadvantages of fuel cells: overall: MnO2(l) → Mn(l) + O2(g)

Storage of fuels, such as hydrogen d 

Anode: bromine gas is liberated:
and methanol, can be difficult due to 2Br−(l) → Br2(g) + 2e−
their flammability.
Cathode: indium is formed:
Advantages of rechargeable batteries:
In3+(l) + 3e− → In(l)
Can be more efficient than a fuel cell.
overall: 2InBr3(l) → 2In(l) + 3Br2(g)
Can be cheaper to run than a fuel cell.

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Exercise 20.7 4 a 
apparatus a:
CH3CH2CH2OH + 2[O] →
1 a i propan-1-ol CH3CH2COOH + H2O
ii hydroxyl apparatus b:

iii alcohol CH3CH2CH2OH + [O] →

CH3CH2CHO + H2O
iv primary
Apparatus b is used to distil off the
b i propan-2-ol aldehyde as it is formed, and so, prevent
further oxidation to the carboxylic acid.
ii hydroxyl
Figure 20.3a is refluxing.
b 
iii alcohol
Figure 20.3b is distillation.
iv secondary
c 
Both methods would produce propanone:
c i ethanal
CH3CH(OH)CH3 + [O] →
ii carbonyl CH3COCH3 + H2O
iii aldehyde 5 CH3CH2OH + H2O →
a 
CH3COOH + 4e− + 4H+
iv Aldehydes are not classed in this way.
3CH3CH2OH + 2Cr2O72− + 16H+ →
b 
d i pentan-2-one 3CH3COOH + 4Cr3+ + 11H2O
ii carbonyl 5CH3CH2OH + 4MnO4− + 12H+ →
c 
iii ketone 5CH3COOH + 4Mn2+ + 11H2O

iv Ketones are not classed in this way. Exercise 20.8

e i butanoic acid
1 CH3COOH + 4[H] → CH3CH2OH + H2O
a 
ii carboxyl
CH3COCH3 + 2[H] → CH3CH(OH)CH3
b 
iii carboxylic acid
HCHO + 2[H] → CH3OH
c 
iv Carboxylic acids are not classed 2 Most reducing agents would further
in this way. reduce the aldehyde to a primary alcohol,
2 a 
−2 so it is difficult to stop the reaction at the
aldehyde stage.
b 
−2
3 a 
−1 in both NaBH4 and LiAlH4
c 
−1
8 b 
A nucleophile is a substance that accepts
d − a pair of electrons to form a dative
5
covalent bond.
e 
−1
4 a 
hydrogen gas
f 
−2
8 CH2CH CHCH3 + H2 →
b 
g −
3 CH3CH2CH2CH3
3 a 
tertiary CH3C CCH3 + 2H2 → CH3CH2CH2CH3
c 
b 
primary or CH3C CCH3 + H2 →
c 
primary CH2CH CHCH3

d 
secondary 5 a 
1

e 
aldehyde b 
2
c 
5
d 
2

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Exercise 20.9 5 2H+ + 2e− → H2 E⦵ = 0 V

a 
Mn2+ + 4H2O → MnO4− + 5e− + 8H+
1 a 
Tendency for Zn2+ ions to be reduced/gain E⦵ = −1.51 V
electrons is less than that of Pb2+ ions. E⦵cell = −1.51, as <0, reaction is not
spontaneous.
reduction: Pb2+(aq) + 2e− ! Pb(s)
b 
oxidation: Zn(s) → Zn2+(aq) + 2e− I2 + 2e− → 2I− E⦵ = +0.54 V
b 
c 
Pb2+(aq) + Zn(s) ! Pb(s) + Zn2+(aq) Fe2+ → Fe3+ + e− E⦵ = −0.77 V
d 
Zinc, as it releases electrons. E⦵cell = −0.23, as <0, reaction is not

2 Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
a  spontaneous

E⦵ = 0.76 + 0.34 = 1.10 V Fe2+ → Fe3+ + e− E⦵ = −0.77 V

c 

6Fe2+(aq) + Cr2O72−(aq) + 14H+(aq) →

b  Br2 + 2e− → 2Br− E⦵ = +1.09 V
2Cr3+(aq) + 6Fe3+(aq) + 7H2O E⦵cell = +0.32, as >0, reaction is

⦵
E = −0.77 + 1.36 = 0.59 V spontaneous.

Sn(s) + Cl2(g) → Sn2+(aq) + 2Cl−(aq)

c  overall reaction:
E⦵ = 0.14 + 1.36 = 1.50 V 2Fe2+ + Br2 → 2Fe3+ + 2Br−
3 a 
cell 1: E⦵ = 2.12 V 6 a 
E⦵cell > 0
3Zn(s) + 14H+(aq) + Cr2O72−(aq) → ΔG⦵ < 0
b 
3Zn2+(aq) + 2Cr3+(aq) + 7H2O
7 Use ΔG⦵ = −nFE⦵
cell 2: E⦵ = 3.73 V
Deduce the number of electrons by looking at
3Mg(s) + 14H+(aq) + Cr2O72−(aq) → one of the substances in the overall equation.
3Mg2+(aq) + 2Cr3+(aq) + 7H2O
a 
E⦵ = 1.10 V
As E⦵ (cell 2) > E⦵ (cell 1), Mg must be a
stronger reducing agent than Zn. Zn → Zn2+ + 2e−, so n = 2

b 
E⦵ = 3.73 − 2.12 = 1.61 V ΔG⦵ = −2 × 96 500 × 1.10

Mg(s) + Zn2+(aq) → Mg2+(aq) + Zn(s) = −212 300 J mol−1

c 
anode: Mg/Mg2+ = −212 kJ mol−1 (3sf)

4 a 
Half-equations are as follows: b 
E⦵ = 0.59 V

Fe2+(aq) + 2e− ! Fe(s) E⦵ = −0.45 V 6Fe2+(aq) → 6Fe3+(aq) + 6e− so n = 6

Sn2+(aq) + 2e− ! Sn(s) E⦵ = −0.14 V ΔG⦵ = −6 × 96 500 × 0.59

As E⦵(Sn2+/Sn) > E⦵(Fe2+/Fe), Sn2+ ions = −341 610 J mol−1

can oxidise Fe(s). The reaction will occur
= −342 kJ mol−1 (3sf)
spontaneously.
c 
E⦵ = 1.50 V
Fe(s) + Sn2+(aq) → Fe2+(aq) + Sn(s)
Sn(s) → Sn2+(aq) + 2e− so n = 2
b 
As E⦵(I2/I−) > E⦵(Mg2+/Mg), I2 can
oxidise Mg2+, but I− cannot oxidise Mg. ΔG⦵ = −2 × 96 500 × 1.50
The reaction will not occur spontaneously.
= −289 500 J mol−1
c  ⦵ ⦵
As E (Ag /Ag) > E (SO4 /H2SO3), Ag
+ 2− +

can oxidise H2SO3. The reaction will occur = −290 kJ mol−1 (3sf)
spontaneously.
H2SO3(aq) + 2Ag+(aq) + H2O(l) →
SO42−(aq) + 4H+ + 2Ag

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Exercise 20.10 4 a 
carbon graphite or platinum
cathode: Cu2+ + 2e− → Cu
b 
1 a 
cathode: H+ and Sn2+
anode: 2H2O → O2 + 2OH− + 4e−
anode: OH− and Cl− c 
decrease
b 
cathode: H+ and Mg2+ d 
Increase due to the formation of OH−
ions at the anode.
anode: OH− and SO42−
e 
Solution would become paler in colour as
c 
cathode: H+ and Na+ [Cu2+] decreases.
anode: OH− and NO3− The cathode would become coated with
orange coloured copper metal.
d 
cathode: H+ and Ca2+
5 a 
cathode
anode: OH− and Br−
b 
The metal that you want the object to be
2 a 
concentration, temperature, nature of the coated in.
electrodes, pH
c 
A soluble salt of the metal that you want
b 
The standard electrode potentials, to coat the metal with, such as its nitrate.
2X− → X2 + 2e−, for Br− (−1.09 V)
and I− (−0.54V) are less negative 6 + –
than the electrode potential for electron flow
2H2O → O2 + 4H+ + 4e− (−1.23 V).
This suggests that the oxidation of the
halogens is more favourable than the object to be electroplated
oxidation of water. In the case of Cl− ions, silver anode
submerged in solution
the electrode potentials are very close at cathode
in value, so concentration becomes a
significant factor.
Cu2+ + 2e− → Cu (+0.34 V)
c  solution containing Ag+ ions,
e.g. AgNO3 (aq)
2H2O + 2e− → H2 + 2OH− (−0.83 V)
anode/positive electrode:
Value of the standard electrode potential
for Cu2+/Cu is more positive, so the Ag(s) → Ag+(aq) + e−
reduction of Cu2+ is more favourable cathode/negative electrode:
than the reduction of H+.
Ag+(aq) + e− → Ag(s)
3 a
Solution Product at anode Product at cathode
i sodium chloride Cl2 H2
2Cl− → Cl2 + 2e− 2H+ + 2e− → H2
ii magnesium bromide Br2 H2
2Br− → Br2 + 2e− 2H+ + 2e− → H2
iii copper(II) sulfate O2 Cu
4OH− → O2 + 2H2O + 4e−
Cu2+ + 2e− → Cu
iv acidified water O2 H2
4OH− → O2 + 2H2O + 4e− 2H+ + 2e− → H2

b 
Pure water is a very poor conductor
of electricity.

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Exam-style questions e 
M=
m
=
0.50
= 392[1]
n 1.275 × 10 −3
1 B
M((NH4)2SO4•FeSO4) = 284
2 D
therefore, xH2O = 392 − 284 = 108[1]
3 A 108
therefore, x = = 6[1]
4 C 18
5 B 13 a 
most reactive X > Z > W > Y
least reactive
6 D
if completely correct[2]
7 C
if one in the incorrect place[1]
8 D
b 
Ag/Pd/Hg/Pt/Au[1]
9 B
c 
Metal Z would become coated with
10 A
orange copper.[1]
11 a Species Oxidation number The solution would become paler
of vanadium in colour.[1]
VCl2 +2[1]
anode: Fe(s) → Fe2+(aq) + 2e−[1]
14 a 
VO2 +
+5[1]
cathode: Cu2+(aq) + 2e− → Cu(s)[1]
NH4VO3 +5[1]
anode and cathode correctly assigned[1]
2V3+ + Zn → 2V2+ + Zn2+[1]
b  Cu2+ + Fe → Cu + Fe2+[1]
b 
c 
reduction: c 
In left-hand beaker: iron electrode
2NO3 (aq) + 4H (aq) + 2e →
− + − would become smaller.[1]
2NO2(g) + H2O(l)[1] The solution would become a deeper
colour (green).[1]
oxidation:
In right-hand beaker: cathode would
V2+(aq) + H2O(l) → become thicker as it is coated in pink/
VO2+(aq) + 2H+(aq) + 2e−[1] orange copper.[1]
MnO4−(aq) + 8H+(aq) + 5Fe2+(aq) →
12 a  The solution would become a paler
2Mn2+(aq) + 4H2O + 5Fe3+(aq)[1] (blue) eventually turning colourless.[1]
25.50 × 0.00100 Cd(s) + 2NiO(OH)(s) + 2H2O(l) →
15 a 
b 
n(MnO4−) = v × c =
1000 Cd(OH)2(s) + 2Ni(OH)2(s)[1]
n(MnO4−) = 2.55 × 10−5 mol[1] b 
E⦵ = +0.49 + 0.82 = 1.31 V[1]
c 
n(Fe2+) = 5 × 2.55 × 10−5 ΔG⦵ = −nFE⦵ = −2 × 916 500 × 1.31
c 
n(Fe2+) = 1.275 × 10−4 mol[1] ΔG⦵ = −252 830 J mol−1
d 
n((NH4)2SO4.FeSO4•xH2O) = or −253 kJ mol−1[1]
1.275 × 10−4 × 10 as 25.00 cm3 sample
was taken from the 250 cm3 solution Ni(OH)2(s) + OH−(aq) →
d 
NiO(OH)(s) + H2O(l) + e−[1]
n((NH4)2SO4FeSO4•xH2O)

= 1.275 × 10−3 mol[1]

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16 Cathode reactions could be either of the Anode reactions could be either of the
following: following:
Cu2+ + 2e− → Cu (E⦵ = +0.34 V) 2Br− → Br2 + 2e− (E⦵ = −1.09 V)
2H2O + 2e− → H2 + OH− (E⦵ = −0.83 V) 2H2O → O2 + 4H+ + 4e− (E⦵ = −1.23 V)
selection of correct half-equations[1] selection of correct half-equations[1]
As E⦵(Cu2+/Cu) > E⦵(H2O/H2), the reduction As E⦵(H2O/O2) < E⦵(Br−/Br2), the
of Cu2+ is more favourable and copper oxidation of Br− is more favourable and
will be produced at the cathode.[1] bromine will be produced at the anode.[1]

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Chapter 21
Exercise 21.1 5 a C2H6 + Br2 → C2H5Br + HBr
b C3H8 + Cl2 → C3H7Cl + HCl
1 a Yes; there is an odd number of electrons.
c CH4 + Br2 → CH3Br + HBr
b Yes; there is an odd number of electrons.
6 a Cl H H H H H
c 
Yes; the 3p electrons are arranged 3px2
3py1 3pz1. H C C C H H C C C H
d Yes; there is an odd number of electrons. Cl H H Cl Cl H
e 
No; all the outer-shell electrons are H Cl H H H H
paired, 3s2.
H C C C H H C C C H
2 a yes (11 outer-shell electrons)
H Cl H Cl H Cl
b no (16 outer-shell electrons)
b C3Cl8
c no (34 outer-shell electrons)
d no (24 outer-shell electrons) Exercise 21.2
e no (32 outer-shell electrons) 1 Initiation: a step that starts a reaction.
f no (34 outer-shell electrons) Propagation: a step that enables a reaction
to continue.
g yes (13 outer-shell electrons)
Termination: a step that ends a reaction.
h yes (13 outer-shell electrons)
2 a Br2 → 2Br•
3 a Br Br 2Br
b homolytic fission
b H O O H 2 H O
c heat or UV light
c O O
N N 2 O N d increases
O O O e 
Halogen–halogen bond is weaker than
C H bond.
4 a H H
3 a C2H6 + Cl• → C2•H5 + HCl
H C OH H C OH
C2H5• + Cl2 → C2H5Cl + CL•
H H
b b 
A chain reaction is a reaction that
H H H H H H H H
happens through a series of steps which
occur repeatedly.
H C C C C H H C C C C H
c 
Both propagation steps have the same
H H H H H H H H number of radicals on both sides of the
c equation, so the total number of radicals
H H H H does not change.

H C C H Cl H C C + H Cl 4 C2H5• + C2•H5 → C4H10

H H H H C2H5• + Br• → C2H5Br

Br• + Br• → Br2

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5 Propagation steps in the reaction are as follows:

C2H6 + Cl• → C2•H5 + HCl
C2•H5 + Cl2 → C2H5Cl + Cl•
The product of the second step could undergo further substitution by collision with a chlorine radical.
This could produce 1,2-dichlorobutane according to the following equations:
C2H5Cl + Cl• → C2•H4Cl + HCl
C2•H4Cl + Cl2 → C2H4Cl2 + Cl•
6 Substitution can occur in more than one position, as a hydrogen on the central carbon or on an
end carbon could be removed by the reaction with a bromine radical. The removal of a central
H would give 2-bromopropane. The removal of H from one of the end carbon atoms would give
1-bromopropane.

Exam-style questions
1 A
2 D
3 D
4 C
5 A
6 a C3H8 + Br2 → CH3CH2CH2Br + HBr [1]
UV light initiates the reaction by breaking the Br Br bond [1]
b 
Br2 → 2Br• [1]
c C3H8 + Br• → CH3•CH2CH2 + HBr [1]
CH3CH2CH2• + Br2 → CH3CH2CH2Br + Br• [1]
7 O O O

C R + C R + R1 + C
R R1 R1

R–R + CO

for each pair of fish-hook arrows [1]

Penalise double-headed arrows only once.
8 H H H H H H H H

X C C C C X C C C C

H H H H H H H H

for pair of fish-hook arrows [1]

for correct product [1]

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Chapter 22
Exercise 22.1 4
C C C C C C
+
1 a OH−: yes E+ E :Nu E Nu
b H+: no
c NH3: yes
Exercise 22.3
d CN−: yes 1 coordination bond

e H2O: yes 2 It can donate a pair of electrons to one of the H

atoms of NH4+ to form a coordination bond.
f Na+: no
H +
2 CH3CH2CH2Cl + OH− →
a 
CH3CH2CH2OH + Cl− HO– H N H
propan-1-ol H
CH3Br + NH3 → CH3NH2 + HBr
b  3 One of the H atoms of water accepts a pair of
methylamine electrons from NH3.

CH3CH2CH(I)CH3 + H2O →
c  H H +
CH3CH2CH(OH)CH3 + HI
O H N H HO– + H N H
butan-2-ol
H H H
d (CH3)CBr + CN− → (CH3)CCN + Br−
4 Ligands donate a pair of electrons to vacant
3 a chloride ion orbitals on the transition metal, so the ligands
act as a Lewis base and the transition metal
b bromide ion acts as a Lewis acid.
c iodide ion
5 a NH3: base
d bromide ion
b AlCl3: acid
4 hydrolysis
c Cu2+: acid
5 a Nu δ+ δ–
C X Nu C + X– d Cl−: base
e CO: base
b coordination bond
f BF3: acid
Exercise 22.2
6 a Lewis acid: Ag+
1 Carbon–carbon double bond has a high
Lewis base: NH3
electron density/electron rich.
b Lewis acid: CH3Cl
2 a HBr: yes
Lewis base: OH−
b Na+: no
c Lewis acid: BF3
c H2O: yes
Lewis base: NH3
d OH−: no
d Lewis acid: HF
e NO2+: yes
Lewis base: NaNH2
3 a but-1-ene + Br2
e Lewis acid: Cd2+
b ethene + H2O
Lewis base: CN−
c but-2-ene + HI

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f Lewis acid: BH3 c 

It is the product of one step in the
reaction rather than an imaginary half-
Lewis base: CH3NH2
way position in a reaction.

Exercise 22.4 d trigonal planar, 120°

e 
Only one substance takes part in the rate-
1 a CH3 CH3
determining step.
HO– δ+ δ–
nucleophile C Br HO C + Br–
H H f rate = k[(CH3)3CBr]
H H 3 a 
During the SN2 mechanism, the shape
b bond bond of the molecule is inverted, so only one
forming breaking product is formed.
CH –
3 b 
The carbocation intermediate formed
transition during the SN1 mechanism is planar,
state HO C Br negative
charge and there is an equal probability of the
HH nucleophile attaching to this from both
Potential energy

sides. This leads to the equal probability

reactants of forming two different optical isomers.
4 SN1 produces both isomers. As there is 16 % of
products one isomer, 32 % of the reaction proceeds via the
Reaction coordinate SN1 mechanism, producing 16 % of each isomer.

c S: substitution The SN2 mechanism produces only a single

isomer, which must be the other 68 %.
N: nucleophilic
Therefore, 68 % SN2 and 32 % SN1.
2: molecularity of the reaction is
two/there are two substances reacting 5 fastest: 1-iodoethane > 1-bromoethane
in the rate-determining step > 1-chloroethane
d rate = k[CH3CH2Br][OH−] 6 The C I bond is weaker than C Br < C Cl.
2 a Br This makes the iodide ion the best leaving
slow
+ – group, as the least amount of energy is needed
H3C C CH3 rds H3C C CH3 + Br
to break the C I bond.
CH3 CH3
7 As the rate depends on the concentration of
OH the halogenoalkane and not on the hydroxide
+ fast
ion concentration, the rate-determining step
HO– + H3C C CH3 H3C C CH3 must be the first step, which involves breaking
of the carbon–halogen bond.
CH3 CH3
b 8 As the rate depends on the leaving group, the
+ bond breaking process is more significant.
H3C C CH3

activation CH3
energy for
Potential energy

step 1 activation
energy for step 2
intermediate

reactants
products

Reaction coordinate

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Exercise 22.5
1 heterolytic
2 a 
H end of HBr, as the molecule is polar and Hδ+ is attracted to the electron rich C C.
b H H H H

C δ+ δ–
H C H H C H
H Br
C H C+ :Br– H C Br
H H
H H

c carbocation
3 a 
A dipole is induced in the Br2 molecule as it approaches the electron rich carbon–carbon double bond.
The Br atom nearest to the double bond has a slight positive charge.
b H

H C
Br +
H C

4 CH3 H CH3 H CH3 CH3

CH3 C C CH3 CH3 C C CH3 CH3 C CH2CH3 CH3C CH2CH3 + H+

+
H+ H O+ OH
O H
H H
H

5 a 7 a
H H H H H H H H H H H H H H

H C C C H and H C C C H H C C C C H and H C C C C H
+ +
H H Br H Br H H H H H H H
1-bromopropane 2-bromopropane primary secondary
b see labels in part a
b 2-bromopropane
c secondary carbocation
6 a two products:
d 
Alkyl groups are electron releasing and
major: 2-chloro-2-methylpropane slightly stabilise the positive charge on the
minor: 1-chloro-2-methylpropane carbon atom. The secondary carbocation
has two alkyl groups, whereas the primary
b one product: 2-bromobutane only has one, so the secondary is more
c two products: stabilised.

major: butan-2-ol 8 Markovnikov’s rule states that H will attach to

the C that has more H atoms already attached.
minor: butan-1-ol This leads to the formation of a more
substituted (tertiary rather than secondary
d one product: 1,2-dibromopropane
rather than primary) carbocation, which is
more stable, as it has more electron-releasing
alkyl groups.

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Exercise 22.6 iv H H [1]

1 H C C H

E H OH
E+ + E + H+
H
b 
A reaction in which two or more
molecules are joined together with
2 The intermediate has four electrons
no other products  [1]
delocalised in a p cloud over five of the six
where the non-organic reagent
carbon atoms in the benzene ring.
accepts a pair of electrons to
3 reagent: concentrated nitric acid form a coordination bond.[1]
electrophile: NO2+ ion c 
The carbon–carbon double bond
is electron rich/has a high
stage 1: generation of the electrophile, NO2+ : electron density. [1]
HNO3 + H2SO4 → NO2+ + H2O + HSO4−
12 a H H H H [1]
stage 2:
H C C C C H
NO2
NO2+ + NO2 + H+ H H Cl Cl
H
1,2-dichlorobutane [1]
stage 3: regeneration of the catalyst
b H H H H [1]
H+ + HSO4− → H2SO4
H C C C C H
Exam-style questions H OH H H

1 D butan-2-ol [1]
2 D c Br [1]
3 A
4 A
3-bromo-2,5-dimethylhexane [1]
5 C
13 a 
Reaction scheme for 2-bromopropane [3]
6 D H H H

7 B H C C C H

8 D H Br H
9 C +OH–(aq) +NH3
+CN–
10 A
11 a i H H [1] i
H H H
iii H H H

H C C C H H C C C H

H C C H H OH H ii H H H
H NH2 H
H C C C H

H H H CN H

ii H H [1] b Br– [1]

H C C H c 
Reaction when one atom or group
of atoms is replaced by another  [1]
Br Br where the non-organic reagent
iii H H [1] donates a pair of electrons to form
a coordinate bond. [1]
H C C H

H Br

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d 
The carbon–halogen bond is polar./ 15 a i H H H H [1]
The nucleophile is attracted to the
δ+ carbon. [1] H C C C C H

e 
Carbon–halogen bond is weaker than H H
carbon–hydrogen bonds in alkanes. [1] ii The carbocation intermediate
14 a [1] is planar  [1]
OH
and OH− can approach from
either side. [1]

3-methylbutan-2-ol [1] b CH3CH2 CH2CH3

HO– δ–
C Br H O C + Br–
b H CH3 H H [1] H δ+
H
CH3 CH3
H C C C C OH

H CH3 H H
SN2 mechanism identified [1]

3,3-dimethylbutan-1-ol [1] both curly arrows correct [1]

c NH2 [1]
3D drawing showing inversion of shape [1]
c Rate iodo > bromo > chloro, [1]

5-methylheptylamine [1] as C I bond weaker than C Br < C Cl [1]

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16 a [1]

OH

SN1 [1]

b
+ HNO3 + H2O
Br Br
NO2 in any position

for organic product [1]

for rest of equation [1]
electrophilic substitution [1]

c Br [1]
Br

Br

d Br
Br

and
Br Br
major product minor product

for each structure[1]

for correctly identifying major product [1]
electrophilic addition [1]

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