Cambridge International AS and A level Chemistry

c i dm3 mol−1 (1) d The 0.8 mol dm−3 hydrochloric acid is more concentrated. It has
(0.442) 2
more hydrogen ions per unit volume than the 0.4 mol dm−3 acid.
ii 9.40 × 105 =
(0.234)2 × [S2] So the collision frequency is greater.
(0.442)2
[S2] = × (9.40 × 105) = 3.80 × 10 −6 (dm3 mol−1)
( .234 )2 Exercise 9.2
Correct answer (3). If these not scored, 1 mark for correct
substitution in equation, 1 mark for correct rearrangement of a CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l)
equation. b i
pSO
2 time / s 0 20 40 60 80 100 120 140
d i Kp =
3
(1) mass CO2 / g 0.00 0.10 0.20 0.28 0.34 0.39 0.425 0.45
2
pSO × pO
2 2 Table continued with the other values.
(80 100)2 ii 60
ii Kp = = 9.14 × 10 −4 Pa−1
(10 100)2 × (68 800)
All correct (3). If not then 1 mark for correct substitution B
50
including the squares, 1 mark for correct unit.
Total = 15

Mass of CO2 released / g

40
Question 3
a Ethanoic acid partially ionises / dissociates in water (1) Nitric acid 30
ionises / dissociates completely in water (1)
b CH3CO2H is conjugate with CH3CO2− (1)
20
H2O is conjugate with H3O + (1)
[CH3CO2−] [H +] [CH3CO2−] [H3O +]
c i Kc = ALLOW: (1)
[CH3CO2H] [CH3CO2H] [H2O] 10
ii It is present in great excess (1)
so its concentration is effectively constant. (1)
0
d Nitric acid has a higher concentration of hydrogen ions than 0 50 100 150 200 250 300 350
ethanoic acid (1) Time / s
14 so more collisions per second compared with ethanoic acid
(or reverse argument). (1) iii The one at 160 s
ALLOW: nitric acid is an oxidising acid for 1 mark iv 1st 20 seconds: = rise 0.1 g/20 s = 5 × 10 −3 g s −1
run
e i (0 to +2) = +2 (1) 0.2 − 0.1 g
20–40 seconds: rise = = 5 × 10 −3 g s −1
ii (+5 to −3) = −8 (1) run 40 − 20 s
Total = 11 v The graph begins to curve / the line is not straight.
vi Take a tangent to the curve.
0.53
c i 0.53 g so moles = = 0.012 mol
Chapter 9 44
ii From the equation: 2 mol HCl form 1 mol CO2. So moles HCl =
Exercise 9.1 0.012 × 2 = 0.024 mol
mol 0.024
a i B and C Volume (dm3) = = =
concentration (in mol dm−3) 0.40
ii A: the molecules do not have enough energy to react when 0.06 dm3 / 60 cm3
they collide / the molecules have less energy than the iii 0.012 mol × 24 = 0.288 dm3 / 288 cm3
activation energy. iv Yes: because mass of gas is very small / air current can affect
C: the molecules have not collided in the correct orientation. the balance / decimal places
iii The molecules have energy greater than or equal to the OR
activation energy and collide with the correct orientation. No: because the graduations on a gas syringe are thicker lines
b i and only read to nearest 2 cm3. Larger volumes being read
enthalpy H/kJ mol−1

so less % error / syringe plunger constantly moving so more

Ea difficult to read accurately.
reactants
d See line B in answers to (b)(ii) above.
ΔHr
products
Exercise 9.3
a i A few molecules have small amount of energy, a large number
reaction pathway of molecules have energies near the average, a very small
number of molecules have very high energy.
ii Exothermic because the reactants have more energy than
ii Activation energy. The minimum energy required by
the products.
molecules to react when they collide.
c A reaction will speed up if the frequency of successful collisions
iii The proportion of molecules with energies equal to and
increases, and the proportion of particles with energy greater
above the activation energy.
than the activation energy increases.
 Answers

b i Average kinetic energy of the molecules increases (slightly). b Add known mass of catalyst to hydrogen peroxide. (1)
ii Frequency of collisions increases. Record volume of gas in burette (1) at particular times. (1)
iii Reaction rate increases. Repeat with same mass of different catalyst. (1) Same
c i 20 °C: Ek = 3 RT = 3 × 22.4 × 293 = 9844.8 units volume and mass of hydrogen peroxide. (1) All other
2 2 conditions / named conditions kept constant. (1)
3 × 22.4 × 303
30 °C: Ek = 3 RT = = 10 180.8 units c
2 2
ii The % increase in kinetic energy is only 3.4% which is far less Ea uncatalysed
than the doubling of rate every 10 °C. reaction
d When the sample is heated, the mean energy of the molecules 2H2O2

Enthalpy
increases. There is a wider spread of energy values. A greater
proportion of the molecules exceed the activation energy Ea catalysed
compared with the proportion at a lower temperature. reaction
2H2O + O2

Exercise 9.4
a The activation energy for the catalysed reaction is lower. So there
is a greater proportion of molecules with energy values above the Progress of reaction
activation energy. Axes labelled (1)
b i Enzymes are biological catalysts. They are proteins / more Reactants and products labelled (1)
complex than inorganic catalysts / the catalytic action occurs Reactants above products and to the left of the products (1)
in only one part of the molecule (active site). Correct activation energy for catalysed reaction (1)
ii Correct activation energy for uncatalysed reaction (1)
Total = 17

Question 2
E+ P
a Heterogeneous, because the catalyst is in a different phase
Enthalpy

Ea for the
from the reactants and products / because the catalysts
ΔHr uncatalysed
reaction are solid and the reactants and products are not. (1)
b Catalyst lowers the activation energy. (1) 15
E+S Greater proportion of reactant molecules has energy
Ea for the catalysed above the activation energy (1)
reaction for catalysed reaction. (1)
c Decrease in pressure causes molecules to move further apart. (1)
Frequency of successful collisions is reduced. (1)
Progress of reaction
d
c i In homogeneous catalysis the reactants, products and
catalyst are all in the same phase; in heterogeneous catalysis
the catalyst is in a different phase from the reactants and
products. C3H8 Ea
Enthalpy

ii Equation 1: heterogeneous
Equation 2: heterogeneous
Equation 3: homogeneous ΔHr C3H6 + H2

Exam-style questions
Question 1 Progress of reaction

a i Decreases rate (no mark on own but if not correct max. 1 for Axes labelled (1)
question) Reactants and products labelled (1)
Idea that particles have less kinetic energy on average (1) Reactants above products and to the left of the products (1)
Lower proportion of reactant particles has energy Correct activation energy (1)
greater than activation energy (1) Arrow for enthalpy change in correct direction and labelled (1)
ii Increases rate (no mark on own but if not correct max. Total = 11
1 for question) Question 3
Increasing the pressure forces particles closer together (1)
Frequency of successful collisions increases (1) a i Increases rate (no mark on own but if not correct max. 1
iii Increases rate (no mark on own but if not correct max. for question)
1 for question) More particles per unit volume at higher concentration /
Adding a catalyst lowers the activation energy (1) particles closer together (1)
Greater proportion of particles has energy above the Greater frequency of successful collisions. (1)
activation energy (1) ii Increases rate (no mark on own but if not correct max. 1
for question).
 Cambridge International AS and A level Chemistry
Magnesium powder has a greater surface area for the
same mass (1)
More magnesium ions / atoms exposed for the
hydrogen ions to collide with (1)
iii Increases rate (no mark on own but if not correct max. 1
for question).
Idea that particles have more kinetic energy on average (1)
Greater proportion of reactant particles has energy greater
than activation energy (1)
16 cm3
b i (1) = 0.8 cm3 s −1 (1)
20 s
ii 0.25 mol dm−3 (1)
The magnesium is in excess so the acid is the limiting
reagent. (1) The volume of hydrogen produced is half
that of B, so the moles and (for the same volume) the
concentration is half that for B. (1)
iii The increased gradient reflects the increased rate of
reaction / increase in temperature increases reaction rate (1)
The final volume is the same because there are the same
number of moles of acid / the acid is the limiting reagent (1)
Total = 13
Chapter 10
Exercise 10.1
a 1 with C; 2 with F; 3 with A; 4 with D; 5 with B; 6 with E
b Sodium chloride dissolves in water to form a neutral solution
because the polar water molecules surround the positive
and negative ions and separate them. Aluminium chloride is
16
hydrolysed by water and the solution becomes acidic. Chlorides
of silicon, phosphorus and sulfur react with water. The gas,
hydrogen chloride, is released, some of which dissolves in
water and reacts to form an acidic solution.
c i PCl5 + 4H2O → H3PO4 + 5HCl
ii SO3 + H2O → H2SO4
iii Mg(OH)2 + 2HCl → MgCl2 + 2H2O
iv SiO2 + 2NaOH → Na2SiO3 + H2O
v 2Na + 2H2O → 2NaOH + H2
vi Al2O3 + 3H2SO4 → Al2(SO4)3 + 3H2O
vii SiCl4 + 2H2O → SiO2 + 4HCl
Exercise 10.2
a i There is a general increase in ionisation energy across the
period. This is because successive atoms have one more
proton in their nucleus so there is an increased nuclear
charge. The outer electrons are in the same principal
quantum shell and there is no significant difference in
shielding. So the attractive effect of the increased nuclear
charge on the electrons makes it more difficult to remove an
outer electron from an atom across the period.
ii The additional electron in aluminium goes into a p orbital
which is, on average, slightly further from the nucleus and has
slightly more shielding. These effects overcome the effect of
the increased nuclear charge. In sulfur, the added electron
goes into an orbital so that its spin opposes that of the
electron already in the orbital. This gives the outer electrons
additional stability so an outer electron is less easily removed.
iii K: value should be slightly less than Na (actual value =
419 kJ mol−1)
Ca: value should be slightly less than Mg but greater than K
(actual value = 590 kJ mol−1)
b Across a period, the number of protons (positive charges)
increases. So the nuclear charge also increases. The number of
electrons (negative charges) also increases across a period. Each
electron added to the atom of successive elements goes into the
same principal quantum shell. So the shielding of outer shell
electrons by inner shell electrons does not increase significantly.
Across a period, the greater attractive force between the nucleus
and the outer electrons pulls them closer to the nucleus.
c From sodium to silicide, the ionic radius decreases for similar
reasons detailed for the atomic radius (part b). The outer
electrons are in the second quantum shell because the ions
are formed by loss of the outer electrons and so the ionic
radii are smaller than the corresponding atomic radii. The
values for phosphide to chloride are much higher because
the outer electrons are in the next quantum shell (the third).
So the outer electrons are further from the nucleus and the
attraction to the nucleus is much less. The values decrease
from phosphide to chloride for similar reasons detailed for the
atomic radius (part b).
d i Group 1
ii Decreases from Group 1 to Group 13 or 14 and then increases
to a maximum.
iii The atomic radius decreases gradually across a period but the
atomic volume decreases then increases.
iv The atomic volume depends on how the atoms are packed
in the structure, whether they are packed so that there is a
lot of space between some of the atoms or whether they are
packed more efficiently.
v It increases (compare similar points on the curve, e.g. Li with
Na with K).
Exercise 10.3
a It increases to a maximum (at Si) and then decreases to very low
values.
b i They have molecular structures with only weak forces of
attraction (van der Waals’ forces) between the molecules.
ii Each aluminium atom can provide 3 electrons to the ‘sea’
of delocalised electrons in the metallic structure. A sodium
atom can only provide 1 electron. A greater number of
delocalised electrons and a higher ionic charge (3+ for Al)
mean that there are greater forces of attraction between
the ions and the electrons so making it more difficult to
overcome these.
iii Ne: element before Na so about the same level as argon.
ALLOW: 5–100 K (actual value 25 K)
K: next element after Ar value should be nearer to that of Na
but slightly lower. ALLOW: 250–400 K (actual value 336 K)
Ca: next element after K so should be higher than potassium.
ALLOW: 900–1300 K (actual value 1112 K)
c i They are metals so have delocalised electrons which are
responsible for the transfer of charge throughout the whole
structure.
ii Each aluminium atom can provide 3 electrons to the ‘sea’ of
delocalised electrons in the metallic structure. A sodium atom
can only provide 1 electron.
iii It has a simple molecular structure so there are no delocalised
electrons (or mobile ions).
d i The ratio of chlorine to other element increases to a
maximum in Group 14 or 15 and then decreases.
ii CCl4, SiCl4, NCl3, PCl5
iii P = +5, S = +4