Book Answers Edexcel As Chemistry PDF
Book Answers Edexcel As Chemistry PDF
Book Answers Edexcel As Chemistry PDF
The core
principles of
chemistry
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Introduction.....................................................................................................iv
Chapter 5 Energetics......................................................................................18
Chapter 6 Bonding........................................................................................ 24
This Teacher Guide accompanies the Edexcel AS Chemistry textbook (2nd edition), by George
Facer, published by Philip Allan Updates.
The answers to the end-of-chapter questions are not model answers. They are designed to
help the student understand the answer. The examiner notes after the answer, indicated by
the icon , are additional points to help the student:
e
Answers to the chapter summary worksheets (see the textbook CD-ROM) are given at the end of
each chapter of this Teacher Guide.
The answers to the practice unit tests are model answers that include all that examiners look for
when awarding marks, together with some extra explanation. Each marking point is indicated
by a ✔.
Relative atomic mass values are not given in the questions, because the student is expected to
use the periodic table. All Edexcel’s theory exam papers have a periodic table printed on the back
page. The textbook has an identical version inside the back cover.
This guide includes a CD-ROM, designed so that answers to individual questions and the
explanatory comments can be cut and pasted and then issued to students after they have done
their homework.
A-level examiners are instructed not to be too literal in following the mark scheme. The
important point is that what has been written is correct and answers the question. There are
several occasions in this Guide when different wording is used from that in the textbook, but
either is equally acceptable. An example of this is:
n textbook — the bombarding electrons in a mass spectrometer have a high kinetic energy
Some answers are expanded to show the logic of the calculation. For instance, the conversion of
23.7 cm3 of solution to dm3 in the answer to Question 9 of the first chapter is set out as
1 dm3
23.7 cm3 × = 0.0237 dm3
1000 cm3
Name
If the name of a substance is asked for, examiners will accept either the name or the formula, but
if both are given, both must be correct. The command word ‘identify’ is often used. The answer
here can be a name or a formula. If the formula is required, only the formula and not the name
will score the mark.
Molecular formula
The added up formula, such as C2H4Cl2, is what is required. This is normally the answer to
questions involving percentage composition of compounds.
O O
Gas evolved is not an observation (it is a deduction). Bubbles of gas or effervescence are
observations.
Preferred colours
Flame tests
Cation Preferred colour Acceptable colours
Lithium Red Carmine, deep red, magenta or crimson
Sodium Yellow (not orange) —
Potassium Lilac Mauve or purple
Calcium Red or brick red Orange-red
Strontium Crimson Red
Barium Pale green Apple green or yellowy-green
Significant figures
If a question asks for appropriate or a specific number of significant figures, the answer must be
given to the correct number of significant figures.
Never round up to one figure, even if the answer is 5.0. The exception to this is when calculating
the number of atoms or the number of molecules of water of crystallisation in a formula.
In calculations from titration data, always give the answer to three or more significant figures.
Do not eound up to less than three signifcant figures in intermediare steps in a calculation.
Signs
Always give a + or a - sign in your answers to ∆H questions and to those on oxidation
numbers.
Conditions
You must state:
n the temperature range necessary or whether the substance has to be heated under reflux
The core
principles of
chemistry
3 The only two elements that are liquids are bromine and mercury.
e Some people think that francium is a liquid at room temperature. However, only a few francium atoms
have ever been made and those underwent rapid radioactive decay, so no-one has seen enough of the
element to be sure of its physical state.
5 12 kg = 12 000 g
e There are 1000 g in 1 kg. Remember that the number of grams is always bigger than the number of
kilograms.
1000 mg
7 0.0234 g × = 23.4 mg
1g
e There are 1000 mg in 1 g, so what you have to do in this calculation is to multiply the mass in grams by
the ratio 1000 mg/1 g. Note how the unit g cancels, leaving mg as the final unit.
1000 cm3
8 22.4 dm3 × = 22 400 cm3
1 dm3
e 1 dm3 = 1000 cm3, so the volume in dm3 has to be multiplied by the ratio 1000 cm3/1 dm3.
volume in cm3
9 volume in dm3 =
1000
so 23.7 cm = 0.0237 dm3
3
1 dm3
This is the same as 23.7 cm3 ×
1000 cm3
e 1000 cm3 = 1 dm3, so the volume in cm3 has to be divided by 1000.
The volume in dm3 is always less than the volume in cm3. This type of conversion is often required in
titration calculations.
10 a 1 mol of CO2 contains 6.02 × 1023 carbon dioxide molecules. Each molecule contains three
atoms, so there are 3 × 6.02 × 1023 = 1.81 × 1024 atoms.
b 1 mol of CaCl 2 contains 1 mol of Ca 2+ ions and 2 mol of Cl – ions. Therefore, there are
2 × 6.02 × 1023 = 1.20 × 1024 Cl– ions in 1 mol of CaCl2.
e The Avogadro constant, NA (6.02 × 1023 mol–1), is the number of molecules or groups of ions in 1 mol of
the substance.
12 The ratio of calcium hydroxide to nitric acid in the equation is 1:2. Therefore, 0.0642 mol of
nitric acid react with
0.0642 mol HNO3 ×
1mol Ca OH( )2 = 0.0321 mol Ca(OH)
2
2 mol HNO3
2 a Isotopes have the same number of protons but a different number of neutrons. Therefore,
B and D are isotopes of element number 17 (chlorine). B is a 35Cl atom and D is a 37Cl+ ion.
Isotopes can be neutral (atoms) or charged (ions).
b Atoms are neutral if the number of electrons is the same as the number of protons. Thus B and
F are neutral atoms.
e B is a 35Cl atom and F is an 40Ar atom.
c Cations are positively charged ions because they have more protons than electrons. A, C and
D are cations.
e A is K+, C is Mg2+ and D is Cl+.
d Anions are negatively charged ions because they have more electrons than protons. Element
E (Br–) is the only anion.
e For atoms and ions to have the same electronic configuration, they must have the same number
of electrons. Element A (K+) and F (Ar) both have 18 electrons, arranged 2,8,8.
3 There are two reasons. The more important is that most elements consist of a mixture of isotopes
(tin has ten naturally occurring isotopes) and so the average mass is not a whole number. The
second reason is that the relative mass of an isotope is not quite a whole number. For example,
the relative mass of sodium (which has only one isotope, 23Na) is 22.9898. This is because
protons and neutrons do not have a mass of exactly one and when they join to form a nucleus,
some of their mass is changed into energy.
4 Let the % of 65Cu be x. This means that the % of 63Cu is (100 – x).
65x + 63(100 − x)
relative atomic mass = = 63.5
100
65x + 63(100 − x) = 6350
65x − 63x = 6350 − 6300 = 50
2x = 50
x = 25
The abundances of the two isotopes are 65Cu = 25.0% and 63Cu = 75.0%.
e Note that the answer is given to three significant figures, because the data in the question were given to
three significant figures.
5 The relative atomic mass is the sum of the % of each isotope multiplied by its mass, all divided
by 100.
(28 × 92.2) + (29 × 4.7) + (30 × 3.1)
relative atomic mass of silicon = = 28.1
100
e Note that the value given on your calculator is 28.109. However, this must be changed to the one decimal
place required by the question.
Always check that your answer agrees with the value given in the periodic table at the back of the exam
paper, but remember that most values in the table have been rounded up to one decimal place.
6 Look in the periodic table for element number 13. This is aluminium. Aluminium has 13 protons
and 14 neutrons and therefore has a relative mass of 27 (13 + 14). The particle in the question
has three electrons fewer than the number of protons, so it has a charge of 3+. The particle is:
27A13+
13
7 a The peaks in a mass spectrum are caused by positive ions. Bromine exists as Br2 molecules
and there are two isotopes of bromine, of relative masses 79 and 81. The peak at m/e 158 is
caused by the (79Br–79Br)+ ion, the one at 160 by the (79Br– 81Br)+ ion and the one at 162 by the
(81Br– 81Br)+ ion.
b The peaks at 158 (due to the ion containing the Br-79 isotope only) and at 162 (due to the ion
containing the Br-81 isotope only) are the same height, so the relative abundance of the two
isotopes must be the same.
e Students studying statistics will know that in a 50:50 mixture of the two isotopes, the chance of a
79Br−79Br molecule is
1 × 1 = 1
4
It is the same for 81Br−81Br. However, the chance of a 79Br−81Br molecule is
2 × 1 × 1
as there are two ways (head−tail and tail−head) of obtaining this species. Thus, the peak heights are
1 : 1 : 1 or 1:2:1
4 4
c The energy of the bombardment in the mass spectrometer may cause the molecular ion to
dissociate into an atom and a monatomic ion. The equation for the formation of the peak at 79
is either:
8 Positive ions are formed when the vaporised atom or molecule is bombarded with fast-moving
electrons. The kinetic energy of these electrons is great enough to cause the removal of
an electron from the outermost orbital of the atom or of one of the bonding electrons in the
molecule.
e They can also be formed by rapid laser-induced evaporation of a solution of protonated large molecules,
such as pharmaceuticals.
9 The third shell has three types of orbitals, s, p and d. There are one s-orbital, three p-orbitals and
five d-orbitals, making a total of nine orbitals.
e Each orbital can hold two electrons, which is why the third shell can hold 18 electrons.
10 The lowest energy level is the 4s-orbital, followed in increasing order by the 4p-, 5s-, 4d-, 5p-,
6s- and 5d-orbitals.
e Remember that the d-orbitals fill ‘late’, after the next s-orbital has been filled.
12 Sodium in its ground state is 1s2 2s2 2p6 3s1. In an excited state, the 3s-electron is promoted to a
higher level such as the 3p level, so one answer is 1s2 2s2 2p6 3p1. Another correct answer is 1s2
2s2 2p6 4s1.
$ % $ $ $
14 Periodicity is the term used to describe a regular pattern of physical or chemical properties. An
example is that the first ionisation energies reach a maximum value at regular intervals (at each
noble gas).
15 Boron has a nuclear charge of +5 and the electronic configuration 2,3. Thus, it has two inner
shielding electrons. Its effective nuclear charge is approximately +3 (+5 – 2). Magnesium has
12 protons in its nucleus and the electronic configuration 2,8,2. Therefore, there are ten inner
shielding electrons, giving it an approximate nuclear charge of +2 (+12 – 10). Bromine has 35
protons and the electronic configuration 2,8,18,7. The nucleus is shielded by 28 inner electrons,
so the approximate effective nuclear charge is +7 (+35 – 28).
Bromine has the largest effective nuclear charge and magnesium the smallest.
e Remember that the effective nuclear charge is approximately equal to the nuclear charge (number of
protons) minus the number of inner (shielding) electrons.
The argument used in this answer ignores the repulsion between electrons in the outer orbit, which
reduces the effective nuclear charge from that calculated.
16 Negative ions are bigger than their parent neutral atoms; positive ions are smaller. Thus the
order of increasing radius is K+ < Cl < Cl–.
17 a K(g) → K+(g) + e–
b Ar(g) → Ar+(g) + e–
c Br(g) → Br+(g) + e–
e Note that all the species on the left are gaseous atoms that lose one electron.
18 F4+(g) → F5+(g) + e–
e The fifth ionisation energy is the energy for the removal of the fifth electron, and not for the removal of
five electrons.
19 a Mg(g) + e– → Mg–(g)
b N(g) + e– → N–(g)
e Note that all the species on the left are gaseous atoms that gain one electron.
20
1st ionisation energy
Na Mg Al Si P S Cl Ar
The general trend in the first ionisation energy is upwards as the effective nuclear charge
increases. Moving from sodium to argon, the nuclear charge steadily increases. However, the
number of shielding electrons remains the same because these elements all have ten inner
electrons.
There is a slight decrease at aluminium because the outer electron is in the 3p-orbital and is,
therefore, at a higher energy level than the 3s-electrons in magnesium. Thus less energy is
required to remove it.
There is another dip at sulfur. This is because the electronic configuration of sulfur is [Ne] 3s2
3px2 3py1 3pz1. The two electrons in the 3px -orbital repel each other, making it slightly easier to
remove one of them.
21 Helium has two electrons that are totally unshielded and so are extremely difficult to remove.
Neon has ten protons in the nucleus and the 2p-electrons are shielded by two inner (1s) electrons;
argon has 18 protons and the 3p-electrons are shielded by ten inner electrons; and lastly krypton
has 36 protons with the 4p-electrons shielded by 28 electrons. So although the nuclear charge
increases, so does the number of shielding electrons. These two effects cancel each other out.
The ionisation energy decreases from neon to krypton because the radii of the outer electron
shells increase, which results in the electrons being held less firmly and, therefore, being easier
to remove.
22 There is a big jump in ionisation energy between the sixth and the seventh values. The seventh
electron is therefore being removed from an inner shell. Therefore, element X has six outer
electrons and is in group 6 of the periodic table.
(ii) The answer is A. The general trend in a period is an increase, with slight dips at the third and
sixth elements in periods 2 and 3. Answer A fits this pattern.
(iii) The answer is D. There is always a steady decrease in first ionisation energy as a group is
descended.
2 The answer is C. The lowest frequency means the smallest energy difference. Energy levels
become closer together as the orbit number increases. Therefore, 3 → 2 is of lower energy than
2 → 1.
3 The answer is C. The third orbit has three types of orbital, s, p and d. There is just one 3s-orbital,
but three 3p- and five 3d-orbitals, making a total of nine different orbitals in the third orbit.
e Remember that each orbital can hold two electrons, so the third orbit can hold 2 × 9 = 18 electrons.
4 The answer is B. All four ions have the electron configuration of neon. Positive ions are smaller
than isoelectronic negative ions and highly charged positive ions are smaller than cations with
lower charge. (The opposite is true for negative ions.) Thus Al3+ is smaller than Na+, which is
smaller than F−; O2− is the largest of the four ions.
5 The answer is B. Electron affinity is the energy change for the addition of an electron to each of
one mole of gaseous atoms or ions. The first electron affinity is the energy charge per mole for
adding one electron to a gaseous atom, here Cl(g), to form a gaseous ion with a single negative
charge.
6 The answer is D. Bromine is Br2. There are no lines at 159 and 161, so there cannot be a 80Br
isotope because this would give an ion of mass 159 (79 + 80) and one of mass 161 (80 + 81). The
lines in a mass spectrum are caused by positive ions, so the answer must be (79Br– 81Br)+ because
79 + 81 = 160.
The simplest whole number ratio of 1.5:3:1 is obtained by multiplying them all by 2, i.e. 3:6:2.
The empirical formula is C3H6Br2.
e After division by the smallest number, you should round the values to 1 decimal place. If the ratio
is not a whole number ratio, try to obtain integers by multiplying all the numbers by 2. If that fails,
multiply by 3.
b The mass of the empirical formula is (12.0 + 2.0 + 19.0) = 33.0. This is half the molar mass,
so the molecular formula is C2H4F2.
e To find the molecular formula, multiply the empirical formula by the ratio of molar mass divided by
empirical mass. In this example it is 66.0/33.0, which equals 2.
4 a Calcium ions are 2+ and chloride ions are 1–, so the formula is CaCl2.
b Silver ions are 1+ and nitrate ions are 1–, so the formula is AgNO3.
c Copper(ii) is Cu2+ and phosphate is PO43–. For a neutral compound you need three copper ions
and two phosphate ions, making charges of +6 and –6. Therefore, the formula is Cu3(PO4)2.
5 a As there is one manganese ion to each carbonate ion, the charges have the same numerical
value. Carbonate ions are 2–, so the manganese ions in this compound must be 2+.
b The charge on two vanadium ions must equal the charge on three sulfate ions. Each sulfate is
–2, so three sulfate ions have a total charge of –6. This means that two vanadium ions have a
total charge of +6, so each has a charge of +3.
8 For equations a–c, the simplest way is to realise that the component ions of the compound
combine to give the precipitate. All other ions are spectators.
d Aqueous solutions of strong acids are totally ionised, so when they react as acids, the ionic
equation contains H+(aq). Solids, even if ionic, must be written in full.
e Aqueous alkalis are fully ionised, so in neutralisation reactions OH–(aq) ions are in the
equation. The reaction is between H+ and OH– ions and the ionic equation is:
H+(aq) + OH–(aq) → H2O(l)
9 For solids:
mass
moles =
molar mass
1.11 g
a amount of CaCO3 = = 0.0111 mol
[40.1 + 12.0 + (3 × 16.0)]g mol –1
2.22 g
b amount of Ba(OH)2 = = 0.130 mol
[137.3 + 2 × (16.0 + 1.0)]g mol −1
e Make sure that you give your answer to the correct number of significant figures. Here, the data in the
question are given to three significant figures, so the answer is also given to three significant figures.
mass 4.56 g
11 molar mass of the hydrated salt = = = 246 g mol–1
moles 0.0185 mol
MgSO4 contributes [24.3 + 32.1 + (4 × 16.0)] = 120.4 g mol–1;
therefore, 246 – 120.4 = 125.6 g mol–1 is due to x moles of water:
x(2.0 + 16.0) = 125.6
125.6
x= = 6.98
18.0
mass 10.0 g
14 moles of Ba(OH)2 = = = 0.05838 mol
molar mass (137.3 + 34.0)g mol –1
There are two OH− ions per formula unit of Ba(OH)2, so:
number of hydroxide ions = 2 × 0.05838 × 6.02 × 1023 = 7.03 × 1022
e Remember that the number of atoms, molecules or ions is always a huge number, usually around 1023.
The number of moles is usually less than 1.
3 The answer is D.
Mr = (2 × Na) + (1 × C) + (3 × O) + (10 × H2O) = 46.0 + 12.0 + 48.0 + (10 × 18.0) = 286.0 g mol−1.
4 The answer is B. Phosphorus(v) has a valency of 5 and oxygen a valency of 2. Swapping over the
valencies gives the formula P2O5.
e Phosphorus pentachloride exists as the dimer P4O10 but the formula P2O5 is also acceptable.
5 The answer is C. Equation A balances for atoms (three calcium atoms and two phosphate groups
on each side). It also balances for charge: left-hand side has 6+ and 6− charges, which is neutral,
as is the right-hand side.
Equation B has two lead, four nitrogen and twelve oxygen atoms on each side, so it balances.
Equation C balances for atoms, but not for charge. The charges on the left-hand side are 3+ and
2+ = 5+. On the right-hand side they are 2+ and 4+ = 6+.
e Beware. This is an example of a negative question — ‘does not balance’. The answer that is chemically
wrong is, therefore, the correct response. You will find several questions of this type in your A-level
exams.
6 The answer is A.
moles = concentration × volume in dm3 = 0.10 mol dm−3 × 25/1000 dm3 = 0.0025 mol
e Remember that you have to divide by 1000 to convert a volume in cm3 to one in dm3. The fact that there
are 2NaOH in the equation is irrelevant.
= 0.03176 mol × 2 = 0.06352 mol
to moles, then using the reaction stoichiometry and finally converting back to mass. The second method
fits all types of calculation, so is the better one to use.
mass 4.50 g
8 a amount (moles) of Fe = = = 0.0806 mol
molar mass 55.8 g mol −1
amount of copper(ii) sulfate = concentration × volume in dm3
= 2.00 mol dm–3 × 0.0500 dm3 = 0.100 mol
d Sodium hydroxide is the limiting reagent, so there will be an excess of sulfuric acid. Therefore,
red litmus will stay red and blue litmus will turn red.
e Even though there are more moles of sodium hydroxide than sulfuric acid, the sodium hydroxide is
the limiting reagent because 2 moles of it are needed for every mole of sulfuric acid.
or
24.3 g of Mg produces 95.3 g of MgCl2
6.075
so 6.075 g produces 95.3 × = 23.825 g of MgCl2
24.3
e Option A used some atomic numbers rather than atomic masses. The formula for magnesium chloride is
MgCl2 — option B used MgCl and C used Mg2Cl.
2 The answer is D.
mass
amount (moles) = = 0.0250
molar mass
there are 5 ions per formula, so there are 5 × 0.025 = 0.125 mol of ions
number of ions = 0.125 × 6.02 × 1023 = 7.53 × 1022
e Option A is the number of moles, B is the moles of ions and C is the number of ‘molecules’ or ion groups.
3 The answer is A.
mass
amount (moles) of rubidium =
atomic mass
8.55 g
= = 0.100 mol
85.5 g mol −1
mass of 0.100 mol of RbO2 = 0.100 mol × 117.5 g mol−1 = 11.75 g
4 The answer is B.
mass
amount (moles) of CuO =
molar mass
7.95 g
= = 0.100 mol
79.5 g mol −1
theoretical yield = 0.100 mol × molar mass of hydrated copper sulfate
= 0.1 × 249.6 = 24.96 g
actual yield of product
percentage yield = × 100
theoretical yield of product
23.0 × 100
= = 92.1 = 92% to two significant figures
24.96
so B is the correct answer.
5 The answer is B.
mass
amount (moles) of Al =
atomic mass
1.076 g
= = 0.03985 mol
27.0g mol −1
3
amount (moles) of hydrogen = 2 × 0.03985 = 0.05978 mol
so volume = 0.05978 × 24.0 = 1.43 dm3
∆H = –297 kJ mol−1
∆H = +2800 kJ mol−1
SO2(g) 6CO2(aq) + 6H2O(l)
5 –463 kJ mol–1
P(s) + 21–2Cl2(g) PCI5(s)
∆Hr –124 kJ mol–1
PCl3(l) + Cl2(g)
7 ∆Hr
C2H4(g) + H2O(l) C2H5OH(l)
e Always label a Hess’s law diagram with either ∆H or the values of ∆H.
6 × ∆Hc (H2)
6 × ∆Hc (C) ∆Hc (glucose)
6CO2(g) + 6H2O(l)
By Hess’s law:
∆Hf (glucose) = [6 × ∆Hc(C)] + [6 × ∆Hc(H2)] – ∆Hc(glucose)
∆Hf (glucose) = [6 × (–393.5)] + [6 × (–285.8)] – (–2816) = –1260 kJ mol–1
e A Hess’s law diagram has to be drawn because the calculation cannot be carried out using the formula,
∆Hr = ∆H(products) − ∆H(reactants).
10 Strong acids are totally ionised in dilute solution, so whatever the acid, the reaction is always:
H+(aq) + OH–(aq) → H2O(l)
Thus the enthalpy of neutralisation always has approximately the same value.
e In practice, enthalpies of neutralisation of strong acids are not exactly the same because of the different
enthalpies of solution of the salts formed.
11 The C=C and the H–Br bonds are broken (endothermic) and new C–C, C–H and C–Br bonds are
formed (exothermic).
12 The C=C and the Cl–Cl bonds are broken (endothermic) and C–C and two C–Cl bonds are made
(exothermic).
13 Procedure:
l Weigh out 16 g (0.1 mol) of anhydrous copper sulfate.
l Pour 100 cm3 of distilled water into an expanded polystyrene cup.
l Place the cup firmly in an empty beaker and measure the temperature to 0.2°C every 30 seconds
for 3 minutes.
l On the fourth minute, add the copper sulfate and stir with a glass rod.
l Measure the temperature every 30 seconds until the temperature stops rising and then for
another 3 minutes.
e A good way to write plans is to use bullet points. This stops the answer from becoming a rambling
account from which important points might be omitted.
Calculation:
l Plot the points on a piece of graph paper with the temperature on the y-axis.
l Draw a smooth line using the readings for the first 3 minutes and another line for the last
3 minutes.
l Extrapolate these lines back to the 4-minute point.
l Measure the temperature difference between these two lines at the 4-minute point (the time
when the copper sulfate was added). This is the corrected temperature change, ∆T.
−Q
∆H =
moles of copper sulfate taken
∆H is negative if the temperature rises (an exothermic reaction) or positive if the temperature
falls (an endothermic reaction).
It is assumed that:
l no heat is lost to the surroundings
l the density of the solution is 1 g cm–3
l the specific heat capacity of the solution is approximately the same as for water (4.18 J g–1 °C–1)
l there would be no further heat change on diluting the solution
14 ∆H for this reaction cannot be measured directly because too much heat is required to decompose
calcium carbonate. The clue is in the substances that the question allows you to use to plan an
indirect route:
calcium carbonate + acid → calcium chloride + water + carbon dioxide
calcium chloride + water → calcium oxide + acid
CaCO3(s) + 2HCl(aq) → CaCl2(aq) + H2O(l) + CO2(g) ∆H1
CaCl2(aq) + H2O(l) → CaO(s) + 2HCl(aq) ∆H2
∆H1 is the heat change for the reaction of calcium carbonate with hydrochloric acid; -∆H2 is the
heat change for the reaction of calcium oxide with hydrochloric acid. If ∆H1 and ∆H2 are found
by experiment, ∆H for the reaction can be calculated.
To find ∆H1:
l Weigh out a known amount of calcium carbonate — for example, about 5 g.
l Place 100 cm3 of 2.0 mol dm−3 hydrochloric acid (an excess) in a polystyrene cup supported in
a beaker.
l Measure the temperature of the acid every 30 s for 3 minutes.
l At 3.5 minutes, add the calcium carbonate slowly, making sure that none fizzes over.
l When all the calcium carbonate has been added, measure the temperature every 30 s until the
and another line for the last 3 minutes. Extrapolate these lines back to the 3.5-minute point
and measure the difference in temperature of the two points at 3.5 minutes.
−(100 g × 4.18 J g −1 °C −1 × ∆T )
∆H1 =
moles of CaCO3
l Repeat for the reaction between calcium oxide and hydrochloric acid.
−(100 g × 4.18 J g −1 °C −1 × ∆T)
−∆H2 =
moles of CaO
l ∆Hr = ∆H1 + ∆H2
e Beware of signs. Both reactions are exothermic, so their ∆H values are negative. To obtain ∆H2, the
equation for the second reaction has to be reversed.
b There must be an excess of sodium hydroxide to ensure that all the acid reacts.
mass
16 amount (moles) of magnesium sulfate =
molar mass
6.0 g
= = 0.0498 mol
120.4 g mol −1
heat produced = moles × −∆H = 0.0498 mol × 91 kJ mol-1 = 4.53 kJ = 4530 J
heat = mass × specific heat capacity × ∆T
heat
so ∆T =
mass × specific heat capacity
4530 J
= = 19.8°C
56 g × 4.08 J g −1 °C −1
b The two main reasons why the value is less exothermic than the data book value are that:
l not all the heat produced is absorbed by the water and some heats the air around the beaker
Other reasons are that combustion might not have been complete or some methanol might
have evaporated between blowing out the flame and weighing the burner.
volume
18 amount (moles) of propane gas burnt =
molar volume
0.208 dm3
= = 0.00867 mol
24.0 dm3 mol −1
heat change, Q = mass × specific heat capacity × change in temperature
= 100 g × 4.18 J g–1 °C–1 × (61.5 – 19.4)°C = 17 600 J = 17.6 kJ
−17.6 kJ
∆Hc(propane) = = –2.03 × 103 kJ mol–1
0.00867 mol
e Remember:
l to convert the volume of gas from cm3 to dm3
l the temperature rose, so the reaction is exothermic and ∆H is negative
l to give your answer to three significant figures because the data are expressed to three significant
figures
The answer is lower than the book value because of considerable heat losses during the experiment.
2 The answer is A.
amount (moles) of copper sulfate = concentration × volume in dm3
= 0.500 mol dm−3 × 0.0250 dm3 = 0.0125 mol
3 The answer is B.
−Q
∆H =
moles
−2970
= = −286 000J mol−1 = −286 kJ mol−1
0.104
e There are two points that need careful consideration. First, the data are in joules (J) but the four choices
are in kilojoules (kJ), so the number obtained has to be divided by 1000. The second point is that heat is
produced, so the reaction is exothermic and ∆H is negative, so options A and C are wrong.
4 The answer is C. The data are about enthalpy of formation and reaction, so you can use the
formula:
∆Hr = Σn∆Hf(products) − Σn∆Hf(reactants)
= ∆Hf(CO2) + 2 × ∆Hf(H2O) − ∆Hf(CH4)
5 The answer is A. When gaseous water turns to liquid water, heat is produced because the process
is exothermic. Therefore, ∆Hf(H2O)(l) is more exothermic than ∆Hf(H2O)(g), so option A is
correct.
6 The answer is B. The definition of any enthalpy of combustion is for 1 mol of the substance being
burnt. Options A and C are incorrect because the equations have 2C4H10 on the left. Option C
is also wrong because combustion must be complete. Option D is incorrect because it is not
combustion. Water is a liquid under standard conditions, so B is the correct answer.
2 a Mg + 2HCl → MgCl2 + H2
e State symbols should be included if the reaction produces a precipitate. Otherwise, unless they are
specifically asked for, it is not necessary to include them.
3 a An ionic bond is the electrostatic attraction between a positively charged ion (the cation) and
a negatively charged ion (the anion).
e An ionic bond is the attraction between ions, not the losing and gaining of electrons by the constituent
atoms.
b Calcium has an electron configuration [Ar] 4s2. Fluorine has the electron configuration [He]
2s2 2p5. Each calcium atom loses two electrons to form a Ca2+ ion that has the electron config-
uration of the noble gas argon. These two electrons are gained by two fluorine atoms and two
F– ions are formed, each with the electron configuration [He] 2s2 2p6, which is that of the
noble gas neon. These ions attract each other, forming the bond.
e You must give the electron configuration before and after the formation of the ions.
Note that in calcium fluoride, there are two fluoride ions for each calcium ion. Therefore, the
dot-and-cross diagram for the compound calcium fluoride is:
2+
F Ca F
e The calcium ion has eight electrons in its outer orbit, which is the third shell. These must be shown in the
dot-and-cross diagram.
4 In decreasing order of size of radius: Na > Cl– > Mg > Cl > Na+ > Mg2+
e Atoms get bigger when they gain electrons and form negative ions. The species Cl−, Cl, Na and Mg
have electrons in three shells; the positive ions, Na+ and Mg2+, have electrons in two shells. Therefore
the positive ions are the smallest. Moving across the periodic table, neutral atoms become smaller, so a
magnesium atom is smaller than a sodium atom and a chlorine atom is smaller than a magnesium atom.
Cl− is larger than Cl, and Na is larger than Cl. Na and Cl– are similar in radius, but a sodium atom is slightly
bigger than a chloride ion.
5 In decreasing order of polarising power: Al3+ > Mg2+ > Na+ > K+
e Polarising power depends on the charge on the ion and on its radius. Aluminium, magnesium and
sodium are all in period 3. Of the three ions, aluminium has the highest charge and the smallest radius,
so it is the most polarising. Potassium is in period 4, so it has the largest radius and, as it is only 1+, its
polarising power is the smallest.
6 A covalent bond and a dative covalent bond both consist of a pair of electrons shared by two
atoms. In a covalent bond each atom donates one electron; in a dative covalent bond both
electrons come from the same atom.
e The bond is the attraction between the two atoms caused by the sharing of a pair of electrons.
8 The electron configuration of nitrogen is [He] 2s2 2p3 and of phosphorus is [Ne] 3s2 3p3. Both
elements have five electrons in the valence shell. However, the maximum number of electrons in
the second shell, which is the outer shell of nitrogen, is eight. This means that nitrogen can only
form three covalent bonds. The three unpaired 2p-electrons and three electrons from the other
atoms in the molecule are shared. This fills the 2p-orbital and the second shell. The valence
electrons of phosphorus are in the third shell, which can hold up to 18 electrons. One of the 3s-
electrons is promoted into an empty 3d-orbital and its five unpaired electrons are used to form
five covalent bonds.
e Do not say that nitrogen has no empty orbitals into which it can promote a 2s-electron. It does not have
an empty orbital in the second shell. The empty orbitals in the third shell cannot be used in bonding
because too much energy is required to promote a 2s-electron into a third-shell orbital. In addition to
forming three covalent bonds, nitrogen can also provide two electrons to form a dative covalent bond,
as in the NH4+ ion.
9 A σ-bond is caused by the head-on overlap of two atomic orbitals. The shared electrons are on
the line between the centres of the two atoms. A π-bond is the result of a sideways overlap of
two p-orbitals (or a p- and a d-orbital), so that the shared electrons are above and below the line
joining the centres of the two atoms.
e A σ-bond can be caused by the overlap of:
l two s-orbitals, as in hydrogen
l one s- and one p-orbital, as in HCl
l two p-orbitals, as in Cl2
A π-bond is always found together with a σ-bond, making a double bond.
Cl C Cl
Cl
e Carbon tetrachloride has four σ-bonds.
e Carbon dioxide has one σ- and one π-bond between each oxygen atom and the central carbon atom.
Apart from in carbon monoxide, carbon has four bonds in all of its compounds.
O S O
e The sulfur atom has the electron configuration [Ne] 3s2 3p4. It can form six covalent bonds because one
3s- and one 3p-electron are promoted into empty 3d-orbitals. Two of these bonds are π-bonds and four
are σ-bonds.
Xe
F F
F
e The heavier noble gases can form compounds. Xenon has the electron configuration [Kr] 4d10 5s2 5p6.
Electrons can be promoted from its 5p-orbitals into empty 5d-orbitals and bonds can then form. The
energy requirement for this is quite high, so it is only energetically favourable if strong bonds, such as
those with the small element fluorine, are formed.
2 The answer is A. The strength of a metallic bond depends mainly on the ionic radius and charge.
Solid aluminium has a lattice of Al3+ ions that are more highly charged and are smaller than
Mg2+, K+ or Na+ ions, and there are three more delocalised electrons per ion. These three factors
all make the metallic bond in aluminium the strongest.
4 The answer is B. The sum of the ionic radii in sodium chloride is the radius of Na+ plus the radius
of Cl−. A metallic radius is always slightly bigger than the corresponding ionic radius (the ions
are not touching), so the answer is B not C. Option D is incorrect because, in the same period,
2+ ions are smaller than 1+ ions
5 The answer is D. The magnitude of the lattice energy depends mostly on the charge of the ions
and the sum of their radii. Ca2+ is more highly charged than Na+ or K+. The O2− ion is more
charged than Cl− and is smaller than Cl− and S2−. Therefore, CaO has the highest exothermic
lattice energy.
6 The answer is A. Covalent character is caused by polarisation of the anion. The greater the
degree of covalency, the greater is the difference between the Born–Haber and the theoretical
lattice energies. Small, highly charged ions are the most polarising; large and highly charged
anions are the easiest to polarise. Mg2+ is smaller than Ca2+ and the ion is more highly charged
than Na+ or K+. I− is larger than Cl−, so the I− ion in MgI2 is the most polarised. Therefore,
magnesium iodide has the greatest covalent character.
7 The answer is B. It is impossible to have two σ-bonds between the same two atoms. The sideways
overlap of two p-orbitals results in a π-bond that is part of a double bond, but not all of it.
8 The answer is C. The strength of a covalent bond depends mostly on the small size of the atoms.
(There are exceptions to this. For example, the F–F bond is weaker than the Cl–Cl bond.) The second-
period atoms, nitrogen and oxygen, are smaller than the third-period atoms, phosphorus and sulfur.
The trend across a period is for the atoms to become smaller, so an oxygen atom has a smaller radius
than a nitrogen atom. Therefore, the O–H covalent bond is the strongest of the four.
9 The answer is C. The definition is for the formation of one mole of atoms from the element in its
standard state. Bromine is a liquid at 1 atm pressure and 298 K, so the answer is C.
e Option A represents twice the enthalpy of atomisation.
10 The answer is D. Do not confuse ionisation energy (always loss of an electron) with electron
affinity (always gain of an electron). The second ionisation energy is for the removal of an
electron from each ion of a mole of gaseous 1+ ions forming a mole of 2+ ions.
e Option C is the sum of the first and second ionisation energies. Option B is the second electron affinity
and A is the sum of the first and second electron affinities.
11 The answer is A. This is a difficult question, possibly best attempted by drawing out the structures
of the species. PCl4 + comes from a PCl5 molecule (whch has five covalent σ-bonds) that loses a
Cl− ion. The other species all contain dative bonds. In NH4 +, there is a dative bond between the
lone pair of electrons on the nitrogen of NH3 and an H+. In PCl6 −, it is between a Cl− ion and a
PCl5 molecule. In Al2Cl6 there are two dative bonds, one to each aluminium atom in an AlCl3
molecule from the other AlCl3 molecule.
4 Br H H Br Br H
H C C C H H C C C H
Br H H H H H
1,1-dibromopropane 1,2-dibromopropane
Br H Br H Br H
H C C C H H C C C H
H H H H Br H
1,3-dibromopropane 2,2-dibromopropane
e 2,3-dibromopropane is identical to 1,2-dibromopropane.
5 Cl H H H H Cl H H
H C C C C H H C C C C H
H H H H H H H H
1-chlorobutane 2-chlorobutane
H H
H C H H C H
Cl H H H
H C C C H H C C C H
H H H H Cl H
1-chloro-2-methylpropane 2-chloro-2-methylpropane
e Start by drawing the longest chain here it is four carbon atoms. Then, add chlorine to different
positions on that chain. Next, branch the chain and see if chlorine could go in different positions.
Putting the chlorine in the top CH3 in place of a hydrogen ion is another way of writing 1-chloro-2-
methylpropane (the molecule is bent through 90°).
CH2=CHCH2CH2CH3 C C C C
H H H CH2CH3
9 (CH3)2C=CHCH3 + HI → (CH3)2CICH2CH3
10 The purple colour of the potassium manganate(vii) solution would be replaced by a brown
precipitate. The organic product is butane-2,3-diol, CH3CH(OH)CH(OH)CH3.
e Do not forget to state the original colour as well as the final appearance. The brown precipitate is
manganese(iv) oxide, MnO2.
11 In the reaction between ethene and bromine, bromine attacks the electron-rich π-bond. In
ethane, all the bonds are σ-bonds, so there is no centre of high-electron density. The propagation
step of the photochemical substitution reaction with ethane involves the reaction of a bromine
radical with an ethane molecule. This is a slow reaction. It is energetically unfavourable because
of the relatively weak C–Br bond that is formed.
e The mechanism of the reaction between ethene and bromine is electrophilic addition; between ethane
and bromine it is free-radical substitution.
12 C2H5 H C2H5 H
C C C C
H H H H n/
2
n
e The subscript is 2 because the equation for the polymerisation showing one repeat unit is:
C2H5 H
n C2H5CH=CH2 → C C
H H n
but the equation for the polymerisation showing two repeat units is:
C2H5 H C2H5 H
n C2H5CH=CH2 → C C C C
H H H H n/
2
2 The answer is D. Geometric isomerism is only possible if there are two different atoms or groups
on both the carbon atoms of the double bond. Pent-2-ene has a CH3 group and a hydrogen atom
on one carbon of the C=C group and a C2H5 group and a hydrogen atom on the other, so it exists
as two geometric isomers:
and
e Cyclohexene has one hydrogen atom on each of the carbon atoms in the C=C group. Propene and
but-1-ene have two hydrogen atoms on one of the carbon atoms. Therefore, none can form geometric
isomers.
3 The answer is C. The isomers are but-1-ene and the two geometric isomers of but-2-ene and
2-methylpropene:
and
4 The answer is B. Ethane and methylpropane are alkanes and have only σ-bonds. When ethene
polymerises, the double bond breaks, so poly(ethene) does not contain any double bonds.
Cyclohexene has a double bond, which consists of a σ-bond and a π-bond, so B is the correct
response.
5 The answer is D. The general formula for the homologous series of alkanes is C nH2n+2.
6 The answer is B. The important step that determines the rate of reaction is that between the
halogen radical and the alkane.
e Option A is not correct because the reaction is between chlorine radicals and the alkane not chlorine
molecules. Options C and D are incorrect — the Cl–Cl bond is the stronger.
7 The answer is B. The initial attack is by a δ+ Br atom. Therefore, all the possible products must
contain bromine. This means that option B is false and is the correct answer to this negative
question.
e The intermediate carbocation, CH2BrCH2+, can pick up a Br-, H2O (followed by loss of H+) or a Cl-, so all
the other options are true.
8 The answer is A. When the double bond breaks, the two groups add on to the previously double-
bonded carbon atoms. Therefore, option B is incorrect. Potassium ions do not replace H in OH
groups, so options C and D are also incorrect.
9 The answer is C. First, the reaction of alkenes with hydrogen halides is an addition reaction.
Second, the attack is by δ+ hydrogen in HBr. The attacking reagent is an electrophile, so the
reaction is electrophilic addition.
2 The answer is A. ‘Parts per million’ is a measure by mass. 1 dm3 of water weighs 1000 g. Here,
this contains 5.4 × 10−6 × 1000 g of Al 3. So there are 5.4 × 103 g = 5.4 mg of Al3+ ions in the
solution.
3 The answer is A.
mass
amount (moles) =
molar mass
10 g
= = 0.1 mol
100 g mol −1
moles
concentration =
volume
0.1 mol
= = 0.40 mol dm−3
0.250 dm3
4 The answer is B.
1
1 dm3 of gas = = 0.0417 mol
24
butane forms carbon dioxide in a 1:4 molar ratio
so amount (moles) of carbon dioxide produced = 4 × 0.0417 = 0.167 mol
mass = moles × molar mass = 0.167 mol × 44.0 g mol−1 = 7.3 g
5 The answer is A. Atom economy is the number of atoms in the desired product compared with
the number of atoms in the starting materials, expressed as a percentage. In this example it is:
8 × 100 = 53.3%
15
6 The answer is C.
molar mass of ethanol =46.0 g mol−1; molar mass of ethanoic acid = 60.0 g mol−1
mass
amount (moles) of ethanol =
molar mass
23 g
= = 0.50 mol
46.0 g mol −1
maximum theoretical yield of ethanoic acid = 0.5 mol as the reaction has a 1:1 ratio
maximum theoretical mass of ethanoic acid = moles × molar mass
= 0.5 mol × 60.0 g mol−1 = 30.0 g
actual yield
percentage yield = × 100
maximum theoretical yield
16 g
= × 100 = 53.3%
30.0 g
e The percentage yield is never equal to the actual mass of product × 100 divided by the mass of reactant.
In this instance, such a calculation would give the answer 69.6%, i.e. option D.
7 The answer is B.
mass
amount (moles) of calcium chloride =
molar mass
111.1 g
= = 1.000 mol
111.1 g mol −1
number of formula units = moles × Avogadro constant
= 1.000 × 6.02 × 1023 = 6.02 × 1023
number of ions = 3 × 6.02 × 1023 = 1.81 × 1024
e Do not forget that calcium chloride has three ions per formula, one Ca2+ and two Cl−.
8 The answer is B.
20 nmol of steroid per dm3 = 2.0 nmol of steroid per 100 cm3 = 2.0 × 10−9 mol per 100 cm3
(1 nmol = 10−9 mol)
number of molecules = moles × Avogadro constant = 2.0 × 10−9 × 6.02 × 1023 = 1.204 × 1015
9 The answer is B.
∆Hr = Σ ∆Hf(products) − Σ ∆Hf(reactants)
= 2 × −395 − (2 × −297 + 0) = −196 kJ mol−1
10 The answer is B. You cannot use ‘products – reactants’ here because you are not given enthalpy
of formation data. The question has to be solved using a Hess’s law cycle (direct ∆H = sum of
indirect ∆H values).
The direct route is: elements → ethane.
The indirect route is: elements (and oxygen) → combustion products → ethane (and oxygen):
1 1
2C(s) + 3H2(g) (+3–O
2 2) C2H6(g) (+3–O
2 2)
2CO2(s) + 3H2O(l)
11 The answer is A. Beware! ∆Hf is for the formation of 1 mol. It is equal to one-half of ∆Hr because
the equation has 2 moles of ammonia, NH3, on the right-hand side. ∆Hr is found from bond
enthalpies. (Remember that bond breaking is endothermic and bond making is exothermic.)
bonds broken = 1 × N≡N and 3 × H–H = +946 + (3 × 436) = +2254 kJ
bonds made = 6 × N–H = 6 × −391 = −2346 kJ
∆Hr = +2254 + (– 2346) = −92 kJ
so ∆Hf = 0.5 × −92 = −46 kJ mol−1
13 The answer is C.
∆T = 18.7 − 22.4 = −3.7°C
heat change, Q = mass × specific heat capacity × ∆T
= 100 g × 4.18 J g−1 °C−1 × 3.7 = 1546.6 J = 1550 J (3 s.f.)
e You must use the mass of the water being heated, not the mass of the solute. The latter gives option A as
the answer.
14 The answer is A. A thermometer reading that is always 2° too high gives readings for both the
starting and the final temperatures that are 2° too high. This has no effect on the value of ∆T,
and so none on the accuracy of the experiment.
e The reason that option D is incorrect is that it would result in not all the acid being neutralised, which
would affect the value of ∆H.
15 The answer is D. The reaction is exothermic, so the value of ∆H is negative. Options A and C can,
therefore, be ignored.
amount (moles) of sulfuric acid = concentration × volume in dm3
= 0.500 mol dm−3 × 0.025 dm3 = 0.0125 mol
The data are for the equation:
H2SO4 + 2NaOH → Na2SO4 + 2H2O
−heat produced
so ∆H per mole of H2SO4 reacted =
moles
−1.46 kJ
= = −116.8 kJ
0.0125 mol
The definition of enthalpy of neutralisation is per mole of water produced not per mole of sulfuric
acid reacted, so:
enthalpy of neutralisation = 12 × −116.8 = −58.4 kJ mol−1
16 The answer is C. When determining the significant figures for numbers less than 1, the zero
in front of the decimal point and zeros immediately after the decimal point are not counted,
whereas zeros at the end of the number are counted. Written in scientific notation, the number
is 2.10 × 10−2, which is clearly to three significant figures.
17 The answer is A. Ionisation energy relates to a gaseous atom losing an electron and becoming a
positive ion.
18 The answer is A. Oxygen has the electronic configuration 1s2 2s2 2px2 2py1 2pz1. When an O+ ion
is formed the electron in the highest energy level is lost — one of the 2px electrons.
19 The answer is B. The chain is five carbon atoms long, so the stem name is pent-. The highest
priority atoms attached to the C=C group are the oxygen (atomic number 8) on the left-hand
carbon and the carbon (atomic number 6) on the right-hand carbon of the double bond. These
are on opposite sides of the double bond and so the prefix E is given to the name.
20 The answer is B. A is wrong as there is always restricted rotation about a carbon dioxide bond.
C and D are wrong as 2-methylbut-2-ene does not have geometric isomers.
21 The answer is C. The peak at 158 is caused by (79X–79X)+ and that at 162 by (81X– 81X)+. Since
there is no peak at 159, there cannot be an 80X isotope (79X– 80X has a mass of 159). This cuts
out options A, B and D. The double intensity of the peak at 160 is caused by the two ways of
combining 79X and 81X — (79X– 81X)+ and (81X–79X)+ (similar to the way that, when tossing two
coins, the chances of the head–tail combination is twice as likely as either head–head or tail–
tail).
22 The answer is B. The compound does not decolorise bromine water, so it cannot be an alkene.
Therefore, option B is false and is the correct answer.
23 i The answer is B. There is a big jump after the third ionisation energy when an electron is
removed from an inner shell.
ii The answer is A. The ionisation energies decrease down a group as the atomic radius
increases.
iii The answer is C. In a period, there is a general upward trend with a slight dip between the
second and third elements. This is because the electron is being removed from a higher-
energy p-orbital, rather than from an s-orbital, as is the case for the second element.
Section B
24 a i Ionisation is achieved by the bombardment of the gaseous substance with a beam of high-
energy (fast-moving) electrons ✓.
iii They are then deflected by a magnetic field ✓. (Heavier ions are deflected less.)
25 a The first ionisation energy of an element is the energy required to remove one electron ✓ from
each of a mole ✓ of gaseous atoms ✓ of that element.
b i Sodium has a nuclear charge of +11 and the outer electron is shielded by ten inner electrons.
The effective nuclear charge is therefore about +1. In magnesium, the nuclear charge of +12
is also shielded by ten inner electrons, so its effective nuclear charge is about +2 ✓. Also,
the atomic radius of a magnesium atom is less than that of a sodium atom ✓. Together these
factors result in it being harder to remove an electron from a magnesium atom than from a
sodium atom ✓. Therefore, magnesium has a larger first ionisation energy.
ii Aluminium has the electronic configuration [Ne] 3s2 3p1 and that of magnesium is [Ne] 3s2 ✓.
The 3p-electron is at a higher energy level than a 3s-electron and so is slightly easier to
remove. In addition, the 3s-electrons partially shield the 3p-electron ✓.
26 a i Free-radical substitution ✓
ii Electrophilic addition ✓
e The equations are CH3CH3 + Cl2 → CH3CH2Cl + HCl (substitution) and CH2=CH2 + Cl2 → CH2ClCH2Cl
(addition).
b i A homologous series is a series of compounds that all have the same general formula ✓. Each
one differs from the next by CH2 ✓ and either they have similar chemical properties or they
show a trend in physical properties ✓.
+
Step 2 H2C CH CH2 CH3 → H2C CH CH2 CH3
: Br−
Br Br Br
✓
iv 1-bromobutan-2-ol/CH3BrCH(OH)CH2CH3
v The purple ✓ potassium manganate(vii) solution turns to a brown precipitate ✓. The organic
product is CH2OHCH(OH)CH2CH3/butan-1,2-diol ✓.
e Don’t give the name and the formula in case one is wrong. +1 and –1 score 0.
vi CH3
H CH2
carbon skeleton ✓
C C
continuation bonds ✓
H H n
27 a The standard enthalpy of formation, ∆Hf °, is the enthalpy change when 1 mol ✓ of a substance
is formed from its elements ✓ in their standard states under standard conditions of 1 atm
pressure and a stated temperature (usually 298 K) ✓.
–1325 kJ
b i C2H5Cl(g) + 3O2(g) 2CO2(g) + 2H2O(l) + HCl(g)
1 1
2C(s) + 2–2H2(g) + –2Cl2(g) + 3O2(g) ✓✓
e The formulae in the Hess’s law cycle are awarded 1 mark. Labelling with arrows in the correct directions
gains the second mark. Make sure that you label the Hess’s law diagram either with symbols or ∆H
values.
Note that when chloroalkanes burn, hydrogen chloride gas is one of the products.
ii
✓
Ea
Enthalpy
C2H4 + HCl
✓ CH3CH2Cl
e 1 mark is for showing the energy level of products as lower than the energy level of reactants and for
labelling ∆Hr. The hump with activation energy shown gains a second mark.
iii The bond enthalpies used in the calculation are the average of the enthalpies of the bonds
in a range of different compounds ✓.
e The C−Cl bond enthalpy in C2H5Cl is slightly different from the C−Cl bond enthalpy in CH3Cl.
2+
28 a i Mg
−
ii I
e For parts (i) and (ii), there is 1 mark for both electronic configurations being correct and 1 mark for both
charges being correct.
b i The difference between the two values in magnesium iodide is 383 kJ. For magnesium
fluoride, it is 44 kJ. The iodide ion has the same charge as the fluoride ion (1−) but it has
a much bigger radius ✓. This means that the anion is much more polarised ✓ by the Mg2+
ion, so magnesium iodide has more covalent character ✓ than magnesium fluoride. This
causes its lattice energy obtained from the Born–Haber cycle to have a higher value than the
theoretical value calculated on the basis of the compound being wholly ionic.
e The marks are for:
l size and charge of anions
l a comparison of polarisation of the anions
l comparison of covalent character
Do not confuse ions with atoms. This is a common error. To score the first mark, you must either state
that the charges on the two anions are the same or give the charge. Do not say that magnesium iodide is
covalent — say that it has ‘some covalent character’.
ii The main factors that determine lattice energy are ionic radius and charge. Calcium and
magnesium ions are both 2+, but calcium ions have a smaller radius ✓ than magnesium ions
and are, therefore, more strongly attracted ✓ to the fluoride ions. This means that the lattice
energy of magnesium fluoride is more exothermic than that of calcium fluoride.
Application of
core principles
of chemistry
b Oxygen is in group 6 and has the electron configuration [He] 2s2 2p4. Two of the six valence
(outer shell) electrons are used in bonding with the two fluorine atoms. Therefore, there are
four unused electrons, i.e. two lone pairs.
c Carbon is in group 4 and has the electron structure [He] 2s2 2p2. There are four valence
electrons that are all used in bonding, since one σ- and one π-bond are formed with each of
the two oxygen atoms. Therefore, there are no lone pairs.
e To work out the number of lone pairs (essential when predicting the shape of a molecule), you must
calculate the number of electrons in the outer orbit of the central atom. These are the valence electrons.
Subtract the number of bonds from the number of valence electrons to find the number of unused
electrons. The number of lone pairs is half the number of unused valence-shell electrons.
2 a P
H H
Phosphorus is in group 5 of the periodic table, so it has five valence electrons. It forms
three covalent bonds in PH3, so it has one lone pair. The electron pairs are arranged tetra-
hedrally around the central atom because all four pairs repel each other to the position of
maximum separation. The three hydrogen atoms take up a pyramidal arrangement around
the phosphorus atom.
b S
Cl Cl
Sulfur is in group 6 of the periodic table, so it has six valence electrons. It forms two covalent
(σ) bonds and so has four (6 – 2) unused electrons. Therefore, there are two bond pairs and
two lone pairs around the sulfur atom. This means that a tetrahedral arrangement of electron
pairs produces the least repulsion between the electron pairs. The two chlorine atoms are
arranged in a bent (v-shaped, non-linear) shape around the sulfur atom.
c O
P
–O
O–
–O
The phosphorus atom, [Ne] 3s2 3p3, is bonded to one oxygen atom by a double (σ + π) bond and
to the other three oxygen atoms by single bonds. It forms five bonds, so there are no lone pairs.
There are four sets of electrons around the phosphorus atom. These repel each other to a
position of maximum separation. Therefore, the ion has a tetrahedral shape.
e When counting the number of electron pairs around the central atom, count a double (σ + π) bond as
one set. Thus the number of σ-bonds and lone pairs determines the electron arrangement around the
central atom. In this example there are four σ-bonds and no lone pairs, so the electron arrangement is
tetrahedral.
d F
F
As F
F
F
Arsenic is in the same group of the periodic table as phosphorus. Therefore, it has five valence
electrons. One 4s-electron is promoted into an empty 4d-orbital and all five electrons are used
in bonding to the five fluorine atoms. Thus, there are no lone pairs. The five (bonding) pairs
of electrons repel each other and the molecule has the shape of a trigonal bipyramid.
e Practise drawing this awkward shape.
e H C N
Carbon is in group 4 of the periodic table and has four valence electrons. All these electrons
are used in bonding (one σ-bond to the hydrogen atom and one σ- and two π-bonds to the
nitrogen, making a total of four bonds). Therefore, there are no lone pairs on the carbon. The
two sets of electrons repel each other and the molecule is linear.
e For all questions about shapes of molecules or ions you must first work out the number of valence
(outer shell) electrons on the central atom, the number of bonds and hence the number of lone pairs.
This gives you the arrangement of the electron pairs. The lone pairs are ‘invisible’ but repel the bond
pairs and so affect the shape of the molecule or ion.
3 a The bond angle in the PH3 trigonal pyramid is less than 109.5° (the tetrahedral angle). This is
because of the greater repulsion between a lone pair and a bond pair than between two bond
pairs.
e The bond angle might be expected to be the same as in ammonia (107o), but, for complex reasons, it is
less than this.
b The bond angle in the non-linear SCl2 molecule is considerably less than the tetrahedral angle.
This is because of the strong lone pair–lone pair repulsion. The angle is similar to that in water,
which is 104.5°.
d F
F 90°
120° As F
F
F
The bond angles in the trigonal bipyramidal AsF5 molecule are 120o between the fluorine
atoms and the arsenic atom in the triangular plane, and 90o between the top or bottom
fluorine atom and those in the plane.
4 a The bond is polar, with the iodine atom being δ+ and the chlorine atoms δ–. This is because
chlorine is more electronegative than iodine and draws the bonding electrons towards itself.
Iodine has two lone pairs of electrons, so the molecule is not trigonal planar and, therefore,
has a dipole moment.
b Fluorine is the most electronegative element and so is δ– and the less electronegative oxygen
is δ+.
The shape of this molecule is bent because of the two lone pairs on the oxygen atom. Therefore,
the molecule is polar.
e This is the only bond in which the oxygen atom is δ+ and, therefore, oxygen has a positive oxidation
number.
c Oxygen is more electronegative than carbon, so the C=O bonds are polar with the carbon
atom δ+ and the oxygen atoms δ–. However, as the molecule is linear and so symmetrical, the
polarities cancel out and the molecule is non-polar.
d Carbon and iodine both have electronegativities of 2.5, so the bond is non-polar. The C–H
bond is polar as carbon is more electronegative than hydrogen, which becomes d+. As the
molecule is not symmetrical, it is polar.
5 a The small radius and high electronegativity of the nitrogen atom result in the formation of
hydrogen bonds between ammonia molecules. Instantaneous induced dipole forces (dispersion
forces) are also present.
c Oxygen fluoride is very polar, but does not contain hydrogen and so cannot form hydrogen
bonds. Its intermolecular forces are permanent dipole–dipole forces and dispersion forces.
e All molecules have dispersion forces between them. Hydrogen bonds are a special type of permanent
dipole−dipole forces.
6 Both hydrogen fluoride and hydrogen chloride are very polar molecules containing a δ+ hydrogen
atom and a δ– halogen atom. However, a chlorine atom is too big to form a hydrogen bond with a
δ+ hydrogen in another molecule. Only very small atoms, such as fluorine, oxygen and nitrogen,
can form hydrogen bonds with δ+ hydrogen atoms.
b Vanadium is a metallic solid, with a delocalised cloud of electrons between vanadium ions.
d Glucose is a hydrogen-bonded molecular solid. The δ+ hydrogen atoms in the –OH groups
form intermolecular hydrogen bonds with the δ– oxygen atoms in other molecules.
8 a In graphite, each carbon atom forms three σ-bonds with three other carbon atoms in the same
plane. The fourth 2p-electron is in an orbital above and below the hexagonal plane of the carbon
atoms. These p-orbitals overlap with their neighbours and the electrons become delocalised.
These electrons are mobile and solid graphite conducts electricity by the movement of these
electrons under an applied potential. In diamond, each carbon atom is covalently bonded to
four others in a giant three-dimensional tetrahedral arrangement. All the electrons are fixed
between the atoms and cannot move through the solid. Therefore, diamond does not conduct
electricity.
e Remember that metals and graphite conduct electricity by a flow of electrons, whereas molten or
dissolved ionic compounds conduct by a flow of ions.
b Although all the π-electrons in a fullerene molecule are delocalised, they are not connected to
neighbouring fullerene molecules and so do not conduct electricity. However, C60 polymers do
conduct. When C60 molecules react with potassium metal, the resulting compound conducts
as a solid.
9 The fullerene C60 has the unusual optical property of being transparent to light of low-to-
medium brightness and becoming opaque when the light is intense. It could be used as a coating
for sensitive optical devices, allowing low-intensity light through but preventing intense light
from damaging the optics of the device.
or
Carbon nanotubes are much stronger than steel. Bundles of these nanotubes are light in weight
and incredibly strong. They conduct electricity as efficiently as does copper. They could,
therefore, be used in electrical apparatus that has to withstand high tensile forces.
10 a Solid silicon forms a giant atomic lattice similar to diamond. To melt it, a huge amount of
energy must be supplied to break the four covalent bonds to each atom. Therefore, the solid has
a very high melting temperature (1410°C). Phosphorus is a simple molecular solid, consisting
of an arrangement of P4 molecules. The forces between these molecules are weak dispersion
forces. Therefore, less energy, and hence a lower temperature, is needed to separate the P4
molecules and melt the solid.
e When answering questions about melting solids, you should first state the type of solid and the forces
that hold the particles together. Then, discuss the relative strength of these forces and relate them to the
energy required to separate the particles and break up the solid (lattice) structure.
b In solid sodium, there is a cloud of delocalised electrons (a ‘sea’ of electrons) amongst a lattice
of sodium ions. These electrons are not fixed in position and, therefore, are able to move under
an applied electric potential. These mobile electrons are the reason why solid sodium conducts
electricity. Solid sodium chloride consists of a lattice of alternate sodium and chloride ions,
which are fixed in position. The ions cannot move when an electric potential is applied, so
solid sodium chloride does not conduct electricity.
e In molten sodium chloride the ions are free to move and conduct electricity.
11 The general trend in boiling temperature from PH3 to BiH3 is upward. The intermolecular forces
involved are permanent dipole–dipole forces and dispersion forces. As the polarity of the bonds
decreases down the group, the permanent dipole–dipole forces decrease slightly. However, as
the number of the electrons in the molecules increases from 18 in PH3 to 86 in BiH3, the strength
of the dispersion forces increases considerably. Therefore, an increasing amount of energy is
required to separate the molecules and boil the substances. Ammonia, NH3, is an anomaly.
The dispersion forces between ammonia molecules are much weaker than in the other group 5
hydrides. However, because the nitrogen atom is so small and considerably δ−, it forms hydrogen
bonds with the δ+ hydrogen atoms in neighbouring molecules. These intermolecular hydrogen
bonds are much stronger than the dispersion forces, which are the dominant forces in the other
hydrides. Therefore, ammonia has an anomalistic high boiling temperature.
e When answering questions about boiling, you should first state the type of force between the particles
in the substances. Discuss the relative strengths of these forces and relate them to the energy required
to separate the molecules.
12 Propanone has 32 electrons per molecule and butane has 34. This means that the dispersion
forces are almost identical. Propanone is very polar because of the large difference in elec-
tronegativity between carbon and oxygen, whereas butane is non-polar. Thus propanone has
13 Hydrogen bromide is more polar than hydrogen iodide, so it has stronger permanent dipole–
dipole intermolecular forces. However, the dispersion forces are stronger in hydrogen iodide
because it has 54 electrons as opposed to 36 in hydrogen bromide. This increase in the strength
of the dispersion forces more than compensates for the decrease in permanent dipole–dipole
forces and, therefore, hydrogen iodide has a higher boiling temperature.
e Permanent dipole–dipole forces play little part in the value of the boiling temperature. It has been
calculated that the contribution of this force in HCl is about 10% of that of the dispersion force. This is
because the molecules are constantly moving around and rotating, so the δ+ end of one molecule is
rarely next to the d– end of another molecule. They only become important when comparing polar and
non-polar molecules that have a similar number of electrons (see Question 12).
14 The solubility of a covalent molecular substance in water depends mostly on the strength of the
hydrogen bonds that are formed with the water molecules. The nitrogen in ammonia, NH3, is δ−
and has a lone pair of electrons. Therefore, it forms a hydrogen bond with a δ+ hydrogen atom in
a water molecule. The δ+ hydrogen atoms in an ammonia molecule form hydrogen bonds with δ−
oxygen atoms in water molecules. The energy released by the formation of these hydrogen bonds
compensates for breaking the intermolecular hydrogen bonds between ammonia molecules and
those between water molecules.
The δ− chlorine atom in chloromethane is too large to form hydrogen bonds. The hydrogen atoms
in chloromethane are not sufficiently δ+ and are not bonded to an electronegative atom. Thus
chloromethane cannot form hydrogen bonds with water molecules. Therefore, it is insoluble in
water.
e It is a common misconception that polar solvents, such as water, dissolve polar solutes. The dipole–
dipole forces are too weak to compensate for the disruption of the hydrogen bonding between water
molecules.
l gaseous ions bonding with water molecules → solution (exothermic as with all bond
formation)
If these factors balance, the ionic solid dissolves. Magnesium, Mg2+, ions are small and highly
charged, so they bond strongly with the δ− oxygen atoms in water. The Cl− ions bond to the
δ+ hydrogen atoms. Each magnesium ion is bonded to six water molecules. Enough energy is
released in the formation of this hydrated ion, and the hydrated chloride ion, to compensate for
the large lattice energy value.
2 The answer is C. Sulfur forms three double bonds, one with each of the oxygen atoms. Therefore,
all six valence electrons are used in bonding, so there are no lone pairs. The three pairs of
s-bonding electrons repel to a position of maximum separation, which is trigonal planar.
3 The answer is B. Xenon has eight electrons in its outer orbit. Four of these are used in bonding,
one to each fluorine atom. Therefore, there are four electrons remaining, so there are two lone
pairs.
4 The answer is A. All four compounds have polar bonds, but compounds B, C and D are
symmetrical, so the dipoles cancel and the molecules are non-polar.
5 The answer is D. There are no intermolecular hydrogen bonds because the chlorine atom is
too large to form them. Covalent bonds are strong, but do not occur between the molecules of
hydrogen chloride. Although the H–Cl bond is polar, the permanent dipole–dipole forces are
weaker than the induced (London or dispersion) forces.
e It is a common misconception that permanent dipole forces are stronger than induced (London) forces.
6 The answer is B. Fluorine in hydrogen fluoride, HF, is more δ− than the oxygen in water and it
also has a smaller radius. This means that a single hydrogen bond between the hydrogen atom
in one hydrogen fluoride molecule and the fluorine atom in another is stronger than a single
hydrogen bond between water molecules. However, there are twice as many intermolecular
hydrogen bonds in water.
e Statement D is true but does not answer the question.
7 The answer is A. There are no lone pairs around the hydrogen, so the covalent bond pair and the
hydrogen bond pair are at 180° to each other.
e The angle around the hydrogen-bonded hydrogen atom is always 180°, even in complex molecules such
as DNA and proteins.
8 The answer is C. All the statements are true, but only option C explains why graphite is less
dense than diamond.
e The packing within the plane in graphite is closer than that in diamond, but the layers in graphite are
much further apart than are the bonded atoms in both forms of carbon.
9 The answer is A. Diamond is a giant atomic structure with strong covalent bonds between the
atoms. Silicon carbide is similar in that each silicon atom is bonded to four carbon atoms and
each carbon atom to four silicon atoms. To melt either structure, many strong covalent bonds
have to be broken. This only happens at an extremely high temperature.
e Neither diamond nor silicon carbide forms molecules and neither is ionic, so options B, C and D are
incorrect.
10 The answer is C. Statements A, B and C are all true. However, only the lower number of electrons
results in weaker intermolecular forces, which is why C is the correct response.
e Statement D is incorrect because hydrogen chloride is more polar than hydrogen iodide. This is because
chlorine is more electronegative than iodine.
11 The answer is A. Butane, CH3CH2CH2CH3, has fewer electrons and so has weaker induced forces.
Pentane, dimethylpropane and methylbutane (options A, C and D respectively) are isomers and,
therefore, have the same number of electrons. The straight-chain pentane has better packing
and, hence, stronger intermolecular forces than its branched isomers.
b HI to I2 is oxidation. The I– ion in HI loses an electron to become an I atom, which then joins
with another I atom to form an I2 molecule.
c Sn4+ to Sn2+ is reduction. The Sn4+ ion gains two electrons to become an Sn2+ ion.
2 a Cr2+(aq) → Cr3+(aq) + e–
The overall equation is found by multiplying the first equation by 2 and the second equation
by 5 and then adding them together:
2MnO4 –(aq) + 6H+(aq) + 10HI(aq) → 2Mn2+(aq) + 5I2(s) + 8H2O(l)
Manganate(vii) ions are reduced to Mn2+ ions, which is a change in oxidation number of five
per manganese. The oxidation number of each iodine atom changes by one, so 5HI are needed
per MnO4 –. Two MnO4 – ions will produce 8H2O, so the equation needs six hydrogen ions to
go with the ten hydrogen atoms from 10HI to form the eight molecules of water. Note that the
overall charge on each side is +4.
e The following equation is also acceptable:
1
MnO4 –(aq) + 3H+(aq) + 5HI(aq) → Mn2+(aq) + 2 I2(s) + 4H2O(l)
b The vanadium in VO2+ is in the +5 state (see the answer to Question 3c).
c The vanadium in VO2+ is in the +4 state (see the answer to Question 3c).
b An oxidising agent is reduced. The oxidation number of bromine changes from +5 in KBrO3
to zero in Br2. The oxidation number has decreased, so the bromine in the KBrO3 has been
reduced. Therefore, KBrO3 is the oxidising agent. It has oxidised the bromine in KBr from the
–1 state to zero.
9 The oxidation number of the carbon atoms in the C2O42– ion is +3:
2x + 4(–2) = –2
so,
2x = − 2 + 8 = + 6
x = +3
The carbon atom in CO2 is in the +4 state, so each carbon atom changes by +1. The total change
in oxidation number per C2O42– ion is +2.
2 The answer is C. Note that this is a negative question — ‘is not disproportionation’. The copper
is reduced from +2 to +1 and oxidised from 0 to +1, but there are two different copper species
on the left-hand side of the equation and only one on the right, so it is not a disproportionation
reaction. In A, the oxygen in H2O2 is in the –1 oxidation state and is simultaneously oxidised to
zero in O2 and reduced to –2 in H2O. In B, the chlorine in Cl2 is oxidised to OCl– (zero → +1)
and reduced to Cl– (zero → –1). In D, the manganese in MnO42– is in the +6 state. It is oxidised
to MnO4 – (+7) and simultaneously reduced to MnO2 (+4).
e The reverse reaction, 2CuCl2-(aq) → CuCl2(aq) + Cu(s) + 2Cl−(aq) is a disproportionation.
3 The answer is B. Sodium tetrathionate, Na2S4O6, is neutral, so the oxidation numbers add up to
zero. Each Na is +1, each oxygen is –2, totalling +2 –12 = −10. There are four sulfur atoms, so
the oxidation number of each must equal 10 divided by 4, i.e. 2.5.
4 The answer is A. The oxidation numbers in potassium superoxide add up to zero and, as it is
a superoxide, the oxidation number of oxygen is not –2. (It is also not –2 in peroxides.) The
oxidation number of potassium is always +1, so the oxidation numbers of the two oxygen atoms
must add up to –1. Therefore, the oxidation number of oxygen in potassium superoxide is – 12 .
5 The answer is A. The oxidation number of manganese changes from +7 to +2, which is a change
of five. Therefore, there must be five electrons in the equation. An alternative way to work this
out is that the half-equation must balance for charge. The charge on the right-hand side is +2,
so that on the left-hand side must also be +2. This is achieved if there are five electrons:
1− + 5− + 8+ = 2+
2 The nuclear charge increases down the group, but the number of inner shielding electrons
increases by the same amount. However, the atomic radius increases down the group. Thus, the
outer electrons are further from the nucleus and so are held less firmly. This means that less
energy is required to remove a 3s-electron from a magnesium atom than is required to remove
a 2s-electron from a beryllium atom. Less still is needed to remove a 4s-electron from a calcium
atom and so on.
e Do not just say that shielding increases down the group — there is more to shield. The critical point is
that the atomc radius increases. The further an electron is from the nucleus, the easier it is to remove.
3 Calcium has atomic number 20 and the electron configuration 2,8,8,2. Potassium has atomic
number 19 and the electron configuration 2,8,8,1. In calcium, the nuclear charge of 20 is
shielded by 18 inner electrons. In potassium, the nuclear charge of 19 is also shielded by 18
inner electrons. Thus the outer electrons in calcium are less well shielded and are harder to
remove. In addition, a calcium atom has a smaller radius than a potassium atom making it even
harder to remove one of its outer (4s) electrons.
e Remember that, across a period, the atomic radius decreases as the atomic number increases. This is
because of the increasing pull of the nucleus on the shells of electrons.
4 The electron configuration of magnesium is 1s2 2s2 2p6 3s2. The first ionisation energy is for the
removal of one of the 3s-electrons and the second is for the removal of the other 3s-electron,
but from a positive ion. This makes the second ionisation energy larger than the first. The 3s-
electrons are shielded by the two electrons in the first shell and the eight electrons in the second
shell. The third ionisation involves removing an electron from the 2p-subshell. This electron is
only shielded by the inner two 1s-electrons. Therefore, it experiences a much stronger pull from
the nucleus than the better shielded 3s-electrons. Thus there is a big jump between the second
and third ionisation energies.
e A simpler answer, which would just score the marks, would be to state that the third electron comes
from an inner shell and so is harder to remove. The explanation above shows why it is harder to remove.
1
5 a 2Mg + O2 → 2MgO or Mg + 2 O2 → MgO
b Ba + 2H2O → Ba(OH)2 + H2
c Mg + Cl2 → MgCl2
6 The thermal stability of group 1 nitrates increases down the group. This is because the polarising
power of the cation decreases as the ionic radius increases. The lower the polarising power of
the cation, the less the electron cloud of the anion is distorted. Thus it is harder to cause decom-
position.
e The ease of decomposition depends on the charge density of the cation. Charge density is loosely
defined as the charge on the ion divided by its radius. In this example, all the group 1 cations have a
charge of +1, but their radii increase down the group causing a decrease in charge density. In questions
that ask for a comparison of the ease of decomposition of a group 1 nitrate with that of the nitrate of
the group 2 element in the same period, two factors have to be compared. First, the group 2 cation is 2+
whereas the group 1 cation is 1+. Second, the ionic radius of the group 2 cation is smaller than that of the
group 1 cation. These two factors result in the polarising power of the group 2 cation being greater than
that of the group 1 cation and make the group 2 nitrate easier to decompose. A similar argument is used
to compare the decomposition of carbonates.
b The formula mass of BaO2 is 169.3. This is the same as the molar mass, so the molecular
formula is also BaO2.
12 a When strontium nitrate is heated it first melts. On further heating a brown gas is seen bubbling
off from the molten compound.
e Oxygen is produced but cannot be seen. Its presence can be detected by the relighting of a glowing
splint. The brown gas is nitrogen dioxide.
13 Both magnesium and calcium ions are 2+. However, a magnesium ion has a smaller radius than
a calcium ion. This means that a magnesium ion polarises a carbonate ion more than a calcium
ion does. Therefore, magnesium carbonate is easier to decompose than calcium carbonate and
does so at a lower temperature.
e It is important to write something about both the charges and radii of the two cations. Make sure that
you do not use the word ‘atom’ when you mean ‘ion’. This is a common error.
f Ibuprofen and NaOH react in a 1:1 ratio. So, amount of ibuprofen in 25 tablets = amount of
NaOH reacted = 0.0243 mol
0.0243
g amount (moles) of ibuprofen in 1 tablet = mol = 9.72 × 10 –4 mol
25
molar mass of ibuprofen, C12H17COOH = [(12 × 12.0) + 17.0 + 12.0 + (2 × 16.0) + 1.0)]
= 206.0 g mol–1
mass of ibuprofen in 1 tablet = moles × molar mass
= 9.72 × 10 –4 mol × 206.0 g mol–1
= 0.200 g = 200 mg
e This question is about a back titration. If such a question is asked at AS, it will be structured in a similar
way to this one. However, you must have a clear idea of the different experimental stages:
l adding excess sodium hydroxide
l after the reaction, making the solution up to 250 cm3
l titrating portions of this diluted solution, containing excess sodium hydroxide, with standard acid
2 The answer is A. The more the anion is polarised, the greater is the covalent character of the
compound. The Mg2+ ion is the most polarising, so MgCl2 has the most covalent character.
3 The answer is D. All four metals have the same number of delocalised electrons, so the relative
strengths of the metallic bonds depend mainly on the metallic radius. The metallic radius of
magnesium is the smallest, so it has the strongest metallic bond. The metallic radius of barium is
the largest, so it has the weakest metallic bond and, therefore, the lowest melting temperature.
e The type of packing also affects the melting temperature. However, this is less important than the
charge and the metallic radius, and it is ignored at A-level.
4 The answer is A. Solubility is a balance between lattice energy and the sum of the hydration
energies of the ions. Both the lattice energy and the hydration energy of the cations decrease
down the group. However, because the hydroxide ion is of a similar size to the cations, the lattice
energy decreases more and this causes the enthalpy of solution to be more exothermic (or less
endothermic). Therefore, the hydroxides of the lower members of the group are more soluble.
e The lattice energy depends on the sum of the ionic radii. Therefore, it alters markedly when the cation
and the anion are of similar size (e.g. with hydroxides). Thus solubility increases down the group. If the
anion is much bigger than the cation (e.g. with sulfates), the decrease in the lattice energy is much less
and solubility decreases down the group.
5 The answer is A. Only the nitrate of the most strongly polarising group 1 cation decomposes
on heating to form the metal oxide, nitrogen dioxide and oxygen. Nitrates with less polarising
cations decompose to the nitrite and oxygen. All the group 1 cations are 1+. Of these, lithium
has the smallest ionic radius and so is the most strongly polarising. Therefore, on heating,
lithium nitrate decomposes giving off brown fumes of nitrogen dioxide. When nitrates of the
less polarising cations are heated, they do not produce brown fumes.
e The equations are:
2LiNO3 → Li2O + 2NO2 + 1 O2 and KNO3 → KNO2 + 1 O2
6 The answer is D. The nitrate of the most polarising group 2 cation decomposes the most easily;
that of the least polarising cation is the hardest to decompose and requires a higher temperature.
Barium, Ba2+, is the least polarising of the group 2 cations, so barium nitrate takes the longest
time to produce brown fumes of nitrogen dioxide.
e Notice that the correct answers to these six multiple-choice questions about trends in a group are either
the top element in the group or the bottom one — option A or D.
7 The answer is C. Methyl orange is yellow in alkaline solution, red in acid solution and a mixture
of red and yellow — orange — when in neutral solution. In this example, the alkali is in the
conical flask. Therefore, the colour at the start of the titration is yellow and becomes orange at
the end point.
e If the indicator turns red, the end point has been overshot, which is why option D is incorrect. If the
alkali were in the burette and acid in the conical flask, the correct answer would be B.
8 The answer is B. The initial titre has an accuracy of ±0.05 cm3. The final reading is also accurate
to ±0.05 cm3, making the total potential error ±0.10 cm3.
0.10 × 100
This makes the maximum percentage error = 1.25%
8.00
3 Steamy fumes mixed with a brown gas would be seen. Three gases are produced:
l hydrogen bromide — the steamy fumes
e This answer is the same as that for the reaction of concentrated sulfuric acid on sodium bromide.
4 Bromine is a brown gas or fuming brown liquid. It turns a solution of potassium iodide red-
brown.
e Bromine also turns damp starch-iodide paper dark blue. Remember that the test paper must be damp.
A mark is often lost because this is omitted.
b The iodide ions in KI are oxidised from –1 to zero. Therefore, potassium iodide is the reducing
agent.
e Remember that in a redox reaction, a reducing agent becomes oxidised.
c Add a solution of starch, which will turn dark blue-black in the presence of iodine.
7 The first electron affinity requires an electron to be brought towards the positive nucleus of a
neutral atom and into the outer orbit. This is an exothermic process. More energy is released
the nearer an electron approaches the nucleus. Bromine has a smaller atomic radius than iodine,
so the electron gets closer to the bromine nucleus than it does to the iodine nucleus. Therefore,
more energy is released and the electron affinity is higher.
e The sign in thermochemistry gives the direction of the heat change. A more negative value means a
bigger heat change.
8 One method is to dissolve the solid, add aqueous silver nitrate and observe the precipitate.
Then add dilute ammonia. If the precipitate does not dissolve in dilute ammonia, concentrated
ammonia is then added. Possible observations are:
l a white precipitate that is soluble in dilute ammonia. This indicates calcium chloride.
l a cream precipitate that does not dissolve in dilute ammonia but is soluble in concentrated
l steamy fumes mixed with a brown gas. This indicates calcium bromide.
l clouds of violet vapour and a gas that smells of rotten eggs. A yellow deposit is left. This
10 Chlorine is the stronger oxidising agent. It oxidises a solution of potassium bromide to bromine.
The solution changes from colourless to brown. Iodine does not oxidise potassium bromide to
bromine. Therefore, on mixing the two solutions, there is no colour change.
mass of LiClO3 = moles × molar mass = 0.0492 mol × 90.4 g mol–1 = 4.45 g (or 4.44 g if the
numbers were not rounded during any stage of the calculation)
e Remember that it is essential that the units of volume and molar volume are the same, i.e. either dm3
or cm3.
13 The flame test shows that Z is a barium compound. This was confirmed by the formation of a
white precipitate when dilute sulfuric acid was added:
Ba2+(aq) + SO42−(aq) → BaSO4(s)
The second test on the solution shows that Z contains iodide ions:
I−(aq) + Ag+(aq) → AgI(s)
Silver iodide is a pale yellow solid that is insoluble in both dilute and concentrated ammonia.
Therefore, the solid Z is barium iodide, BaI2.
e In justifying your answer you must make sure that you use all the pieces of experimental evidence given
in the question.
2 The answer is C. The chlorine in OCl− is reduced from oxidation number +1 to zero and the
chlorine in Cl− oxidised from oxidation number −1 to zero. The chlorine on the left-hand side of
this equation is in two different species, so the reaction cannot be disproportionation.
e Option D is incorrect because the definition of synthesis is ‘making a compound from simpler species’.
The term has been expanded to cover a series of reactions that make a desired product, for example in
photosynthesis. Neither applies to the reaction in this question.
3 The answer is B. The oxidation numbers in a neutral compound add up to zero. The oxidation
number of sodium is always +1 and that of oxygen is −2 (except in oxygen fluoride, peroxides
and superoxides):
so, (2 × +1) + (6 × −2) = −10
The oxidation number of the four sulfur atoms must add up to +10, so the oxidation number of
sulfur in Na2S4O6 is + 10 = +2.5.
4
4 The answer is B. Beware — this is a negative question. Option B is false (and therefore the
correct answer) because the electronegativities decrease down the group, so the electronega-
tivity difference between the hydrogen and the halogen is less in HI than in HBr.
e It is worth checking the other responses, unless you are totally sure that you have selected the correct
answer. This is particularly important in negative questions such as this. Statement A is true because the
oxidising power decreases from fluorine to astatine. Statement C is true because the reducing power of
the anions increases down the group (as the oxidising power of the elements decreases). Statement D is
also true — silver chloride is soluble in dilute ammonia, so it also dissolves in concentrated ammonia.
5 The answer is B. Iodine is present at the start and, when the colour has faded to pale straw, starch
is added and an intense blue colour is produced. Sodium thiosulfate is then added dropwise
until the blue colour disappears.
e The starch must not be added too early otherwise a solid black complex is formed irreversibly with the
iodine.
6 The answer is C. Do not confuse steamy fumes of the hydrogen halides (HF, HCl, HBr and HI)
with the white smoke that is produced when a gaseous hydrogen halide is mixed with ammonia
gas. Thus the answer is not option A. Concentrated sulfuric acid reacts with ionic bromides, such
as silver bromide, to give steamy fumes of hydrogen bromide (together with some red–brown
bromine gas and colourless sulfur dioxide).
e The substances given in option B would produce bromine, which is a red–brown volatile liquid. Those in
option D would react to form a colourless solution.
7 The answer is D. It is the halogens (apart from fluorine), not the hydrogen halides that react with
alkali in disproportionation reactions:
X2 + 2OH− → X− + OX− + H2O
Thus statement D is false and is the correct answer to this negative question.
e Hydrogen bromide is oxidised by chlorine dissolved in water to give a brown solution of bromine.
It reacts with silver ions to give a cream precipitate of silver bromide. Its intermolecular (dispersion/
London/van der Waals) forces are stronger than those of hydrogen chloride, so it has a higher boiling
point. Therefore, options A, B and C are all true statements.
8 The answer is A. It is essential that all the oxidising agent reacts, so excess potassium iodide
is added to a measured volume of the solution of the oxidising agent. Option C is ambiguous.
Which reaction?
3
Fraction of molecules with energy E
Tc
Th
Ea
Kinetic energy, E
A decrease in temperature decreases the average kinetic energy of the molecules. Therefore,
the area under the curve to the right of the activation energy is smaller for the Tc curve than for
the Th curve. This means that a smaller proportion of collisions have the necessary activation
energy to result in reaction, so the reaction rate is slower. There is also a slight reduction in the
frequency of collision, but this effect is swamped by the reduction in the proportion of successful
collisions.
e The crucial points are that:
l the molecules have less energy
l fewer colliding molecules have energy ≥ activation energy (area under the curve to the right of the
activation energy value)
l a smaller proportion of the collisions result in reaction
l the rate is slower
4 a Halving the volume results in the molecules being much closer together, so the frequency of
collision increases. This results in a faster reaction, i.e. an increased reaction rate.
b The addition of more hydrogen increases the rate because the probability of a hydrogen
molecule colliding with an iodine molecule is increased. It is the increase in the frequency of
H2–I2 collisions that results in an increase in the rate.
e Do not talk about more collisions, but about the increase in the frequency of collision or more collisions
per unit time.
Ecat
Reactants
∆Hr
Products
c Platinum is a solid and hydrogen peroxide is in solution. They are in different phases, so
platinum is a heterogeneous catalyst in this reaction.
e Mixtures of solids can be in separate phases (e.g. salt and sand). Miscible liquids (ethanol and water)
form a single phase; immiscible liquids (petrol and water) are in two phases. Gaseous mixtures are
always in a single phase.
d Gas syringe
Calibrated
tube
OR
Measurements taken:
l mass of platinum and mass of an equal number of moles of manganese(iv) oxide
l in each case, time taken to produce a given volume of oxygen, e.g. 40 cm3
1
rate of reaction is proportional to
time
change × 100
c percentage of acid reacted =
original
0.005 × 100
= = 20%
0.025
d i There is a large change in the amount of acid (and hence, because the volume remains
constant, a large percentage change in concentration). This causes the rate to alter consider-
ably during the time of the measurement, which means that in this instance the assumption
that rate is proportional to 1/t is not very accurate.
ii Take a larger volume of acid (50 cm3 would mean a 10% change in concentration of the acid
during the reaction).
or
Increase the initial concentration of the acid (a 2.0 mol dm−3 solution would mean a 10%
change in concentration).
Either of these changes would make the assumption that rate is proportional to 1/t fair,
because the rate would not change by more than 10% during the course of the experiment.
e The reaction is exothermic, so the temperature rises as the magnesium reacts. This alters the reaction
rate. Increasing the volume of acid to 50 cm3 would halve the temperature rise and so reduce the error
caused by the exothermic nature of the reaction. Doubling the concentration would have no effect on
the temperature rise.
7 a
Fraction of molecules with energy E
Ecat Euncat
Kinetic energy, E
The catalyst causes the reaction to go via a different route that has lower activation energy.
The area under the curve to the right of Ecat is greater than that to the right of Euncat. This
means that a greater proportion of the colliding molecules have at least this smaller amount
of energy. Therefore, more of the collisions result in reaction, so the rate increases.
e The Maxwell−Boltzmann distribution used to explain catalysis has one curve and two activation
energies. To describe the effect of temperature, there are two curves and one activation energy.
b The platinum catalyst used in catalytic converters contains active sites where the catalysed
reactions take place. The lead in this type of petrol would irreversibly bind to these sites, thus
‘poisoning’ the catalyst.
2 The answer is C. Pressure has no effect on the rate because the reactant calcium hydrogen
carbonate is in solution. This eliminates options A and B. Lowering the concentration and
lowering the temperature both result in a decreased reaction rate, so C is the correct response.
3 The answer is B. A shorter time requires a faster rate. Smaller lumps of solid have a larger surface
area resulting in an increase in rate. This highlights options B and C as potential answers. Option
B is the correct response because the acid is more concentrated and the temperature higher
than in option C. Each of these factors causes an increase in reaction rate and, hence, a shorter
reaction time.
4 The answer is D. This is another negative question. Adding argon at constant volume will not
alter the chances of a sulfur dioxide molecule colliding with an oxygen molecule and so will
have no effect on the rate. Response D is false and so is the correct answer to this negative
question.
e Decreasing the volume causes the frequency of collision to increase and increase the reaction rate.
Option A is a true statement. Increasing the temperature results in more colliding molecules having
energy ≥ Ea. These molecules are more likely to react on collision, thus increasing the rate. A catalyst
provides an alternative path with a lower activation energy. This results in more successful collisions,
thus increasing the rate.
5 The answer is B. The faster the reaction, the lower is the activation energy.
e Statement C is not true. Many exothermic reactions (e.g. that between hydrogen and oxygen) are so
slow that they do not occur at room temperature — the reactants are kinetically stable. Statement D is
not true. A catalyst lowers the activation energy by providng an alternative route. It has no effect on the
kinetic energy of the molecules. Only an increase in temperature causes an increase in kinetic energy.
b The state of dynamic equilibrium is reached when the rate of dissolving solid sodium chloride
is equal to the rate at which sodium and chloride ions join to form solid sodium chloride. Once
equilibrium has been established, the concentration of dissolved salt does not change.
e The dynamic nature of this process is why the many tiny crystals gradually turn into a smaller number
of slightly larger crystals on standing. Heating speeds up the process. Some precipitates consist of such
tiny crystals that they pass through a filter paper. They can be filtered effectively if the suspension is
allowed to stand or is heated.
2 At the start there is no ammonia. The amount of the ammonia rises as the amounts of hydrogen
and nitrogen fall. When the system reaches equilibrium, there is no further change in the
amounts of any of the substances.
Moles
2.4 H2
2
1
0.8 N2
0.4 NH3
0
Equilibrium Time
reached
e The amounts of hydrogen and nitrogen decrease by 20%. Therefore, at equilibrium there will be 0.8 mol
of N2 and 2.4 mol of H2 (0.8 × 3). 2 mol of NH3 are formed from 1 mol of N2, so 0.4 mol (2 × 0.2) of ammonia
will be present at equilibrium.
3 To produce nickel metal from the complex, the position of the equilibrium has to be driven
to the left. The reaction as written is exothermic, so the reverse (right-to-left) direction is
endothermic. In order to drive the equilibrium in the endothermic direction, the temperature
must be increased.
e Remember that an increase in temperature drives a reversible reaction in the endothermic direction,
and a decrease in temperature drives it in the exothermic direction. You should make it very clear in
your answer that the reverse direction is endothermic. Avoid phrases such as ‘an increase in temperature
favours the endothermic direction’. An increase in temperature ‘favours’ (increases the rate of) both the
forward and the reverse reaction. However, it increases the rate of the endothermic reaction more than
that of the exothermic reaction, which is why the position shifts in the endothermic direction.
5 A decrease in temperature increases the solubility of the carbon dioxide. Therefore, lowering the
temperature drives the position of equilibrium to the right. This is because the forward reaction
is exothermic.
e It may be easier to consider the effect of increasing temperature. This makes the carbon dioxide less
soluble, so the position shifts to the left. The right-to-left direction is endothermic, so ∆H for the reaction
as written is negative (exothermic).
6 Manufacturing processes require a high equilibrium yield that is obtained quickly at low cost.
The reaction is endothermic, so increasing the temperature would increase the yield. However,
too high a temperature results in added expense because of heat loss and the corrosive effect
of high-temperature steam. The extra cost of a temperature higher than 750°C would not be
recovered by the slightly higher yield and faster rate. A catalyst is used so that equilibrium is
reached rapidly at an economic temperature, i.e. the yield per hour of product is high enough to
make the process economically viable.
e In this example, rate and yield are both improved by an increase in temperature. No compromise
temperature (rate versus yield) is needed.
8 An increase in pressure drives the position of equilibrium to the side of the equation that has
fewer gas molecules or moles.
a There are three gas molecules on the right and two on the left. An increase in pressure drives
the equilibrium to the left.
b There are two gas molecules on the right and one on the left. An increase in pressure drives
the position of equilibrium to the left, reducing the yield of hydrogen.
e The C does not count as it is a solid and not a gas.
c There are nine gas molecules on the left and ten on the right. An increase in pressure drives
the position of equilibrium to the left.
d There are one-and-a-half moles of gas on the left and one on the right. An increase in pressure
drives the equilibrium to the right.
e A good answer to this type of question will:
l state the theory
l count the moles or molecules of gas on each side (or state which is the endothermic direction for
questions about an increase in temperature)
l state the direction in which the position of equilibrium moves
b An increase in pressure drives the equilibrium to the side with fewer gas molecules. In this
example, the left-hand sde has one gas molecule and the right-hand side has none, so the
position of equilibrium is driven to the right. This results in a higher percentage of iodine
trichloride in the equilibrium mixture.
e Make sure that you answer the question. In this case it asks for the change in the equilibrium mixture not
the change in the equilibrium position.
c The red–brown iodine monochloride would melt. The colour of the equilibrium mixture would
become increasingly red–brown and less orange as the position of equilbrium shifts in the
endothermic direction (to the left).
10 Adding concentrated hydrochloric acid greatly increases the concentration of chloride ions.
Therefore, the position of equilibrium moves to the right, resulting in more lead chloride
dissolving as it forms PbCl42– ions.
e This is an example of the application of Le Chatelier’s principle. As the concentration of one of the
reactants is increased, the equilibrium shifts to remove the extra reactant added. Similarly, if one of the
products of a reversible reaction is removed (e.g. by precipitation or neutralisation), the equilibrium
shifts to the right to produce more product.
2 The answer is D. There are four gas molecules on each side of the equation, so a change in
pressure has no effect on the equilibrium position. Therefore, options A and B are incorrect. The
reaction is exothermic, so the temperature has to be lowered to drive the position of equilibrium
in the endothermic direction. This means that option D is the correct answer.
3 The answer is A. The Pb2+ ions react with the CrO4 − ions to form a precipitate of lead chromate(vi).
The removal of the CrO4 − ions causes the equilibrium position to shift to the right. This produces
more CrO4 − ions which react with more Pb2+ ions. This continues until all the Pb2+ ions are
precipitated as yellow lead chromate(vi).
e D is wrong because there are enough CrO42– ions in the equilibrium mixture to form a precipitate with
lead ions. Lead chromate(vi), PbCrO4, is yellow not orange, so option B is incorrect.
4 The answer is C. An increase in temperature causes the equilibrium position to shift to the left
(the endothermic direction). Therefore, less ammonia is present in the equilibrium mixture.
However, equilibrium is reached faster, so less ammonia is made more quickly, i.e. option C.
e An increase in temperature increases the rate of both the exothermic and endothermic reactions, so
option A is incorrect. Catalysts (apart from enzymes) work better at higher temperatures, so option B is
also incorrect. Note that an increase in temperature increases the rate of the reaction in the endothermic
direction more than it increases the rate in the exothermic direction. This is one explanation of why the
equilibrium position shifts in the endothermic direction when the temperature is increased.
b Fluorine is the most electronegative element, so the C–F bond is more polar than the C–O
bond or the O–H bond. Therefore, fluoromethane is more polar than methanol.
2 Solubility of an organic compound in water depends upon its ability to form hydrogen bonds with
water molecules. Fluoromethane does not have any δ+ hydrogen atoms, whereas the hydrogen
of the –OH group in methanol is very δ+. Both molecules have small δ– atoms, but the lack of δ+
hydrogen in fluoromethane means that it is insoluble.
e An incorrect rule is that polar molecules dissolve in polar solvents such as water. The solute has to
disrupt hydrogen bonds between water molecules, so equally strong (or stronger) solute−solvent
interactions must be present. Thus, organic molecules that can hydrogen bond with water — rather
than polar molecules such as CH3F — will dissolve in water, as long as they do not have a long
hydrophobic chain.
3 Ethanol and methanol form intermolecular hydrogen bonds of almost identical strength. In
addition, both substances have instantaneous induced dipole–induced dipole (dispersion) forces
between their molecules. These forces are stronger in ethanol than in methanol because ethanol
has more electrons per molecule. The combined intermolecular forces are stronger in ethanol
and so more energy is required to separate its molecules. Therefore, ethanol has a higher boiling
temperature than methanol.
e Boiling simple covalent molecules is nothing to do with covalent bond strength because no covalent
bonds are broken. All substances have dispersion forces between their molecules.
5 The hydrolysis requires the carbon–halogen bond to be broken as the nucleophilic OH – ion
attacks the carbon atom. The carbon–iodine bond is weaker than the carbon–chlorine bond, so
it breaks more easily. Therefore, hydrolysis of 2-iodopropane has a lower activation energy and
so occurs at a faster rate.
e The C−I bond is weaker than C−Cl because the atomic radius of iodine is larger than that of chlorine.
Remember: weak bond = small activation energy = fast rate.
6 One common halogenated polymer is poly(chloroethene) or PVC. It has many uses, including
window frames, drain pipes and guttering, and electrical insulation of wires. Like most man-
made polymers it is non-biodegradable. Therefore, it can accumulate in landfill sites and, if
discarded, can cause permanent litter.
Another example is PTFE, which is used as a coating on non-stick cooking utensils. It produces
toxic fumes when disposed of by incineration.
e Its stability to rainwater (even acid rain) and bacterial action are important properties of PVC. This is why,
unlike wooden frames, UPVC window frames do not need the protection of regular painting.
The lack of biodegradability is not caused by the strength of the bonds in the polymer. Natural
polymers, such as proteins and carbohydrates, contain very strong bonds, but enzymes have evolved
that catalyse their hydrolysis.
7 a CH 3CH(CH 3)CH 2CH 2OH, CH 3CH 2CH(CH 3)CH 2OH and (CH 3)3CH 2OH are examples of
branched-chain primary alcohols. Their skeletal formulae are:
OH
OH
OH
OH
OH
8 Shake a sample of each with bromine water. Hexene will decolorise it from brown to colourless,
whereas hexanol and hexanoic acid will have no effect.
Add phosphorus pentachloride to samples of the remaining two liquids. Both will give steamy
fumes. Next, add a solution of sodium hydrogencarbonate to samples of these two liquids. Only
the hexanoic acid will give off bubbles of gas that turn limewater cloudy. Alternatively both
liquids can be tested with damp blue litmus paper. Hexanol will have no effect but hexanoic acid
will turn it red.
e
Remember that phosphorus pentachloride gives steamy fumes of hydrogen chloride with any
compound containing an −OH group — it is not specific to alcohols.
9 When heated under reflux with dilute sulfuric acid and potassium dichromate(vi), the organic
substance remaining is:
11 −
H CH3 H CH3 H CH3
−
N C: C Cl → N C C Cl → N C C + Cl −
H3C Cl ✓ CH3 ✓
H CH3 H CH3
then C+ :C N− → C
H3C C N−
CH3 ✓
e The marks are for:
l a curly arrow from the σ-C–Cl bond to the chlorine atom
l the intermediate carbocation
l a curly arrow from the carbon of the CN− ion towards the positively charged carbon in the
intermediate
You are not expected to know this mechanism, but you should be able to work it out from your
knowledge of the mechanism of the reaction of a halogenoalkane with hydroxide ions. Either
mechanism would score full marks.
12 2-iodopentane has a long hydrocarbon chain, which makes it almost insoluble in water.
Therefore, there will be little contact between it and the OH− ions from the aqueous sodium
hydroxide. The organic substance is more soluble in aqueous ethanol and can, therefore, come
into contact with the hydroxide ions.
b The compound turns bromine water colourless, so it must contain a C=C bond. It is a carboxylic
acid and, therefore, contains the –COOH group. The simplest structural formula is:
O
H2C CHC
OH
Propenoic acid
9.0 g
c amount (moles) of X taken = = 0.10 mol
90 g mol –1
volume 4.8 dm3
amount (moles) of HCl gas produced = = = 0.20 mol
molar volume 24 dm3 mol −1
ratio of HCl:X = 2:1
Therefore, there are two –OH groups per molecule of X. Thus, one structure for X is
CH 2 OHCH 2 CH 2 CH 2 OH. Others are CH 2 OHCH(OH)CH 2 CH 3, CH 2 OHCH 2 CH(OH)CH 3,
(CH3)2C(OH)CH2OH and CH2OHCH(CH3)CH2OH.
CH2OHCH2CH2CH2OH + 2PCl5 → CH2ClCH2CH2CH2Cl + 2POCl3 + 2HCl
e Substance X cannot be a carboxylic acid, as one −COOH group would give rise to only 1 mole of HCl.
mass 78.5 g
17 amount (moles) of 2-chloropropane = = = 1.00 mol
molar mass 78.5 g mol −1
amount of propene produced = 30% of 1.00 mol = 0.30 mol
amount of 2-iodopropane produced = 90% of 0.30 mol = 0.27 mol
mass of 2-iodopropane produced = mol × molar mass
= 0.27 mol × 170 g mol–1 = 46 g
6 The answer is C. Acidified potassium dichromate is an oxidising agent and will oxidise primary
and secondary alcohols (and aldehydes), but not tertiary alcohols (or ketones). Ethanol (option
A) is a primary alcohol. Butan-2-ol (option B) and hexan-2-ol (option D) are secondary alcohols
and so are oxidised. 2-methylpropan-2-ol, CH3C(OH)(CH3)2, is a tertiary alcohol and so will not
reduce dichromate(vi) ions to green Cr3+ ions.
b The ions are accelerated towards the negative terminal of a cathode and pass through a hole
in the cathode.
c The ions are deflected by a magnetic field perpendicular to the direction in which they are
moving. Lighter ions are deflected more than heavier ions.
2 The peak at 74 is due to the molecular ion. The peak at 29 could be due to either C2H5+ or
CHO+. The C2H5+ ion cannot be formed from either X or Y; CHO+ could be formed from either.
However, the peak at 31 is due to a CH2OH+ ion, which can only come from Y. Substance X
would produce peaks at 15, due to CH3+, and at 59, due to CH(OH)CHO+. The absence of these
two peaks confirms that the unknown substance is Y.
e You must answer the question fully by explaining all the peaks present and giving reasons why the other
two peaks are absent.
There are two ways of obtaining a mass of 160: 79Br– 81Br and 81Br–79Br. Therefore, the peak at
m/e = 160 is twice the height of that at 158, caused by (79Br–79Br)+, and that at 162, caused by
(81Br– 81Br)+.
e The 1:2:1 ratio is similar to that obtained when tossing two coins at once. The chances of two heads, a
head and a tail and two tails are in the ratio 1:2:1.
There are also two peaks at m/e = 79 and 81, caused by 79Br+ and 81Br+, formed from the decom-
position of a molecular ion, but none at m/e = 80 as there is no 80Br isotope.
5 The molar mass of propanone, CH3COCH3, is 58 g mol–1. The peak at m/e = 58 is caused by the
molecular ion (CH3COCH3)+, which is formed by the process:
CH3COCH3 + e– → (CH3COCH3)+ + 2e–
The peak at m/e = 43 is 15 units less than the molecular-ion peak. It is caused by the ion
(CH3CO)+ formed by the loss of CH3 from the molecular ion:
(CH3COCH3)+ → (CH3CO)+ + CH3•
The peak at m/e = 15 is due to a CH3+ ion, also formed by fragmentation of the molecular ion:
(CH3COCH3)+ → CH3CO• + CH3+
e A common error is to omit the positive charge on the ions whose m/e values are detected.
8 Polar molecules absorb energy in the infrared region of the electromagnetic spectrum. It is
because oxygen is more electronegative than hydrogen and because the water molecule is not
linear that a water molecule is polar. The light coming from the Sun contains higher frequencies
than the infrared radiated by the Earth back towards space. The water vapour absorbs some of
this infrared radiation, trapping energy in the atmosphere and so keeping the Earth warm.
e Polar water molecules also absorb in the microwave region, which is why aqueous liquids heat up in a
microwave oven.
9 a Anthropogenic means caused directly or indirectly by mankind. Human beings have no input
into a natural cause. A forest fire caused by lightning is a natural source of carbon dioxide;
mining and burning coal is an anthropogenic cause of carbon dioxide.
b The two main anthropogenic sources of oxides of nitrogen are burning fuel at a high
temperature in car and aeroplane engines and in the decay of nitrogen-containing chemical
fertilisers — for example, ammonium nitrate. A natural source is the combination of nitrogen
and oxygen in the air during a thunderstorm or bacterial decay of organic matter in the soil.
10 Spectrum A: the peak at wavenumber 1715 cm–1 is caused by a C=O bond and the peak at
1421 cm–1 by a C–C bond.
Spectrum B: the peak at wavenumber 1716 cm–1 is caused by a C=O bond and the peak at
1416 cm–1 by a C–C bond, but the peak at 2986 cm–1 is caused by an O–H bond.
Both propanal and propanoic acid have C=O and C–C bonds, but only propanoic acid has an
O–H bond. Thus, spectrum B is that of propanoic acid and spectrum A that of propanal.
e The broadness of the peak around 3000 cm–1 is caused by the intermolecular hydrogen bonding of the
–OH group on one molecule with the C=O group on another.
11 The C–H bonds in the alkyl groups (–CH3 and –CH2–) give a peak at around 2900 cm−1, the C=O
bond in the ester gives a peak at around 1740 cm−1 and the C–C bond in the C2H5 group gives a
peak at about 1430 cm−1.
2 The answer is C. Look for a molecule that does not have any polar bonds. The Cl2 molecule
consists of two hydrogen atoms, which have the same electronegativity, so the bond is not
polar.
3 The answer is B. The four molecules are isomers of molar mass 88.0 g mol−1. Therefore, each has
a molecular ion peak at m/e = 88. The peak at 45 is due to a COOH+ ion, so the substance could
be either B or C. The peak at 29 is due to a C2H5+ ion, which shows that the compound must be
option B. The infrared data are inconclusive. The peak at 3010 cm−1 could be due to a C–H bond
in an alkene or to a hydrogen-bonded O–H in a carboxylic acid. The peak at 1715 cm−1 could be
due to the C=O in a carboxylic acid, so it only rules out option A.
e If the peak at 3010 cm−1 were broad, it would be due to the O–H bond in a carboxylic acid and not to a
C–H bond in an alkene.
4 The answer is D. This question is straightforward factual recall. As a rough guide, the more
complex the molecule, the more ways it has of absorbing infrared radiation and so the higher is
its global warming potential.
5 The answer is D. There is much more water vapour than there are other greenhouse gases in the
air and in clouds. Water vapour is by far the greatest contributor to (natural) global warming.
e Anthropogenic carbon dioxide contributes less than 1% to the greenhouse effect.
6 The answer is B. Visible light is at a higher frequency and, therefore, a shorter wavelength than
the infrared radiation emitted by the Earth.
e To be infrared active, a molecule must have at least one polar bond. If the dipoles cancel out, making
the molecule non-polar, it would still be infrared active due to asymmetrical stretching. The symmetrical
stretching in non-polar carbon dioxide is not infrared active because it does not result in a change in
dipole moment. Ozone is not linear because the central oxygen atom has a lone pair of electrons.
traditional piston engine, nitrogen oxides are produced by the combination of the nitrogen
and oxygen in air at the high temperature of the engine.)
l Its energy per gram is high. However, this is only an advantage if weight is crucial — for
Disadvantages include:
l It cannot be stored as a liquid unless the temperature is kept below −240°C.
l Refuelling with either cold liquid hydrogen or gaseous high-pressure hydrogen is dangerous.
e Do not say that hydrogen fuel is carbon neutral. The hydrogen has to be manufactured. The two
possibilities for manufacture are from methane and steam, which has a high carbon footprint, and by
the electrolysis of water. The generation of electricity also has a high carbon footprint.
2 Bioethanol is made from sugar or grain. The processes of growing these crops and transporting
them to factories are fuel intensive. Fermentation is exothermic, but the distillation required to
obtain ethanol from the dilute solution uses a considerable amount of energy.
3 Transesterification is the conversion of one ester into another, by reacting it with either a
carboxylic acid or an alcohol. An example is biodiesel, which is made by reacting vegetable
oil (an ester of propane-1,2,3-triol and long-chain acids) with methanol in the presence of an
alkaline catalyst. The products are the methyl esters of the acids and propane-1,2,3-triol.
4 The advantage of using algae as a source of biodiesel is that algae are potentially efficient
in using the energy from sunlight to produce organic oils. It is also a useful way of utilising
wastewater and does not need good agricultural land. The disadvantage is that the method has
not yet been developed into a commercially viable process.
5 One reason why wind power is not carbon zero (carbon neutral) is that the manufacture and
erection of the aero-generator — either on land farms and especially in offshore wind farms
— release a great deal of carbon dioxide from the various processes involved. Another reason is
that there must be back-up power stations burning fossil fuels for when the wind does not blow
strongly enough to generate sufficient electricity.
6 Very much less electrical energy is used making aluminium from recycled cans than when
manufacturing it from bauxite. Bauxite is a non-renewable resource, so recycling cans reduces
the amount of the mineral that is used and preserves it for future generations.
7 The atom economy is the percentage of the atoms in the reactants that are converted into the
desired product.
8 Plastics made from fossil fuels are not natural products, so enzymes have not evolved that can
break them down. This means that they are not biodegradable. The energy from sunlight may
cause the polymer to decompose, but this is a photochemical, rather than a biological, process.
9 Burning organic substances that contain chlorine can produce harmful products such as
hydrogen chloride and chlorinated dioxins.
11 A free radical is a species, usually neutral, that has an unpaired electron. Examples are a chlorine
atom, Cl•, and a methyl radical, CH3•.
12 A (chemical) chain reaction is one in which a radical reacts with a molecule to produce a different
radical and a product molecule. The new radical then takes part in a further reaction producing
another radical and so on, until a chain-breaking process stops the reaction.
e In nuclear physics a chain reaction is one in which a product of the first nuclear reaction causes a second
nuclear reaction to take place. The fission of 238U produces several neutrons, each of which is capable of
causing further fission.
13 Under normal atmospheric conditions, the C–H bond in HCFCs is oxidised. Therefore, the
chemical does not diffuse into the stratosphere where it would cause ozone depletion. CFCs do
not contain any C–H bonds and are not oxidised easily. They diffuse into the stratosphere, where
they are decomposed by ultraviolet radiation to produce chlorine radicals that initiate a chain
reaction which removes ozone.
2 The answer is A. To be able to store enough hydrogen in the car it has to be either liquefied
or compressed under extremely high pressure. It cannot be liquefied at temperatures above
−240°C.
e Being flammable is an essential property of a fuel. The energy density of hydrogen per kg is higher than
that of other fuels.
3 The answer is A. For hydrocarbon fuels, the amount of carbon dioxide produced for a given
amount of energy released decreases as the hydrogen-to-carbon ratio increases. The ratio for
methane is 4:1, for butane is 2.5:1 (10:4) and for octane is 2.25:1 (9:4). Thus methane produces
the least amount of carbon dioxide per kilojoule of energy released. Coal contains almost no
hydrogen and so produces the most carbon dioxide per kJ.
4 The answer is C. Oils are esters and do not ferment to ethanol. Therefore, option C is false and
is the correct answer to this negative question.
e Bioethanol is made by converting carbohydrates such as starch or sugar into glucose, which is then
fermented to ethanol and carbon dioxide. Therefore, options A, B and D are all true.
5 The answer is D. Algae can be used to make vegetable oils, not sugars. Hence, they are used in
biodiesel production.
e The final step in DMF production is the conversion of fructose to DMF. It is insoluble in water and has a
high energy density, so statements A, B and C are all true.
6 The answer is A. There are 11 reactant atoms on the left-hand side of the equation and only 2
atoms of iron (the desired product) on the right.
2
atom economy = × 100 = 18%
11
7 The answer is D. Poly(propene) is a non-natural substance made from propene, which is derived
from crude oil.
e Silk and cellulose are natural polymers (silk is a polyamide and cellulose is a polysaccharide). Biopol is a
polyester made from a natural organic chemical, so bacteria have evolved that break the polymer down.
8 The answer is A. Ultraviolet radiation splits oxygen molecules into oxygen radicals. When an
oxygen radical reacts with another oxygen molecule, ozone is formed. The other chemicals in
the list destroy ozone.
2 The answer is C. Phosphorus has five valence electrons. Three of these are used in bonding,
leaving one lone pair. The three bonding pairs and the one lone pair of electrons repel and the
atoms take up a pyramidal position with the lone pair above the pyramid.
e Boron has three valence electrons, so there are no lone pairs in BF3, which is therefore planar. Chlorine
has seven valence electrons, so there are three bond and two lone pairs in ClF3 and thus it is not
pyramidal. All six valence electrons of sulfur are used in SO3, which is planar.
3 The answer is A. All four species contain polar bonds. Apart from HCN, they are symmetrical
and their dipoles cancel. The hydrogen of HCN is δ+ and the nitrogen is δ−, so the molecule is
polar (has a dipole moment).
4 The answer is D. The conditions for hydrogen bonding are a δ+ hydrogen atom covalently bonded
to a δ− fluorine, oxygen or nitrogen atom. Only the amine, CH3CH2NH2, fulfils these criteria.
e Propanone and methoxymethane both have a δ− oxygen atom but neither has a hydrogen atom joined
to the oxygen. Fluoroethane has a very δ− fluorine atom but, again, no hydrogen atom joined to it.
5 The answer is C. For molecules with a similar number of electrons, the intermolecular forces in
decreasing strength are:
hydrogen bonds > induced dipole > permanent dipole
Hydrogen bonding (A) is impossible because there is neither a suitable δ− atom nor a δ+ hydrogen
atom. Covalent bonds (D) are even stronger but are within the molecule (intramolecular) —
they are not intermolecular forces. Permanent dipole forces (B) are usually weaker than induced
dipole forces and in this example the bonds in C2H5I are only very slightly polar.
7 The answer is B. The oxidation number of chromium atoms in K2Cr2O7 is +6 and in Cr2(SO4)3 it
is +3. Therefore, the oxidation number goes down by 3.
8 The answer is D. Equation A has two chlorine atoms on the right-hand side and only one on the
left. Equation B does not balance for charge (left-hand side is +5; right-hand side is +6). Equation
C has the electron on the wrong side (oxidation is loss of electrons, not gain).
9 The answer is B. The only group 1 nitrate that decomposes to produce nitrogen dioxide (brown
fumes) is lithium nitrate. Group 2 nitrates decompose to give the metal oxide, oxygen and
nitrogen dioxide. Sodium nitrate is the only one that does not give brown fumes of nitrogen
dioxide, so is the correct response to this negative question.
e Sodium nitrate decomposes into sodium nitrite, NaNO2, and oxygen.
11 The answer is B.
mass
amount (moles) of NaOH =
molar mass
1.2 g
= = 0.030 mol
40.0 g mol −1
moles
concentration =
volume in dm3
0.030 mol
= = 0.60 mol dm−3
0.050 dm3
12 The answer is D. When calculating the mean, you must choose consistent titres. In this example,
26.65 cm3 and 26.45 cm3 are consistent and their mean is 26.55 cm3.
e 27.00 cm3 is different by more than 0.20 cm3 from the other titres, so it is not a consistent titre.
13 The answer is A.
amount (moles) of hydrochloric acid = concentration × volume in dm3
= 0.0500 mol dm−3 × 0.02375 dm3 = 0.001188 mol
ratio of Ba(OH)2:HCl = 1:2
so moles of Ba(OH)2 = 12 × 0.001188 = 5.94 × 10−4 mol
moles
concentration =
volume in dm3
5.94 × 10−4 mol
= = 0.02375 mol dm−3
0.02500 dm3
e The answer 0.02375 is obtained by no rounding up intermediate values during the calculation. This is the
correct procedure. Rounding gives 0.02376.
15 The answer is D. The strength of the hydrogen–halogen bond is the critical factor. The larger the
halogen atom, the weaker the bond and the stronger is the acid. Hydrogen iodide, which has the
weakest bond, is the strongest acid.
e In questions about trends in a group of the periodic table, the answer is always the element at either
the top or the bottom of the group. If you do not know the answer, choose either the top or the bottom
option — you have a 50% chance of getting it right.
16 The answer is A. Statement A is false. Hydrogen chloride and gaseous ammonia react to form a
white smoke, not steamy fumes. Gaseous hydrogen chloride itself appears as steamy fumes.
e The other three statements are all true. Chlorine disproportionates with hot aqueous NaOH to form NaCl
(−1 oxidation state) and NaClO3 (+5 oxidation state).
The equation is: 3Cl2 + 6NaOH → 5NaCl + NaClO3 + 3H2O.
Silver chloride is decomposed by light to metallic silver and chlorine. The blue complex with starch is
used as the indicator in iodine titrations.
17 i The answer is B. An increase in pressure and an increase in temperature would both increase
the rate.
ii The answer is A. An increase in pressure drives the equilibrium to the right (the side with
fewer gas molecules). A decrease in temperature drives the equilibrium to the right because
the reaction left to right is exothermic.
19 The answer is A. The only difference between these molecules is the halogen. Fluorine is the
most electronegative so is more δ− than the other halogens in these compounds. This makes the
C–F bond, and hence the molecule, more polar.
e Note the comment after Question 15 about periodic table trends.
20 The answer is D. The critical point is not the polarity of the carbon–halogen bond but its strength.
Iodine has the largest radius of the four halogens, so it has the weakest carbon–halogen bond.
Therefore, the hydrolysis of CH3CH2I is the easiest and fastest.
e Note the comment after Question 15 about periodic table trends.
21 The answer is D. Sulfuric acid is reduced by iodide, which is the strongest reducing agent of the
four options. The iodide ions are oxidised to iodine, so there would be no hydrogen iodide to
react with the alcohol.
e Note the comment after Question 15 about periodic table trends.
22 The answer is B. A nucleophile contains a lone pair of electrons that are used to form a covalent
bond. Nucleophiles are negative ions, or molecules that contain a covalently bonded oxygen or
nitrogen atom. Radicals are not nucleophiles, so option B is the correct answer to this negative
question.
23 The answer is C. The CN− ion is a nucleophile and is substituted for the chlorine in the molecule.
Reaction A is free-radical substitution. Reaction B is electrophilic addition and D is oxidation.
24 The answer is D. This type of arrow (full-headed) represents the movement of a pair of electrons.
In this mechanism, the pair of electrons goes towards an atom (e.g. carbon) forming a new
covalent bond, not an ionic bond.
25 The answer is B.
mass
amount (moles) of 2-chlorobutane =
molar mass
12.3 g
= = 0.133 mol
92.5 g mol −1
theoretical yield of butan-2-ol = 0.133 mol
= 0.133 mol × 74.0 g mol−1 = 9.84 g
7.54 g × 100
percentage yield = = 76.6%
9.84 g
e The percentage yield is never ‘mass of product × 100/mass of reactant’. You have to work out the
theoretical yield and then calculate the actual yield as a percentage of the theoretical yield.
26 The answer is A. The i.r. peak at 1720 cm–1 indicates a C=O group (option A or B). Alcohols (and
acids) react with sodium, so it cannot be option C or D. It has a peak in its mass spectrum at m/e
= 29, which means that it has either a CHO or a C2H5 group (options A or C). The only molecule
that fits all the data is the one in A.
27 The answer is A. Biodiesel is often mixed with petrodiesel, but does not have to be. McDonald’s
uses pure biodiesel made from its own old frying oil to power its lorries. Statements B, C and D
are true. Algae can produce oils that can be converted to biodiesel using methanol in a transes-
terification reaction.
28 The answer is D. Ultraviolet light causes ozone to decompose into O2 and an oxygen radical.
Nitric oxides and CFCs are destroyers of ozone. HCFCs, however, are oxidised in the lower
atmosphere and do not reach the stratosphere. Therefore, they do not destroy the ozone layer.
Section B
29 a Although the nuclear charge increases, the number of shielding electrons increases by the
same amount ✓. The atomic radii increase down the group, making it easier to remove an outer
electron ✓.
e Do not give ‘the amount of shielding increases’ as the only reason — the amount to shield (the nuclear
charge) also increases.
b i Ca + 2H2O → Ca(OH)2 + H2 ✓
30 a A nucleophile is a species with a lone pair of electrons that it uses to form a covalent bond ✓. It
is usually a negative ion or a molecule with a covalently bonded oxygen or nitrogen atom.
−
b H H H H H H
−
N C: C l → N C C l → N C C + l−
✓ H ✓ H ✓ H
c The C–I bond in 2-iodopropane is weaker than the C–Br bond in 2-bromopropane ✓, so the
activation energy is lower ✓ and the reaction is faster.
d An increase in temperature cause the molecules to have greater kinetic energy and, hence,
to move faster. This results in an increase in the frequency ✓ of collisions and also means
that more molecules have energy greater than or equal to the activation energy, Ea ✓. The
effect of this is to increase the proportion of molecules that react on collision ✓ and, therefore,
to increase the rate. The energy factor has a much greater effect than the increase in the
frequency of collision ✓ .
e Do not say that:
l there are more collisions — it is their frequency (number per second) that alters
l there will be more successful collisions — ‘more of the collisions are successful’ or ‘a greater
proportion of the collisions are successful’ will score the mark
31 a i H
✓
H3C CH3
C or (CH3)2CHNH2
+ –
H3N Cl
ii CH3CH=CH2 ✓
c H H CH3
32 a i I− → 12 I2 + e− or 2I− → I2 + 2e−
e This is an oxidation (OIL) reaction, so the electron in this half-equation is on the right-hand side and the
reactant, iodide ion, is on the left.
b P
✓
I I
Phosphorus is in group 5 and has five valence electrons. Three of these are used in bonding
with the iodine atoms, so there is one lone pair ✓. The three bond pairs and the lone pair
repel each other to a position of maximum separation ✓, which is a pyramidal arrangement of
atoms.
c The P–I bonds are polar, with the phosphorus atom δ+ and the more electronegative iodine
atoms δ− ✓. The dipoles of the three bonds do not cancel ✓, so the molecule is polar.
e In this instance the dipoles do not cancel. However, if the dipoles do cancel, you must be careful to
always use the word ‘dipole’ — never say ‘the charges cancel’.
If you did not realise that the phosphorus atom in PI3 has a lone pair of electrons and, hence, state
(wrongly) that the molecule is planar, you could score the marks in part (c) by saying that the dipoles
cancel and that the planar molecule is not polar. This is an example of consequential marking.
d A molecule of phosphorus triiodide, PI3, contains 174 electrons (the sum of the atomic numbers
of one atom of phosphorus and three atoms of iodine); a molecule of phosphorus trichloride,
PCl3, contains 66 electrons ✓. This means that the induced dipole (London/dispersion/van der
Waals) forces between phosphorus trichloride molecules are weaker ✓ than those between
phosphorus triiodide molecules, so less energy is required to separate them. Therefore,
phosphorus trichloride has the lower melting temperature.
e The first mark could be obtained by saying that phosphorus triiodide has more electrons than
phosphorus trichloride (or that phosphorus trichloride has fewer electrone than phosphorus triiodide).
Do not say that the strength of the intermolecular forces is connected with either the size of the
molecules, the mass of the molecules, or the strength of the permanent dipole forces. Any comparison
of covalent bond strength will fail to score because covalent bonds are not broken on melting.
Section C
33 a i C4H9OH + 6O2 → 4CO2 + 5H2O ✓
e State symbols are not required as they were neither asked for nor is it a thermochemical question.
iii 1 mol of 2-butanol produces 4 × 44.0 = 176.0 g of carbon dioxide and 2650 kJ of energy
176.0 g × 1000 kJ
carbon footprint per 1000 kJ = = 66.4 g ✓ of carbon dioxide
2650 kJ
This is almost the same as the carbon footprint of petrol.
iv The peak at m/e = 59 is 15 less than the value for the molecular ion peak and is caused by
the loss of CH3. The peak is due to either the +CH2CH(OH)CH3 ion or the CH3CH2CH(OH)+
ion ✓.
The peak at m/e = 45 is 29 less than the value of the molecular ion peak and is caused by the
loss of C2H5. This peak is due to the +CH(OH)CH3 ion ✓.
Peak A is at about 3350 cm−1 and is due to the hydrogen-bonded O–H bond stretch ✓.
Peak B is at about 2900 cm−1 and is due to the alkane C–H bond stretch ✓.
e When identifying peaks in mass spectra remember to include the charge. When identifying peaks in
infrared spectra remember to include the wavenumber.
e The formula CH3CH2COCH3 does not show the double bond in the C=O group and so would not score
the mark.
b i Hydrogen will evaporate and an explosive mixture of hydrogen and air ✓ will build up in
the enclosed space of the garage.
iii A homogeneous catalyst is in the same phase as the reactants (all in the gas phase or all
dissolved in the same solvent). A heterogeneous catalyst is in a different phase from the
reactants ✓.
c
Enthalpy
Enthalpy
Ea Ecat
Reactants Reactants
Intermediate
Products Products