1

Answers to self-assessment
questions in Chapters 1 to 21
1 Stoichiometric relationships
9 Ag(NO3)2(aq) + 2NaCl(aq) → AgCl(s) + 2NaNO3(aq)
1 a Heat produced; colour change
Ag+(aq) + Cl−(aq) → AgCl(s)
b Magnesium + iodine → magnesium iodide
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
c Compounds can be decomposed; elements cannot
be decomposed. H+(aq) + OH−(aq) → H2O(l)
 lements contain one type of atom; compounds
E Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s)
have two or more different atoms bonded together.
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
2 a Melting
Na2CO3(s) + 2HCl(aq) → 2NaCl(aq) + CO2(g) + H2O(l)
b Freezing or solidifying
CO 32−  (aq) + 2H+(aq) → CO2(g) + H2O(l)
c Boiling
10 2 : 1
d Boiling
11 0.01 mol × 6.02 × 1023 mol−1 = 6.02 × 1021
e Vapour deposition 9 × 10 23
12 = 1.5 mol
f Sublimation 6.02 × 10 23
3 a 40°C and 90°C 13 Number of oxygen atoms = (9 × 1023 × 3) = 2.7 × 1024
b Solid, liquid and gas. 35.45
15 = 3.93 = 4
9.01
c There is no change in temperature; the thermal
energy (heat) is used to separate the particles and 16 Molar mass of magnesium carbonate, MgCO3
overcome the intermolecular forces or chemical = [24.31 + 12.01 + (3 × 16.00)]
bonds. = 84.32 g mol−1
4 C(s) + 2H2O(g) → CO2(g) + 2H2(g) 17 Molar mass of carbon dioxide, CO2
= [12.01 + (2 × 16.00)]
12  [2 × 18]   44   
[2 × 2] = 44.01 g mol−1
Recall that the Ar or Mr in grams is one mole, so: 18 Molar mass of hydrated iron(ii) sulfate crystals,
Total mass of products = 44 g + 4 g = 48 g, note that FeSO4·7H2O
this is the same as the reactants: 12 + 36 = 48 g. = 55.85 + 32.07 + (4 × 16.00) + 7 × [(2 × 1.01) + 16.00]
= 278.06 g mol−1
Mass of hydrogen = 4 g
54 g
% atom economy = 4 × 100 = 8.3% 19 Amount of water molecules = = 3.0 mol
48 18 g mol −1
5 a Element
500 g
b Compound 20 Amount of calcium = = 12.5 mol
40 g mol −1
c Compound
0.18 g
d Element 21 Amount of water = = 0.010 mol
18 g mol −1
e Mixture of compounds 22 Mass of calcium carbonate(g) = 0.40 mol × 100 g mol−1
f Mixture of elements with a compound                = 40 
g
1.00 g
6 Homogenous; heterogeneous; homogenous; 23 Molar mass (g mol−1) = = 500 g mol−1
heterogeneous; homogenous; homogenous; 0.00200 mol
homogenous; homogenous;
7 Fe2(PO4)3, NH4I, Al(NO3)3, CaBr2 and Fe2O3. 24 Mass of a single molecule of
 44.01g mol −1 
8 SiCl4 + 4H2O → H4SiO4 + 4HCl CO2 =  −1 
× 1000
 6.02 × 10 mol 
23

2KClO3 → 2KCl + 3O2

   = 7.31 × 10−20 kg

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  2

22 g Dividing through by smallest number:

25 Amount of propane = = 0.50 mol
44 g mol −1 6.1225 10.2010.20
1.0201.020

Hence, 22 g of propane contains (6 × 10 × 0.50 =
23
1.020 1.0201.020
1.0201.020
3 × 1023) molecules of propane and since each molecule 6 10 1
of propane contains 11 atoms (3 carbon atoms and
8 hydrogen atoms), the total number of atoms is Empirical formula: C6H10O
(11 × 3 × 1023) = 3.3 × 1024. To determine the molecular formula:
The total number of carbon atoms is (3 × 3 × 10 ) 23 196 = [(6 × 12) + (10 × 1) + 16] × n = 98 × n
= 9 × 1023 and the total number of hydrogen atoms is Hence n equals two and the molecular formula is
(8 × 3 × 1023) = 2.4 × 1024. C12H20O2.
39.13
26 Amount of atoms: C: = 3.258 mol; 20.4 g
12.01 32 Amount of hexan-1-ol = = 0.200 mol
102 g mol −1
52.17 8.70
O: = 3.261 mol and H: = 8.61 mol Hence, the theoretical amount of hex-1-ene produced is
16.00 1.01
0.200 mol (since there is excess phosphoric(v) acid).
Dividing through by smallest: 1 : 1 : 2.6 and then
multiplying through by 3: C3H8O3 mass(g)
Amount of hex-1-ene =
molar mass(g mol −1 )
27 Lead Oxygen
             
= 0.200 
mol
Combining masses: 41.4 g (44.6 g − 41.4 g) = 3.2 g
Rearranging, mass of hex-1-ene = 84 g mol−1 × 0.200 mol
41.4 g 3.2 g                = 16.8 g
Amount of atoms:
207g mol −1 16 g mol −1
Since only 10.08 g of hex-1-ene was produced, the
Ratio of amounts:   0.2 0.2 10.08 g
percentage yield is × 100 = 60%.
Empirical formula: PbO 16.8 g
12.01 33 Volume occupied = 1.35 mol × 22.7 dm3 mol−1
28 Mass of carbon in CO2 = × 0.6875 g = 0.1876 g
44.01          = 30.6 dm3
2.02  175  3
Mass of hydrogen in H2O = × 0.5625 g = 0.06305 g   dm
18.02 1000 
34 Amount of gas = = 7.71 × 10−3 mol
0.1876 g 22.7dm3 mol −1
Amount of carbon atoms = = 0.01562 mol
12.01g mol −1
2.85dm3
35 Amount of carbon dioxide =
0.06305g 22.7dm3 mol −1
Amount of hydrogen atoms = = 0.06243 mol
1.01g mol −1               = 0.126 mol
Empirical formula is CH4. Number of molecules = 0.126 × 6.02 × 1023 mol−1
12             = 7.59 × 1022
29 Percentage by mass of carbon = × 100 = 75%
16
mass 39.95g
4 36 Density = = = 1.76 g dm−3
Percentage by mass of hydrogen = × 100 = 25% volume 22.7 dm 3
16
Sum of percentages by mass = (75% + 25%) = 100% 7.44 dm 3
37 Amount of gas = = 0.328 mol
22.7dm 3 mol −1
46
30 Percentage by mass of sodium = × 100 = 14.3%
322 20.8 g
Molar mass = = 63.4 g mol−1
32 0.328 mol
Percentage by mass of sulfur = × 100 = 9.9%
322 3.06g
38 Amount of KClO3 = = 0.025 mol
64 122.5g mol −1
Percentage by mass of oxygen = × 100 = 19.9%
322 0.84 dm 3
180 Amount of O2 = = 0.0370 mol
Percentage by mass of water = × 100 = 55.9% 22.7dm 3 mol −1
322
The simplest molar ratio is 2 : 3 and hence the balanced
31 Carbon Hydrogen Oxygen equation must be
Combining masses: 73.47 g 10.20 g 16.33 g 2KClO3(s) → 2KCl(s) + 3O2(g)
Amount of atoms: 73.4773.47
10.2073.47
10.20
16.3310.20
16.33
16.33 V1 × T2 4.50 dm 3 × 350 K
12 121 12 16
1 16
1 16 39 V2 = = = 5.25 dm3
T1 300 K
Ratio of amounts: 6.1225 10.20 1.020

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  3

97000 Pa 101 325Pa 5.0

40 = V2 = 25.0 × = 83.3 cm3
298 K T2 1.5
50 Amount of sodium hydroxide
298 K
T2 = 101 325 Pa × −3
= 0.100 mol dm × 41.0 cm = 4.10 × 10−3 mol
3
97000 Pa
T2 = 311.3 K = (311.3 − 273) = 38.3°C 1000
Amount of HX equals 4.1 × 10−3 mol because the acid
T P 3000 K
41 2 = 2 = = 10 and base are reacting in a 1 : 1 molar ratio:
T1 P1 300 K
HX(aq) + NaOH(aq) → H2O(l) + X− Na+(aq)
P2 Hence, molar mass of HX =
= 10 :1
P1 mass(g) 0.558 g
= = 136 g mol−1
amount(mol) 4.10 × 10 −3 mol
1.05 × 10 Pa × 60 cm
5 3
1.01 × 10 Pa × V2 5
42 =
333K 273K
51 Amount of potassium hydroxide
1.05 × 10 Pa × 60 cm × 273K
5 3 17.5dm 3
V2 = = 51 cm3 = × 0.150 mol dm−3 = 2.63 × 10−3 mol
(1.01 × 10 5 Pa × 333K) 1000
20.0 dm 3
Amount of phosphoric acid = × 0.0656 mol dm−3
PV −3
= 1.31 × 10  mol 1000
; n = 101325Pa × 4 × 10 m
3 −3
43 PV = nRT; n =
RT 8.314 JK −1 mol −1 × 273K The two chemicals react in a 2 to 1 molar ratio and
         = 0.1786 mol hence the equation is:
mass(g) H3PO4(aq) + 2KOH(aq) → K2HPO4(aq) + 2H2O(l)
Amount of gas = ;
relative molecular mass 52 a 2NaOH(aq) + H2SO4(aq) → Na2SO4(aq) + 2H2O(l)
mass(g) b Amount of sodium hydroxide used in the titration
relative molecular mass =
amount(mol) 25.0 dm 3
= × 1.00 mol dm−3 = 0.0250 mol NaOH
12.64 1000
Relative molecular mass (Mr) = = 70.7 c From the equation, amount of H2SO4
0.1786
= amount of NaOH ÷ 2 = 0.0125 mol in 20.0 cm3,
RT −3 −1 −1
so ‘scaling up’ to 1000 cm3 to obtain the
; Mr = 2.615kg m × 8.314 JK mol × 298 K
44 Mr = d
P 101.325kPa concentration of diluted sulfuric acid
        = 63.9 1000 × 0.0125mol dm −3
= = 0.625 mol dm−3
0.5mol 20.0
45 Concentration = = 0.1 mol dm−3 d ‘Scaling up’ from 50.0 to 1000 cm3 gives the
5.0 dm 3
concentration of the original concentrated sulfuric
4.00 g 0.625 × 0.0125mol dm −3 × 1000
46 Amount of sodium hydroxide = acid solution =
40.0 g mol −1 50.0
             = 0.100 mol       = 12.5 mol dm−3
0.100 mol 53 a MgO(s) + 2HCl(aq) → MgCl2(aq) + 2H2O(l)
Concentration of sodium hydroxide =
0.200 dm 3
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)
                   = 0.50 mol 
dm−3
b Amount of hydrochloric acid added to the
47 Amount of hydrated copper(ii) sulfate
magnesium oxide
= 0.50 mol dm−3 × 0.0250 dm3 = 0.0125 mol
100 dm 3
Mass of hydrated copper(ii) sulfate = × 2.00 mol dm−3 = 0.200 mol
1000
= 0.0125 mol × 249.7 g mol−1 = 3.12 g c Amount of excess hydrochloric acid titrated
48 Molar mass of hydrogen chloride 19.7dm 3 × 0.200 mol dm −3
= (1.00 g mol−1 + 35.5 g mol−1) = 36.5 g mol−1 = = 0.00394 mol HCl,
1000
14.6 g
Amount of hydrogen chloride in 100 cm3 = since the mole ratio of NaOH to HCl is 1 : 1
36.5g mol −1
                  
= 0.400 mol d Amount of hydrochloric acid reacting with the
magnesium oxide = 0.200 mol − 0.00394 mol
Hence, the concentration of hydrogen chloride          = 0.196 
mol
= 0.400 × 10 = 4 mol dm−3
49 M1 × V1 = M2 × V2;
5.0 mol dm−3 × 25.0 cm3 = 1.5 mol dm−3 × V2

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 4

e Amount of magnesium oxide that reacted

0.196 mol
2 Atomic structure
= = 0.098 mol (1 : 2 molar ratio in 1 Mass of one mole of electrons
2
equation). The molar mass of magnesium oxide is = 9.109383 × 10−31 g × 6.02 × 1023 mol−1
40.3 g mol−1, hence the mass of magnesium oxide = 5.48 × 10−7 g = 5.48 × 10−5 kg
reacting with acid = 0.098 mol × 40.3 g mol−1 = 3.95 g Charge on one mole of electrons
3.95g = 1.602189 × 10−19 C × 6.02 × 1023 mol−1
and hence percentage purity = × 100 = 97%.
4.08g = 9.64 × 104 C
54 The amount of solution made with distilled water 2 Volume of atom = 4 × π × (10−10 m)3/3 = 4.2 × 10−30 m3
should be 500 cm3.
24.00  Volume of nucleus = 4 × π × (10−16 m)3/3
Amount of Cr2 O72− =  dm3 × 0.100 mol dm−3
 1000  = 4.2 × 10−48 m3
= 0.0024 mol Percentage of atom that is nucleus
Amount of Fe in 20.00 cm = 6 × 0.0024 mol
2+ 3 = 4.2 × 10−48 m3/4.2 × 10−30 m3 × 100 = 10−16%
= 0.0144 mol 3 A hydrogen atom consists of one proton and one
Amount of Fe in 500 cm solution
2+ 3 electron. Mass of hydrogen atom is the sum of the
proton and electron masses (ignoring the mass defect).
 500 
= × 0.0144 mol = 0.36 mol
 20  1.672622 × 10 −27 + 9.109383 × 10 −31 g
= 1837 times heavier
Amount of Fe2+ = amount of FeSO4.xH2O 9.109383 × 10 −31 g
mass
Molar mass = 4 A probability density curve is a plot prepared by
amount plotting the calculated electron probability (|ψ|2)
101.2 g against the distance from the nucleus (r). Radial
Molar mass = = 281.1 g mol−1
0.36 mol probability electron distribution curves give the
Molar mass of FeSO4 = 151.91 g mol−1 probability of finding the electron at a given distance
from the nucleus (regardless of the angular position).
Molar mass of water molecules The probability of finding an electron at a node is zero.
= 281.1 g mol−1 − 151.91 g mol−1 = 129.2 g mol−1
129.2 g mol −1 Radial probability density curves for three atomic orbitals:
Number of water molecules = = 7; x = 7
18.02 g mol −1
 26.20 
55 Amount of S2 O 32− =  dm3 × 0.500 mol dm−3
 1000 
4πr 2 ψ 2

= 0.0131 mol
1
Amount of I2 reacting with S2 O 32− = × 0.0131 mol
2
= 0.00655 mol
2
Amount of MnO4−/KMnO4 = × 0.00655 mol r
5 For 1s orbital

= 0.00262 in 25.00 cm3

 1000 
Concentration of KMnO4 =  × 0.00262 mol
 25.00 
Node
4πr 2 ψ 2

4πr 2 ψ 2

= 0.105 mol dm−3

56 Amount of KMnO4 solution
 12.15 
= dm3 × 0.0100 mol dm−3
 1000 
r r
For 2s orbital For 2p orbital
= 0.0001215 mol
The particles (atoms or molecules) are identical in
3NO 2− (aq) + MnO 4− (aq) + 2H+(aq) →
terms of physical properties but distinguishable in
3NO 3− (aq) + Mn2+(aq) + H2O(l) terms of position, path or trajectory. The equilibrium
Amount of NO 2− = 0.0001215 mol × 3 = 0.0003645 mol distribution is the most probable way of distributing
the particles among various allowed energy states.
Mass of NaNO2 = 0.0003645 mol × 69.00 g mol−1 There is no theoretical limit on the number of particles
= 0.02515 g in a given energy state, but the density of particles is
 0.025  sufficiently low and the temperature sufficiently high
Percentage by mass of NaNO2 =  × 100
 1.00  that no more than one particle is likely to be in a given
= 2.5% state at one time.
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  5

5 The third hydrogen species listed in the question should be 12 H. superposition, both decayed and not decayed at the same
Protons, neutrons and electrons: 1, 2, 2; 1, 2, 0; 1, 1, 2; time. Until the box is opened, an observer does not know
and 2, 0, 0. whether the cat is dead or alive. It is considered to be
both alive and dead at the same time until it is observed.
6 Ar = (mass isotope 1)(abundance isotope 1) +
(mass isotope 2)(abundance isotope 2) 11 Ti3+: 1s2 2s2 2p6 3s2 3p6 3d1
  = 192.22 = (191)x + (193)(1 − x) Cr2+: 1s2 2s2 2p6 3s2 3p6 3d4
  = 191x + 193 − 193x Cu: 1s2 2s2 2p6 3s2 3p6 4s1 3d10
   = −2x + 193; 2x = 193 − 192.22; x = 0.39
P3−: 1s2 2s2 2p6 3s2 3p6
Therefore the abundance of 191Ir is 39% and that of 193Ir
is 61%. Cl: 1s2 2s2 2p6 3s2 3p5
7 Carbon-60 was first detected as an unusually abundant Ga: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p1
species in mass spectra recorded on carbon clusters
12 i Li atom is 1s2 2s1 atom (excited state)
produced by laser vaporization of graphite in a flow of
helium gas. The most abundant carbon cluster had a ii H atom is 1 s1 H− (hydride ion) (ground state)
molecular mass of 720. iii S atom is 1s2 2s2 2p6 3s2 3p4 atom (ground state)
8 Ultraviolet radiation: higher frequency, smaller iv N atom is 1s2 2s2 2p3 N+ (unipositive ion) (excited
wavelength, greater energy and higher wave number. state)
Infrared radiation: lower frequency, greater wavelength, v F atom is 1s2 2s2 2p5 F− (fluoride ion) (excited state)
lower energy and lower wave number.
13 The electrons in atoms are uniquely described by four
9 a Frequency, energy or wavelength. electron numbers. The principal quantum number
b Frequency: decreasing; wavelength: increasing, left (n) describes the energy of the orbital – the shell. The
to right. angular quantum number (l) describes the shape of the
orbital: s, p, d and f. The third quantum number, known
c When sufficient energy (thermal or electrical) is
as the magnetic quantum number (m), describes the
supplied, electrons can be promoted (excited) to
orientation in space of a particular orbital. (It is called
higher energy levels in an atom. The electrons are
the magnetic quantum number because the effect of
unstable in higher levels and rapidly emit radiation
different orientations of orbitals was first observed in the
and fall back into lower energy levels. As the energy
presence of a magnetic field).
levels are fixed, the energy lost between any higher
level and a lower level is also of a certain fixed value Rules governing the allowed combinations of quantum
so the radiation emitted will only have certain fixed numbers:
frequencies (i.e. specific colours). This means that the The three quantum numbers (n, l, and m) that describe
atomic spectrum of an element will consist of a series an orbital are integers: 0, 1, 2, 3, and so on. The
of lines of different colours (on a black background), principal quantum number (n) cannot be zero. The
d Main energy level 2 (second shell) i.e. n = 2 allowed values of n are therefore 1, 2, 3, 4, and so on.
The angular quantum number (l) can be any integer
e Each element has its own characteristic line
between 0 and n − 1. If n = 3, for example, l can be
spectrum. Therefore an element can be identified
either 0, 1, or 2. The magnetic quantum number (m)
by its line spectrum just as a criminal can be
can be any integer between −l and +l. If l = 2, m can be
identified from a fingerprint.
either −2, −1, 0, +1, or +2.
f An unknown yellow emission line was observed in
the solar spectrum during an eclipse.
3 Periodicity
g In a continuous spectrum the radiations
corresponding to all the wavelengths (within a 1 The periodic table is a tabular arrangement of the
certain range) are present. In an emission spectrum chemical elements organized in the basis of their atomic
only a limited number of radiations corresponding number, electron configurations and recurring chemical
to a small number of wavelengths (within a certain properties. Elements are presented in order of increasing
range) are present. atomic number into groups, periods and blocks.

10 This is a thought experiment illustrating the principles There are many alternative forms of the periodic table,
of quantum mechanics. A cat is placed in a sealed including spiral and helical, many of which highlight
box along with a Geiger counter, a vial of poison, or emphasize chemical or physical properties of the
a hammer and a radioactive substance. When the elements that are not as apparent in the long form of
substance undergoes decay, the Geiger counter detects the periodic table.
the ionizing particle and triggers the hammer to release 2 X is magnesium: 1s2 2s2 2p6 3s1; Y is phosphorus: 1s2 2s2
the poison which kills the cat. Radioactive decay is a 2p6 3s2 3p3 and Z is argon: 1s2 2s2 2p6 3s2 3p3.
random process and the atom exists in a state known as
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  6

3 P is argon (group 18; period 3); Q is bromine (group 17; 3 Chlorine–chlorine: 0; covalent (non-polar)
period 4) and R is calcium (group 2 and period 4).
Hydrogen–fluorine: 1.8; covalent (highly polar)
4 Graphs can be plotted as line graphs (with smooth
Carbon–chlorine: 0.6; covalent (polar)
curves). The physical property on the vertical axis
and the halogen along the horizontal axis. The data Beryllium–chlorine: 1.6; covalent (polar)
for fluorine, chlorine, bromine and iodine can be
Carbon–hydrogen: 0.4 covalent (polar)
extrapolated to astatine.
4 Phosphorus tribromide or phosphorus(iii) bromide;
5 There is generally a correlation between electron
phosphorus pentachloride or phosphorus(v) chloride;
affinity and electronegativity, because they both
lead(ii) chloride, lead(iv) chloride, iodine monochloride
are measures of an affinity of an atom for electrons.
or iodine(i) chloride and sulfur hexafluoride or
However, the electron affinities of nitrogen and
sulfur(vi) fluoride.
phosphorus are relatively low. This is due to the
presence of half-filled p sub-shells which increases 5 H H H

+
inter-electron repulsion and decreases electron affinity. C H C H C H

+
+

+
6 Indium is classified as a metal. It is in group 13 and H H H
hence expected to form indium(iii) ions, In3+. It is     CH3  
CH3
+ −
 CH3
●

expected to be a relatively unreactive metal that is not

6 Resonance structures for the ethanoate ion:
expected to react with water. It is expected to be an
excellent thermal and electrical conductor.
O O
7 Volumes, concentrations and temperatures of chemicals
including the catalyst must be controlled. The reacting H3C C H3C C
mixtures should be made homogenous by stirring. O O

Resonance structures for the cyanate ion:

4 Chemical bonding and
structure O C N O C N O C N

1 Ca: 1s2 2s2 2p6 3s2 3p6 4s2

7 +
CH3 (trigonal planar); −CH3 (tetrahedral); PH3
Ca2+: 1s2 2s2 2p6 3s2 3p6
(trigonal pyramidal); AsH5 (trigonal bipyramidal) and
F: 1s2 2s2 2p5 NH2− (bent, V-shaped or non-linear)
F−: 1s2 2s2 2p6 8 Colourless (when pure), very hard, high melting and
Each calcium atom loses two electrons; each fluorine boiling (or sublimation) points, chemically unreactive,
atom gains one electron. poor thermal and electrical conductor.
Na: 1s2 2s2 2p6 3s1 It can be used as an abrasive, in cutting tools and

Na : 1s 2s 2p
+ 2 2 6 brakes. Grains of silicon carbide can be sintered
together to form very hard ceramics.

O: 1s2 2s2 2p4
9 Iodine monochloride molecules are associated in the

O2−: 1s2 2s2 2p6
solid and liquid states by dipole–dipole forces and

Each sodium atom loses one electron; each oxygen London (dispersion) forces. The non-polar bromine
atom gains two electrons. molecules are only associated via London (dispersion)
Al: 1s2 2s2 2p6 3s2 3p1 Al3+: 1s2 2s2 2p6 forces.
O: 1s2 2s2 2p4 O2−: 1s2 2s2 2p6
Each aluminium atom loses three electrons; each
oxygen atom gains two electrons.

2 Group 1 2 13 14 15 16 17 18
Element Li Be B C N O F Ne
Electron arrangement 2,1 2,2 2,3 2,4 2,5 2,6 2,7 2,8
Electron configuration 1s2 2s1 1s2 2s2 1s2 2s2 2p1 1s2 2s2 2p2 1s2 2s2 2p3 1s2 2s2 2p4 1s2 2s2 2p5 1s2 2s2 2p6
Number of electrons in outer shell 1 2 3 4 5 6 7 8
Common simple ion Li+ Be2+ None None N3− O2− F− None
Electron arrangement of ion 2 2 – – 2,8 2,8 2,8 –
Electron configuration of ion 1s 2
1s 2
– – 2
1s 2s 2p2 6 2
1s 2s 2p 2 6
1s2 2s2 2p6 –

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  7

10 Carbon disulfide has a higher boiling point than The energy difference between the transition state
carbon dioxide because molecules of CS2 have more peak and the products will be 335 kJ mol−1.
electrons than molecules of CO2. This results in the
Ea = 335 − 92 = +243 kJ mol−1
London (dispersion) forces being stronger between
molecules of CS2, hence more thermal energy is b The activation energy will be lowered to a value less
required to separate them. than +243 kJ mol−1.
Hydrogen peroxide has more electrons than water, 5 a Molybdenum(vi) oxide and silicon(iv) oxide.
which gives a greater polarizability and hence stronger
b The traditional method uses concentrated nitric
(London) dispersion forces. The hydrogen peroxide
acid whereas the new method uses only dilute nitric
has a much greater dipole moment than does the
acid. The traditional method uses concentrated
water molecule. The greater dipole–dipole attraction
sulfuric acid in a powerful mixture with nitric acid;
also contributes to the expected increased boiling
this is not used at all in the new method.
point. Hydrogen peroxide exhibits hydrogen bonding
and with one additional oxygen atom, compared to The temperature used in the new method is higher

water, there are more sites available to form hydrogen than that of the traditional method.
bonds. With potentially more hydrogen bonding in 6 In answering this question refer to Figures 6.17, 6.18 and
hydrogen peroxide, the boiling point will be greater 6.19 on page 207.
(unless decomposition occurs).
a Sketch a graph similar to Figure 6.17.

5 Energetics/thermochemistry b Activation energy is the minimum combined

kinetic energy the colliding molecules must have in
1 °C × 9 + 32 = °F and (°F − 32) × 5 = °C order to react.
5 9
2 A perpetual motion machine is a hypothetical device c See Figure 6.17.
that produces work without consuming energy (i.e. it
creates energy). Such a device would violate the first d See Figure 6.19; draw a line at a lower energy value
law of thermodynamics (law of conservation of energy). than your first Ea.
e Shade the area under the graph between the two
values for activation energy; see Figure 6.19.
6 Chemical kinetics
f See Figure 6.18.
1 Sketch a similar graph to Figure 6.6, but the
‘products’ level on the right should be higher than the 7 a At higher pressure the same number of molecules
‘reactants’. The other labelled items are the same as in are packed closer together and will collide more
Figure 6.6. frequently (the concentration of the gases is
effectively increased) and so there is more chance of
2 Collision 1 is the only successful type of collision
reaction.
because the orientation of the molecule is correct both
in terms of the H–Cl molecule interacting with the b At higher concentration there are more particles
pi electron cloud of the carbon–carbon double bond in a given volume and so the collision frequency
and the polarization of the attacking molecule. The is increased and so there is more chance of
hydrogen atom is slightly positive (δ+) and interacts reaction.
with the negative pi cloud. c There is a greater surface area of the solid exposed
Collision 2: the H–Cl molecule is wrongly orientated for the same mass of solid when it is finely divided
with the Cl atom (δ−) towards the pi cloud; resulting in and so there is more chance of reaction.
repulsion. d There are two factors here: the molecules have
Collisions 3 & 4: in both the H–Cl molecule is colliding greater combined kinetic energy and so collide more
with the wrong region of the ethene molecule. frequently; also when they do collide the combined
kinetic energy is more likely to equal or exceed the
3 a Base your sketch on Figure 6.6, but put the actual
activation energy and so there is more chance of the
reactants (N2 + 3H2) and products (2NH3) on the
collision producing a reaction. This second factor is
appropriate levels. You can label the activation
the more significant of the two.
energy at this stage.
8 a Sample B has the highest value of mean kinetic
b Using a broken line sketch in a peak that is below
energy.
that in (a).
b Convert the temperatures of the samples to Kelvin:
c Note that the activation energy is lower in the
presence of a catalyst. A 298 K; B 323 K; C 273 K; D 149 K
4 a The sketch of the energy profile for the uncatalysed The mean kinetic energy of a sample of particles is

reaction will as drawn in 3(a). The energy difference proportional to the absolute temperature. Sample A
between reactants and products will be −92 kJ mol−1. has double the mean kinetic energy of sample D.

Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  8

9 22 g of CO2 (= 0.5 mol) produced in a volume of 4 dm3 frequently and, more importantly, a greater proportion
in 15 s of collisions will result in a reaction as more collisions
0.5 involve particles whose total kinetic energy is equal to
Rate = 4
15
= 8.3 × 10−3 mol dm−3 s−1 or greater than the activation energy for the reaction.
10 0.06 mol dm−3 of iodine produced in 30 s e These factors, including the dimensions of the flask,
0.06 must be kept constant so that the experiments are
Rate = = 2 × 10−3 mol dm−3 s−1 comparable, with only one variable changed; the
30
cross must be viewed through the same depth of
11 a Sketch a diagram similar to Figure 6.31 on page 214
solution each time.
without the small tube on the string. Show a strip
of magnesium ribbon in the acid. Draw the graph, f Extrapolate your curve and estimate a value for the
labelling the axes and plotting the points accurately. time taken at 70°C.
b Draw a tangent to the curve at time zero and g Sketch a curve on your graph which is steeper than
calculate the slope using slope = ∆y/∆x (see Figure the experimental curve.
6.26 on page 212).
h Use an ice-water bath to achieve a temperature
c Reaction is fastest at the start as the concentration between 0°C and 5°C; equilibrate the solutions to
of the acid is greatest at this point. The graph this temperature before mixing them to react.
curves as the rate decreases because the acid (and
magnesium) is being used up and the collision
frequency decreases. Eventually the curve flattens to
7 Equilibrium
a plateau as the magnesium is all used up and there 1 a The rates of the forward and reverse reactions are
is no further reaction (see Figure 6.25 on page 611). equal; there is no change in the concentrations of
the components of the equilibrium mixture even
d Volume of gas produced in 150 s = 75.6 cm3. though reactions are taking place.
75.6
Average rate of reaction = = 0.504 cm3 s−1 b The reaction must be taking place in a closed system.
150
e The magnesium has all been reacted and no more 2 a Sketch a graph using Figure 7.9b on page 227 for
gas is produced. The acid (15 × 10−3 mol) is in excess guidance; the two curves do not meet.
of the magnesium (4.17 × 10−3 mol).
b Sketch a graph in which the rate of the forward
f Sketch a line on your graph which lies beneath the reaction decreases and that of the reverse reaction
first line and levels out at 38 (37.8) cm3 of hydrogen gas. increases until they meet at a shared value.
g This graph should be steeper initially but should [Fe(SCN)]2+ 
level out at 75.6 cm3 of gas. The reaction will 3 a i Kc =  3+
[Fe ][SCN− ]
be faster than in the first experiment as the
magnesium is powdered, but the same amount of [NO]4 [H 2 O]6
gas is produced. Sketch a curve to show this. ii Kc =
[NH 3 ]4 [O 2 ]5
h This graph will start more slowly (less steep 1
gradient) than the first graph and move towards b Kc for the reverse reaction = or 0.25.
4.0
levelling at the same volume of gas – it probably will
not level off on your scale. 4 a The equilibrium will shift to the left, favouring
reactants, to restore equilibrium concentrations
i Sketch a diagram similar to Figure 6.18 on page 207; that fit the same value of Kc.
remember that the first experiment is at the higher
temperature. b The equilibrium position will shift to the left, to
replace ethanol and restore the equilibrium at the
Draw in the areas representing the activation energy.
 constant value of Kc.
At the higher temperature more particles will have
energy greater than or equal to the activation energy 5 a If the concentration of Fe2+ ions is increased then
and therefore more collisions will result in product the equilibrium position will shift to use the added
formation. Hence the rate of reaction will increase. ions and restore equilibrium concentrations that fit
the same Kc.
12 a Average temperatures: A 24; B 32; C 39; D 49; E 57
b The addition of water reduces the concentration
b Draw the graph, labelling the axes and plotting of all the ions in solution equally; there will be no
the points accurately. Draw a smooth best-fit curve change in the equilibrium position.
using the points.
6 a i Increasing pressure will shift the equilibrium
c The rate is fastest in experiment E. to the left as the reactants occupy less volume
d The rate is fastest at the highest temperature. The (there are fewer moles of gas on the reactants
particles are moving fastest and therefore collide more side of the equation).

Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  9

ii There will be no change in the equilibrium

position as there are equal numbers of moles of
8 Acids and bases
gas on the two sides of the equation. 1 a Base and acid
iii Increasing the pressure will favour the reactants b Base and acid
side of the equation. The equilibrium position c Base and acid
will shift to the left as there are fewer moles of
gas on this side of the equation; the reactants d Base and acid
occupy less volume than the products. e Acid and base
b Decreasing the pressure will favour the products, 2 a H2O is the acid; OH− is the conjugate base; CO 32−
shifting the equilibrium to the right, as this is the base and HCO 3− is the conjugate acid.
represents an expansion (the products will occupy a
greater volume). b H2SO4 is the acid and SO42− is the conjugate base;
H2O is the base and H3O+ is the conjugate acid.
7 a Increasing the temperature always favours the
endothermic process (that absorbs the heat), so 3 a H2SO4(aq) + CuCO3(s) → CuSO4(aq) + H2O(l) +
the equilibrium will shift to the left (favouring                  CO2(g)
the reactants) as the reverse reaction is b 2HBr(aq) + Ca(HCO3)2 (s or aq) → CaBr2(aq) +
endothermic. 2H2O(l) + 2CO2(g)
b The forward reaction is endothermic, so this will c 2H3PO4(aq) + 3Na2CO3 (s or aq) → 2Na3PO4(aq) +
be favoured by increasing the temperature; the 3H2O(l) + 3CO2(g)
equilibrium position will shift to the right.
44 d 2CH3COOH(aq) + Ca(s) → Ca(CH3COO)2(aq) +
8 a Moles of ester = = 0.50 mol CH3COOC2H5                   H2(g)
88
36 e 2(NH4)3PO4(aq) + 3Ba(OH)2 (aq) → 6NH3(g) +
Moles of water = = 2.0 mol
18 3H2O(l) + Ba3(PO4)2(aq)
 1.0 
b Moles of NaOH used in titration =  × 29.5
 1000  4 a Sulfuric acid and silver(i) nitrate
              = 2.95 × 10−3 mol b Magnesium oxide and nitric acid
Mol of acid in 25 cm3 of equilibrium mixture = c Potassium hydroxide and hydrochloric acid
2.95 × 10−3 mol d Barium hydroxide and ethanoic acid
Mol of acid in 250 cm3 of equilibrium mixture 5 pH= −log10(0.1) = 1
= 2.95 × 10−2 mol (or 0.0295 mol)
c 
Ethyl ethanoate Water Ethanoic acid Ethanol

Start / mol 0.50 2.0 – –

At equilibrium / mol 0.4705 1.9705 2.95 × 10−2 2.95 × 10−2
At equilibrium / mol dm -3
0.4705 / V 1.9705 /V −2
2.95 × 10 / V 2.95 × 10−2 / V

6 pH= −log10(3.00 × 10−7) = 6.52

[CH 3 COOH][C 5 H 5 OH]
d Kc = 7 pH = −log10(2 × 0.0100) = 1.70
[CH 3 COOC 5 H 5 ][H 2 O]
Note that the volume, V, will cancel out in the 8 pOH = −log10(2.50 × 10−3) = 2.60; pH + pOH = 14.00;
expression when the values are fed in. Therefore pH = 11.40
(2.95 × 10 −2 )2 9 pOH= −log10(0.0100 × 2) = 1.70; pH = 14.00 − 1.70
Kc = = 9.38 × 10−4 = 12.30
(0.4705)(1.9705)
3.646 g
10 Amount of hydrogen chloride = = 0.1 mol
e The H+ ions added will still be available to titrate 36.46 g mol −1
with the alkali and interfere with the result. 0.1 mol H+(aq) in 250 cm3 solution, hence concentration
f Add a defined volume of acid as a catalyst using a is 0.4 mol dm−3.
microsyringe. 11 Amount of HCl(aq) = 2.5 × 10−3 mol;
g Phenolphthalein would be a suitable indicator. amount of NaOH = 1.5 × 10−3 mol;
amount of excess HCl(aq)/H+(aq) = 1 × 10−3 mol in 40 cm3;
1000 
concentration =  × 1 × 10−3 mol = 0.025 mol dm−3;
 40 
pH = −log10(0.025) = 1.60

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  10

12 [OH−(aq)] = 0.01 mol dm−3; pOH = 2; pH = 12; 6 a H2O2 + 2I− + 2H+ → I2 + 2H2O

H+(aq) = 10−12 mol dm−3
b 6Fe2+ + Cr2 O 72− + 14H+ → 6Fe3+ + 2Cr3+ + 7H2O
13 Individual answers.
c 4Cl2 + S2 O 32− + 5H2O → 8 Cl− + 2SO42− + 10H+
14 a H2SO4(aq) + MgCO3(s) → MgSO4(s) + H2O(l) +
7 Individual answers.
                  CO2(g)
8 a  Lithium and bromine
b H2SO3(aq) + Fe(s) → FeSO3(aq) + H2(g)
b Caesium and nitrogen
c 2HNO3(aq) + CaCO3(s) → Ca(NO3)2(aq) + H2O(l) +
                   CO2(g) c Iron and bromine
d 2HNO2(aq) + Fe(aq) → Fe(NO2)2(aq) + H2(g)
15 Individual answers. 10 Organic chemistry
1 a C8H18
9 Redox processes b C16H34 and C17H36
1 a +5 d +5 c i 198 K and 372 K
b +2 e +5 ii 218 K and 402 K.
c +3 f +4 2 Draw the graph, labelling the axes and plotting the
points accurately. Draw a smooth best-fit curve using
2 a Ammonium dichromate(vi)
the points.
b Potassium chromate(vi)
The curve shows a smooth trend of increasing density
c Vanadium(v) oxide (see Figure 10.8 on page 326).
d Ammonium vanadate(v) 3 Five chain isomers to be found:
e Copper(ii) sulfate(vi)-1-water CH2=CHCH2CH2CH3 CH3CH=CHCH2CH3
CH2=C(CH3)CH2CH3 CH2=CHCH(CH3)CH3
f Copper(i) sulfate
CH3CH=C(CH3)CH3
g Zinc nitrate(v)
4 a i Hex-2-ene
h Scandium(iii) chloride
ii 3-Methylpent-1-ene
3 Two arsenic atoms are oxidized from +3 to +5 per mole
iii 2-Methylpent-1,4-ene.
of As2O3 (loss of 4e− ); therefore if 5 moles is oxidized,
a total of 20 e− are lost/change in oxidation number = b a(i) and a(ii) (hex-2-ene and 3-methylpent-1-ene).
20 and if 4 moles MnO4− is reduced, a total 20 e− are
c Pent-1-yne, CH≡CCH2CH2CH3
gained/change in oxidation number = 20. Therefore
each Mn(vii) gains 5 e−/change in oxidation number is Pent-2-yne, CH3C≡CCH2CH3
5; hence Mn(ii)/Mn2+. 3-Methylbut-1-yne, CH≡CCH(CH3)CH3
4 Fe(s) + 2H (aq) → Fe (aq) + H2(g)
+ 2+
5 a Tertiary
8H+(aq) + MnO4− (aq) + 5Fe2+(aq) → b Secondary
   5Fe3+(aq) + 4H2O(l) + Mn2+(aq)
c Primary
Amount of MnO4− = 0.00068 mol;
Amount of Fe2+ = 0.0034 mol 6 1,1-dibromoethane, CHBr2CH3

Mass of iron = 0.0034 mol × 55.85 g mol−1 = 0.1899 g 1,2-dibromoethane, CH2BrCH2Br

0.1899 A 50:50 mixture of these products is formed.
Percentage purity = = 95%
0.200 7 Mr of ethanol = 46; Mr of octane = 114
5 6H+(aq) + 5H2O2(aq) + 2MnO 4− (aq) → 1371
Enthalpy per g of ethanol = = 29.8 kJ g−1
5O2(g) + 10H+(aq) + 2Mn2+(aq) + 8H2O(l) 46
Amount of H2O2 = 0.001 mol; 5512
Enthalpy per g of octane = = 48.4 kJ g−1
Amount of MnO4− = 0.0004 mol; 114
Volume of H2O2 = 20 cm3;
(48.3 − 29.8) 
volume of O2 = 0.001 mol × 22.7 dm3 mol−1 = 22.7 cm3. % increase for burning octane =  × 100
 29.8 
                = 62%

Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  11

11 Measurement and data 10 Stopwatch (a) has poor resolution (only two digits and Δt
= 1 s), but it is accurate within its limits since its reading
processing matches the true reading rounded off to two digits.
1 a 25 × 10−9 m e 6 × 10−6 m3 Stopwatch (b) is not very accurate since it displays
b 245 s f 4 × 10   kg m  s
6 −1 −2 an inaccurate reading compared to the true value,
and it has poor resolution (only two digits of display
c 8 × 10−6 kg g 14 × 106 s−1 and Δt = 1 s).
d 275 K h 295 × 10−6 m Stopwatch (c) has excellent resolution with 5 digits and
2 a Systematic d Random Δt = 0.001 s, but the reading is very inaccurate.

b Random e Systematic Stopwatch (d) is both accurate (reading close to true

value) and has excellent resolution. Nothing can be
c Systematic f Systematic concluded about precision because we have only one
3 More readings could be obtained by carrying out reading.
more titrations. Then the consistent values can be If we repeat the measurement many times, it is
selected and the average taken. The Dixon’s Q-test, expected that stopwatch (c) or (d) would be the
or simply Q test, establishes whether one (and only most precise as well – they have the most potential
one) measurement from a small set of replicated to be precise – but we cannot tell from the given
measurements (typically 3 to 10) can be statistically information.
rejected or not.
11 a 13.5 cm3 (1 dp)
4 a ± 0.01 g
b 1900 J (2 sf)
b ± 0.001 s
c 1.01 g cm−3 (3 sf)
 5 
c  × 60 = ± 3 mph
 100  d 1.99 kJ mol−1 (2 dp)
d ± 0.05 mm e 268.1 cm (1 dp)
e 0.005 f 1.7 × 102 cm3 (2 sf)
5 a 29.72 ± 0.04 g 4 (1 sf)
b 10.06 ± 0.02 h 0.1712 (4 dp)
c 1.119 ± 0.07 12 25.0

d 2.5 ± 0.7 20.0

SVP/mm Hg

6 a 7.78% 15.0

b 0.23% 10.0

c 1.2% 5.0

d 0.21% 0.0
0 5 10 15 20 25 30
7 a 8.0 m ± 3.0 m
3 3
Temperature/degrees Celsius
1
b 1.4 m 2 ± 0.5 m
c 3.0 ± 0.3 m 13 25.00
Amount of product/

d 3.0 m ± 1.0 m 20.00

nanomol per min

−3
6.75 × 10 cm 15.00
8 = 2.97 × 10−7 moles of helium
2.27 × 1000 cm mol −1 10.00
atoms;
5.00
He2+(g) + 2e− → He(g); number of helium atoms =
1.82 × 1017; 0.00
Avogadro constant = 6.1 × 1023 mol−1 0 50 100 150 200 250

9 Random errors include: measurement errors in the
Substrate concentration
/micromole per litre
measurement of masses. Systematic errors include:
Maximum rate of enzyme activity approximately 25.00
loss of magnesium oxide; incomplete oxidation of
nanomol min−1
magnesium; presence of oxide layer on magnesium; side
reactions involving magnesium reacting with nitrogen
and carbon dioxide in the air and the silica in the
crucible.
Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  12

14 14 h
y = 0.5169x – 0.8228 3 Δx × Δp =
12 R2 = 0.9978 4π
Concentration/picograms

h 6.63 × 10 −34 Js
per cubic centimetre

10 Δp = =
4 π∆x 4 π × 1.00 × 10 −11 m
8
= 5.28 × 10−24 kg m s−1
6
Δp = 5.28 × 10−24 kg m s−1 = mΔv
4
p 5.25 × 10 −24 kgms −1
2
Δv = = = 5.79 × 106 m s−1
m 9.11 × 10 −31 kg
0 1
0 5 10 15 20 25 30 4 Kinetic energy = 2 mv2;
Intensity of emission/ 1
arbitrary units
2
× 9.109383 × 10−31 kg × v2 = 3.00 × 10−25 J

15 Individual answers. 2 × 3.00 × 10 −25 J

v= = 8.12 × 102 m s−1
9.109383 × 10 −31 kg
16 Individual answers.
h 6.63 × 10 −34 kgm 2 s −1
17 a 0 λ= = −31 −1
mv 9.109383 × 10 kg × 8.12 × 10 ms
2

b 1
= 8.96 × 10−7 m
c 0 h 6.63 × 10 −34 kgm 2 s −1
5 λ = =
18 c = ν × λ; 3.00 × 108 m s−1 = ν × 1515 m; ν = 198 020 Hz mv 9.109383 × 10 −31 kg × 1.600 × 10 2 ms −1
19 E = hν; E = 6.63 × 10−34 J s × 4.60 × 109 s−1 = 3.05 × 10−24 J = 4.55 × 10−6 m
E = 3.05 × 10−24 J × 6.02 × 1023 mol−1 = 1.84 J mol−1 6 Individual answers.
5.0 × 10 s 13 −1
c 3.00 × 10 8 ms −1
20 Wavenumber = = 1.67 × 105 m−1 7 c = ν × λ; λ = ν ; λ = = 219 m; radio waves
3.00 × 10 8 m s −1 1368 × 10 3 Hz
1 c 3.00 × 10 8 ms −1
21 Wavelength = = 0.05714 m; 8 c = ν × λ; ν = ν ; = = 5.17 × 1014 s−1
17.50 m 5.800 × 107 Hz
c = ν × λ; 3.00 × 108 m s−1 = ν × 0.05714 m;
hc 6.63 × 10 −34 Js × 3.00 × 10 8 m s −1
ν = 5.25 × 109 s−1 (Hz). 9 E = =
λ 780 × 10 −9 m
22 Symmetrical and asymmetrical stretching of the = 2.55 × 10−19 J
primary amine group:
10 The hydrogen atom has 1 proton, but the helium ion
H H (He+) has 2 protons. The effective nuclear charge
(electrostatic force experienced by the electron) will be
N [1] N [1]
greater in the helium ion (He+), hence it will have the
H H greater ionization energy.
23 There are three sets of hydrogen atoms (protons) in The increase in shielding (electron–electron repulsion)
the ratio 2 : 3 : 3. From the chemical shift values and is less than the increase in nuclear charge.
the molecular formula these peaks could be due to
11 Successive ionization energies of calcium:
CH2–O–C=O, CH3–C=O and CH3–C. The only
structure consistent with this data is ethyl ethanoate, 6.00
Log10 ionization energy

CH3COOC2H5. 5.00
of calcium/kJ mol–1

4.00

12 Atomic structure 3.00

2.00
1 Individual answers.
1.00
2 c = ν × λ; 3.00 × 108 m s−1 = ν × 2.42 × 10−9 m;
0.00
ν = 1.24 × 1015 Hz 0 5 10 15 20
E = hν ; E = 6.63 × 10−34 J s × 1.24 × 1014 s−1 Number of electrons removed
= 8.22 × 10−20 J
The only stable oxidation state relates to the removal
E = 8.22 × 10−20 J × 6.02 × 1023 mol−1 = 49 491.6  J mol−1 of the two 4s electrons. The next eight electrons to
= 49 kJ mol−1 be removed are from the third shell (3p and then 3s).
The increase in ionization energy occurs because the
next eight electrons are removed from the inner second

Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  13

shell (2p and then 2s). Finally in the first shell the 3 In the copper atom [Ar] 3d10 4s1 the number of
1s electrons are removed. The electrons in the first, exchanges is 20 from the two sets of five parallel
second and third shells are referred to as core electrons. electrons in the d shell. The number of exchanges in
There are slight increases within the second and third the alterative configuration [Ar] 3d9 4s2 is 16 from a
shells corresponding to a change in sub-shell. set of five plus a set of four in the d sub-shell; the two s
electrons are antiparallel. The exchange energy is less
Successive ionization energies of vanadium:
and this configuration is not adopted.
7
4 2, 0, 5, 3, 4, 1, 0
Log10 ionization energy
of vanadium/kJ mol–1

6
5 5 Cr2+(g): 2; Cr3+(g): 1; Cr4+(g): 0
4
6 The graph shows a relatively large increase after
3 the fifth ionization energy suggesting that the sixth
2 electron must come from an inner shell. The removal
1 of the first two electrons requires slightly less energy
0 than the next three, which suggests that these are
0 5 10 15 20 25
two 4s electrons. Therefore the element is vanadium
Number of electrons removed
(4s2 3d3).
The electron configuration of vanadium is 1s2 2s2 2p6 7 Amount of KMnO4/ MnO 4 − = 0.02 × 9.8/1000
3s2 3p6 3d3 4s2. The successive ionization energies for = 1.96 × 10−4 mol
vanadium are more gradual as 3d and 4s subshells are
close in energy hence the element can show the +2, Amount of Fe2+ in 10 cm3 = 5 × 1.96 × 10−4 mol
+3 and +4 oxidation states. The simple ion V5+ is not = 9.8 × 10−4 mol
favoured as this would mean removing electrons from
Amount of Fe2+ in 100 cm3 = 9.8 × 10−4 mol × 10
the 3p sub-shell as well.
= 9.8 × 10−3 mol

13 The periodic table – the Mass of iron = 9.8 × 10−3 mol × 55.85 g mol−1 = 0.547 g

transition metals Percentage by mass of iron = 0.547/2.41 × 100 = 22.7%

1 Property 4f 3d
8 a Tetrahydroxozincate ion
Electron Variable Variable b Tetraaquazinc ion
configurations of
ions c Hexacyanoferrate(iii)
Stable oxidation Invariably +3 Variable, but +2 is d Tetraamminedichlorochloride cobalt(iii) ion
states usually stable
e Tetramminediaquacopper(ii) ion
Coordination Commonly Usually 6 but can be
numbers in 8–10 4 for later elements f Hexaaquairon(iii) ion
Complexes
Hydration energy High High to moderate
g Tetrachlorocuprate(ii) ion
Ligand exchange Fast Fast or slow h Dichlorotetramminechromium(iii) ion
reactions depending on
the electron 9 a [Pt(Cl6)]2−
configuration
b Cu(en)2]2−
Electronic spectra Sharp lines Broad bands
of ions c [(NH3)4(H2O)2Cr]SO4
Crystal field effects Weak Strong d [(H2O)4(OH)2Al]Cl
in complexes
Multiply bonded None Quite common, e.g.
e [(CN)2Ag]−
atoms in − f [(NH3)4Ni](ClO4)2
MnO4 and CrO42−
complexes
g [CoCl2(en)2]Cl
2 Vanadium is a d-block metal since it is a member of h [3Na(AlF6)]
a block of elements in which the d sub-shell is being
progressively filled. It is a transition metal because it 10 [(NH3)6Ni]2+ and [CuCl4]2−
forms two stable ions with incomplete d sub-shells. 11 Individual answers.
Cu3+: 1s2 2s2 2p6 3s2 3p6 3d8 4s0 12 Valence bond description of the tetrachlorocuprate(ii)
Co : 1s 2s 2p 3s 3p 3d 4s
3+ 2 2 6 2 6 6 0 ion:
3d 4s 4p 4d
Cr2+: 1s2 2s2 2p6 3s2 3p6 3d2 4s0 [Ar]

Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  14

3−
13 Splitting diagram for [FeF6 ], a high-spin complex, H2O OH2
five unpaired electrons. The hybridization in the Fe3+ H2O OH2
H2O H2O
ion is sp3 d2:
Fe3+ Fe3–
H2O H2O H2O OH2
H2O OH2

purely ionic purely covalent

The purely ionic structure does match with the

3d 4s 4p 4d
observed chemical properties of coordination
3d 4s 4p 4d
complexes. However, there are objections to the
covalent description because the charge distribution
c 3 × 10 8 ms −1 is such that the iron(iii) centre bears a three minus
14 ν = ; ν = = 7.32 × 1014 s −1
λ 410 × 10 −9 m charge and the oxygen atoms of the water ligands each
E = hν, so carry a single positive charge. This would be unrealistic
6.6 × 10 −34 Js × 7.32 × 1014 s −1 in view of the electronegativity values of these elements
E= = 4.83 × 10 −19 J (iron, 1.8; oxygen, 3.4), which predicted that the iron–
λ
oxygen bond would be polarized in the sense Feδ+–Oδ−.
4.83 × 10 −19 × 6.02 × 10 23
E= = 290.8 kJmol −1 The problem was addressed by Pauling via his
1000 electroneutrality principle which suggested that the
actual distribution of charges within a molecule is such
14 C
 hemical bonding and that the charges on any single atom are within the
structure range +1 to −1. Consider the hexaaquairon(iii) ion.
1 Individual answers. An ionic description results in a +3 charge on the
metal centre, whilst a covalent description gives the
2 Individual answers. metal a −3 charge. The electroneutrality principle
suggests that the ideal charge on the metal centre is
3 O N O O N O O N N
zero. That would be achieved if the iron centre gains a
0 +1 0 +1 +1 –1 –1 +1 +1 total of three electrons from the 1+
preferred Lewis structure six oxygen donor atoms; in other 2
1+ OH 1
2 2+
words, if each oxygen loses one 2
4 H2: (σ1s)2, H 2+ : (σ1s)1, H 2− : (σ1s)2 (σ*1s)1 H2O OH 2
half of an electron rather than
the whole electron which the Fe 1
5 He2+ has the configuration (σ1s)2 (σ*1s)1 and hence a 1+
2 2
+

bond order of (1 –  12) = 12. As the bond order is positive, fully covalent model demands. H2O OH2
OH2
this ion can be formed (in the gaseous state at low Pauling described this situation as 1+
2
pressure). 50% covalent (or 50% ionic).
He2 has the configuration (σ1s)2 (σ*1s)1 and hence a
bond order of zero. Hence this molecule is unstable
with respect to its atoms and cannot be prepared. 15 Energetics/thermochemistry
1
6 The electronic configuration of a nitrogen atom is 1 2
O2(g) → O(g); 14 P4(s) → P(g); B(s) → B(g)
1s2 2s2 2px1 2py1 2pz1. Hence a nitrogen atom has three 2 Enthalpy change = 6.04 × 2.38/28 .01 = 0.513 kJ = 513 J
singly occupied orbitals. One 2pz–2pz sigma bond
is formed. The other two pi bonds are 2px –2px and 3 Q = mcΔT; Q = 100 g × 4.18 J g−1 K−1 × 0.91°C = 380.38 J
2py –2py. Thus the nitrogen molecule has three bonds: = 400 J
one sigma and two pi bonds that are perpendicular to Amount of Ag+ = 0.005 mol; amount of Cl− = 0.005 mol
each other and perpendicular to the z-axis, that is, the
axis of the sigma bond. Hence, a triple bond is formed. Enthalpy change = −400 J/0.005 mol = −80000 J mol−1
= −80 kJ mol−1
π bond
x x 4 Percentage error = (80 − 70)/70 × 100 = 14%; provide a
y y lid for the cup; provide thermal insulation around the
beaker.
z z
5 N2−(g) + e− → N3−(g); the repulsion between the
incoming electron and the electrons in the anion is
σ bond greater than the attraction between the incoming
formation of a nitrogen molecule
electron and the protons in the nucleus.

Al2O3(s) → 2Al3+(g) + 3O2−(g); work has to be done to
7 The limiting ionic and dative covalent descriptions of overcome the electrostatic forces of attraction between
the hexaaquairon(III) ion are shown below. the highly charged ions.
Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  15

6 −416 = 216 + 249 + 992 + (−141) + 753 + x; x = −2485; lattice enthalpy of sodium oxide = +2485 kJ mol−1

2Na+(g) + O2–(g)

2Na+(g) + O(g) ΔH 2nd EA

= +753 kJ mol–1
ΔH 1st EA(O) = –141 kJ mol–1
2Na+(g) + O–(g)

2 × ΔH 1st IE (Na) = (2 × 496) = 992 kJ mol–1

2Na(g) + O(g) reverse
LE
ΔH at(O2) = +249 kJ mol–1 Na2O(s)
2Na(g) + 1 O2(g)
2

1 O (g) 2 × ΔH at(Na) = (2 × 108) = 216 kJ mol–1

2Na(s) + 2 2
start
ΔH f (Na2O) = –416 kJ mol–1
Na2O(s)
end
−635 = 178 + 1150 + 590 + 249 + (−141) + 753 + x; x = −3414; lattice enthalpy of calcium oxide = + 3414 kJ mol−1
Ca2+(g) + O2–(g)

∆H 2nd EA(O)
Ca2+(g) + O(g)
= +753 kJ mol–1
1 bond enthalpy of O2 ∆H 1st EA(O)
2
= 1
× 498 kJ mol–1 = –141 kJ mol–1
2
Ca2+(g) + O–(g)
Ca2+(g) + 1 O (g)
2 2

∆H 1st IE = 590 kJ mol–1

reverse
∆H 2nd IE = 1150 kJ mol–1 LE
CaO(s)
1
Ca(g) + 2 O2(g)

∆H at(Ca) = +178 kJ mol–1

1
Ca(s) + 2 O2(g)
start
∆H f (CaO) = –635 kJ mol–1
CaO(s)
end

7 −431 = 861 + 121 + 403 + x + −9695; x = −1121; first electron affinity of chlorine = −1121 kJ mol−1
Rb+(g) + Cl(g)
ΔH EA(Cl) = x kJ mol–1
Rb+(g) + Cl–(g)
ΔH 1st IE(Rb) = 403 kJ mol–1

Rb(g) + Cl(g)
1
2 bond enthalpy of
Cl2 = ( 12 × 242) kJ mol–1
reverse LE RbCl(s)
Rb(g) + 12 Cl2(g)
= –695 kJ mol–1

ΔH at(Rb) = +86 kJ mol–1

Rb(s) + 12 Cl2(g)
start
ΔH f (RbCl) = –431 kJ mol–1
RbCl(s) RbCl(s)
end

Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  16

8 4 The methanol should be present in a large excess so

NH4+ (g) + Cl–(g) that this concentration remains effectively unchanged
(effectively constant).
hydration enthalpy of NH4 +
5 a 5 minutes = 300 seconds
NH4 + (aq) + Cl–(g) 0.27
lattice Average rate of reaction =
300
enthalpy hydration enthalpy of Cl–
  = 9.00 × 10−4 mol dm−3 s−1
NH4+ (aq) + Cl–(aq) b Plot the graph, labelling the axes and plotting the
NH4Cl(s) + (aq) enthalpy of solution points accurately. Draw a smooth curve of best fit
using the points.

9 ΔH1sol = (−650 + 340 + 287) = −23 kJ mol−1 Draw a tangent to the curve at time zero

and calculate the slope using slope = ∆y/∆x
start ∆H sol end (see Figure 6.26 on page 212).
KI(s) + (aq) KI(aq)
c Draw tangents and find their slopes for the other
(K+)
∆H hyd
specified concentrations.
–650 kJ mol–1
∆H hyd(I–) d The concentrations of cyclopropane are 1.50,
(–340) + (–287) 1.20, 0.90, and 0.60 mol dm−3, respectively
K+(g) + I–(g) + (aq)
e Plot the graph accurately and draw a line of best fit
10 a Little change f Decrease through the points. The graph is a straight line of
b Decrease g Decrease slope k. Find the slope of your graph.
c Decrease h Little change 6 a Connect the reaction flask to a gas syringe and
follow the increase in volume of nitrogen released
d Increase i Decrease with time.
e Increase j Increase b Plot the graph accurately and draw a line of best
11 ΔS = [2 × 87.4 J K  mol ] − [(4 × 27.3 J K−1 mol−1) +
1 −1 −1 fit through the points. See Figure 16.7 on page 561
(3 × 205.0 J K−1 mol−1)] = −549.4 J K−1 mol−1 for the method of finding successive half-lives. The
reaction is first order if the half-lives are constant.
12 ΔG1 = (−569 kJ mol−1 + −394 kJ mol−1) −
(−1012 kJ mol−1) = +49 kJ mol−1 c The reaction is first order with respect to
[benzenediazonium chloride] as successive
13 ΔG1 = ΔH1 − TΔS1; ΔG1 = +49100 J mol−1 − (298 K ×
half-lives are equal.
198 J K−1 mol−1) = 431996 J mol−1 = + 432 kJ mol−1 (hence
not spontaneous) 7 a  NO + NO → N2O2
0 = ΔH1 − TΔS1; 0 = +49100 J mol−1 − N2O2 + O2 → 2NO2
(T × 198 J K−1 mol−1); T = 2479 K = 2206°C Sum of the two equations gives 2NO + O2 → 2NO2
457.9
14 ΔG = ΔH − TΔS ; 0 = 457.9 − T × 0.56; T =
1 1 1
b Draw diagram similar to Figure 16.18 on page 572
0.56
= 818 K (since ΔH1 is positive (endothermic) the but the first peak is lower than the second as the
reaction proceeds in the forward direction above this activation energy for the second step is greater than
temperature. that of the first step.
8 Carry out the exercise to visualize the steps in the
16 Chemical kinetics mechanism for this reaction.

1 Overall order = 2; units of k are mol−1 dm3 s−1 9 Sketch a diagram similar to that for the catalysed
reaction in Figure 16.20 on page 573. The activation
2 Rate = k[propene] [bromine] energy for the combined later fast steps is lower than
= 30(0.040)2 = 30(1.6 × 10−3) = 0.048 mol−1 dm3 s−1 that of the slow, rate-determining, first step.
3 Rate = k[HI]2 10 a 2XY2 → X2 + 2Y2
25 × 10 = k (2.00)
−5 2
b Rate = k [XY2]2
25 × 10 −5
k= = 6.25 × 10−5 mol−1 dm3 s−1 c Units of k are mol−1 dm3 s−1.
4.00
25 × 10−5 mol  = (25 × 10−5) × (6.02 × 1023) d Draw diagram similar to Figure 16.18 on page 572.
 = 1.505 × 1020 molecules
1.505 × 1020 molecules of HI decompose per second

Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  17

17 Equilibrium b Kc = 0.166; in this case, for a reaction where there

are the same number of moles of gas on both sides
1 2SO2 + O2  ⇋ 2SO3 of the equation, Kp = Kc.
Initial/mol: 2 1.4 0 c The equilibrium constant value is less than 1.00
Equilibrium/mol: 1.7 1.25 0.3 and so the equilibrium is well to the reactants side
of the equation.
Equilibrium/mol dm : 1.7/3 1.25/3 0.3/3
−3

[SO 3 ]2 (0.1)2 5 a Zero

Kc = = 2
[SO 2 ] [O 2 ] (0.566) (0.416)
2
b ΔG1 = −RT lnKc
0.01 ΔG1 = −(8.31 × 298) ln (1.7 × 1012)
= = 0.075
0.311 × 0.416
= −2476 × (−28.16) = + 69728.2 J mol−1
2 SO3 + NO 
⇋ NO2 + SO2 ΔG1 = +69.73 kJ mol−1
Initial/mol dm−3: 0.030 0.030 0 0
Equilibrium/mol dm : (0.030 − x) (0.030 − x) x
−3
x 18 Acids and bases
[NO 2 ][SO 2 ] x2 1 a CH2 CH2
Kc = 6.78 = =
[SO 3 ][NO] (0.030 – x)2 Lewis base
x H3C O CH3
Taking square roots of both sides: 6.78 =
(0.030 – x)
2.60 (0.030 − x) = x
F B F Lewis acid
0.078 − 2.60x = x
Therefore 3.60x = 0.078 F

x = 0.022
b Cl
[SO3] = [NO] = 8 × 10−3 mol dm−3 and [NO2] = [SO2] = Cl
0.022 mol dm−3 Al
Cl
Cl Al Cl
3 H2(g) + CO2(g) ⇋ H2O(g) + CO(g) Lewis base Cl Cl
Initial/mol: 2.00 2.00 1.00 1.00 Lewis acid Cl
Equilibrium/
mol: (2.00 − x) (2.00 − x) (1.00 + x) (1.00 + x)
Equilibrium/ c
(2.00 − x) (2.00 − x) (1.00 − x) (1.00 − x)
mol dm−3:
10 10 10 10 H3N Ag NH3 H3N Ag NH3
Lewis Lewis
[H 2 O][CO] base acid
Kc = 2.10 =
[H 2 ][CO 2 ]
Note that the volumes will cancel out d H CH3
(1.00 + x)2
Therefore: 2.10 = H3C O Lewis CH3
(2.00 − x)2 acid
(1.00 + x) O Li O Lewis base
Taking square roots of both sides: 2.10 =
(2.00 − x)
1.45 (2.00 − x) = (1.00 + x) H3C H
O
1.90 = 2.45x
CH3 H
x = 0.78
1.78
[H2O] = [CO] = = 0.178 mol dm−3
10 e H
1.22
[H2] = [CO2] = = 0.122 mol dm−3 O OH
10 OH
4 a ΔG1 = −RT ln Kp for a gas phase reaction B H HO B OH
1.38 × 1000 = −(8.31 × 298 × ln Kp); note the O O
conversion of kJ to J OH
(8.31 × 298)  2476  H
ln Kp = − = −   = −1.79
1380 1380  Lewis acid

Kp = e−1.79 = 0.166

Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  18

f Lewis base
Cl Cl Cl Cl Cl Cl
Lewis AI Lewis
AI acid AI AI
acid
Cl Cl Cl Cl Cl Cl
Lewis base

2 a III [H + (aq)] × [CH 3 COO − (aq)]

15 Ka =
b IV [CH 3 COOH(aq)]
c V but since [H+(aq)] = [CH3COO−(aq)];
d I [H + (aq)]2
Ka =
e II [CH 3 COOH(aq)]
3 The Lux–Flood theory is used in geochemistry and then rearranging, [H+(aq)] = [CH 3 COOH(aq)] × K a
the electrochemistry of molten salts. This definition
describes an acid as an oxide ion acceptor and a base an [H+(aq)] = 1.8 × 10 −5 × 0.1 = 1.34 × 10−3 mol dm−3
oxide ion donor, for example,
and then pH = −log10[H+(aq)]
CaO (base) + SiO2 (acid) → CaSiO3
= −log10(1.34 × 10−3  mol dm−3) = 2.87
4 Kw = [H+(aq)] × [OH−(aq)];
+
1.00 × 10−14 = 5.4 × 10−4 × [OH−(aq)]; 16 NH3(aq) + H2O(l) ⇋ NH 4 (aq) + OH− (aq)
[OH−(aq)] = 2 × 10−4 mol dm−3
([OH − × NH +4 ])
5 H (aq) = 9.55 × 10
+
−14
= 3.09 × 10  mol dm ; pH = 6.5
−7 −3 Kb =
[NH 3 (aq)]
6 a  pH = −log10(0.01) = 2 [OH − ]2 [OH − ]2
Kb = ; 1.8 × 10−5 = ;
b pOH = −log10(0.01) = 2; pH = 12 [NH 3 (aq)] [0.50]
c pOH = −log10(0.02) = 1.7; pH = 12.3 1.8 × 10 −5
[OH−(aq)] = = 6 × 10−3 mol dm−3;
d pH = −log10(0.02) = 1.7 0.50
7 H+(aq) = 10−pH; H+(aq) = 10−2.80 = 1.58 × 10−3 mol dm−3 pOH = 2.22; pH = 11.8
1.26 g 17 [H+(aq)] = 10−pH; [H+(aq)]=10−6.80 = 1.58 × 10−7 mol dm−3;
8 Amount of HNO3 = −1 = 0.02 mol in
100 cm3 of solution. 68.02 g mol Kw = 1.58 × 10−7 mol dm−3 × 1.58 × 10−7 mol dm−3
= 2.51 × 10−14 mol2 dm−6; [OH−(aq)]
Concentration of HNO3 = 0.2 mol dm−3; = 1.58 × 10−7 mol dm−3
pH = −log10(0.2) = 0.69
18 [H+(aq)] = 10−3.20 = 6.3 × 10−4 mol dm−3;
1000 Kw = 1.00 × 10−14;
9 Dilution factor is = ×100; this will be an increase
10 1.00 × 10−14 = 6.3 × 10−4 × [OH−(aq)];
in pH of 2; since a change of one pH unit corresponds
[OH−(aq)] = 1.58 × 10−11
to a change in H+ of 10.
19 [OH−(aq)] = 10−1.0 = 0.10 mol dm−3;
10 pOH = −log10(0.100) = 1
molar mass of NaOH = (22.99 + 16.00 + 2.02)
11 [OH−(aq)] = 10−pOH; [OH−(aq)] = 10−2; = 41.01 g mol−1;
[OH−(aq)] = 0.01 mol dm−3 44.01g
mass of NaOH required = = 8.202 g
12 pH + pOH = 14; pH + 1 = 14; pH = (14 − 1) = 13 5

13 pH + pOH = 14; 2 + pOH = 14; pOH = (14 − 2) = 12 20 [H+(aq)] = 0.05 mol dm−3 × 2 = 0.10 mol dm−3;

[OH−(aq)] = 1.00 × 10−7 mol dm−3
14 pH = −log10[H+(aq)]
21 [OH−(aq)] = 2 × 0.25 mol dm−3 = 0.50 mol dm−3;
[H+(aq)] = −antilog(3.10) or 10−3.10 = 7.94 × 10−4 mol dm−3 pOH = 0.30; pH = 14.00 − 0.30 = 13.70
[H + (aq)] × C 6 H 5 COO − (aq)]
Ka = 22 pKa = −log10Ka; Ka = 1.74 × 10−5;
[C 6 H 5 COOH(aq)]
but since [H+(aq)] = [C6H5COO−(aq)] H+(aq) = ([CH 3 COOH(aq) × K a ) ;

[H + (aq)]2 H+(aq) = 0.125 × 1.74 × 10 −5 = 1.47 × 10−3 mol dm−3;

Ka =
[C 6 H 3 COOH(aq)] pH = 2.83
−4 2
(7.94 × 10 )
Ka = = 6.3 × 10−6 mol dm−3
0.1
Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  19

23 Kb = antilog 9.13 = 7.41 × 10−10; Hydrogen ions have greater electrode potential and
OH = 0.50 × 7.41 × 10
− −10
= 1.925 × 10 ;
−5 hence are a stronger oxidizing agent than lithium
ions. Hydrogen gas is discharged at the cathode.
pOH = 4.71; pH = 9.28
2H+(aq) + 2e− → H2(g)
24 [H+(aq)] = 10−pH = 10−5.74 = 1.82 × 10−6;
An oxidation process takes place on the anode
1.82 × 10−6 = 0.025 × K a; Ka = 1.325 × 10−10 surface and hence for competing oxidation
processes, the one with the lower reduction
25 Ka × Kb = Kw; 1.8 × 10−4 × Kb = 1.00 × 10−14; potential will occur.
Kb = 5.56 × 10−11 Hydroxide ions (from the ionization of water) have
19.23g a lower electrode potential and hence a stronger
26 Amount of Sr(OH)2 = = 0.158 mol
121.64 mol −1 reducing agent than iodide ions. However, iodide
[Sr2+(aq)] = 0.158 mol dm−3; [OH−(aq)] = 0.316 mol dm−3 ions are present in high concentration and will be
discharged at the anode. Carbon (graphite) is an
pOH = −log10[OH−(aq)] = 0.5; pH = 13.5 inert electrode. (In practice there will be a mixture
27 Amount of H+(aq) = 2.5 × 10−3; of iodine and oxygen).
amount of OH−(aq) = 1.5 × 10−3; 2I−(aq) → I2(aq) + 2e−
amount of excess H+(aq) after neutralization =
1 × 10−3 mol in 40 cm3 of solution b Hydrogen ions have a greater electrode potential and
hence are a stronger oxidizing agent than barium ions.
[H+(aq)] = 25 × 1 × 10−3 mol = 0.025 mol dm−3; pH = 1.6 (Barium is more reactive than calcium and should
therefore have a more negative standard electrode
potential). Hydrogen gas is discharged at the cathode.
19 Redox processes Hydroxide ions are the only anion present and hence
1 Zinc atoms > lead(ii) ions > sulfate ions > iodide ions discharged as oxygen molecules at the anode. Carbon
(graphite) and platinum are inert electrodes.
2 Co2+ + 2e− → Co x V
2H+(aq) + 2e− → H2(g);
Cu2+ + 2e− → Cu +0.34 V
4OH−(aq) → O2(g) + 4e− + 2H2O(l)
E1cell = (+0.34) − x = +0.62
c The copper electrode is an active electrode:
x = (+0.34) − (+0.62) = −0.28 V copper dissolves at the anode and it deposits at the
3 a Fe(s) + Ni2+(aq) → Fe2+(aq) + Ni(s); cathode. At the cathode copper(ii) ions undergo
E1 cell = (0.45 V) + (−0.26 V) = +0.19 V reduction. At the anode copper atoms dissolve to
release copper(ii) ions.
b 2MnO4−(aq) + 16H+(aq) + 10I−(aq) → 5I2(s) +
2Mn2+(aq) + 8H2O(l); Cu2+(aq) + 2e− → Cu(s); Cu(s) → Cu2+(aq) + 2e−
E1cell = (−0.54 V) + (1.51 V) = +0.97 V Carbon (graphite) is an inert electrode. Copper(ii)
c 2Cr3+(aq) + 7H2O(l) + 3F2(g) → 6F−(g) + Cr2O72− ions have a more positive electrode potential and
(aq) + 14H+(aq); hence are a stronger oxidizing agent than hydrogen
E1 cell = (2.87 V) + (−1.36 V) = +1.51 V ions. (Nitrate ions are stable and not discharged.
They resist oxidation at the anode because the
d 2Ag+(aq) + Cu(s) → Cu2+(aq) + 2Ag(s); nitrogen is in +5 oxidation state). Hydroxide ions
E1cell = (0.80 V) + (−0.34 V) = +0.46 V from the dissociation of water are discharged as
4 Ecell = (0.059/1) × (log10 0.100/0.001) = 0.118 V oxygen. Copper atoms have a less positive electrode
potential and hence are a stronger reducing agent
5 E1cell = (−0.80 V) + (1.23 V) = +0.43 V; than hydroxide ions.
ΔG1 = −nFE1 = −4 × 96500 C mol−1 × 0.43 V
= −165980 J mol−1 = −166 kJ mol−1 Cu2+(aq) + 2e− → Cu(s);
4OH−(aq) → O2(g) + 4e− + 2H2O(l)
6 The E1 value for this related reaction will not change
and standard electrode potential is an intensive property d At the cathode hydrogen ions undergo reduction.
independent of amount (see page 655). The standard Hydrogen ions have a more positive electrode
electrode potentials of the two half equations are not potential and hence are a stronger oxidizing agent
halved even though the stoichiometry in this reaction is than sodium ions. Hydrogen gas is discharged.
halved. The ∆G1 value will be halved as the amount of 2H+(aq) + 2e− → H2(g)
electrons transferred in the reaction is halved.
Hydroxide ions have a more negative electrode
7 a A reduction process takes place on the cathode potential and hence a stronger reducing agent than
surface and hence for competing reduction chloride ions. However, chloride ions are present in
processes, the one with the higher reduction high concentration and will be discharged at the
potential will occur. anode. Carbon (graphite) is an inert electrode.

Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  20

2Cl−(aq) → Cl2(aq) + 2e− f Aprotic polar

With a dilute solution of chloride ions, hydroxide g Non-polar
ions will be discharged as oxygen gas. (In practice
h Aprotic polar
a mixture of chlorine and oxygen will be formed).
2 a The mechanism is a nucleophilic substitution
4OH−(aq) → O2(g) + 4e− + 2H2O(l)
(SN2). OH− is the nucleophile that attacks at the
5.4 g electron-deficient carbon atom (δ+) to which the
8 Amount of aluminium atoms = bromine atom is attached. The molecule inverts its
26.98 g mol −1
tetrahedral structure as a result of the attack. See
= 0.20 mol;
Figure 20.3 on page 673 for detail of the movement
amount of electrons = 0.60 mol;
of electrons in this mechanism, and Figure 20.5 on
charge transferred = 5.00 A × 11580 s = 57900 C; page 674 for an illustration of the inversion which
57900C takes place.
amount of electrons = = 0.60 mol,
96500 C mol −1 b Rate = k [C2H5Br] [OH−]
hence Al3+.
The reaction takes place in a single concerted
9 Charge (C) = 2.00 A × (15 × 60) s = 1800 C; step involving both of the reacting species in
1800C this rate-determining step. The reaction is
amount of electrons = = 0.0187 mol;
96500 C mol −1 therefore bimolecular. SN2 stands for substitution,
Cu2+(aq) + 2e− → Cu(s); nucleophilic, bimolecular.
amount of copper atoms = 9.326 × 10−3 mol; c Polar aprotic solvents will not interact with the
mass of copper = 9.326 × 10−3 mol × 63.55 g mol−1 = attacking nucleophile forming a ‘solvent shell’. The
0.593 g nucleophile remains ‘naked’. A nucleophile with a
10 Charge (C) = 4.00 A × 370 s = 1480 C; solvent shell is going to be slower in attacking the
1480 C target molecule. By using an aprotic solvent and
amount of electrons = = 0.0153 mol; allowing the nucleophile to react all of the time, we
96500 C mol −1
are greatly speeding up the reaction. SN2 reactions
2H+(aq) + 2e− → H2(g); amount of H2 = 7.67 × 10−3 mol; performed with nucleophiles in polar aprotic
volume of H2 = 7.67 × 10−3 mol × 2.27 m3 mol−1 solvents occur about 1000 times faster than those in
regular protic solvents.
= 1.74 × 10−2 m3 = 174 cm3
d DMF is a better solvent for this reaction as it is
11 3.00 A passed for 30 minutes (1800 s)
a polar aprotic solvent whereas water is a polar
Charge = 3.00 A × 1800 s = 5400 C protic solvent which will shield the nucleophile
5.60 g by forming a solvent shell. Water has hydrogen
Amount of lead produced = = 0.027 mol
207.2 g mol −1 atoms that are attached to a highly electronegative
Pb2+(aq) + 2e− → Pb(s) element, oxygen.
Therefore, moles of electrons passed = 0.027 mol × 2 3 a Chlorine is more electronegative than bromine and
= 0.054 mol so the Cl atom will be δ− and the Br atom δ+.

0.054 mol electrons = 5400 C b 1-Bromo-2-chloropropane, CH3CHClCH2Br

1 mol electrons = 100 000 C 2-Bromo-1-chloropropane, CH3CHBrCH2Cl

Charge on one electron = −1.602 × 10−19 C c 1-Bromo-2-chloropropane is the more likely product
as the bromine is added first on the terminal carbon
100000
Number of electrons in 1 mol = atom. This produces a secondary carbocation
1.602 × 10 −19 intermediate that is more stable than the possible
= 6.24 × 1023; primary carbocation. This means that the chlorine
is likely to be added to the second carbon atom in
Avogadro constant = 6.24 × 1023
the chain.
4 Pent-1-ene: the major product will be 2-bromopentane
20 Organic chemistry as this involves the formation of the more stable
1 a Non-polar secondary carbocation intermediate, as predicted
by Markovnikov’s rule. The other product is
b Polar protic 1-bromopentane.
c Aprotic polar Pent-2-ene: a 50 : 50 mixture of 2-bromopentane and
d Protic polar 3-bromopentane is formed, as both would involve
the formation of a secondary carbocation as an
e Aprotic polar intermediate.

Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015
  21

5 M1: free radical substitution E-1-Bromo-2-methylbut-1-ene drawn with the –Br and
the –CH2CH3 groups on carbons 1 and 2 on opposite
M2: electrophilic addition
sides of the double bond.
M3: nucleophilic substitution
12 CH3CH=C(CH3)CH2CH3
M4: electrophilic substitution
Z-3-Methylpent-2-ene drawn with the methyl group on
6 a Reduction with LiAlH4 in diethyl ether; reflux; add carbon 2 and the ethyl group on carbon 3 on the same
dilute acid to complete reaction. side of the double bond (trans-3-methylpent-2-ene).
b Not a possible route. E-3-Methylpent-2-ene drawn with the methyl group on
carbon 2 and the ethyl group on carbon 3 on opposite
c Reaction with bromine vapour (or in an organic
sides of the double bond (cis-3-methylpent-2-ene).
solvent) in sunlight (UV light).
d Reaction with chlorine or bromine in an organic
solvent (in dark). Chapter 21 Measurement and
e Heat with concentrated sulfuric acid and then add analysis
water.
1 C4H8O2
f Reaction under reflux (50°C) with a nitrating
mixture of concentrated nitric acid and
A B C
concentrated sulfuric acid.
g Reflux with tin and concentrated hydrochloric acid.
h Warm with sodium dichromate(vi)/concentrated 5 4 3 2 1 ppm
sulfuric acid in distillation apparatus. O
7 But-1-ene → react with HBr → 2-bromobutane →
react with NaOH solution → butan-2-ol → oxidation CH3 C O CH2 CH3
with Na2Cr2O7 / concentrated H2SO4 → butanone (B) (A) (C )

OR 2 The high C : H ratio in the molecular formula

But-1-ene → react with conc. H2SO4/add water butan- suggests the presence of a benzene ring and this
2-ol → oxidation with Na2Cr2O7 / concentrated H2SO4 is confirmed by the peak at δ = 7.6. The broad
→ butanone peak at 10.8 is typical of the –O–H of a carboxylic
acid (which reacts with sodium). The two proton
The second method may give the greater yield as it single peak at δ = 3.7 is a –CH2– group flanked
involves fewer stages by a benzene ring and a –COOH group, both of
8 1-Chlorobutane → react with NaOH solution → which cause a high field resonance. The structure is
butan-1-ol → oxidation with Na2Cr2O7 / concentrated therefore C6H5–CH2–COOH.
H2SO4 under reflux → butanoic acid 3 There are three times as many combinations giving a
CH3CH2CH2CH2Cl + OH → CH3CH2CH2CH2OH
− net magnetic moment of +1 or −1 compared with +3
or −3.
CH3CH2CH2CH2OH + 2[O] → CH3CH2CH2COOH +
H2O

9 Just b and c can show cis-trans isomerism.

For b see the example of 1,3-dichlorocyclobutane in
Figure 20.52 on page 701; in this case the two methyl net moment +3 +1 –1 –3
groups can be on the same side of the plane, or one +1 –1
+1 –1
above and one below.
For c see Figure 20.51 on page 701 as a guide; note that 4 Functional magnetic resonance imaging can detect
in this case there are complex examples involving the changes in blood oxygenation caused by increased
substituents on all three carbon atoms. metabolism of activated parts of the brain. It has
10 Cis-but-2-ene-1,4-dioic acid and trans-but-2-ene-1,4-dioic become a powerful tool for cognitive neuroscience
acid. research and brain activity mapping to preserve
critical functions in patients requiring neurosurgery.
See Figure 20.53 for the structures of these two isomers. Oxyhemoglobin is paramagnetic (due to the presence
11 CHBr=C(CH3)CH2CH3 of unpaired electrons in the iron(iii) ion, Fe3+) and gives
Z-1-Bromo-2-methylbut-1-ene drawn with the –Br and an enhanced relaxation, and hence a signal, close to
the –CH2CH3 groups on carbons 1 and 2 on the same the blood supply.
side of the double bond.

Chemistry for the IB Diploma Second Edition © Christopher Talbot, Richard Harwood and Christopher Coates 2015