June 2023

Some of the material in this booklet might be familiar to you,

but other parts may be completely new. The questions are
designed to be more challenging than those on typical A-level
papers, but you should still be able to attempt them. Use your
scientific skills to work through the problems logically.
If you do become stuck on one part of a question, other parts
might still be accessible, so do not give up. Good luck!

• The time allowed is 90 minutes under exam conditions.

• Attempt all the questions.
• Write your answers in the answer booklet provided, giving only the
essential steps in any calculations.
• Specify your answers to the appropriate number of significant
figures and give the correct units.
• Please do not write in the right-hand margin.
• A periodic table and necessary constants are included on the next
page.

Page 1
 1 2 18
s-block He
Period H He Group Number 2
1 1 2 13 14 15 16 17 4.003
1.008 4.003 p-block
Symbol
Li Be atomic number B C N O F Ne
2 3 4 mean atomic mass 5 6 7 8 9 10
6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18
Na Mg Al Si P S Cl Ar
3 11 12 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
22.99 24.31 d-block 26.98 28.09 30.97 32.06 35.45 39.95
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
4 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.63 74.92 78.97 79.90 83.80

5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.95 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29
Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
6 55 56 * 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.34 174.97 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98
Fr Ra + Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
7
87 88 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118

f-block
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
Lanthanoids: * 57 58 59 60 61 62 63 64 65 66 67 68 69 70
138.91 140.12 140.91 144.24 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05
+ Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No
Actinoids: 89 90 91 92 93 94 95 96 97 98 99 100 101 102
232.04 231.04 238.03

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The Avogadro constant NA = 6.022 ×1023 mol–1
1. This question is about electron counting and curly arrows

It could be said that chemistry is all about electrons

since bonding interactions are formed as electrons
are transferred or shared between atoms. During
chemical reactions, electrons are redistributed
between different atoms as bonds are made and
broken. At all stages, all electrons must be
accounted for – electrons are never created or
destroyed in chemical reactions.

If an isolated atom has the same total number of

electrons as its atomic number, it is a neutral atom;
otherwise, it is a charged ion. Only electrons in the
outermost shell, the so-called valence shell, are
used in bonding. The number of electrons in the
valence shell for a neutral atom, Nneutral, is equal to
the Group Number for elements in Groups 1 to 12
Chemists love curly arrows. Yum, yum!
of the periodic table, and (Group Number minus
10) for elements in Groups 13 to 18.

(a) (i) How many valence electrons do each of the following atoms have?
Cl Sr Nb Xe
(ii) How many valence electrons do each of the following ions have?
S2– O+ N+ Tl+ B3+ Na–
In molecules, individual atoms may often be shown with charges, such as on the oxygen in H3O+:

O
H
H
H

Such charges are known as formal charges. They are a result of how we allocate the electrons
within the species. If it is assumed that each bond represents a pair of electrons shared equally
between two atoms, the oxygen atom in H3O+ has three electrons used in bonds to the hydrogen
atoms, and so together with a lone pair, the oxygen formally has five electrons around it. (To clarify,
a shared pair of electrons counts as one electron to each atom, whereas for a lone pair, both
electrons are with the atom concerned.) Since an oxygen atom needs six electrons in its valence
shell to be neutral, if it formally has five, it must have a charge of +1.
The problem with this model is the assumption that the electrons are shared equally between two
atoms – they are not. Since oxygen is more electronegative than hydrogen, the electrons in each
O–H bond are more associated with the oxygen rather than the hydrogens. In fact, calculations
suggest the oxygen atom in H3O+ actually has a slight negative charge.

(b) Which of the following BEST describes the charge on EACH hydrogen atom in H3O+?

i) just less than +1 ii) +1 exactly

iii) at least +1 iv) just less than + 1/3
v) +1/3 exactly vi) at least +1/3

Page 3
We can calculate the formal charge for any atom by comparing
how many electrons an atom X actually has in its valence shell,
NX, and subtracting it from the number the neutral atom X needs
in its valence shell, Nneutral:
FORMAL
CHARGES

Formal charge = Nneutral – NX

where we calculate NX by summing up one electron for each

bond to X (two for each double bond, and three for each triple
bond), and two for every lone pair on atom X.

(c) Add the formal charges to the non-neutral atoms in the following structures. (All lone pairs
have been shown.)
(i) (ii) (iii) (iv) O
S CH3 O N
O N S
O O N CH3
CH3
O
dimethyl sulfoxide ozone methyl azide sulfolane
(a common solvent) (explosive solid) (an organic solvent)

In practice, formal charges would usually be shown on structures and this might be used to
calculate how many lone pairs atoms would have if drawn in that way.
(d) Add all the lone pairs to every atom in each of the following structures. (Note the shapes
given are not necessarily representative of their real shapes.)
(i) O (ii) (iii) O (iv) O
Cl
S N P
O OH
HO OH O CH3 (H3C)2N N(CH3)2
N(CH3)2
sulfuric(IV) acid chloric(III) acid nitromethane HMPA

There are often different ways of drawing structures depending on how we consider the electrons to
be allocated. There are pros and cons with the different ways, for example, some structures may
suggest unrealistic charges (like in H3O+), others structures may break the ‘8-electron rule’. Curly
arrows may be used to formally show ‘movement’ of electrons, or how it is possible to interconvert
structures. The arrow starts where the electrons are (e.g. on a lone pair, or in a bond), and the
head shows where the electron pair ends up – usually on an atom as a lone pair, or between two
atoms as a new bond. An example for sulfur(IV) oxide is shown below.
(2x)+
S S S S
O O O O O O O O
x– x–

A B C D

The curly arrows show how to reallocate electrons to convert a structure to the one to the right of it.
The special double-headed straight arrow is used to indicate that the structures are the same but
just with their electrons distributed in a different way. Structures A and C must make an equal
contribution to how the real molecule is since they are the same but reflected. This suggests each
S-O bond is perhaps between a single and a double bond, and the charge on each oxygen is
actually the same (as suggested in D). Structure B shows a different way of assigning the
electrons, but suggests there are more than 8 electrons around the sulfur (10). This is acceptable
for elements from Period 3 in the Periodic Table and below, but not for elements from Period 2.

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Curly arrows are particularly useful for understanding the redistribution of electrons during chemical
reactions. For example, consider the reaction between hydroxide ion and ethanoic acid:
O O
O + O
H H H H
O O

(Note that lone pairs are only shown as necessary – not all are shown.)
It turns out that the two C–O bonds in the ethanoate ion are equal in both length and strength. We
can show this by formally redistributing the electrons from structure E to structure F. In reality, the
ion is more like G with equal charges on the oxygens (but not exactly one half each since the
oxygens still pull more electron density from the carbons and even the hydrogen atoms in the ion).
O O –
O½

O O ½–
O
E F G
(e) In your answer booklet, draw the curly arrows and any necessary lone pairs to convert
structure E to structure F.
Hydroxide ion can also deprotonate propanone, H, to form the enolate ion J:
O O
O + O
H H H H
CH2
H J
The enolate ion is better represented with the negative charge on the oxygen rather than on the
carbon.
(f) (i) Use curly arrows to show how J may be converted to a form with the charge on oxygen.
(You will also need to draw the structure of the form with the charge on oxygen.)
(ii) How do you think the C–O bond strength in the enolate ion compares with that in the
ketone?
Same Stronger Weaker
(iii) How do you think the (carbonyl-C)–CH2 bond strength in the enolate ion compares with
that in the ketone?
Same Stronger Weaker
(iv) Even though there is more electron density in total on the oxygen, most of the time the
enolate ion acts as a nucleophile attacking from carbon. Circle the best reason for this.
A Oxygen is more electronegative than carbon
B The electrons on carbon are higher in energy than those on oxygen
C The electrons on carbon are lower in energy than those on oxygen
The enolate ion can even act as a nucleophile and attack some unreacted propanone:
O
O

K
CH2
(v) Draw the structure of the product K.

Page 5
We can use curly arrows to help
understand this simple synthesis
of the drug terbinafine, the active
ingredient in products such as
LamisilTM, used in treating
athlete’s foot.
The synthesis starts with a hydrocarbon, denoted L–H, which is deprotonated using a strong base
to form anion L– (with formula C H –). L– then reacts with acrolein, M, to initially form anion Z–
6 9
which is then protonated to form the key intermediate, Z (shown below). Z reacts with acid HBr to
form compound Q, losing water in the process. In the final step, Q reacts with R to form protonated
terbinafine.
L–H + B L + B–H
(a strong, [ C6H9 ]
generic base)

L + Z
M
O
H

Br
H–Br

OH2 OH
key intermediate Z

– H2O
N
H

– Br protonated
Q +
terbinafine

(g) (i) Give the structure of L–H and draw a curly arrow mechanism for the formation of L–.
(ii) Draw a curly arrow mechanism for the reaction between of L– and M to give Z– (the
structure of Z– should also be drawn out, of course).
(iii) Give the structure of Q.
(iv) Draw a curly arrow mechanism for the reaction between Q and R, and hence draw the
structure of protonated terbinafine.

Page 6
2. This question is about the crazy chemistry of bismuth.

Bismuth, Bi, is a particularly fascinating element.

Directly underneath two poisonous elements arsenic
and antimony in Group 15, and coming after the
toxic elements mercury, thallium and lead in Period
6, and before the dangerously radioactive elements
in the periodic table, bismuth metal has been used
as a ‘safe’ and even ‘healthy’ alternative to lead, for
example in fishing weights and even shotgun pellets.
The metal crystallises in artificial-looking step-
shapes, often with beautiful iridescent colours due to IMAGE: wikipedia
a thin layer of oxide.
(a) (i) When heated in a flow of chlorine gas, bismuth forms bismuth(III) chloride. Give the
equation for this reaction.
(ii) Predict in which of the following ranges you expect the bond angle in gaseous bismuth(III)
chloride to fall:
a) 95º–108º b) 108º–110º c) 110º–119º d) 119º–121º e) >121º
(iii) When heated to redness in air, bismuth burns with a blue flame to give an oxide
containing 89.70% bismuth. Give the formula for this oxide. What is the oxidation state of
the bismuth in this oxide?
(iv) What do you predict the maximum oxidation state of bismuth to be?
(v) Bismuth only forms one simple halide in which the bismuth is in its maximum oxidation
state. Give the formula of this compound.

For many years bismuth was thought to be the last non-radioactive element in the periodic table,
but calculations suggested this ought not be the case. Finally, in 2003, researchers detected the
emission of an alpha particle (a helium nucleus) from bismuth-209 and determined its half-life to be
an incredible 2.01´1019 years (over a billion times the age of the universe). This means you would
have to wait about 25 minutes* for one atom in a mole of Bi to have a 50% chance of decaying!
(b) Which isotope is formed when bismuth-209 emits an alpha-particle?

When bismuth(III) chloride is reacted with methyl magnesium iodide, CH3MgI, trimethyl bismuthane,
Bi(CH3)3, is formed as a colourless oil which spontaneously combusts in air. Remarkably, this
reactive liquid is currently being investigated for use in ionization detectors for use in Positron
Emission Tomography to produce high-resolution images of brains. The standard enthalpy change
of combustion, ΔcHo, has been measured for liquid Bi(CH3)3.
(c) (i) Give the equation for the complete combustion of Bi(CH3)3.
(ii) Use the data below to calculate the standard enthalpy change of formation of Bi(CH3)3(l).

ΔcHo [ Bi(CH3)3(l) ] = –2912 kJ mol–1 ΔfHo [ CO2(g) ] = –394 kJ mol–1

ΔfHo [ H2O(l) ] = –286 kJ mol–1 ΔfHo [ Bi2O3(s) ] = –574 kJ mol–1

*We thought about asking you to calculate this, but our brains fried trying to work it out ourselves…

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(d) (i) Use the following data to derive an algebraic expression for the average Bi–CH3 bond
strength, x, in Bi(CH3)3(g). Your expression should be in terms of the quantities a – f and
you should indicate the coefficients for each of these quantities in your answer booklet.
thermodynamic quantity symbol value / kJ mol–1
ΔfHo [ Bi(CH3)3(l) ] a from (c)(ii)
ΔfHo [ CH4(g) ] b –75
ΔvHo [ Bi(CH3)3(l) ] c 35
ΔatHo [ H2(g) ] d 218
ΔatHo [ Bi(s) ] e 208
C–H bond strength in CH4(g) f 429

x= a b c d e f kJ mol–1

(ii) Use your value from (c)(ii) and the values of b – f to calculate the Bi–CH3 bond strength.

It is relatively easy to grow

beautiful crystals of bismuth since
it is one of the few elements 60°
Å

whose solid form is less dense

35
4.5

11.814 Å
than its liquid form. In other
words, like ice on water, solid Bi 60°
floats on top of liquid Bi.
4.535 Å
view looking down
the top face

1 Å = 10–10 m
view showing the
whole shape

Shown above is the unit cell for Bi. The 3-D shape outlined in black is called a right rhombic prism
which consists of 4 rectangular faces, and two faces which are rhombi. How the Bi atoms are
arranged in the solid structure is generated by stacking the unit cells directly on top of each other in
3-dimensions. Some of the atoms indicated in the unit cell are only partially within the cell, but when
they stack together, the full atom is formed. The two pairs of atoms connected by the dotted lines
lie directly on top of each other when viewed from above (as do pairs of atoms on each of the long
edges). You should not worry about the ‘bonds’ connecting atoms – they just indicate the
immediate closest neighbours within the cell.

(e) (i) By considering how any partial fragments add together, what is the total number of
bismuth atoms contained within 1 unit cell?
(ii) Calculate the mass in g of the atoms contained in 1 unit cell.
(iii) Calculate the volume in both Å3 and cm3 of the unit cell.
(iv) Hence calculate the density of solid bismuth in g cm–3.

Page 8
BiCl3 reacts with water to form bismuth
oxychloride, BiOCl, sometimes knows as pearl-
white. Pearl-white used to be used to whiten
people’s faces in times gone by, and is still used
today in some makeups. The compound is
remarkably non-toxic – in one study rats* fed 5%
BiOCl for 2 years showed no ill effects from it!

A story relates how one bewhitened lady who

entered the hydrogen sulfide-containing bath
waters at Harrogate was shocked when suddenly
her makeup went from white to black. This would
be due to the formation of bismuth(III) sulfide.

(f) (i) Give an equation for the formation of bismuth oxychloride from BiCl3.
(ii) Give an equation for the reaction that shocked the lady in the Harrogate waters. (Hint: this
is not a redox reaction.)

When bismuth metal is dissolved in molten bismuth(III) chloride, a new compound (Z) is formed that
is 83.48% bismuth, by mass. Z was once incorrectly called bismuth monochloride. When Z is
analysed by X-ray crystallography, it is found that the unit cell has a relative formula mass of
6008.12.
(g) (i) Calculate the empirical formula of compound Z.
(ii) Calculate the total formula of the unit cell.
Examination of the X-ray crystal structure shows that all the chlorine atoms are contained within
bismuth-chlorine species that have the formula [Bi2Cl8]l or [BiCl5]m where l and m are the charges
of these species. The bismuth atoms not in the two Cl-containing ions are contained within two
identical cations, [Bip]n+.
(iii) Assuming that each Bi has an oxidation state of +3, and each chlorine, –1, calculate the
values of the charges m and n.
(iv) Given the total formula of the species contained within the unit cell, write the formula of
compound Z in the form (Bip)2(Bi2Cl8)q(BiCl5)r.
(v) What is the formula, including charge, of the [Bip]n+ ion?
(vi) Write a balanced equation for the reaction that occurs when bismuth metal dissolves in
molten bismuth(III) chloride to give compound Z.

* No rats were harmed in the writing of this question.

Page 9
Acknowledgements

We would like to thank those who support C3L6:

University of Cambridge Yusuf Hamied Department of Chemistry

St Catharine's College, Cambridge

Cambridge Chemistry Challenge Ltd.

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