2

Section A

Answer all the questions in the spaces provided.

1 (a) Calcium has atomic number 20.

Complete the electronic structures for a

calcium atom, 1s22s22p6.................................

calcium ion in the +2 oxidation state. 1s22s22p6.................................

[1]

(b) Calcium nitrate, Ca(NO3)2, is used in fertilisers and can be prepared by an acid-base reaction.

Write an equation for the preparation of calcium nitrate by an acid-base reaction.

.............................................................................................................................................. [1]

(c) (i) When anhydrous calcium nitrate is heated strongly, it decomposes to leave a white solid.

Identify this white solid and suggest another observation for this reaction.

. ............................................................................................................................................

. ...................................................................................................................................... [1]

(ii) The ease of thermal decomposition of the Group II nitrates decreases down the group.

Explain this trend.

. ............................................................................................................................................

. ............................................................................................................................................

. ...................................................................................................................................... [2]

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(d) (i) What is meant by the term standard enthalpy change of hydration, ?

. ............................................................................................................................................

. ............................................................................................................................................

. ...................................................................................................................................... [2]

(ii) Use the following data to calculate the lattice energy, , of calcium nitrate, Ca(NO3)2(s).
You may find it helpful to construct an energy cycle.

enthalpy change value

(Ca2+(g)) –1650 kJ mol–1

(NO3–(g)) –314 kJ mol–1

enthalpy change of solution for Ca(NO3)2(s) –19 kJ mol–1

Ca(NO3)2(s) = ........................... kJ mol–1 [3]

(e) The standard enthalpy change of hydration for Ba2+, (Ba2+(g)), is –1305 kJ mol–1.

Suggest an explanation for why the of the Ba2+ ion is less exothermic than the of
the Ca2+ ion.

....................................................................................................................................................

....................................................................................................................................................

.............................................................................................................................................. [2]

[Total: 12]

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2 (a) Complete the table to show the number of unpaired electrons in the outer shell of each of the
gaseous atoms, Na to Ar.

Na Mg Al Si P S Cl Ar
number of
unpaired electrons

[3]

(b) (i) Complete the table for the reactions of two Period 3 chlorides with water.

Period 3 chloride observations pH of solution formed

SiCl 4

PCl 5

[3]

(ii) Write an equation for the reaction between SiCl 4 and H2O.

. ...................................................................................................................................... [1]

[Total: 7]

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3 The transition element iron is the most abundant element in the Earth’s core.

(a) What is meant by the term transition element?

....................................................................................................................................................

.............................................................................................................................................. [1]

(b) In aqueous solution, iron can form complex ions which contain ligands.

(i) Name the type of bonding that occurs between a ligand and a transition element.

. ...................................................................................................................................... [1]

(ii) Which of the following species can act as a ligand?

Complete the table by placing a tick () in the appropriate column to indicate whether the
species can act as a ligand or not.

can act cannot act

species
as a ligand as a ligand
NO3–

BF3

H2NCH2CH2NH2

NH4+

[2]

(c) Manganese ions, Mn2+(aq), show some similar chemical properties to those of copper(II) ions,
Cu2+(aq).

Use this information and the Data Booklet to suggest the formula of the manganese species
formed in each of the following reactions. State the type of reaction taking place in each case.

formula of manganese type of

species formed reaction

Mn2+(aq) + NaOH(aq)

Mn2+(aq) + concentrated HCl

Mn2+(aq) + H2O2(aq)

[5]

[Total: 9]

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4 In aqueous solution, 2-chloro-2-methylpropane, (CH3)3CCl, reacts with sodium hydroxide, NaOH.
This is a nucleophilic substitution reaction.

(CH3)3CCl (aq) + NaOH(aq) → (CH3)3COH(aq) + NaCl (aq)

(a) Show the mechanism for this reaction. Include all necessary curly arrows, lone pairs and
relevant dipoles.

[3]

The rate of this reaction was investigated using a large excess of sodium hydroxide.

(b) The graph below shows the results of the experiment.

0.60

0.50

0.40

[(CH3)3CCl ]
0.30
/ mol dm–3

0.20

0.10

0
0 20 40 60 80 100 120 140 160
time / s

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The reaction is first order with respect to [(CH3)3CCl ]. This can be confirmed from the graph
using half-lives.

(i) What is meant by the half-life of a reaction?

. ............................................................................................................................................

. ...................................................................................................................................... [1]

(ii) Calculate the half-life for this reaction. Show all your working and show clearly any
construction lines on the graph.

[1]

(iii) What would be the effect on the half-life of this reaction if the initial concentration of
[(CH3)3CCl ] was doubled?

. ...................................................................................................................................... [1]

(c) (i) Use the graph in (b) to determine the rate of reaction at 80 s.
Show all your working.

rate = ............................. units ............................. [2]

The rate equation for this reaction is shown.

rate = k [(CH3)3CCl ]

(ii) Calculate the value of the rate constant, k, for this reaction and give its units.

k = ............................. units ............................. [1]

[Total: 9]

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5 X is a metallic element.

(a) (i) Draw a fully labelled diagram to show how the standard electrode potential, E o, of
X2+(aq) / X(s) could be measured.

[4]

(ii) What are the conditions needed for the value measured to be a standard electrode
potential?

. ...................................................................................................................................... [1]

(iii) State the charge carriers that transfer current through

the solutions, ............................. the wire. ............................. [1]

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(b) An electrochemical cell was set up consisting of an X2+(aq) / X(s) half-cell (E o = –0.40 V) and
an Ag+(aq) / Ag(s) half-cell (E o = +0.80 V).

(i) Write an equation for the reaction that would take place if the electrodes of this cell were
connected by a wire.

. ...................................................................................................................................... [1]

When the current was allowed to pass for a period of time,

• the Ag electrode gained 1.30 g in mass,

• the electrode made of metal X lost 0.67 g in mass.

(ii) Calculate the Ar of metal X; hence suggest an identity for X.

Show all your working. Use of the Data Booklet is relevant to this question.

Ar = ...........................

X is ...........................
[4]

[Total: 11]

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6 Boron forms many useful compounds.

(a) The compound diborane, B2H6, can be used as a rocket fuel.

It can be prepared by the reaction of boron trifluoride, BF3, with sodium borohydride, NaBH4.

Balance this equation.

.......BF3 + .......NaBH4 → .......B2H6 + .......NaBF4

[1]

(b) Primary and secondary alcohols can be formed by the reaction of carbonyl compounds with
NaBH4, which is a source of hydride ions, H–.

Complete the mechanism for the reaction of butanone with hydride ions, H–, and draw the
intermediate in the box. Include all necessary curly arrows and relevant dipoles.

O OH
step 1 H+
C H 3C C CH2CH3
H 3C CH2CH3
H
H–

intermediate
[3]

(c) Borane, BH3, is used to synthesise alcohols from alkenes.

The reaction occurs in two steps.

The BH2 group from BH3 bonds to the least substituted carbon atom of the double bond, and
the remaining H from BH3 bonds to the other carbon.

CH3 H CH3 H CH3 H

step 1 [O]
C C + BH3 H C C BH2 H C C OH
CH3 CH3 CH3 CH3 CH3 CH3

(i) Suggest the type of reaction in step 1.

. ...................................................................................................................................... [1]

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(ii) The diol Y can be prepared by the same method.

CH3 OH
H 3C
CH3
OH CH3

Draw the structure of the diene which could be used to prepare diol Y.

[1]

(d) Benzene, C6H6, and borazine, B3N3H6, have planar, cyclic structures.

(i) Describe the structure of and bonding in benzene, C6H6.

. ............................................................................................................................................

. ............................................................................................................................................

. ............................................................................................................................................

. ............................................................................................................................................

. ............................................................................................................................................

. ............................................................................................................................................

. ...................................................................................................................................... [3]

(ii) In borazine, B3N3H6, the boron and nitrogen atoms alternate around the ring. Each ring
atom has a single hydrogen atom bonded to it.
All boron-nitrogen bonds in borazine are 0.144 nm in length, whereas in simple compounds
B–N and B=N bond lengths are 0.154 nm and 0.136 nm respectively.

Suggest and draw the structure of borazine.

[1]

[Total: 10]

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7(a) Sunset Yellow is a yellow colouring agent used in food and drinks, which can be made by the
following route.
In step 3 of this synthesis, a phenol-like compound, S, reacts with intermediate T made from
amine R.
Assume that the –SO3– Na+ group does not react.

step 1
O2N SO3– Na+

Q
R (C6H6NSO3Na)

step 2

S T

step 3 NaOH(aq)

OH

N
N SO3– Na+

Na+ –O3S
Sunset Yellow

(i) Suggest structures for compounds R, S and T and draw them in the boxes above. [3]

(ii) Suggest reagents and conditions for

step 1, . ................................................................................................................................

step 2. . ................................................................................................................................
[3]

(iii) What type of organic salt is formed in step 2?

. ...................................................................................................................................... [1]

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(b) Compound W has the following structure.

NH2
H 2N
O

(i) How many σ and π bonds are present in a molecule of W?

σ bonds ....................... π bonds ....................... [2]

(ii) The products of the reactions of W with cold HCl and with CH3CH2Br are soluble in water
but not in organic solvents.

Complete the table for these reactions of W.

structure of product
reagent type of reaction
(molecular formula given)

HCl

(C4H9N2OCl )

CH3CH2Br

(C6H13N2BrO)

[3]

[Total: 12]

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10 (a) Aspartame is an artificial sweetener that has the structure shown below.

O
O OH
H3C N
H
O NH2 O

aspartame

(i) Draw a circle around each chiral centre in aspartame. [1]

In the stomach, aspartame is hydrolysed by acid to form three organic products.

(ii) On the diagram above, use arrows to indicate the two bonds that would be hydrolysed in
the stomach. [2]

(iii) Draw the structures of the three products formed after complete acid hydrolysis of
aspartame.

[3]

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(b) Aspartame is soluble in water.

By referring to the structure of aspartame, explain why it is soluble in water.

....................................................................................................................................................

....................................................................................................................................................

.............................................................................................................................................. [2]

(c) Recently, nanotechnology has been involved in the development of a new natural sweetener,
Nano Sugar, extracted from sugar cane.

What is the approximate width of a nanoparticle?

.............................................................................................................................................. [1]

[Total: 9]

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