19 This question is about the hydrolysis of halogenoalkanes with hydroxide ions.

(a) The initial rates for the hydrolysis of 2‑bromobutane, CH3CH2CHBrCH3 , were

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obtained for different initial concentrations of the reactants.
Both 2‑bromobutane and the product formed in this reaction exist as pairs
of stereoisomers.

CH3CH2CHBrCH3 + OH– → CH3CH2CH(OH)CH3 + Br–

Initial concentration of Initial concentration of Initial rate of

Experiment 2‑bromobutane hydroxide ions reaction
/ mol dm–3 / mol dm–3 / mol dm–3 s–1

Experiment 1 0.150 0.150 0.027

Experiment 2 0.300 0.150 0.054

Experiment 3 0.450 0.300 0.162

All rates were determined at the same temperature.

(i) State what is meant by the term stereoisomer.
(1)

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(ii) Show that the data in the table are consistent with the SN2 mechanism for this
hydrolysis of 2‑bromobutane.
(3)

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 (iii) In one experiment, a single stereoisomer of 2‑bromobutane was hydrolysed.
Explain the stereochemistry of the product of this reaction.
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(3)

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 (b) 2‑Bromo‑2‑methylbutane, (CH3)2CBrCH2CH3 , can also be hydrolysed with
hydroxide ions. The mechanism for the reaction is SN1 .

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The reaction profile is shown.

Energy

Reactants

Products

Progress of reaction

Explain how all the features of this reaction profile are consistent with
an SN1 mechanism.
(3)

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(Total for Question 19 = 10 marks)

TOTAL FOR SECTION B = 48 MARKS

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 SECTION C
Answer ALL the questions. Write your answers in the spaces provided.
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20 This question is about Group 2 compounds.

(a) Barium carbonate, BaCO3 , decomposes at high temperatures as shown.

BaCO3(s) → BaO(s) + CO2(g)

(i) Calculate the standard entropy change for the system, ∆S system .

Standard molar entropy

Compound
/ J K–1 mol–1

BaCO3 112.1

BaO 70.4

CO2 213.6

(2)

(ii) The lowest temperature at which barium carbonate, BaCO3 ,

decomposes is 712 °C.
Use this information and your answer from (a)(i) to calculate the
standard enthalpy change of the reaction, in kJ mol–1 .
Give your answer to an appropriate number of significant figures.
(3)

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 (b) Magnesium chloride, MgCl2(s), is used in the manufacture of tofu from soya milk.
An experiment was carried out to determine the enthalpy change of solution,

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ΔsolH , of anhydrous magnesium chloride, MgCl2(s).
4.26 g of anhydrous magnesium chloride was added to 200 cm3 of
deionised water in a polystyrene cup. The mixture was stirred to ensure
all the solid dissolved to form a solution.
The temperature of the solution rose by 6.8 °C.
Calculate the enthalpy change of solution, ΔsolH , of
anhydrous magnesium chloride, MgCl2(s).
Include a sign and units with your answer.
[Specific heat capacity of the solution = 4.18 J g–1 °C–1]
(3)

(c) The standard enthalpy change of solution, ΔsolH , of anhydrous MgCl2(s), can also
be determined using a Hess Cycle.
(i) Complete the Hess Cycle shown by adding appropriate formulae,
with state symbols, to the empty boxes.
(1)

lattice energy

standard enthalpy standard enthalpy

changes of hydration change of solution

Mg2+(aq) + 2Cl–(aq)

[Lattice energy = –2526 kJ mol–1

Standard enthalpy change of hydration of magnesium ions = –1920 kJ mol–1]

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 (ii) Calculate the standard enthalpy change of hydration of chloride ions,
ΔhydH [Cl–(g)] , using the cycle and data in (c)(i) and your answer to (b).
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[If you did not obtain a final answer to (b) use a value of –155 kJ mol–1 .
This is not the correct value.]
(3)

(d) The theoretical lattice energy for magnesium chloride, MgCl2(s),

is –2326 kJ mol–1 .
(i) Give two assumptions used in theoretical calculations of lattice energy.
(2)

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