Winter 1997 CH2

1.

The equilibrium reaction

2SO2(g) + O2(g) 2SO3(g)
is used in the manufacture of sulphuric acid, using V2O5+ as a catalyst.
(a)

(i)

Given that the enthalpies of formation of SO2 and SO3 are 297
and 395 kJ mol1 respectively, calculate the enthalpy of reaction, H, of the
forward reaction, assuming it goes to completion.

(2)

(ii)

State and explain what happens to the equilibrium position of this reaction as the
temperature is raised.
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(2)

(iii)

The temperature used in practice for the industrial process is a balance between
economics and chemistry. Suggest three reasons which determine the choice of an
operating temperature of around 450C.
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(3)

(iv)

What effect does the catalyst have on the position of equilibrium in this reaction?
..........................................................................................................................
(1)

(v)

Sketch an enthalpy-level diagram for this reaction, showing on it the uncatalysed

and a possible catalysed route.

(4)

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(b)

(i)

Write an expression for the equilibrium constant Kc for the reaction.

(1)

(ii)

Explain with reference to your answer to (b)(i) the effect of increasing the
concentration of oxygen in the system at constant temperature.
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(2)

(iii)

A steel vessel of volume 1 dm3 has introduced into it 0.2 mol of SO3, 0.04 mol of
SO2 and 0.01 mol of O2. Show that this mixture is not at equilibrium and indicate
in which direction the system will move in order to achieve equilibrium at 700 K.
(Kc at 450C is 1.7 106 mol1 dm3.)

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(3)
(Total 18 marks)

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2.

Consider the following series of reactions and answer the questions which follow.
C 6 H12 O 2
A

NaOH (aq)

C4 H10 O
B

NaOH(aq)
ethanolic KOH

C 4 H8
F

HBr

C 4 H9 Br
E

CH 3 CO 2 Na+
C

HCl(aq)
CH 3 CO 2 H
D

H 2 /Pt
C4 H10
G

(a)

(i)

What type of reaction is represented by the conversion of E to F?

..........................................................................................................................
(1)

(ii)

The product F exists in two steroisomeric forms. Draw them, and state the feature
of the molecule which makes this isomerism possible.

(3)

(iii)

Give a simple chemical test, stating what you would see, for the functional group
present in F.
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(2)

(iv)

F is more reactive than G. Suggest in terms of the bonding of these compounds

why this is so.
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(2)

(b)

Compound E displays optical isomerism.

(i)

State what this means.

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(1)

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(ii)

Sketch the optical isomers of E.

(2)

(c)

The reaction of E to give B is a nucleophilic substitution.

(i)

What is meant by the term nucleophile?

..........................................................................................................................
(1)

(ii)

Give the structural formula for B.

(1)

(iii)

Give a simple chemical test for the functional group in B, and say what you
would see.
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(2)

(d)

The type of reaction exemplified by A B + C is important in the manufacture of soap.

(i)

What type of reaction is this?

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(1)

(ii)

A could be reacted with aqueous acid to give B and D. If the same quantity of A
was treated with aqueous acid, instead of aqueous alkali, how would the yield of B
differ? Explain your answer.
..........................................................................................................................
..........................................................................................................................
(1)

(e)

Consider the reaction C D.

(i)

Name D.
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(1)

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(ii)

Identify the acid-base conjugate pair in this reaction.

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(1)

(iii)

Explain why the reaction occurs.

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(2)

(iv)

A quantity of A was reacted with NaOH, acidified and the volatile acid D distilled
out. D was then added to a solution containing 0.0250 mol (an excess) of NaOH.
The excess NaOH from this reaction required 28.7 cm3 of 0.100 mol dm-3 HCl for
complete reaction. What mass of A was reacted with NaOH in the first place?

(4)
(Total 25 marks)

3.

This question is about the reaction between bromomethane and aqueous hydroxide ions
CH3Br + OH CH3OH + Br .
(a)

An increase in temperature increases the rate of this reaction.

Explain the increase by referring to the collision frequency and the collision energy of the
molecules.
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....................................................................................................................................
(3)

(b)

By sketching the energy distribution of the molecules at a given temperature, T, show how
the presence of a catalyst will increase the rate of the reaction.

(3)

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(c)

Define the following terms used in reaction kinetics.

(i)

Overall order of reaction

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(1)

(ii)

Rate constant
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(1)

(d)

In the reaction between bromomethane and aqueous hydroxide ions at constant

temperature the concentration of bromomethane at various times is given in the table.
time/min

[CH3 Br]/mol dm3 0.100

10

20

30

0.074

0.057 0.043

40

50

60

0.033

0.025 0.019

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0.014

Winter 1997 CH2

(i)

Plot a graph to show that the reaction is first order with respect to bromomethane.

(4)

(ii)

If the concentration of the hydroxide ion doubles, all other factors remaining
constant, the rate of the reaction doubles. What is the order of reaction with respect
to the hydroxide ion?
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(1)

(iii)

Hence write a rate equation for this reaction.

..........................................................................................................................
(1)

(iv)

Based on the kinetic information obtained above write the mechanism for the
reaction between CH3Br and aqueous OH- ions.
(3)
(Total 17 marks)

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Winter 1997 CH2

4.

This question is about the reaction between bromomethane and aqueous hydroxide ions
CH3Br + OH CH3OH + Br .
(a)

An increase in temperature increases the rate of this reaction.

Explain the increase by referring to the collision frequency and the collision energy of the
molecules.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(3)

(b)

By sketching the energy distribution of the molecules at a given temperature, T, show how
the presence of a catalyst will increase the rate of the reaction.

(3)
(Total 6 marks)

5.

Define the following terms used in reaction kinetics.

(a)

Overall order of reaction

........................................................................................................................
........................................................................................................................
(1)

(b)

Rate constant
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........................................................................................................................
(1)
(Total 2 marks)

6.

In the reaction between bromomethane and aqueous hydroxide ions at constant temperature the
concentration of bromomethane at various times is given in the table.
time/min

[CH3 Br]/mol dm3 0.100

10

20

30

0.074

0.057 0.043

40

50

60

0.033

0.025 0.019

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0.014

Winter 1997 CH2

(a)

Plot a graph to show that the reaction is first order with respect to bromomethane.

(4)

(b)

If the concentration of the hydroxide ion doubles, all other factors remaining constant, the
rate of the reaction doubles. What is the order of reaction with respect to the hydroxide
ion?
........................................................................................................................
(1)

(c)

Hence write a rate equation for this reaction.

........................................................................................................................
(1)

(d)

Based on the kinetic information obtained above write the mechanism for the reaction
between CH3Br and aqueous OH- ions.
(3)
(Total 9 marks)

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