Summer 2000 CH6

1.

Hydrogen peroxide H2O2 can act as both an oxidising and as a reducing agent.
The half-reactions involved are
H2O+2H++2e2H2O
H2O2O2+2H++2e
(a)

Hydrogen peroxide reduces aqueous manganate(VII) ions in the presence of sulphuric

acid.
(i)

Deduce the half equation for the reduction of manganate(VII) ions in acid solution
to give manganese(II) ions.
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(1)

(ii)

25.0cm3 of a solution of hydrogen peroxide required 14.8cm3 of 0.0200 mol dm3

potassium manganate(VII) solution for complete oxidation.
Calculate the concentration in mol dm3 of the hydrogen peroxide.

(3)

(b)

Hydrogen peroxide oxidises iodide ions, I, to iodine, I2.

(i)

Deduce the equation for the reaction between hydrogen peroxide and iodide ions.
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(2)

(ii)

25.0cm3 of the same hydrogen peroxide solution as in (a)(i) was added to excess
aqueous potassium iodide. The iodine liberated was titrated with 0.100 mol dm3
sodium thiosulphate solution. The volume of the sodium thiosulphate required was
also 14.8cm3. Explain in terms of the reactions involved why the volume of the
titrant was the same in both experiments
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(3)

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(iii)

In this titration starch is used as an indication. Explain why an indicator is usually

used in this titration whereas in the titration in (a)(i) an indicator was not necessary.
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(2)

(c)

Hydrogen peroxide decomposes on warming to give water and oxygen:

2H2O22H2O+O2
(i)

100-volume hydrogen peroxide is the most concentrated commercially-available

solution of the compound. It gives 100cm3 of oxygen for every 1cm3 of solution
that decomposes. Why is it wise to keep this solution in the refrigerator?
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(2)

(ii)

By a consideration of the oxidation states involved, explain the nature of the

decomposition reaction.
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(2)

2.

Zingerone is a constituent of oil of ginger which makes ginger hot. Zingerone could be obtained
from coniferyl alcohol.

OCH 3

OCH 3

HO

HO
CH 2 CH 2 COCH3

CH

CHCH 2 OH

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Summer 2000 CH6

For the purposes of this question these substances can be represented as RCH2CH2COCH3 and
RCH=CHCH2OH. Assume that the R group is unreactive.
(a)

Coniferyl alcohol could be converted into zingerone by the series of reactions given
below:

RCH

CHCH 2OH

oxidation

step 1

RCH

CHCHO

step 2

RCH

CHCH(OH)CH 3
oxidation
step 3

RCH

CHCOCH 3
H2 /Pt
step 4

RCH 2 CH 2 COCH3
(i)

Suggest suitable reagents which could be used in step 1

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(1)

(ii)

The conditions need to be carefully controlled so as to avoid further oxidation of

the aldehyde. Outline how you would carry out the experiment so as to minimise
further oxidation.
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(2)

(iii)

Step 2 involves the use of a Grignard reagent. Give the formula of an appropriate
Grignard reagent and outline how you could make this Grignard reagent from a
halogenoalkane.
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(3)

(b)

Step 4 is:
OCH3

OCH 3

HO

HO
Pt

+H2
CH

CHCOCH 3

CH 2 CH 2 COCH 3

The reaction takes place at room temperature.

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(i)

The hydrogenation reaction uses platinum, a transition metal, as a catalyst. On

what property of transition metals does their catalytic activity often depend?
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(1)

(ii)

The benzene ring is not reduced under the conditions used. Explain this in terms of
structure and bonding in the benzene ring.
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(3)

(iii)

At room temperature catalytic hydrogenation does not affect the C=O group either.
If you wished to reduce this group, give the reagent and conditions you would use
and give the structure of the product.
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(3)

(c)

Using R as before, draw a representative length of the polymer chain that would form if
coniferyl alcohol, RCH=CHCH2OH, undergoes polymerisation.

(2)
(Total 15 marks)

3.

(a)

Consider the homogeneous equilibrium

PCl5(g)
(i)

PCl3(g) + Cl2(g)

What is meant by homogeneous equilibrium?

(1)

(ii)

Write an expression for Kp for this equilibrium including units.

(2)

(iii)

Given that PCl5 is 33% dissociated at 700 K and 1.1 atm total pressure, find the
value of Kp under these conditions.

(iv)

The enthalpy of formation of PCl5(g) is 399kJ mol1, and that for PCl3(g) is

(3)

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Summer 2000 CH6

306kJmol1. Find H for the forward reaction.

(2)

(v)

State and explain the effect on the equilibrium position of this reaction if the
temperature were to be increased.
(2)

(b)

When phosphorus pentachloride reacts with excess water, one of the products is
hydrochloric acid. Solutions of aqueous hydrochloric acid form an azeotropic mixture
showing a negative deviation from Raoults Law. The azeotrope contains a mole fraction
of HCl of about 0.2.
(i)

Give the equation for the hydrolysis of phosphorus pentachloride.

(ii)

Draw a boiling temperature/composition diagram for aqueous hydrochloric acid.

(HCl boils at 85C, water at 100C.)

(1)

(4)

(iii)

Choose a liquid composition other than that of the azeotrope, and explain what
happens when your chosen mixture is fractionally distilled.
(3)

(c)

Phosphorus pentachloride also reacts with alcohols, but cannot be used as a definitive
qualitative test for them. Why is the reaction of alcohols with phosphorus pentachloride
not a definitive test?
(1)

(d)

Other phosphorus halides, such as phosphorus tri-iodide, are used to make

halogenoalkanes from alcohols.
Write the equation for the reaction between phosphorus tri-iodide and ethanol.
(2)

(e)

Chloroalkanes can be made from alcohols and sodium chloride in 50% aqueous sulphuric
acid. A similar reaction is unsuitable for the production of iodoalkanes using sodium
iodide. By comparison of the reactions of sodium chloride and sodium iodide with
sulphuric acid, explain why this is so.
(4)
(Total 25 marks)

4.

(a)

Give the principles which enable you to predict the shape of a particular molecule, given
its formula. Draw dot-and-cross diagrams for SiCl4 and XeF4, and hence draw the shapes
of each of these molecules.
(6)

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(b)

When 2-bromopropanoic acid, CH3CH(Br)COOH, is reacted with sodium hydroxide in

aqueous solution, 2-hydroxypropanoic acid is formed. The reaction takes place by an SnI
mechanism.
(i)

Write an equation for the reaction between 2-bromopropanoic acid and hydroxide
ions.
(1)

(ii)

Explain why 2-bromopropanoioc acid can show optical isomerism. State how this
could be detected.
(2)

(iii)

If a single optical isomer of 2-bromopropanoic acid is reacted with sodium

hydroxide, the resulting 2-hydroxypropanoic acid mixture is not optically active.
Write a reaction mechanism for the reaction, and explain why optical activity is
lost.
(5)

(c)

Optical activity is not confined to organic compounds; chirality is also seen in some
chromium compounds. 1,2-diaminoethane, H2NCH2CH2NH2, forms an octahedral
complex with chromium (III) ion. This complex ion [Cr(H2NCH2CH2NH2)3]3+ is chiral,
and the structure of one isomer is shown below.
N

N
Cr +

N
N

N.

where 1,2-diaminoethane is shown as N

Sketch the structure of the other isomer and say why the complex ion is chiral.
(2)

(d)

A student was given a chromium compound Z to analyse. The following information was
obtained:
Z was orange;
a solution of Z acidified with sulphuric acid converted propan 2-ol to propanone;
a solution of Z, acidified with sulphuric acid, reacted with a solution of iron(II) ions in
a 1 : 6 molar ration Z:Fe2+ to give a green solution;
on heating an alkaline solution of Z, ammonia was evolved;
Account as fully as you can for the above observations and identify Z.
(9)
(Total 25 marks)

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Summer 2000 CH6

5.

Sorbic acid has the formula

CH3CH=CHCH=CHCOOH
Together with its potassium salt sorbic acid is used in foodstuffs as an inhibitor of fungal and
mould growth.
(a)

Sorbic acid can show geometric isomerism.

(i)

Explain carefully why sorbic acid shows geometric isomerism.

(2)

(ii)

State, with a reason, the number of geometric isomers that sorbic acid has.
(2)

(b)

Sorbic acid and potassium sorbate together form a buffer system.

(i)

What is a buffer system?

(2)

(ii)

Write the chemical equations that are relevant to the functioning of the mixture as a
buffer, and use them to explain how buffering action arises. You may represent
sorbic acid as RCOOH and potassium sorbate as RCOOK.
(5)

(c)

Sorbic acid will react with a solution of bromine in tetrachloromethane.

(i)

Write an equation for the complete reaction of sorbic acid with bromine.
(1)

(ii)

A 7.00g sample of sorbic acid was reacted with a solution of bromine in

tetrachloromethane; 125cm3 of the solution was required. Calculate the
concentration of the bromine solution in mod dm3.
(4)

(d)

The bromine-containing product from (c)(i) can be reacted with sodium hydroxide in
aqueous ethanol to give a substitution reaction.
(i)

Explain why aqueous ethanol is used as the solvent rather than, say, ethanol alone.
(2)

(ii)

Write the structural formula of the product.

(1)

(e)

Potassium sorbate can function as a soap.

(i)

Explain why this is so.

(1)

(ii)

Soaps are in general made by the alkaline hydrolysis of fats. Write an equation to
illustrate this reaction.
(3)
(Total 25 marks)

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6.

This question explores the differences and similarities between manganese, a transition metal,
and aluminium, a main group metal.
(a)

The following information will be required for this question.

E /V
2H2O+O2 + 4e

4OH

+0.40

MnO 4

MnO 4 + e
2

+0.56
MnO2+2H2O

4H+ + MnO 4 + 2e

+2.26

Manganate(VI), MnO 4 , is a green ion of manganese.

(i)

One way of preparing manganate(VI) ions might be to oxidise manganese(IV)

oxide with manganate(VII) ions in aqueous acidic solution. Derive the overall
equation for this reaction, and show whether it is feasible under standard
conditions.
(3)

(ii)

What effect would an increase of pH of the reaction mixture have on the feasibility
of the reaction?
Explain your answer.
(2)

(iii)

If potassium manganate(VII) solution on its own is made very alkaline, it turns

green.
Write the equation for the reaction which is occurring. State, with reasons, what is
being oxidised.
(4)

(b)

The reactions of manganese considered so far arise from its ability to show a variety of
oxidation states. Unlike manganes, aluminium does not have this property.
Explain why manganese has several oxidation states whereas aluminium does not.
(4)

(c)

Aluminium forms a hexaquo ion, [Al(H2O)6]3+, similarly to the transition metals.

(i)

Explain why aqueous solutions of aluminium salts are acidic.

(2)

(ii)

If sodium hydroxide solution is added to an aqueous solution of an aluminium salt,

a white precipitate appears which disappears as more sodium hydroxide is added.
Write a series of equations to explain this behaviour.
(3)

(d)

(i)

What is the significance of the reactions in (c)(ii) with respect to the purification of
bauxite in the extraction of aluminium?
(2)

(ii)

Outline the manufacture of aluminium metal from purified bauxite.

(4)

(e)

The standard electrode potential for the aluminium electrode is such that the metal could,
8

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Summer 2000 CH6

in principle, be oxidised by an acidic solution of manganate(VII) ions. Why in practice

does this reaction not occur?
(1)
(Total 25 marks)

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