2

Answer any four questions.

1 Octane is commonly used as a fuel or a precursor in the production of other chemicals. The
standard enthalpy change of combustion of octane produces 5470kJ of energy per mole of
octane, hence it produces a large amount of energy for a small molecular mass hydrocarbon.
Having a small molecular mass results in octane to have a lower boiling point as compared to
the other fractions of crude oil, making it easier to be removed by fractional distillation as
compared to hydrocarbons which have a larger number of carbon atoms. Hence, octane is a
useful source of fuel for motor vehicles. One of the isomers of octane, 2,2,4-trimethylpentane
(also known as isooctane), is a substance used for the octane-ratings of fuel.

(a) (i) State and explain briefly an ill-effect of the use of fossil fuel has on the environment.

(ii) Suggest and explain briefly a specific alternative to using fossil fuel as fuel for motor
vehicles.
[3]

(b) Draw the structure of an isomer of isooctane which exhibits optical isomerism and contains
5 carbon atoms as the longest chain.
[1]

(c) Reforming takes straight chain hydrocarbons in the C 6 to C8 range from the gasoline or
naphtha fractions and rearranges them into compounds containing benzene rings.

Hydrogen is produced as a by-product of the reactions. A catalytic mixture of Pt and Al 2O3

at a temperature of 500oC and pressure of 20 atm is used.

Reforming of octane produces 1,2-xylene as shown by the equation below.

CH3 CH3

CH 2 CH3 CH3
CH 2 CH 2
+ 4H 2

CH 2 CH 2
CH 2
1,2-xylene
(i) Given the numerical values of standard enthalpy change of combustion of 1,2-xylene
and hydrogen are 4540 kJ mol-1 and 286 kJ mol-1 respectively, draw an energy cycle
and calculate the standard enthalpy change of the reaction that produces 1,2-xylene
from octane.

(ii) Using values in the Data Booklet, calculate the enthalpy change of the reaction which
reforms octane into 1,2-xylene. Explain the difference in your calculation in (c)(i) and
(c)(ii).

(iii Suggest which value (c)(i) or (c)(ii) is a more accurate description of the heat change
) of the reforming of octane into 1,2-xylene. Explain your choice.

(iv Briefly explain whether you expect the above reaction to have to its G value to be
) more negative than its corresponding Hr.
[10]

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(d) 3,4-dimethylphenylamine is a raw material for the production of vitamin B2 and it can be
produced from 1,2-xylene using a 2-steps reaction scheme.

(i) Suggest the 2-steps reaction scheme, stating the reagents and conditions required
and drawing the appropriate intermediate(s).

(ii) Describe the mechanism of the first step in (d)(i).

[6]

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2 (a) Describe the reactions between water and (i) magnesium chloride and
(ii) silicon tetrachloride separately.
Write balanced equations where appropriate.
[4]

(b) The oxide of an element in Period 3 of the Periodic Table dissolves readily in water to give a
colourless solution, Y. When Y is added to an aqueous solution of an aluminium salt, a white
precipitate is observed, which dissolves in excess of Y to give a colourless solution, Z. When
hydrochloric acid is added to Z, a white precipitate is obtained which then dissolves in excess
of hydrochloric acid.

(i) Identify Y and write balanced equations for its reactions with the aluminium salt.

(ii) Explain the reaction of hydrochloric acid with Z .

[4]

(c) The graph below shows the reaction between aqueous sodium hydroxide and a solution of a
saturated alkyl chloride at temperature ToC.

[NaOH]/ moldm-3
0.1

[RCl] = x moldm-3
0.05

[RCl] = 2x moldm-3

a Time

(i) Referring to the graph above, deduce the order of reaction with respect to
sodium hydroxide and RCl and hence write down the rate law.

(ii) Is RCl most likely to be a primary, secondary or tertiary alkyl halide?

(iii Draw a labelled energy profile diagram for the reaction.

)
(iv Briefly explain how one of the graphs above may be obtained experimentally.
)
(v) Aqueous hydrochloric acid and (CH3)2CCHCl are separately reacted with aqueous
sodium hydroxide. How would the rates of reaction of these two compounds compare
with the rate of reaction of RCl in (c) above? Give your reasons

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(vi Identify 2 possible products formed when ethanolic sodium hydroxide is
) heated under reflux with
CH2 Cl

[12]

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3 At temperatures near 800oC, steam passed over hot coke (a form of carbon obtained from coal)
reacts to form CO and H2.

C(s) + H2O(g) CO(g) + H2(g)

The mixture of gases that results is an important industrial fuel called water gas.

(a) At 800oC the equilibrium constant for this reaction, Kp is 14.1atm. What are the equilibrium
partial pressures of H2O, CO and H2 in the equilibrium mixture at this temperature if we
start with solid carbon and 0.100 mol of H2O in a 1.00 dm3 vessel? Give your answer in
atmospheric pressure .
[6]

(b) (i) What is the minimum amount of carbon required to achieve equilibrium under these
conditions?

(ii) What is the total pressure in the vessel at equilibrium?

[3]

(c) (i) At 25oC the value of Kp for this reaction is 1.7 x 10-21. Is the reaction exothermic or
endothermic?

(ii) To produce the maximum amount of CO and H2 at equilibrium, should the pressure of
the system be increased or decreased?
[2]

(d) Menthol is the main component in oil of peppermint, a plant extract obtained from the
leaves and stems of Menthe piperita.

OH
CH3
CH3 CH
CH3

(i) Suggest suitable reagents and conditions to prepare the following compound from
menthol:

CO2H
OH
CH3
CH3 CH
CH3

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(ii) Synthetic menthol can be made from 3-hydroxymethylbenzene through
Friedel-Crafts acylation using (CH3)2CHCl and AlCl3 giving the following intermediate:

OH
CH3
CH3 CH
CH3

Describe simple chemical test which can be carried out to distinguish the intermediate
from synthetic menthol.
[5]

(e) Carvone, C10H14O, is the main flavouring component in spearmint oil. It reacts with
2,4-dinitrophenylhydrazine to yield an orange precipitate but does not react with
Tollens reagent. When carvone is treated with hydrogen gas in the presence of a
nickel catalyst, it reacts to yield a compound A (shown below). Carvone can also
undergo mild oxidation to produce methanal and a compound B (shown below).

OH
H-C-CH2-CH-CH2-C-C-CH3
CH3
O C O OO
CH 3 CH
CH3 CH3

Compound A Compound B

Deduce the structural formula of carvone, showing your reasoning.

[4]

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4 (a) Some data on three nitrogen-containing compounds are given in the table below:

Compound Molecular formula Boiling point/ oC

Dinitrogen pentoxide N2O5 decomposes

nitric acid HNO3 83

nitrosyl chloride NOCl -6.4

(i) Draw diagrams to illustrate the shapes of N2O5 (a symmetrical molecule) and NOCl.
Indicate the relevant bond angles in each case.
(ii) Explain the difference in the boiling points of HNO3 and NOCl in terms of structure and
bonding. [6]

(b) The scheme below shows the final stages in the synthesis of compound M.

Cl
CO2H Cl CH2CH2OH

PCl3

L K

room temperature

Cl
CONHCH2CH CH2 Cl
OH

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(i) Draw the structural formulae of compounds L and K.

(ii) Give the synthetic route, involving not more than three steps, from J to K. In your
answer, suggest the reagent(s) and conditions involved in each step and draw the
structural formulae of the intermediate organic products.

(iii Identify the type(s) of stereoisomerism shown by compound M. State the total number of
) possible stereoisomers.

(iv
In the reaction of L and K to form M, another organic compound can also be formed.
)
Draw the structural formula of the organic compound and explain how its formation may
arise.
(v)
State the type of reaction taking place when compound M reacts with each of the
following reagents:
I sodium metal
II bromine water

[14]

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5 One of the most striking features of the transition elements is that they exhibit variable oxidation
states. This question illustrates the various oxidation states shown by iron in its compounds.

(a) (i) The reaction between iodide ions,I-, and persulfate ions, S2O82-, is slow.
The reaction can be speeded up by adding a small amount of Fe2+ ions.

The initial rate of the slow reaction between iodide ions and persulfate ions can be
studied by using thiosulfate ions. The equations for the reactions are as follows.

2I- + S2O82- I2 + 2SO42- (slow) reaction I

I2 + 2S2O32- 2I- + S4O62- ( fast ) reaction II

In the presence of a constant amount of thiosulfate ions, the iodine being slowly
produced by reaction l will immediately react in reaction ll until all the thiosulfate ions
has been used up. At that point, free iodine will be present in the solution, which will
cause a sudden appearance of a deep blue colour if starch is present.

A series of experiments was carried out using different volumes of the five reagents. The
following results were obtained.

experiment Volume Volume of Volume Volume of Volume Time for

number of I- of distilled of the
S2O82-/c /cm3 S2O32-/c water starch appearance
m3 m3 /cm3 /cm3 of deep blue
colour/s
1 20 20 10 5 5 30
2 20 15 10 10 5 40
3 5 25 10 15 5 t3
4 10 15 10 20 5 80

If the orders of reaction with respect to persulfate ions and iodide ions are both one
respectively, deduce an expression relating the volume of these two reactants and time
taken for the appearance of deep blue colour. Explain your reasoning.

Predict the time, t3, required for the appearance of deep blue colour in experiment 3.

(ii) In the Haber process, the rate of formation of ammonia is increased by using an iron
catalyst.
State the type of catalysis occurring here and describe using the Maxwell-Boltzmann
Distribution curve how the iron catalyst can increase the rate of reaction.
[6]

(b) Iron(III) chloride is a dark brown solid which dissolves in water to give an acidic solution. This
solution is often used, in the electronics industry, to dissolve the copper used in printed circuit
boards.

(i) Explain, with the aid of a chemical equation, why aqueous iron(III) chloride is acidic.

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(ii) Use the Data Booklet to explain why aqueous iron(III) chloride etches (dissolves)
copper. Give relevant chemical equations.
(iii If aqueous iron(III) chloride is treated with zinc followed by aqueous ammonia, what
) product would you expect to be formed?
[5]

(c) (i) A student suggested that aqueous iron(III) iodide could be prepared by the reaction
between aqueous iron(III) sulfate and aqueous barium iodide.

Use relevant E data from the Data Booklet to explain why no iron(IIl) iodide is formed
when these two solutions are mixed, and predict what reaction is likely to occur.

(ii) Iron(III) iodide has been successfully made under non-aqueous conditions by following
method.

Iron pentacarbonyl, Fe(CO)5, is reacted with iodine in hexane solution. This forms a
solution of compound X, whose molecular formula is FeC4O4I2.

A further calculated amount of iodine is added, and the solution exposed to uv light. A
black precipitate of iron(III) iodide results, and a colourless gas is evolved.

State the co-ordination number of iron in the complex, Fe(CO) 5 and hence predict the
shape of the complex, Fe(CO)5 . Describe the bonding between iodine and iron in
compound X and write a balanced equation for the reaction between compound X and
iodine.
[6]

(d) When a solution of NaOCl is added to a strongly alkaline suspension of Fe2O3, a purple
solution results. When BaCl2(aq) is added, a red solid is precipitated with the composition:
Ba, 53.4%; Fe, 21.7%; O,24.9% by mass.

(i) Calculate the empirical formula of the red solid, and hence determine
the oxidation number of iron in the red solid.

(ii) Construct a balanced ionic equation for the reaction between Fe2O3, OCl- and OH-. [3]

--The End--

ACJC 2010 9647/03/Aug/10 Preliminary Examination