Section A Industrial Chemistry

1.(a) A chemical R is made by reacting chemical P with chemical Q in a reversible reaction. P, Q and R are all gases
under the reaction conditions.
Research chemists wanted to know the optimal conditions to use in the manufacture of product R. They carried out
a series of identical reactions under different conditions of temperature and pressure. The percentage conversion of
reactant P at equilibrium was shown in the table below.

Pressure (atm)  % of P being converted

Temperature ( C)
350 16
10 450 12
550 8
350 29
20 450 21
550 11
350 49
40 450 34
550 18

(i) Use the data in the above table,

1). account for the effect of increasing pressure on the percentage of reactant P being converted. (1 mark)

The percentage conversion of reactant P increases with increasing pressure. (1)

2). find out which is the larger one, “ the total number of moles of reactants P and Q ”
or “ the number of moles of product R ”. Explain how you reach for your conclusion. (2 marks)

As increasing pressure increases the percentage conversion of reactant P, (0)

a decrease in the number of moles of gas(es) is favoured. (1)

or conversion of reactants to product involves a decrease in the no. of moles of gas. (1)

 the total no. of moles of reactants P and Q  no. of moles of product R. (1)
(no mark will be given to answer without explanation.)

(ii) Deduce, with reason, whether the reaction is exothermic or endothermic. (2 marks)

The percentage conversion of reactant P decreases with increasing temperature. (0)

the net forward reaction releases heat energy. (1)

 the reaction between reactants P and Q is exothermic. (1)

(no mark will be given to answer without reason.)

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 (iii) The greatest yield in the production of product R operate at 40 atm and 350 C. However, the industrial plant
operate at 20 atm and 450 C. Explain why the operating conditions are lower than the experimental one.
(2 marks)

A compromise between ‘rate of reaction , ‘yield of products and ‘economic consideration . (0)

 if the temp is very low, the reaction proceeds slowly,

the amount of product R produced per unit time ; (1)

 if the pressure is very high, the construction and maintenance costs for the

catalytic chamber that can withstand high pressure ; (1)

As a result, a compromising conditions 450C, 20 atm are adopted.

(most students answer this part poorly.
For high pressure being used. Just say “maintenance cost is too high” only, or say only a word “expensive”.
For high temperature being used. Just say “High temperature speed up reaction”,
that cannot explain the operating temperature and pressure being used.)

(iv) Operating conditions employed should have a conversion of reactant P of 21%. In the manufacture, using these
conditions, it was found that only 11% conversion was achieved. However, the conversion percentage resumes
to 21% when a substance is added. What is that substance? (1 mark)

catalyst, speed up both forward and backward reaction, (1)

shorten the time to reach equilibrium. (0)

1.(b) The chloroalkali industry can provide the raw material, hydrogen, for the manufacture of methanol.

(i) With the help of a chemical equation, explain how hydrogen is produced in the chloroalkali industry. (2 marks)
 
When brine is electrolyzed, at cathode, H (aq) ion is lower than Na (aq) ion in the E.C.S., (1)

H(aq) ion is preferentially discharged, 2 H(aq)  2e  H2(g) (1)

(ii) Write an equation for the manufacture of methanol that consumes hydrogen. (1 mark)

CO(g)  2 H2(g) CH3OH(g) (1)

(most students forget reversible sign.)

(ii) The steammethane reforming is commonly used to make syngas for the production of methanol.
Suggest TWO advantages of using syngas as the raw materials to produce methanol over obtaining hydrogen
from the chloroalkali industry. (2 marks)

Carbon monoxide is present in syngas, which is one of the raw materials to produce methanol.

Hence, there is no need to find a source of carbon monoxide for the production of methanol.

Production of H2(g) only for methanol production using electrolysis of brine will produce

more Cl2(g) and NaOH(aq) than needed. High cost of disposing of excess Cl2(g) and NaOH(aq).

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1.(c) Experiments were carried out to study the kinetics of the following reaction at 180C:
2 ICl(g)  H2(g)  I2(g)  2 HCl(g)   
The following results were obtained.

Initial concentration ( mol dm )

Expt. Initial rate / mol dm s
[ICl(g)] [H2(g)]
1 0.15 0.01 3.30 x 10
2 0.30 0.01 6.60 x 10
3 0.45 0.02 1.98 x 10

(i) Deduce the order of the reaction with respect to both ICl(g) and H2(g), and hence write the rate equation
for the reaction. (3 marks)
The rate equation for the reaction can be expressed as

x y
rate  k [ICl(g)] [H2(g)] where k is the rate constant 180C.

Consider experiments 1 & 2, in which initial [H2(g)] is constant.

Doubling [ICl(g)] doubles the rate.

 with respect to [ICl(g)], the reaction is first order, i.e. x  .

Consider experiments 1 & 3, in which initial [ICl(g)] is constant.

Doubling [H2(g)] doubles the rate.

 with respect to [H2(g)], the reaction is first order, i.e. y  .

The rate equation for the reaction is rate  k [ICl(g)] [H2(g)]

(ii) Calculate the rate constant, k, for the reaction at 180C. (1 mark)

Rate  k [ICl(g)] [H2(g)]

3.30 x 103  k [ 0.15 ] [ 0.01 ]
 rate constant, k  2.20 dm mol s (1 or 2 decimal places, no mark with wrong unit)

(iii) Sketch a graph to show how the rate of the reaction changes with increasing concentration of ICl(g) gas. (1 mark)
rate of reaction / mol dm  min 

[ICl(g)] / mol dm

(most students do not list unit on both axes.)

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 (iv) The following mechanism was proposed for the reaction:
Step 1 ICl(g)  H2(g)  HI(g)  HCl(g)
Step 2 ICl(g)  HI(g)  HCl(g)  I2(g)
Based on this mechanism, sketch a labelled energy profile. (2 marks)

Potential energy

HI(g)  ICl(g)  HCl(g)

H(g)  2 ICl(g)

2 HCl(g)  I(g)
Reaction coordinate
END OF SECTION A

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 Section B Analytical Chemistry (Answer ALL parts of the question in answer book labeled with ‘Analytical Chemistry’.)

2.(a) The table below shows some reactions of an organic compound A (C8H8O).

Reaction Observation

Reaction with Br2 in trichloroethane in the dark No observable change

Reaction with dinitrophenylhydrazine Yellow precipitate is formed

Explain the possible functional group(s) that may be present in compound A. (2 marks)

Since the compound does not react with Br2 in the dark, it is not an alkene. (1)

Since the compound reacts with 2,4dinitrophenylhydrazine to give a yellow precipitate,

it is an aldehyde or ketone. (1)

(b) Compound X, with relative molecular mass of 76, has the following composition by mass :
C : 31.6% H : 5.3% O : 63.1%
The infrared and mass spectra of compound X are given below.

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 (i) Deduce the molecular formula of compound X. (2 marks)

number of carbon atoms  76 x 0.316/12.0  2

number of hydrogen atoms  76 x 0.053/ 1.0  4
number of oxygen atoms  76 x 0.631/16.0  3 (1)

Hence, the molecular formula of compound X is C2H4O3. (1)

(ii) From the given spectral information and the molecular formula obtained in (i), deduce the structural formula
of compound X. Give also the formulae of the species corresponding to m/z of 31 and 45 in the mass spectrum.
(4 marks)

A strong broad band at around 3200 cm of the IR spectrum indicates the presence of OH group.

Such band extends to the region around 2600 cm indicating that the presence of OH group
from carboxylic acid. (1)

3230-3670 cm-1 indicates the presence of -OH group of alkanol.

Or
Since compound X has only two carbon atoms and there can be only one double bond in the molecule,
compound X should contain one CO group and two OH groups. (1)

 
The peak at m/z  45 of the mass spectrum indicates the ion [ HOCO] / [COOH] .
Or

 
The peak at m/z  31 of the mass spectrum indicates the ion [CH2OH] / [CH2OH] . (1)

Hence, the structural formula of X is: (1) (1)

(iii) Suggest chemical tests to confirm the functional groups present in compound X.
State clearly the reagents and conditions used and the expected observations for the tests. (4 marks)

Test for OH group:

add acidified potassium dichromate solution to the solution of X. (1)

The colour of the acidified potassium dichromate solution turns from orange to green. (1)

Test for COOH group:

add sodium carbonate solution / hydrogencarbonate solution to the solution of X. (1)

effervescence occurs. / colourless gas bubbles are evolved. (1)

(c) Chlorine bleach contains hypochlorite ions (OCl) as the active ingredient.
A student conducts an experiment to determine the amount of hypochlorite ions in a sample of bleaching solution and
the procedure is as follows:

Step 1: 25.0 cm3 of the bleaching solution is diluted to 250.0 cm3 with distilled water.

Step 2: 25.0 cm3 of the diluted bleaching solution is transferred into a conical flask.

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 Step 3: Excess amount of dilute sulphuric acid and potassium iodide solution are added to the 25.0 cm3
diluted bleaching solution.

Step 4: The mixture is then titrated with 0.100 M sodium thiosulphate solution, Na2S2O3(aq), until the end point
is reached.

(i) In step 3, when dilute sulphuric acid and potassium iodide solution are added to the bleaching solution, (3 marks)

(I) what will be observed?

The solution becomes dark brown. (1)

(II) write a chemical equation for the reaction.

OCl(aq)  2 H(aq)  2 I(aq)  I(aq)  Cl(aq)  HO(l) (1)

(III) explain why the sulphuric acid and potassium iodide must be in excess.

to ensure all the hypochlorite ions in the bleaching solution react to give I(aq). (1)

(ii) In step 4, (2 marks)

(I) suggest a suitable indicator for the titration.

starch indicator (1)

(II) what is the colour change at the end point of the titration?

from dark blue to colourless (1)

(iii) If 18.50 cm3 of the 0.100 M sodium thiosulphate is required for the titration, calculate the concentration of the
hypochlorite ions in the bleaching solution. (3 marks)

I(aq)  2 S2O3(aq)  2 I(aq)  S4O6(aq)

 –3 18.50 3 –3
no. of moles of S2O3  0.100 mol dm  dm  1.85  10 mol
1000

1.85  103 mol –4

no. of moles of I   9.25  10 mol (1)
2

OCl(aq)  2 H(aq)  2 I(aq)  I(aq)  Cl(aq)  HO(l)

 3 –4
no. of moles of OCl in 25.0 cm of the diluted bleaching solution  9.25  10 mol
 3 –4 250
no. of moles of OCl in 25.0 cm of the original bleaching solution  9.25  10 
25.0
–3
 9.25  10 mol (1)
3
9.25  10 mol
concentration of OCl   0.370 M (1)
25.0
dm 3
1000

End of Section B

End of Paper

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