 Mark Scheme  2013-DSE-CHEM|MOCK EXAM|Paper 2

SECTION A - Industrial Chemistry

1. (a) (i) N≣N (triple bond) is very strong (bond energy = 946 kJ mol-1) and is non-polar. 1
(ii) Any ONE of the following: 1
 The reaction in Haber process has very high atom economy (100%).
 The reactants (N2 and H2) and the product (NH3) are non-toxic and will pose no harm
to the environment.
 The reaction takes place in gas phase. No solvent is required.
 The raw material (N2) is available in large amount in the atmosphere. Depletion is not
a problem.
 The reaction does not require the use of any derivatives.
 A catalyst (Fe) is used.
(iii) Stage 1: 4NH3(g) + 5O2(g)  4NO(g) + 6H2O(l) 1
Stage 2: 2NO(g) + O2(g)  2NO2(g)
Stage 3: 4NO2(g) + O2(g) + 2H2O(l)  4HNO3(aq)
(iv) Any ONE of the following: 1
 CO(NH2)2 has higher percentage by mass of nitrogen than (NH4)2SO4.
 Being less soluble than (NH4)2SO4 in water, CO(NH2)2 fertiliser is less readily leached
into lakes and ponds leading to eutrophication.
 CO(NH2)2 is a slow-release fertiliser. A much smaller amount of CO(NH2)2 will be
washed away by rain water
 (NH4)2SO4 can make the soil acidic while CO(NH2)2 will not.
NOTE: NH3 reacts with CO2 to form ammonium carbamate, which is then dehydrated to give urea: [4]
2NH3(aq) + CO2(g)  H2NCOONH4(aq)
Then, H2NCOONH4(aq)  CO(NH2)2 (aq) + H2O(l)
 Nitric acid is manufactured by the catalytic oxidation of ammonia in the Ostwald process. The raw materials for the
manufacture are ammonia, air and water. The reactions involved are:
(1) Ammonia is catalytically oxidized to form nitrogen monoxide:

4NH3(g) + 5O 2(g) Pt H = –907 kJ mol–1

4NO(g) + 6H2O(l)

(2) The nitrogen monoxide reacts with more oxygen (in air) to form nitrogen dioxide:
2NO(g) + O2(g)  2NO2(g) H = –117 kJ mol–1
(3) Finally, the nitrogen dioxide is dissolved in water in the presence of air to form nitric acid:
4NO2(g) + O2(g) + 2H2O(l)  4HNO3(aq)
Figure 56.9 A flow diagram in the Ostwald process for the manufacture of nitric acid Uses of nitric acid
 To make fertilizers, e.g. NH4NO3
 To make explosives (e.g. TNT)
 To make synthetic fibres e.g. nylon
 To make dyes
 To etch metals
 In refining precious metals

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 Care your mistakes & misconceptions  Polish your -solving skills 

1. (b) (i) From Experiments 1 and 2, under the same initial concentration of F2(g), initial rate 1
doubles when concentration of NO2(g) is doubled.
∴ order of reaction with respect to NO2(g) is 1.
From Experiments 2 and 3, under the same initial concentration of NO2(g), initial rate 1
doubles when concentration of F2(g) is doubled.
∴ order of reaction with respect to F2(g) is 1.
(ii) The rate equation: rate = k[NO2(g)][F2(g)]
Using the information given from Experiment 1,
4.0 × 10-4 = k (2.0 × 10-3) (1.0 × 10-2)
 the rate constant, k = 20 mol-1 dm3 s1 1
[3]
Alternative method to (b) (i)
Let the rate equation be rate = k[NO2(g)]m[F2(g)]n where m and n are the orders of reaction with respect to [NO2(g)]
and [F2(g)] respectively. By substituting the given information into the rate equation, we have
4.0 × 10–4 = k(0.002)m(0.01)n ....................... (1)
8.0 × 10–4 = k(0.004)m(0.01)n ....................... (2)
1.6 × 10–3 = k(0.004)m(0.02)n ....................... (3)
8.0 10 4 k (0.004) m (0.01) n
Dividing (2) by (1),   2  2m  m=1
4
4.0 10 m
k (0.002) (0.01) n

1.6 10 3 k (0.004) m (0.02) n

Dividing (3) by (2),   2  2n  n=1
4
8.0 10 m
k (0.004) (0.01) n

Thus, orders of reaction with respect to NO2 and F2 are 1 and 1 respectively, i.e. rate = k[NO2(g)][F2(g)]

1. (c) (i) [H+] and [CH3COCH3] affect the rate but [I2] does not. 1
Neither Alex’s hypothesis nor Hannah’s hypothesis is correct / Both are partially correct.
(ii) An increase in reaction rate with a rise in temperature is due to the increase in the number 1
of collisions.
More importantly, it is mainly due to the increased number of particles possessing energy 1
equal to or greater than the activation energy.
(iii) (1) Graph showing correct curve for Maxwell-Boltzmann distribution 2

Axes correctly labelled – 1 M

Two activation energies shown with and without catalyst – 1 M
(2) Catalyst provides an alternative pathway with lower activation energy. 1
[6]

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 Mark Scheme  2013-DSE-CHEM|MOCK EXAM|Paper 2

NOTE: We can deduce the rate equation of the iodination of propanone from the experimental results given.

CH3COCH3(aq) + I2(aq)   CH3COCH2I(aq) + HI(aq)
H ( aq )

From the plot of rate against [H+(aq)], the rate is directly proportional to the concentration of H+(aq).
From the plot of rate against [CH3COCH3(aq)], the rate is also directly proportional to the concentration of propanone.
From the plot of rate against [I2(aq)], the rate is independent of the concentration of iodine.
Hence, the rate equation is: rate = k[CH3COCH3(aq)][H+(aq)]

1. (d) (i)
1

(ii) Mass of one mole of cyclohexene = (12.0 × 6 + 1.0 × 10) g = 82.0 g

Mass of four moles of hydrogen peroxide = [4 × (1.0 × 2 + 16.0 × 2)] g = 136 g
Mass of one mole of adipic acid = (12.0 × 6 + 16.0 × 4 + 1.0 × 10) g = 146 g
146 1
Hence, atom economy = 100% = 67.0%
82.0  136 1

(iii) The by-product is water, which is harmless. 1

The use of catalyst can speed up the reaction and make the reaction more efficient.
[4]
 Polyamides (Nylons) … for further information
Condensation polymerisation between a dicarboxylic acid and a diamine gives a polyamide – known as nylon.
 Nylon 6.6: hexanedioic acid (adipic acid) + hexane-1,6-diamine amide linkage

The product, having an amino group and a carboxyl group, undergoes further condensation to form a long polymer chain:

O O H H O O H H
n HO C (CH2)4 C OH + nH N (CH2)6 N H C (CH2)4 C N (CH2)6 N + (2n -1)H2O
n
nylon 6.6 (a polyamide)
or: O O H H O O H H
n Cl C (CH2)4 C Cl + n H N (CH2)6 N H C (CH2)4 C N (CH2)6 N + (2n -1)HCl
n
hexanedioyl dichloride hexane-1,6-diamine nylon 6.6 (a polyamide)

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Note: Hexanedioic acid is used in industry because it is much cheaper than hexanedioyl dichloride. The latter is more suitable for

laboratory preparation because it reacts at a much faster rate.

When a solution of hexane-1,6-diamine is poured

gently onto a solution of hexane-1,6-dioyl dichloride,

a thin white film of nylon is formed at the junction of

the two layers. The nylon film can be pulled up as a

string and wound onto a rod.

 Story of nylon: http://www.chemheritage.org/EducationalServices/nylon/nylon.html Lab: http://pslc.ws/macrog/lab/lab01.htm

Note: The nylon 6.6 produced in this way has a molecular mass of about 10 000 and a melting point of about 250C, and can be converted into

fibers by melt spinning. The fibres are then stretched to about four times their original length. This orients the linear polyamide molecules so

that they are parallel to the fibre axis and allows interchain hydrogen bonds to form between -N—H+ and +C=O- groups on adjacent chains.

This so called ‘cold drawing’ stretching greatly increases the fibre’s strength.

Although nylon can be molded into various shapes, most nylon is made into fibres. These fibres ‘dripsdry’ readily as the polymer

chains have relatively few free amide bonds to attract water molecules by hydrogen bonding. It resists creasing (therefore no ironing is

required after washing) and is not readily attacked by insects. Some nylon is spun into find thread, to be woven into silk-like fabrics, and

some made into yarn that is much like wool. Carpeting, which was once made primarily from wool, is now largely made from nylon. Th e yarn

is also woven into fabric to make parachutes or turned into ropes or racket strings for tennis and badminton rackets.

1. (e) (i) Methane reacts with steam under moderate pressures of about 10-20 atm and temperatures
around 850C in the presence of nickel oxide:
CH4(g) + H2O(g) 3H2(g) + CO(g) H = +206 kJ mol–1 1

(ii) (1) HI 1
CH3OH + CO  CH3COOH

(2) The CATIVA process uses iridium (Ir) as catalyst while the Monsanto process 1
uses rhodium (Rh).
[3]
 The Monsanto process is an important method for the manufacture of acetic acid. It was developed by the Monsanto
Company in 1966. This process operates at a pressure of 30-60 atm and a temperature of 150-200°C and gives a selectivity
greater than 99%. The CATIVA process was developed and introduced by the oil company BP Chemicals in 1996. The
reaction is the same as the one in the Monsanto process. Iridium metal is used to replace the rhodium metal.
Advantages of CATIVA process
 Iridium is much cheaper than rhodium.
 Less water is required.
 The reaction rate is faster. The side reaction that produces CO2 and H2 is not likely to occur. This reduces the amount
of by-products produced and cuts the energy cost of purifying the product.

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 Mark Scheme  2013-DSE-CHEM|MOCK EXAM|Paper 2

SECTION C - Analytical Chemistry

3. (a) (i) Rf value is the ratio of the distance moved by the solute to that of the solvent. 1
6.5 5 .1
(ii) Rf of A =  0.94 ; Rf of B = = 0.74 1
6.9 6 .9
1
The banned substance is B.
(iii) Different Rf values for A and B / 1
Different number of spots (1)
[4]
NOTE: For each spot, a Rf value (retardation
factor) can be calculated.
Under the same condition (temperature,
solvent, etc.), substances with the same Rf
values are likely to be identical.
When the Rf values of various substances
under a particular set of conditions are
The Rf value of a substance differs in different solvents and at known, it may be possible to identity certain
different temperatures. substance by paper chromatography.
The positions of the spots are located by some suitable means:
 Coloured components can usually be seen with naked eyes.
 Some colourless substances may be visible in ultraviolet light. Others must be made visible by spraying the paper
with chemicals which react with the solutes to give coloured substances. For example, amino acids give mauve spots
when the chromatogram is sprayed with ninhydrin and kept at about 110°C for ten minutes.

3. (b) (i) Some white fumes will be observed. 1

NH3(g) + HCl(g)  NH4Cl(s) 1
(ii) The relative molecular mass of CH3NH2 is higher than that of NH3. 1
CH3NH2 moves slower than NH3.
[3]

3. (c) (i) I2 + 2S2O32–  2I– + S4O62– 1

(ii) No. of moles of iodine that reacted with sodium thiosulphate
25.5 1
= 0.0155  
1000 2
= 1.975 10-4 mol 1
No. of moles of ozone = 1.975 10-4 mol 1
(iii) Volume of ozone
= 1.975  10-4 mol  24 dm3 mol-1 = 4.74 10-3 dm3 = 4.74 10-6 m3 1
(iv) Residual ozone is quickly converted into odourless oxygen while residual 1
chlorine persists longer.
OR Chlorine has a persistent unpleasant odour/smell while ozone has not. (1)
OR Chlorine forms HCl in drinking water while ozone does not. (1)
[5]
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 Care your mistakes & misconceptions  Polish your -solving skills 

3. (d) (i) Since there is an absorption peak at about 1700 cm-1, a C=O bond is present in F. 1
From the IR spectrum, there is no broad absorption between 2500-3300 cm-1,
it suggests that there is no O—H bond.
Since F is formed from the oxidation of E by refluxing with acidified potassium 1
dichromate solution, it suggests that F is not an aldehyde but a ketone.

(ii) To show the presence of carbonyl group in F, treat F with 2,4-dinitrophenylhydrazine. 1

Yellow / Orange ppt. would be formed.
To further deduce the carbonyl group is from a ketone instead of an aldehyde, perform
silver mirror test using Tollens’ reagent. F gives a negative result on silver mirror test.

(iii) In the mass spectrum the peak with the highest m/z is 86, this suggest that the molecular
mass of compound F is 86.
Let the molecular formula of F (a ketone) be CnH2nO.
12n + 2n + 16 = 86
14n = 70
n=5
The molecular formula of F is C5H10O.
The peak at m/z = 86 is due to the molecular ion C5H10O+ . 1
+ +
The peak at m/z = 71 is due to CH3CH2CH2C≣O / C3H7CO . 1
The peak at m/z = 43 is due to CH3C≡O+ / CH3CO+ . 1

(iv) The most probable structure of F is

H H H O H O
1
H C C C C C H

H H H H

Since oxidation of E gives a ketone, E is a secondary alcohol.

The structure of E is

H OH H H H OH
1
H C C C C C H

H H H H H

[8]
NOTE: The peak at m/z = 43 might also be due to CH3CH2CH2+. However, it is not as stable as CH3CO+.
The high intensity of the peak at m/z = 43 is more likely due to the more stable CH3CO+.

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