2

1 (a) Butanone can be converted to compound C via the following series of reactions.

(i) Suggest the reagents and conditions for step 1.

……………………………………………………………………………………………... [1]

(ii) In the boxes below, draw the structures of compounds A, B and C.

A B

[3]

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(b) 2-iodobutane is converted to its corresponding alcohol by heating with aqueous sodium
hydroxide.

∆H < 0

The rate equation is:

rate = k[2-iodobutane][NaOH]

(i) Describe the mechanism of this reaction. In your answer you should show all charges
and lone pairs and show the movement of electrons by curly arrows.

[3]

(ii) Draw a fully labelled reaction pathway diagram for the reaction between 2-iodobutane
and sodium hydroxide.

[2]

(c) Describe and explain how the volatilities of the halogens vary from chlorine to iodine.

....………………………..………………………………………………………………………......

....………………………..………………………………………………………………………......

..………………………..…………………………………………………………..……………......

..………………………..…………………………………………………………..……………......

..………………………..……………………………………………………….……………….. [2]

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(d) Some hydrogen halides are unstable to heat.

(i) Write an equation for the reaction undergone on heating a hydrogen halide.

……………………………………………………………………………………………... [1]

(ii) Describe and explain how the thermal stabilities of the hydrogen halides (HCl, HBr
and HI) vary down the group.

....………………………..…………………………………………………………………….

....………………………..…………………………………………………………………….

..………………………..……………………………………..……………………..………..

..………………………..…………………………………………………………..………....

..………………………..……………………………………………………….………… [2]

(e) When sodium thiosulfate, Na2S2O3, is reacted with bromine, NaHSO4 is formed. However,
when Na2S2O3 reacts with iodine, Na2S4O6 is formed instead.

Use the following data, and data from the Data Booklet, to suggest an explanation for this
difference.

S4O62− + 2e− ⇌ 2S2O32− Eo = +0.09 V

4SO2 + 4H+ + 6e− ⇌ S4O62− + 2H2O Eo = +0.51 V
SO42− + 4H+ + 2e− ⇌ SO2 + 2H2O Eo = +0.17 V

....………………………..………………………………………………………...…………………

..………………………..……………………………………..………………………..…..………..

....………………………..………………………………………………………...…………………

..………………………..……………………………………..………………………..…..………..

..………………………..……………………………………………………………..…..………....

....………………………..………………………………………………………...…………………

..………………………..……………………………………..………………………..…..………..

..………………………..……………………………………………………………..…..………....

..………………………..……………………………………..………………………..…..………..

..………………………..……………………………………………………………..…..………....

..………………………..…………………………………………………………..….………… [3]

[Total: 17]

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2 (a) 4-Morpholineethanesulfonic acid (MES) is commonly used to prepare buffer solutions. In

aqueous solution, MES exists as a dipolar ion which dissociates to give H + ions:

FA 1 is a buffer solution prepared from MES with a pH of 5.5. The ratio of MES and its
conjugate base is 4:1.

(i) Determine the pKa of MES.

[1]

(ii) State the mole ratio of MES to its conjugate base if the pH = pKa of MES.

[1]

A student titrated 10.0 cm3 of FA 1 with aqueous sodium hydroxide, and found that
20.0 cm3 of aqueous NaOH was required for complete neutralisation.

(iii) What volume of aqueous NaOH should be added to 10.0 cm 3 of FA 1 such that the
pH of the resulting solution becomes equal to pKa of MES?

[2]

(iv) Write an equation to show why the pH at equivalence point is more than 7.

[1]

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(v) The pH of the solution at equivalence point is 9.4. Suggest a suitable indicator for the
titration of FA 1 with aqueous NaOH, giving a reason for your choice.

Indicators Working range

Congo red 3.0 – 5.0
Cresolphthalein 8.2 – 9.8
Indigo carmine 11.4 – 13.0

..………………………..…………………………………………………………………….…

..………………………..………………………………………………………………….……

..………………………..…………………………………………………………………….…

..………………………..…………………………………………………………………….[2]

(b) Zymase, an enzyme that occurs naturally in yeasts, catalyses the fermentation of sugar
into ethanol and carbon dioxide.

sugar  ethanol + carbon dioxide

Fig. 2.1 shows the results of an investigation of the initial rate of fermentation of sugar by
zymase. In the experiments, the initial concentration of sugar was varied but that of zymase
was kept constant.

(i) Explain fully the shape of the graph.

..………………………..…………………………………………………………………….…

..………………………..………………………………………………………………….……

..………………………..…………………………………………………………………….…

..………………………..…………………………………………………………………….[2]

(ii) Sketch on Fig. 2.1 the shape of the line you would expect when the amount of zymase
added was increased. [1]

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(iii) Three other experiments were carried out to measure the initial rates of fermentation
at different concentrations of sugar and zymase. The results are shown in Table 2.2.

Table 2.2

Experiment [sugar] [zymase] Relative initial

/mol dm–3 /mol dm–3 rate
1 0.20 0.10 1
2 0.40 0.10 2
3 0.10 0.20 1

Deduce the orders of reaction with respect to sugar and zymase, showing how you
arrive at your answers.

[3]

[Total:13]

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3 This question is about alkynes, which are hydrocarbons that contain a carbon-carbon triple
bond.

(a) In the past, ethyne gas, C2H2, was prepared from calcium carbide, CaC2. Calcium carbide
is a crystalline solid with a melting point of approximately 2160 °C.

(i) Draw the dot-and-cross diagram of CaC2.

[1]

(ii) When excess water with a drop of universal indicator is added to some calcium
carbide, ethyne is produced and the solution changes from green before the reaction,
to blue after the reaction is complete.

Write an equation, with state symbols, for this reaction.

..………………………..…………………………………………………………………….[1]

(b) (i) Draw the structure of ethyne, showing correct geometry, and clearly indicate the bond
angle in your drawing. State the type of hybridisation of the carbon atoms in ethyne.

Type of hybridisation of carbon: ………………………………... [2]

(ii) Ethyne gas approaches ideal behavior at room temperature and pressure. Identify,
and explain, two characteristics of ethyne that enable it to exhibit ideal gas behaviour.

..………………………..……………………………………………………………….………

..………………………..……………………………………………………………….………

..………………………..……………………………………………………………….………

..………………………..………………………………………………………………….……

..………………………..………………………………………………………………….…[2]

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(c) When completely combusted, ethyne reacts with oxygen according to the following
equation:
5
C2H2(g) + 2O2(g) → 2CO2(g) + H2O(l)

A fixed-volume flask containing a mixture of ethyne and oxygen is connected to a

manometer.

The manometer consists of a U-tube containing some liquid mercury, which is exposed to
atmospheric pressure at one end. Initially, the mercury levels on both arms are at the same
height, as shown in Fig. 3.1 below.

atmospheric pressure

ethyne / oxygen
mixture manometer

liquid mercury

Fig 3.1

When the mixture in the flask was combusted, the final mercury levels in the manometer
showed a difference in height of 65 mm. All measurements were made at room
temperature and pressure. [“mm Hg” is a unit of pressure, where 760 mm Hg = 1 atm]

The initial partial pressures of ethyne and oxygen are x and y mm Hg respectively. After
the combustion, the partial pressure of ethyne changed by p mm Hg.

(i) Express the total initial pressure in the flask in terms of x and y and state its value in
mm Hg.

[1]

(ii) Express the total pressure after the combustion in terms of x, y, and p;

[1]

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(iii) Hence, show that the difference in height of 65 mm in the mercury levels is due to a
decrease in pressure inside the flask.

[1]
(iv) Determine the value of p to 1 decimal place.

[1]

(v) Hence, calculate

(I) the partial pressure, in mm Hg, of carbon dioxide formed after the
combustion;

(II) the values of x and y, assuming all the oxygen was used up during the
combustion, and only carbon dioxide and water were produced in the
process.

[2]

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(d) In more recent years, ethyne has been largely manufactured from methane. One such
conversion only employs heat, and produces ethyne according to the following equilibrium:

2CH4(g)  C2H2(g) + 3H2(g) - - - - - - - - - - - - - - (1)

Equilibrium compositions during the conversion of methane to ethyne in a 0.100 m3 vessel

may be predicted using the simulated data below.

1.6

1.4 H2
equilibrium amount / mol

1.2
CH4
1

0.8

0.6 C2H2

0.4

0.2

0
0 250 500 750 1000 1250 1500 1750 2000

Temperature / oC

(i) Assuming the gases behave ideally in the range of temperatures shown in the graph,
use the simulated data to calculate the pressure of hydrogen gas in the vessel at
1250 °C.

[2]

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(ii) Show that, for equilibrium (1) at 1250 °C,

(n H )3 (n C 2 H 2 ) where
RT 2
Kp = 2
2 ×( ) R is the molar gas constant
(nCH4 ) V T is the temperature in the vessel
V is the volume of the vessel

and hence, calculate Kp, showing its units.

[3]

(iii) State how the value of Kp for equilibrium (1) would change when the temperature is
changed from 1250 °C to 1000 °C.

..………………………..…………………………………………………………………..…[1]

(e) Terminal alkynes can undergo hydroboration-oxidation reactions, as shown below.

(i) Draw and name the product formed when propyne, C3H4, undergoes hydroboration-
oxidation.

name of product: ………………………………………………………………………….. [2]

(ii) Describe a simple chemical test to distinguish propyne from the product you have
drawn in (e)(i). You may assume that propyne reacts similarly to propene.

..………………………..…………………………………………………………………….…

..………………………..………………………………………………………………….……

..………………………..…………………………………………………………………….…

..………………………..………………………………………………………………….…[2]

[Total: 22]

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4 Aromatic compounds like benzene tend to undergo electrophilic substitution reactions.

(a) Explain why aromatic compounds are reactive towards electrophiles but not nucleophiles.
..………………………..……………………………………………………………..…..………....

..………………………..…………………………………………………………..….………… [1]

(b) Explain why aromatic compounds tend to undergo substitution reactions instead of addition
reactions.
..………………………..……………………………………………………………..…..………....

..………………………..…………………………………………………………..….………… [1]

(c) Benzene is a starting material for the synthesis of phenylamine.

(i) State the reagents and conditions for steps 1 and 2.

step 1: …………………………………………………………………………………………

step 2: ………………………………………………………………………………………[2]

(ii) Phenylamine reacts readily with excess aqueous bromine to give a white solid X.
Identify X and write a balanced equation for the reaction that occurs.

[2]

(iii) Suggest the order of reactivity of benzene, nitrobenzene and phenylamine with liquid
bromine. Explain your answer.
..………………………..…………………………………………………………………….…

..………………………..………………………………………………………………….……

..………………………..…………………………………………………………………….…

..………………………..……………………………………………………………………[2]

(iv) Draw the structure of the monobrominated organic product formed when nitrobenzene
reacts with liquid bromine.

[1]

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In 1931, the German chemist Erich Hückel formulated a theory to help determine if a species
would be considered aromatic. This rule became known as Hückel’s rule.

An aromatic species must satisfy all the following criteria:

1. It must be cyclic.
2. Every atom in the ring must have a p orbital.
3. Each p orbital must overlap the p orbitals from either side in a continuous fashion to
form a closed loop, which means the structure has to be planar for effective overlap.
4. The cyclic system must contain (4n+2) delocalised  electrons, where n is 0 or a positive
integer (1, 2, 3 etc.)

For example, benzene is aromatic because it satisfies all the four criteria, with 6 delocalised
 electrons (n = 1).

(d) Consider the following species.

Which species are not aromatic? Explain your answer briefly.

..………………………..……………………………………………………………..…..………....

..………………………..……………………………………………………………..…..………....

..………………………..…………………………………………………………..….………….[2]

Table 4.1 shows information on three aromatic compounds which obey Hückel’s rule.

Table 4.1

hypothetical resonance
actual structure boiling point/
compound structure of pKb energy/ o
of compound C
compound kJ mol−1

pyridine 8.6 134 115

pyrrole 13.6 100 129

furan 80 31

The hypothetical structures of the compounds in Table 4.1 assume that there is no
delocalisation of  electrons in the rings. However, in reality, delocalisation of  electrons gives
rise to the extra stability of the aromatic compounds. The resonance energy is defined as the
energy difference between the actual structure and hypothetical structure of each compound.

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(e) (i) All the carbon and nitrogen atoms in pyrrole are sp2 hybridised.

Draw the arrangement of all the hybridised and unhybridised orbitals of the nitrogen
atom in pyrrole. Label the orbitals clearly.

[2]

(ii) Pyrrole has six electrons in the delocalised  electron cloud.

How many electrons does the nitrogen atom in pyrrole contribute to the delocalised 
electron cloud? You may find it useful to consider the hypothetical structure of pyrrole.
………………………………………………………………………………………………. [1]

(iii) The nitrogen atom in pyrrole has a lone pair of electrons. Suggest the orbital in which
the lone pair resides.
……………………………………………………………………………………………….[1]

(iv) Hence, using your answers in (e)(ii) and (e)(iii), suggest why the pKb of pyrrole is so
high.

..………………………..…………………………………………………………………….…

..………………………..…………………………………………………………………….[1]

(f) (i) Furan can behave differently from benzene in its reactions. Under certain conditions,
furan undergoes electrophilic addition instead of electrophilic substitution. Based on
your answer in (b), explain this phenomenon, using relevant data from
Table 4.1.

..………………………..…………………………………………………………………….…

..………………………..…………………………………………………………………….…

..………………………..…………………………………………………………………….[2]

(ii) Furan can form hydrogen bonds when added to ethanol. Draw a diagram to show how
hydrogen bonding occurs between one molecule of furan and one molecule of ethanol
and explain how this interaction arises.

..………………………..…………………………………………………………………….…

..………………………..…………………………………………………………………….…

..………………………..………………………………………………………………….…[2]

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(g) The enthalpy changes of hydrogenation of pyridine and compound E can be represented
by the equations below:

H1 = −194 kJ mol−1

H2 = −240 kJ mol−1

Using the information above and relevant data from Table 4.1, complete the energy
diagram below and use it to calculate H3.

H3 = ………………………….. kJ mol−1

[3]

[Total: 23]

END OF PAPER

© Hwa Chong Institution 2019 9729 / 02 / C2 Prelim 2019