Section A [15 marks]

Answer all questions in this section

1 Which compound does not contain tertiary carbon atom?
A Phenol B 1-Methylcyclohexanol C Cyclohexenol D Cyclohexanol
Ans: OH CH3 OH OH H OH
| \ / | \ /
C H C H H C H C H
// \ \ / \/ \ / \ \ \ / \ /
H–C C–H H–C C–H H –C C–H H–C C–H
| || | | | | | |
H–C C–H H–C C–H H –C C–H H–C C –H
\\ / / \ /\ / \ / \ / \ / \
C H C H H C H H C H
| / \ / \ / \
H H H H H H H
There are two ways to state the degree of C, first the degree is the number of C atoms attached to the carbon
concerned. Secondly the number of H attached to the carbon concerned, CH 3 primary, CH2 secondary, CH
tertiary and >C< quartenary. The second rule is to be given preference when in doubt.
The answer is D. Given answer is D

2 Which molecule has a carbon atom with sp3 hybrid orbitals?

A CH3CH3 B CH2 = CH2 C CH ≡ CH D C6H6
Ans: CH3 – CH3 CH2 = CH2 CH ≡ CH H
|
C
// \
H–C C–H
| ||
H–C C–H
\\ /
C
|
H
For hybridisation, Group 14, 15, 16 with single, double and triple bonds are sp 3, sp2 and sp hybridised
respectively.
Answer is A. Given answer is A

3 Which of the following is not a nucleophile?

A OH- B NH3 C NO2+ D NaCN
Ans : A nucleophile which is electron-rich is a negatively charged species or a neutral molecule with lone
pairs that can be donated to another atom to form a coordinate bond. Here OH - is the nucleophilic substitition
in the alkaline hydrolysis of haloalkanes to produce alcohols, NH3 is in the nucleophic substition with
haloalkanes to produce amines and NaCN is :CN- is in the nucleophilic substtition with haloalkanes to
produce nitriles.
Answer is C. Given answer is C
NO2+ is a electrophile in the nitration of benzene by electrophilic substitution mechanism

4 The following shows the structure of three organic compounds that show stereoisomerisms.

HOCH2CH(OH)CH2CH3 CH2=CHCH(CH3)CH2OH CH3CH2C(CH2)=CHCH3

I II III
What type of stereoisomerism is shown by each of the compound?
I II III
A Optical Geometrical Geometical
B Optical Optical Geometical
 C Optical
D Geometical Optical
Ans: HOCH2C*H(OH)CH2CH3
chiral C
Answer is B. Given answer is B
Geometical Optical
Geometrical
CH2=CHC*H(CH3)CH2OH CH3CH2C(CH2)=CHCH3
2 same gp chiral C 2 diff. gps
attached to the unsat. C attached to unsat.C

5 The reaction between methane and bromine is performed in the presence of ultraviolet light. The main
reason for the presence of ultraviolet light is
A break up the C – H bond in ethane
B break up the bromine molecules into bromine atoms
C break up the bromine molecules into bromine ions
D increase the rate of reaction
Ans: There are 3 reactions involving alkanes: halogenation, combustion and cracking. Halogenation is
carried in the presence of uv light and the mechanism is free radical substitution. The free radical mechanism
consists of 3 steps: initiation, propagation and termination. In the initiatioin step, the Cl 2 molecules absorbs
the energy of the uv light and undergoes homolytic fission to form Cl. free radicals.
Answer is B. Given answer is B

6 An organic compound,X, undergoes oxidation and addition with acidified potassium dichromate solution.
What is X?
A Benzene B Toluene C cyclohexane D 2-butene
Ans: The hydrocarbons alkene undergo oxidative cleavage with acidified K 2Cr2O7 or acidified KMnO4 and
forms diols(addition reaction) with cold alkaline KMnO4. The side chains of arenes undergo oxidation with
acidified KMnO4 and acidified K2Cr2O7 to form benzoic acid.
Answer is B. Given answer is D. D is the correct answer. Alkane doesn’t undergo oxidation nor addition
reactions.

7 Benzene and ethylbenzene can be differentiated using

A concentrated nitric acid B bromine in tetrachloromethane
C acidified potassium manganate(VII) D bromine water
Ans: Arenes, such as benzene and ethylbenzene undergo nitration with an equimolar mixture of concentrated
nitric and concentrated sulphuric acid. Bromination without the presence of Lewis halogen carriers is the
electrophilic addition reactions for alkenes. Alkenes also undergo electrophilic addition with bromine water (
The other reaction with bromine water which can be of concern would the addtion of bromine water to
phenol which gives a white precipitate). The side chains of arenes such as in ethylbenzene can be oxidised by
hot acidified KMnO4 to give benzoic acid and if needed liberate CO2. Here acidified KMnO4 is added to
benzene and ethylbenzene separately. When heated, ethylbenzene changes the solution from purple to
colourless whereas benzene shows no visible change.
C6H5C2H5 + 6[O] + --> C6H5COOH + CO2 + 2H2O
Answer is C. Given answer is C

8 A cracking process was carried out on unidecane, C11H24 at 8000C and high pressure. Which of the
following compounds are produced in the process?
A Ethane, propane and pentane B Ethane, propane and pentene
C Ethane, propene and pentene D Ethene, propene and pentene
Ans : There are 3 reactions undergone by alkanes: halogenation, combustion and cracking. Cracking can be
thermal or catalytic. For thermal cracking, high temperature ( 650 0 C to 9000C) and high pressure is used and
the process produces a mixture of smaller alkanes and alkanes. Catalytic cracking invovles a lower
temperature of 4500C and low pressure and the zeolites as catalysts to produce branched alkanes and
aromatic hydrocarbons.
Answer is C. Given answer is C. Note the number of C atoms should add up to 11 and there should be one
smaller alkane

9 Which of the following compounds will react with benzene to form cumene?
A CH3COCl B (CH3)3CBr C C6H5I D CH3CH(Cl)CH3
Ans: The arenes undergo 10 reactions: halogenation by electrophilic substitution and also free radical
substitution for side chains and free radical addition for benzene, nitration, Friedel-Crafts acylation, Friedel-
Crafts alylation, sulphonation, oxidation of side chain and catalytichydrogenation of benzene and
combustion. Cumene is isopropylbenzene or (1-methylethyl)benzene which can be obtained by Friedel-
Craft’s acylation which involves the haloalkanes such as CH 3CH(Cl)CH3 and benzene in the presence of
Lewis halogen carriers
by electrophilic substitution reaction.
Answer is D. Given answer is D

10 Which of the following functional groups is electron-donating when attached to a benzene ring?
A – OH B – COOCH3 C – COCl D – NO 2
Ans: For electrophilic substitution reaction, a prior substituent affects the reactivity and orientation of
subsequent substituent. From Worlander’s rule: saturated groups such as OH and alkyl groups are ring
activating and o-p directing and unsaturated groups such as ester, acyl and nitro groups are ring deactivating
and m-directing, but halogens are ring deactivating but o,p-directing. The ring activating is when the group
donates electrons to the benzene ring.
Answer is A. Given answer is A

11 Which of the following is true about SN2 mechanism?

A It is a first order reaction
B Involves the formation of an acitivated complex
C The reaction occurs in two steps
D tertiary haloalkanes prefer to undergo this mechanism
Ans: Haloalkanes undergo nucleophilic substitution in 7 reactions: alkaline hydrolysis to produce alcohols,
with alcoholic alkali to give alkenes, with cyanide ions to give nitriles, with ammonia to give amines, with
AgNO3 and with water to give alcohols and produces Grignard reagents with Mg turnings. Primary
haloalkanes undergo SN2 and tertiaryhaloalkanes undergo SN1.. SN2 is bimolecular nucleophilic substitution is
is second order reaction overall. It involves one step and the intermediate has a five bonded C.
Answer is B. Given answer is B

12 Which of the following would react with C6H5MgCl, followed by acidic hydrolysisto produce a tertiary
alcohol?
A carbon dioxide B 2-propanol C methanal D 2-methyl-2-pentanol
Ans: Haloalkanes undergo 7 reactions: alkaline hydrolysis to produce alcohols, with alcoholic alkali to
produce alkenes, with cyanide ions to produce nitriles, with ammonia to produce amines, with AgNO 3 to
give precipitates of the halides concerned, with water to produce alcohols, and with Mg turnings to give
Grignard reagents, RMgX. And Grignard reagents with water gives alkanes, with CO 2 yields carboxylic acid,
with methanal gives primary alcohol, with other aldehydes give secondary alcohol and with ketones give
tertiary alcohol.
Answer is . Given answer isD. Methinks option D should be changed to 2-methyl-3-pentanone

13 Ethene can be obtained from bromoethane by reacting the bromoethane with

A aqueous solution of NaOH B ethanolic NaOH C phosphorus pentachloride D dry ether
Ans: The reaction of haloalkanes when heated under relux with alcoholic alkali gives alkenes.
Answer is B. Given answer is B

14 Which of the following organic compounds produces a white precipitate the fatest when it is shaken
vigorously with ethanoic silver nitrate at room temperature?
A CH3CH2CH2Cl B CH3 C -- CH2Cl D Cl -- -- CH3
|
CH3CH2 – C – Cl
|
CH3
Ans: Haloalkanes when heated with an alcoholic alkali and then acidified with nitric acid and then AgNO 3
solution is added, a precipitate is formed. The colour and solubility in NH 3 solution identifies the halogen
atom present: white precipitate which dissolves in dilute ammonia shows the presence of chloroalkane, a
pale cream precipitate which dissolves in concentrated ammonia is bromoalkane and a pale yellow
precipitate which doesn’t dissolve even in concentrated ammonia gives the presence of iodoalkane. Also the
ease of the formation of the silver halide precipitate shows the type of haloalkane and class of haloalkane :
precipitate within a few seconds shows iodoalkane or 3 0 haloalkane, within 2 minutes bromoalkane or 20
haloalkane and after 10 minutes shows the presence of chloroalkane or 1 0 haloalkane
Answer is B. Given answer is B. Haloarenes(option D) don’t undergo the test with AgNO 3 and
(chloromethyl)benzene (option C) is a primary haloalkane

15 The structure of an organic compound X is shown as follows.

– CH2CH3Cl
/
Cl
Which is the structure of the product is compound X is refluxed with aqueous sodium hydroxide solution?

A – CH=CH3 B --CH2CH2OH C --CH2CH2Cl D

--CH2CH2OH
/ / / /
Cl Cl OH OH
Ans: Haloalkanes undergo nucleophilic substitution when heated with aqueous alkali to give alcohols.
Haloarenes don’t undergo nucleophilic substitution.
Answer is B. Give answer is B

Section B [ 15 marks]
Answer all questions in this section
16(a) Explain the term stereoisomerism
Stereoismerism is when molecules with same molecular formula and structural formula but different
_____________________________________________________________________________________
spatial arrangement of atoms.
______________________________________________________________________________[ 2 marks]

(b) What are the two main types of stereoisomerisms?

Optical isomerism and geometrical isomerism
_______________________________________________________________________________[ 1 mark]

(c) Draw all the possible stereoisomers for the following compounds

CH3 – CH – CH = CH – CH2Br
|
OH
Optical isomers H Optical isomers H
| |
C C
/ \
H3C BrH4C3 CH3
C3H4Br
OH OH
Geometic isomerism Geometric isomerism
HOC2H4 CH2Br HOC2H4 H
\ / \ /
C = C C =C
/ \ / \
H H H CH2Br
cis isomer trans isomer

[ 4 marks]
(d)Which of the two isomers will have the same boiling point?
Optical isomers

_______________________________________________________________________________[ 1 mark]

17 3- Methylcyclohexene yields more than one product when it reacts with hydrogen bromide.
(i) Draw the structures of the products formed [ 2 marks]

CH3 CH3
| Br |
/

\
Br
1-bromo-2-methylcyclohexane 1-bromo-3-methylcyclohexane
( There is no major or minor product as the alkene is symmetrical)

(ii) Suggest a reagent which can be used to differentiate 3-methylcyclohexene from 3-methylcyclohexane.
Add cold alkaline KMnO4 to both reagents separately. 3-methylcyclohexene changes the colour from
green to brown while 3-methylcyclohexane gives no visible change.
Answer scheme: Add Br2 in CCl4
_______________________________________________________________________________ [ 1 mark]

(b) The following scheme shows several chemical reactions startging from benzene.

CH2CH3
Step W | KMnO4/H+ C6H5COOH

Br2/uv X

CH(Br) CH3
|

Y(Major product)
(i) State the reagent in step W [ 1 mark]
chloroethane ( Answer scheme : in the presence of AlCl 3)
_______________________________________________________________________________________
(ii) Write an equation for the formation of the electrophile in step W [ 1 mark]
+ -
CH3CH2Cl + AlCl3 --> CH3CH2 + AlCl4

(iii) Draw the strutural formulae of compound X and Y in the boxes provided above [ 2 marks]

Section C

18(a) A hydrocarbon has an empirical formula of C9H10 and relative molecular masss of 118.
(i) Determine the molecular formulae of the hydrocarbon. [ 1 mark]
 From m.f. = (e.f)n
118 = ( 9(12) + 10(1))n
n =1
empirical formula is C9H10

(ii) Draw the structural formulae of the isomers of this hydrocarbon.

Name these isomers according to the IUPAC nomenclature. [ 6 marks]
Since C:H ≈1:1, the compounds are aromatic and the formula doesn’t correspond to the arene formula
with saturated side chain, C9H10 ≠ CnH2n-6 so there must be an unsaturated side chain

CH2CH=CH2 CH3C=CH2
| |

3-phenyl-1-propene 2-phenyl-1-propene

CH=CH2 CH=CH2 CH=CH2

| CH
3 | | /
\
CH3
|
CH3
(2-methylphenyl)ethene (3-methylphenyl)ethene (4-methyphenyl)ethene

(b) An amount of 0.01 mol of a hydrocarbon is burnt in excess oxygen. The products of these combustion are
passed through anhydrous calcium chloride and then through potassium hydroxide solution. The masses of
anhydrous chloride and potassium hydroxide solution increase by 0.72 g and 1.76 g respectively
(i) Detemine the empirical formula and molecular formula of the hydrocarbon [ 4 marks]
mH = (2/18)(0.72)= 0.08 g mC =(12/44)1.76 =0.48 g
CxHy :C:H = 0.01: 0.48/12: 0.08/1 = 0.01: 0.04:0.08 = 1:4:8
empirical fromula is C4H8
(note to scribe: mH + mC = mhydrocarbon = 0.56 g which divided by Mr gives mole)

(ii) Draw the structural formulae of all the isomers of the hydrocarbon [ 4 marks]
CH3CH2CH=CH2 , CH3CH=CHCH3, CH3C(CH3)=CH2 and
1-butene 2-butene methylpropene cyclobutane methylcyclopropane

19(a) 2-methyl-2-iodopropane reacts with warm aqueous sodium hydroxide to produce 2-methyl-2-propanol.
(i) Name and describe the mechanism of the reaction [ 4 marks]
The reaction is called alkaline hydrolysis, the mechanism is S N1 or unimolecular nucleophilic substitution
for 2-methyl-2-iodopropane is a tertiary haloalkane. The S N1 occurs in two steps.
The first step is the slow step is the formation of the carbonium ion
CH3 CH3
| |
CH3 – C – I --> CH3 – C+ + I-
| |
CH3 CH3
The 2nd step, the fast step, is the rapid additon of the OH - nucleophile
CH3 CH3
| |
CH3 – C+ :OH- --> CH3 – C – OH
| |
CH3 CH3
(ii) Draw the reaction energy profile for the reaction [ 3 marks]

Energy

(CH3)3C+

(CH3)3CI + OH-

(CH3)3COH + Cl-

(iii) What would be the effect on the rate of reaction is 2-methyl-2-iodopropane is replaced with 2-methyl-2-
chloropropane. Explain your answer. [ 3 marks]
The rate of a nucleophilic substitution reaction either S N1 or SN2 would depend inversely on the strength of
the C – X, carbon- halogen bond as the rate-determining step involves the breaking of the C – X bond. The
weaker the bond the easier to break the C – X bond and the more reactive the substitution reaction. So 2-
methyl-2-chloropropane with the smaller Cl atom would have a shorter C – Cl bond length and so a bigger
bond strength and more energy is needed to break it and so has a lower rate of reaction.

(b) Compound X can be converted to its isomer, Y, as follows:

Cl
|
CH2CH2Cl CHCH3
/ --> /

X Y

(i) Show how this conversion can be carried out. [ 3 marks]

First heat strongly X under reflux with ethanolic sodium hydroxide solution which gives an alkene

CH2CH2Cl CH=CH2
/ --> /
+ H2O

Then bubble in HCl gas at room temperature to the product above to give a secondary haloalkane

CH=CH2 CH(Cl)CH3
/ --> /
+ HCl

(ii) Which compound X or Y, reacts faster with aqeous solution NaIOH via S N2 mechanism? Give a reason
for your answer. . [ 2 marks]
The reactivity of a nucleophilic substitution, either SN1 or SN2, would be proportional to the degree of the
haloalkane. The greater the degree of the haloalkane the greater the rate of reaction, so Y would react faster.
Another answer, the correct answer: The nucleophilic proceeds mainly by S N1 or SN2 depends on 3 factors:
the degree of the haloalkane, primary haloalkane favours S N2 due to lesser steric hindrance while tertiary
haloalkane favours SN1 due to greater stability of tertiary carbonium ion, the second factor would be the
strength of the nucleophile stronger nucleophile such as negatively charged OH - favours SN2 while weaker
nucleophile such as NH3 favours SN1, the third factor would be the solvent: polar aprotic solvent favours S N2
while polar protic solvent favours SN1. So X a primary haloalkane reacts faster by SN2

20(a) An experiment is conducted by bubbling chlorine gas into methylbenzene in the presence of sunlight
without a catalyst
(i) Draw the structural formulae of all the organic compounds that may be formed [ 2 marks]
CH2Cl CHCl2 Ccl3
| | |

(chloromethyl)benzene (dichloromethyl)benzene (trichloromethyl)benzene

(ii) Write the mechanism for the formation of the compounds. [ 4 marks]
uv
The equation: C6H5CH3 + Cl2 --> C6H5CH2Cl + HCl
The mechanism is free radical substitution
The mechanism has three steps:
Initiation uv
Cl2 --> 2Cl∙
Propagation,
Cl∙ + C6H5CH3 --> C6H5CH2∙ + HCl
C6H5CH2∙ + Cl2 --> C6H5CH2Cl + Cl∙
Termination,
Cl∙+Cl∙ --> Cl2

(b) In another separate experiment, chlorine gas is bubbled into methylbenzene in the presence of aluminium
chloride
(i) Draw t he structural formulae of the major organic compounds formed. [ 2 marks]
CH3 CH3
| Cl |
/

|
Cl

(ii) Write the mechanism for the formation of one of the compounds [ 4 marks]
The reaction : CH3 CH3
| AlCl3 | Cl
+Cl3 --> /

The reaction mechanism is eletrophilic substitution which has 3 steps

1st step: formation of electrophile, Cl+
Cl2 + AlCl3 --> Cl+ + AlCl4-

2nd step, the slow step: electrophilic attack and the formation of the arenium intermediate
CH3 CH3

| | Cl Cl+ --> /
 + H
3rd step: loss of proton and regeneration of benzene ring
CH3 CH3
| Cl
| Cl + --> /
H + H+

H+ + AlCl4- --> HCl + AlCl3

(c) State a chemical test to differentiate between methylbenzene and benzene [ 3 marks]
Add hot acidified KMnO4 to methylbenzene and benzene separately. Methylbenzene changes the
solution from purple to colourless while benzene shows no visible change
CH3 COOH
| |
+2[O] -->