13 Halogenoalkanes

●● TEST YOURSELF ON PRIOR KNOWLEDGE 1

1 a) i) A saturated carbon compound is one which contains only single
bonds between the atoms in their molecules.
ii) A hydrocarbon is a molecule which contains only carbon and
hydrogen atoms.
iii) A homologous series is a series of compounds which have the
same general formula and the same functional group. They show
a gradation in physical properties and display similar chemical
properties and, in organic chemistry, each successive member
differs from the next by a –CH2group.
2 a) C7H16.
b) There are nine isomers with the molecular formula C7H16 (If you
have studied some optical isomerism, there are eleven isomers
counting all the enantiomers ) All of the isomers are chain isomers.
3 C6H14 + 9.5O2 → 6CO2 + 7H2O

●● TEST YOURSELF 2
1 a) Cl H

Cl C C H

Cl H
b) H Br Br H

H C C C C H

H H H H 1

c) H Cl F

H C C C H

H H H
 2 H H H H
H C C Cδ+ C H
H H Br H
3 The carbon-bromine bond is polar as there is a difference in
electronegativity between the two atoms. The carbon-chlorine bond is
more polar as the difference in electronegativity between the carbon and
chlorine atoms is larger than the difference in electronegativity between
the carbon and bromine atoms.
4 a) 1,3-dibromopropane
b) 3-chloro-2-iodopentane
c) 1,1dichloro-1-fluorobutane
d) 1,3-dibromo-3-methylbutane
5 a) C2H5Br
b) C2H5Br
c) CH3CH2CH2CH2Br

●● TEST YOURSELF 3
1 a) free radical substitution
b) i) Cl2 → Cl● + Cl●
ii) Cl● + C2H6 → ●CH2CH3 + HCl
●CH CH
2 3 + Cl2 → Cl● +CH2ClCH3
iii) ●CH2CH3 + Cl● → CH2ClCH3
13 HALOGENOALKANES

●CH CH
2 3 + ●CH2CH3 → CH3CH2CH2CH3
c) There are several different tri-substituted halogenoalkanes you can
draw. Ensure you have either two or four carbons in the molecule
each with three chlorine atoms. You can place a maximum of three
chlorine atoms on the end carbons and two on the carbons in the
chain.

●● TEST YOURSELF 4
1 a) A mechanism is a detailed step-by-step sequence illustrating how an
2 overall reaction occurs.
b) A curly arrow shows the movement of a pair of electrons. It must
begin at a lone pair of electrons or in the centre of a covalent bond
and end at an atom or in the centre of a bond.
c) A nucleophile is an electron pair donor.
d) A base is a proton acceptor.
 2 a) H H H H H H H H

REQUIRED PRACTICAL
H C C Cδ+ C H H C C C C H + Br–
H H Brδ– H H H OH H
–
OH

b) reagent: sodium hydroxide

reaction conditions: aqueous
dissolve halogenoalkane in the minimum volume of ethanol
reflux gently
c) nucleophilic substitution
d) CH3CH2CHBrCH3 + NaOH → CH3CH2CH(OH)CH3 + NaBr
3 a) The halogenoalkane is dissolved in a minimum volume of ethanol. The
halogenoalkane-ethanol solution will mix with an aqueous solution.
b) H H H H H H H H
H C C Cδ+ C H H C C C C H + Br–
H H Brδ– H H H C H
–
C N N
c) 2-methylbutanenitrile
d) CH3CHBrCH2CH3 + KCN → CH3CH2CHCNCH2CH3 + KBr
4 a) 2NH3 + CH3CHClCH3 → CH3CH(CH3)NH2 + NH4Cl
b) 1-methylethylamine
c) The second molecule of ammonia accepts a proton from the
positively charged reactive intermediate.
d) Excess ammonia in a sealed tube under pressure.
e) The organic product is also a nucleophile and can react with the
2-chloropropane producing further substituted amines.

●● REQUIRED PRACTICAL
Preparation of 1-bromobutane
3
1 C4H9OH + HBr → C4H9Br + H2O
2 a) H2SO4 + NaBr → NaHSO4 + HBr
b) Sulfuric acid is reduced by the bromide ion
3 The reaction is exothermic, so this controls the reaction and prevents
violent spitting.
4 Anti-bumping granules
5 Add a still head, add a thermometer, move condenser from upright to
sideways position, put receiver on end of condenser.
 6 a) Shake in a separating funnel, invert and release the pressure, remove
the stopper and run off the layer.
b) Sulfuric acid
7 water
8 Moles of butanol = 21.8/74.0 = 0.29
Moles of sodium bromide = 40/102.9 (excess) = 0.39
Moles 1-bromobutane = 0.29 = mass/136.9; mass = 40 g
% yield = actual yield/theoretical yield = (3.55/40) × 100 = 8.9%
9 Practical – loss during transfer, loss during distillation.
Theoretical – side reactions produce a different product, reaction does
not go to completion

●● ACTIVITY
Preparation of methylpropene gas
1 H

H C H
H

H C C Cl

H
H C H
13 HALOGENOALKANES

H
2 It cannot form hydrogen bonds with water
3 a) C4H9Cl + KOH → C4H8 + KCl + H2O
b) elimination
4 The volume of gas in the apparatus is less as it cools down, and water is
sucked back due to pressure differences.
Remove the delivery tube from the water after heating, or disconnect the
4 delivery tube
5 Density = mass/volume; 0.8 = mass/2; mass = 1.6 g
1.6 = 0.0173
Moles =
92.5
Moles of methylpropene = 0.0173 (1 : 1 Ratio)
Volume methylpropene = 24 × 0.0173 = 0.415 dm3
6 a) C4H9Cl + NaOH → C4H9OH + NaCl
b) nucleophilic substitution.