Raffles Institution

Year 5 H2 Chemistry 2017

Tutorial 10: Hydrocarbons – Alkanes (Suggested Answers)

Self-Check Questions – Suggested Answers

1 (a) (i) 3,3-diethyl-4-methylheptane

(ii) 4-ethyl-2,2,3,6-tetramethyloctane
(iii) 3-ethyl-2,7-dimethyloctane
(iv) 2,2,5-trimethylheptane
(v) 3,3,4-triethylhexane

(b) (i) 2,4,5-trimethylheptane

CH3 CH CH2 CH CH CH2CH3

CH3 CH3 CH3 or

(ii) 3-ethyl-2,4-dimethylhexane

CH2CH3
CH3 CH CH CH CH2CH3
CH3 CH3 or

2 The given compounds have simple molecular structures and can be arranged in the
following order of increasing boiling point:
2-methylpentane < hexane < 3,3-dimethylpentane < 2-methylhexane < heptane
i.e. (e) < (d) < (c) < (a) < (b)

Comparing (c), (a) and (b) vs (e) and (d)

• (c), (a) and (b) are seven-carbon alkanes while (e) and (d) are six-carbon alkanes. (c),
(a) and (b) have more electrons per molecule and hence, larger and more polarisable
electron clouds than (e) and (d). Hence, the instantaneous dipole-induced dipole
interactions in (c), (a) and (b) are stronger and more heat is required for boiling these
alkanes, resulting in them having a higher boiling point than (e) and (d).

Comparing (c), (a) and (b)

• the degree of branching decreases from (c) to (a) to (b)
• there is increasing surface area of contact between molecules from (c) to (a) to (b)
• strength of instantaneous dipole-induced dipole interactions increases from (c) to (a) to
(b)
• higher boiling point from (c) to (a) to (b)

Comparing (e) and (d)

• the degree of branching decreases from (e) to (d),
• there is greater surface area of contact between molecules of (d),
• hence stronger instantaneous dipole-induced dipole interactions in (d)
• higher boiling point for (d)
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3 Reaction (1): Combustion

Δ
burn
+ 9 O2 6 CO2 + 6 H2O

Reaction (2): Free-radical substitution

uv light Cl
+ 2 Cl2 + 2 HCl
Cl

3n + 1
4 CnH2n+2 + O2(g) → n CO2(g) + (n+1) H2O(l)
2

No. of moles of O2
amount of O2/mol

gradient = 1.5

2
0.5
No. of C atomsnumber of
1 0
0 C atoms

5(a) Volume of unreacted O2 and CO2 = 250 cm3

Volume of unreacted O2 = volume of residual gas (after shaking with NaOH) = 100 cm3
Volume of CO2 produced = 250 – 100 = 150 cm3

From the table, x = 5

And (x + y/4) = 8 ⇒ y = 12
Hence, the molecular formula of the hydrocarbon is C5H12.

5(b)

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Practice Questions – Suggested Answers

1(a) Conditions: uv light (or sunlight or heat) and excess CH4 (or limiting amount of Cl2)

1(b) Name of mechanism: free-radical substitution

The mechanism involves a chain reaction which consists of the following steps:

Step (1): Initiation

ultraviolet light
Cl Cl or sun Cl + Cl
light or heat

Step (2): Propagation

(a) CH4 + Cl• → •CH3 + HCl

(b) •CH3 + Cl2 → CH3Cl + Cl•
Then (a), (b), (a), (b), …...
Step (3): Termination
Cl• + Cl• → Cl2
Cl• + •CH3 → CH3Cl
•CH3 + •CH3 → CH3CH3 (trace amount)
1(c) Consider the 2 propagation steps:
(a) CH4 + Cl• → •CH3 + HCl
(b) •CH3 + Cl2 → CH3Cl + Cl•
------------------------------------------------------------------
Overall reaction: CH4 + Cl2 → CH3Cl + HCl
------------------------------------------------------------------
Summation of the 2 propagation steps gives the equation for the overall reaction. In this case, Cl•
serves as a catalyst for the reaction as it participates in the reaction and is regenerated.

The reaction is an example of homogeneous catalysis since the catalyst, Cl•, exists in the same
gaseous phase as the two reactants, CH4 and Cl2.
1(d) ∆Hreaction = ∆Hf [CH3Cl (g)] +∆Hf [HCl (g)] – ∆Hf [CH4(g)] = – 82 – 92 – (–75)
= –99 kJ mol–1

1(e) Note: Not drawn to scale

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2(a)(i) 2(a)(ii) CH2CH3
CH3CH2 C CH2CH3
CH3
or

2(b)(i) ultraviolet light

CH3(CH2)6CH3 + Br2 CH3CH2CHBr(CH2)4CH3 + HBr

2(b)(ii) The mechanism is free-radical substitution which involves a chain reaction consisting of the
following steps:
Step 1: Initiation
ultra-violet light
Br Br Br + Br

Step 2: Propagation

Step 3: Termination

Note: Skeletal formulae may be used.

Step 1: Initiation
ultra-violet light
Br Br Br + Br
Step 2: Propagation

Then (a), (b), …

Step 3: Termination

2(b)(iii) Red-brown (or brown or orange) Orange-red bromine is decolourised and white fumes of HBr
which turn damp blue litmus paper red are formed.
2(b)(iv) A flash of ultraviolet light provides enough energy for some Br2 molecules to undergo homolytic
bond fission to form Br• radicals. Once the Br• radicals are generated in the initiation step, the
chain reaction is started and the propagation steps can proceed successively for many
cycles un-aided.
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2(b)(v) Use an excess of octane (or use a limiting amount of Br2).
2(b)(vi)
∆H of reaction for the 1st propagation step = BE(C–H) – BE(H–I) = +410 – 299 = +111 kJ mol–1

The first propagation step is endothermic due to the breaking of the relatively strong C−H
bond and the formation of the weaker H−I bond. This makes it difficult for the chain
propagation steps to occur. Thus, the formation of 3-iodooctane is energetically unfavourable.
3(a) The mechanism is free-radical substitution which consists of the following steps:
Step 1: Initiation

Step 2: Propagation

(a)
+ Cl + HCl

(b)
+ Cl2 + Cl
Cl
Then (a), (b), (a), (b), ..….

Step 3: Termination

Cl + Cl Cl2

+ Cl
Cl

(trace amount)
3(b) The mechanism is free-radical substitution which consists of the following steps:
Step 1: Initiation

Step 2: Propagation

H + HBr
(a) + Br
H

+ Br + Br
(b) Br Br

Then (a), (b), (a), (b), …...

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 Step 3: Termination

(trace amount)

4(a) 83.72 (100−83.72)

Molar ratio of C to H in alkane F = : = 6.977 : 16.28 = 1 : 2.33 = 3 : 7
12.0 1.0
Note #1:
Hence, the empirical formula of F is C3H7. • Can proceed by trial and error to find
m.
• In this case, m ≠ 1 and m ≠3
Let the molecular formula of F be (C3H7)m, i.e. C3mH7m.
• When m = 2, the molecular formula is
The general formula of an alkane is CnH2n+2. C6H14 which fits that of a six-carbon
In this case, 3m = n alkane.
and 7m = 2n + 2 Note #2:
Upon solving the simultaneous equations, m = 2 • Let F have n carbon atoms and have
Hence, the molecular formula of F is C6H14. the general alkane formula, CnH2n+2.
• Then % of carbon (by mass) in F
12n
=( x 100) = 83.72
14n+2
F undergoes free-radical substitution reaction with Hence n = 6.06 = 6
Br2 to form only two mono-brominated products.
Note #3:
⇒ There are 2 types of H atoms in a molecule of F. • F is not a cycloalkane since percentage
⇒ F has to be of carbon by mass in a cycloalkane is
not 83.72%.

H is a mono-brominated product and is chiral.

⇒ H contains a chiral carbon atom.
⇒ H is

Note: ∗ denotes a chiral carbon atom

G is the other mono-brominated product.

⇒ G is

4(b) To form G from F, the Br atom can replace any one of the 2 tertiary hydrogen atoms.
To form H from F, the Br atom can replace any one of the 12 primary hydrogen atoms.
Hence, based on probability factor and assuming all the hydrogen atoms have the same
reactivity, the approximate molar ratio in which G and H are formed = 2 : 12 = 1 : 6

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5
1,5-dichloropentane 2,4-dichloropentane 3,3-dichloropentane
Cl
CH2 CH2CH2CH2 CH2 CH3 CH CH2 CH CH3
Molar ratio based on CH3CH2 C CH2CH3
Cl Cl Cl Cl
probability factor and Cl
assuming that all the = 6x3 : 4x2 : 2x1
H atoms have the = 18 : 8 : 2
same reactivity = 9 : 4 : 1

The 1st Cl atom can The 2nd Cl atom can replace any
replace any one of the 6 one of 3 primary hydrogen atoms
primary hydrogen atoms. of -CH3 group in 1-chloropentane.

6 X, Y and Z are ethane, propane and butane respectively.

X Y Z
CH3CH3 CH3CH2CH3 CH3CH2CH2CH3
Molar ratio = (½) (½) : (2)(½)(½) : (½) (½)
= ¼ : 2/4 : ¼
= 1 : 2 : 1

*7 Note:
• May have alternative answers. Accept any set of sensible answers.
• Suggested approach: Start from ethane, then propane and so on.

P P1 P2 and P3
CH3CH2CH2CH3 CH3CH2CH2CH2Cl
CH3 CH3

C C
H H
CH3CH2 CH2CH3
Cl Cl

mirror
plane

Q Q1 and Q2 R S

CH3 CH3 CH3 Cl2 HCl

CH3 C CH3 CH3 C CH3 CH3 C CH2Cl
H Cl and H

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