TAMPINES JUNIOR COLLEGE 2013 JC1 H2 Chemistry Tutorial Organic Chemistry: Alkanes Self Check Questions 1 Alkanes consist

of C and H atoms joined by only single covalent bonds, hence alkanes are known as saturated hydrocarbons. 2 Each C atom in alkanes is sp3 hybridised, hence the geometry about each of the C atoms in alkanes is tetrahedral. 3 Alkanes has the general formula CnH2n+2 but cycloalkanes share the same general formula CnH2n with alkenes Hence, cycloalkanes and alkenes exhibit structural isomerism. 4 Alkanes are non-polar molecules held by induced dipole-induced dipole interactions The melting and boiling points of the alkanes increase when the strength of this intermolecular force increases due to an increase in either one of the following factors: (a) the number of electrons per alkane molecule and (b) the surface area of the alkane molecule. An increase in branching makes the alkane molecule more compact and hence decrease the extent of the intermolecular force. 5 6 Alkanes undergo free radical substitution mechanism, which involves three steps. Step 1, initiation, involves the homolytic fission of the halogen molecules (X2) in the presence of sunlight to produce free radicals which are highly reactive species, each having an unpaired electron. (To illustrate the mechanism for this first step, it is important to show two half arrows pointing from the X X bond to each of the X atom with the condition written on the arrow.) 7 Step 2,propagation, involves firstly, the cleaving of C H bonds and the forming of H X bonds (i.e. the abstraction of a hydrogen atom by an X free radical). Secondly, the cleaving of X X bonds and the forming of C X bonds will occur. (i.e. the abstraction of a X atom by an alkyl radical. To substitute a hydrogen atom with a halogen atom, two propagation steps is needed.) 8 Step 3,termination, is the combination of any two free radicals.

Complete the following:

excess CH3CH3 / limited Br2

CH3CH3
excess Br2 / limited CH3CH3

excess air / O2(g)

2CO2 + 3H2O

limited air / O2(g)

CH3CH2Br

CBr3CBr3

2CO + 3H2O

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Cracking involves the breaking down of long chain alkanes to shorter chain alkanes, which are more useful.

11

Catalytic cracking involves SiO2 Al2O3, which is a catalyst. Hence, it requires a lower temperature than thermal cracking.

12

The three main pollutants in exhaust gases arising from the internal combustion engine are carbon monoxide, oxides of nitrogen and unburnt hydrocarbons. The environmental consequences of these pollutants are the destruction of buildings, crops and marine life due to the formation of acid rain. The toxic gases produced also causes the destruction of human lives.

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A catalytic converter is used to convert the toxic combustion by-products from an internal combustion engine into less-toxic substances. The reduction catalyst catalyses the reaction: 2NO(g) + 2CO(g) N2(g) + 2CO2(g) The oxidation catalyst catalyses the reaction: 2CO(g) + O2(g) 2CO2(g) and 2C8H18(g) + 25O2(g) 16CO2(g) + 18H2O(l).

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The five gases that contribute to the enhanced greenhouse effect are carbon dioxide, water vapour, oxides of nitrogen, methane and ozone. The environmental consequences of the enhanced greenhouse effect is global warming which causes the melting of polar ice-caps, flooding of low-lying countries, the rising of sea level and increase in the formation of water vapour.

Discussion Questions 1 C 7(a) (b) (c) 8(a) (b) 9(a) (b) (c) 2 B 3 C 4 C 5 B 6 D

Hydrocarbons or alkanes Nitrogen from the air reacts with oxygen to form NO. N2 + O2 NO Sulfur comes from proteins or amino acids present in the hydrocarbon fuel. 4CO(NH2)2 + 6NO2 4CO2 + 7N2 + 8H2O NO2 is highly toxic. [pollutant (too vague) and causes global warming is not accepted] Alkane (Hydrocarbon is not accepted) 2C14H30 + 43O2 28CO2 + 30H2O (i) (ii) Mass of C14H30 burnt = = 116 tonnes 2C14H30 28CO2 Mr C14H30 = 198 Mr CO2 = 44.0 Mass of CO2 produced = = 361 tonnes (115 tonnes not accepted)

10(a) sunlight or uv light (b) Free radical substitution mechanism Initiation: Cl Cl uv light 2Cl CH2CH3 + HCl ClCH2CH3 + Cl ClCH2CH3 CH3CH2CH2CH3 Cl2

Propagation: CH3CH3 + Cl CH2CH3 + Cl2 Termination: CH2CH3 + Cl 2CH2CH3 2Cl (c)

First propagation step is endothermic as it requires 410 kJ mol-1 of heat to break the CH bond and only 299 kJ mol-1 of heat is evolved when the H I bond is form, hence it is not possible to make iodoalkanes by this method.

11(a) Since A is a mono-carboxylic acid, therefore amount of A = amount of NaOH Mr of A = = = 87.7 88.0 Structure of A is CH3CH2CH2COOH. (b) pV = M of C = =

= 71.9 72.0 Mr of C is 72.0 Structure of alkane C is CH3CH2CH2CH2CH3.

(c) (i) (ii)

P2O5 + 3H2O 2H3PO4 CO2 + 2NaOH Na2CO3 + H2O Increase in mass of P2O5 U-tube by 1.55 g due to H2O(g) absorbed. Increase in mass of NaOH(aq) bottle by 3.03 g due to CO2(g) absorbed. Mr of H2O = 18.0 Amount of water produced = = 0.0861 mol Mr of CO2 = 44.0 Amount of CO2 produced = = 0.0689 mol

(iii)

Since C CO2 and 2H H2O, therefore Amount of C atoms in D = 0.0689 Amount of H atoms in D = 2 x 0.0861 = 0.1722 Hence, C:H ratio in D is 0.0689 : 0.1722 = 2:5 Molecular formula of alkane D is C4H10.

(d) Structure of alkane E is CH3CH2CH2CH2CH2CH3. (2,3-dimethylbutane also accepted) Structure of mono-carboxylic acid B is CH3CH2COOH. (Hint: from the equation provided and acid A contain a C3 hydrocarbon chain and alkane C is a C5 alkane) (e) Since F produces only two isomeric monobromo compounds, therefore F must have only two types of replaceable hydrogen atoms. CH3 CH3 Hence, the structure of F is CH3 C C CH3 H H G is not chiral because it does not have a chiral carbon atom. CH3 CH3 Structure of G is CH3 C C CH3 Br H H is chiral because it has a chiral carbon atom (C*) with four different atom/groups attached to it. Structure of H is CH3 CH3 CH3 C C* CH2Br H H

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Ha Hb Hb Ha Ha C C C C Ha Ha Hb Hb Ha If the substitution is random, substituting any of the six Ha atoms will give rise to 1-bromobutane and substituting any of the four Hb atoms will give rise to 2-bromobutane. Hence, the ratio of 1-bromobutane to 2-bromobutane is 6:4 = 3:2.

Practice Questions [MUST DO as practice! Answers can be found in LMS] 1 (a) butane: CH3CH2CH2CH3 heptane:CH3CH2CH2CH2CH2CH2CH3 (higher b.p.) There is more electrons per heptane molecule, stronger induced dipole-induced dipole interactions, than per butane molecule. (b) 2,3-dimethylbutane: CH3CH(CH3)CH(CH3)CH3 hexane: CH3CH2CH2CH2CH2CH3 (higher b.p.) Hexane is a straight chain alkane, with a greater surface area of contact and hence stronger induced dipole-induced dipole interactions, but 2,3-dimethylbutane is a branched chain alkane. (c) 3,3-dimethylpentane: CH3CH2C(CH3)2CH2CH3 2-methylhexane: CH3CH(CH3)CH2CH2CH2CH3 (higher b.p.) 2-methylhexane has a less branched structure, with a greater surface area of contact and hence stronger induced dipole-induced dipole interactions, but 3,3-dimethylpentane structure is more branched. 2 (a) (b) O=C=O + HOH Br Br BrCCBr + HBr Br Br N.R. N.R. H O HCCOH Cl H 3 H3C-*C-CH2-CH2-CH3 I CH2-CH3 and its mirror image isomer H CH3 I I CH3-*C- CH- CH3 I CH2- CH3 and its mirror image isomer

(c) (d) (e)

X:

CH3CH2CH2CH3

and

CH3 I CH3CHCH3

Y:

CH3-CH2-CH2-CHBr I Br

CH3 I CH3-CH-CH-Br I Br

Possible structural formula of X: 1,1-dibromobutane; 1,2-dibromobutane; 1,3-dibromobutane; 1,4-dibromobutane; 2,2-dibromobutane; 2,3-dibromobutane

Possible structural formula of Y: 1,1-dibromo-2-methylpropane; 1,2-dibromo-2-methylpropane; 1,3-dibromo-2-methylpropane

5(a)
CH3 CH3

CH H C 3 3

CH3

CH3 CH3

(b)
CH3 CH3CH2 C CH2CH2CH2CH2CH2CH3 H
CH3
CH2CH3

or

CH3CH2CH2

C CH2CH2CH2CH2CH3 H

or

CH3CH2CH2

C CH2CH2CH2CH3 H

6(a) Reddish brown bromine undergoes homolytic fission to produce colourless bromine free radicals. During the propagation stage, bromine radical reacts with cyclohexane by extracting a hydrogen atom from cyclohexane to form white acidic vapour of HBr and a cyclohexyl radical. (b) Refer to lecture notes on free radical substitution mechanism. Replace methane with cyclohexane. 7(a) Structural isomerism (positional isomerism) (b) uv light or sunlight (c) Free radical substitution (d) CH2CH2CH3 I Cl 1-chloropropane CH3CHCH3 I Cl 2-chloropropane

As there are 6 H atoms in propane which can be replaced to form 1-chloropropane compared to 2 H atoms in propane which can be replaced to form 2-chloropropane. Thus ratio of 1-chloropropane to 2-chloropropane is 3:1 respectively. 8 Initially: CxHy (g) + (x+y/4) O2 (g) 10 cm3 100 cm3 xCO2(g) + (y/2)H2O(l)

After combustion: Volume of gas remained = unreacted oxygen + carbon dioxide = 80 cm3 After passing through KOH(aq), Volume of gas remained = unreacted oxygen = 50 cm3 Volume of carbon dioxide = 80 50 = 30 cm3 Volume of reacted oxygen = 100 50 = 50 cm3 volume ratio mole ratio 10 CxHy 30 CO2 10 CxHy 50 O2 therefore x = 3 (3 + y/4) = 50/10 therefore y = 8

9(a) mole ratio

17.25% H :

82.75% C (100% 17.25%)

17.25/1.0 : 82.75/12.0 = 17.25 = 6.90 17.25/6.90 : 6.90/6.90 = 2.50 = 1.00 5 : 2

Empirical formula is C2H5. (b) Relative molecular mass = 24 x 2.59 = 62.2 (c) Let (C2H5 )n = 62.2 29n = 62.2 n=2 Molecular formula is C4H10. (d) CH3CH2CH2CH3 and CH3CH(CH3)CH3

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W:

H I HC I H

H I HCH I C I HCH I H

H I CH I H

Since all the twelve hydrogen atoms are identical, replacing any one of the hydrogen atom with a bromine atom will produce the same product, hence only one isomer is formed. 11 A 12 D 13 D 14 B 15 2,3

Mastery Questions 1(a) CH3CH2CH2CH2CH2Cl, CH3CH2CH2CH(Cl)CH3, CH3CH2CH(Cl)CH2CH3 (b) Rate of abstraction of 1o hydrogen : rate of abstraction of 2o hydrogen = 1:4.5 For 1-chloropentane: 6 x 1 = 6 ( since 6 possible 1o hydrogen atoms to be abstracted) For 2-chloropentane: 4 x 4.5 = 18 ( since 4 possible 2o hydrogen atoms to be abstracted) For 3-chloropentane: 2 x 4.5 = 9 ( since 2 possible 2o hydrogen atoms to be abstracted) Thus ratio of 1-chloropentane : 2-chloropentane : 3-chloropentane is 6:18:9 respectively. 2(a) Cl + CH3CH2CH2Br (b) Cl + CH3CH(Br)CH3 CH3CHCH2Br + Cl2 CH3CH(Cl)CH2Br CH3CH(Br)CH2 (rearrangement) CH3CHCH2Br + Cl2
1 radical
o

2 radical

CH3CH(Cl)CH2Br (c) 2o alkyl radical is more stable than a 1o alkyl radical, hence rearrangement takes place.