Alkanes 2008

Alkanes
and
Free Radical
Substitution
New Way Chemistry for
New Way Chemistry for Hong Kong A-Level Book 3A
Preparation
of Alkanes
Crude Oil as a Source of Alkanes

Petroleum Refining
The first step is fractional distillation

separate petroleum into fractions
based on the volatility of its
components
performed in a petroleum refinery
a fractionating tower is used
Petroleum Refining
A petroleum refinery
4
A simplified diagram of a fractionating tower
Contains H2S
Removed by
treatment with
a weak base
Typical fractions obtained by fractional distillation

of petroleum
Fraction
Fuel gas
(e.g. LPG)
Petrol
Boiling
Number of carbon
point range
atoms that the
(oC)
molecules contain
< 40
14
Gaseous fuel,
raw materials for
manufacture of
chemicals
40 150
5 10
Fuel for motor

vehicles
10 14
For making town

gas
14 25
Fuel for trucks,

lorries and
locomotives
Naphtha
Gas oil
(Diesel oil)
Major uses
220 350
Typical fractions obtained by fractional distillation

of petroleum
Fraction
Boiling
Number of carbon
point range
atoms that the
(oC)
molecules contain
Major uses
Fuel oil
> 350
> 25
Fuel for cargo

ships and
generating
electricity in
power stations
Lubricating
oil
> 350
> 25
Lubricating oil for

moving parts of
machinery
Bitumen
> 350
> 25
For surfacing
roads and roofs
Cracking of Petroleum
Cracking of Petroleum
Convert hydrocarbons from heavier
fractions into lighter fractions
Performed in the absence of air
Providing lighter fractions of petroleum,
alkenes and sometimes H2 and C
C11H24
C14H30
9
C9H20 + CH2=CH2
C8H18 + 2CH2=CH2 + 2C + 2H2

Thermal Cracking
The process is done at high temperature
in the absence of catalysts
Hydrocracking
The process is done at very high pressure
of H2 in the absence of catalysts
Alkanes obtained are mainly unbranched
10
Catalytic Cracking
When a mixture of alkanes from the
heavier fractions is heated
at relatively low T & P
in the presence of catalysts
The molecules break down and rearrange
into smaller, highly branched hydrocarbons
11
Unbranched petrol is not a good motor fuel

It burns before it is ignited by the spark plug
of the petrol engine (pre-ignition).
The shock wave creates the characteristic
metallic pinging sound (engine knocking)
A waste of energy
Branched (anti-knocking) petrol can be
produced by reforming.
12
Reforming
Straight-chain alkanes are heated
under pressure in the presence of a
platinum catalyst
reforming
13
Laboratory
Preparation
of Alkanes
14
1.
Hydrogenation of alkenes
15
H2
H2
Ni, 200C
high P
Pt, 25C
Methods 2 and 3 below are specific to the

preparation of methane and benzene.
16
2.
Decarboxylation of sodium ethanoate or
sodium benzoate by heating with soda lime
(NaOH + CaO)
CH3COONa(s)
COONa (s)
17
NaOH(s) from
soda lime
fusion
NaOH(s) from
soda lime
fusion
CH4 + Na2CO3
+ Na2CO3
RCH2COONa + NaOH
More
difficult
Na2CO3 + RCH3 + other CxHy
Not easy to separate mixture into individual

alkanes.
Not suitable for preparing alkanes other than
methane.
18
3. Heating aluminium carbide with HCl

(Optional)
Al4C3 + 12HCl
19
heat
3CH4 + 4AlCl3
4.
Reduction of halogenoalkanes (optional)

RH
RX
1. Mg / dry ether
2. H2O
RH
RH
20
(Grignard reaction)
Reactions of
Alkanes
21
Reactivity of Alkanes
Inertness to chemical reactions
strong C
C and C
H bonds
C and H have nearly the same

electronegativity
C
H bonds are only slightly polarized
not easily attacked by charged particles
Alkanes paraffin little affinity

22
Two Ways of Breaking Covalent Bonds :

1. Homolytic fission
2. Heterolytic fission
23
Homolytic fission (homolysis)
A + B
24
Symmetrical breaking
Free radicals each containing an

unpaired electron
Homolytic fission (homolysis)
A + B
25
The movement of single

electron is represented by a
half-curly arrow
Free radicals are very

reactive(unstable). They tend to
look for an additional electron to
complete the octet.
Homolytic fission is favoured

1. when the bonding atoms have equal or
similar electronegativities;
2. at high temperature;
3. when the reaction mixture is exposed to UV
light;
4. in the presence of peroxides ( - O O - )
(All favour the formation of free radicals)
26
Heterolytic fission (heterolysis)

A
A+ + B
Unsymmetrical
breaking
A
27
when B is more
electronegative
A + B+
when A is more
electronegative
Heterolytic fission (heterolysis)

A
A+ + B
A + B+
The movement of an electron pair is

represented by a curly arrow.
28
Hetrolytic fission is favoured

1. when the bonding atoms have significantly
different electronegativities;
2. in the presence of a polar solvent which can
stabilize the ions formed by ion-dipole
interaction.
29
Q.23
Homolytic fission
H
H
30
Q.23
carbanion
H
H
H
H
C
H
31
C
H
Q.23
H
carbocation or
carbonium ion
32
H
H
C
H
1. Pyrolysis (Cracking)
Homolytic fission of C C and/or C H
bonds
e.g. C6H14
33
heat
catalyst
C3H8 + C3H6
Q.24
34
C6H14
C2H6 + C4H8
C6H14
C4H10 + C2H4
C6H14
CH4 + C5H10
C6H14
C2H4 + C4H8 + H2
C6H14
C2H6 + C3H8 + C
Q.25
CH2
H
CH2
+
35
2.
Combustion
When alkanes react with sufficient

oxygen
carbon dioxide and water are formed
release a large amount of heat
known as complete combustion
36
Combustion
General equation for the complete
combustion of an alkane:
3n 1
CnH2n+2 + (
)O2
2
37
nCO2 + (n + 1) H2O
Combustion
Alkanes are a common fuel
Methane is the main component of natural
gas
Butane is a component of bottle gas
Butane is used as the

fuel for a portable gas
burner
38
Q.26
In limited supply of oxygen,
Large alkanes with high carbon contents
39
3. Halogenation (free radical substitution)
Alkanes react with halogens to give

haloalkanes and hydrogen halide
RH + X2
UV light or heat
RX + HX
or peroxide
X2 = F2, Cl2, Br2 or I2
40
Halogenation
One or more hydrogen atoms in methane
are substituted by chlorine atoms
depend on the relative amounts of
methane and chlorine
41
Halogenation
UV light
CH4(g) + Cl2(g)
CH3Cl(g) + HCl(g)
UV light
CH3Cl(g) + Cl2(g)
UV light
CH2Cl2(g) + Cl2(g)
UV light
CHCl3(g) + Cl2(g)
42
CH2Cl2(g) + HCl(g)
CHCl3(g) + HCl(g)
CCl4(g) (g) + HCl(g)
Halogenation
When methane is in excess
chloromethane predominates in the
products
When chlorine is in excess
tetrachloromethane predominates in
the products
43
Halogenation
The reactivity of halogens decreases
in the order:
F2 > Cl2 > Br2 > I2
Not a good method to prepare
haloalkanes since it is difficult to
separate the resulting mixture into
individual haloalkanes.
44
Q.27(a)
CH3
CnH2n+2 = 72
12n + 2n + 2 = 72
C
H3C
n=5
CH3
CH3
All 12 H atoms are identical and only ONE kind

of monochlorinated product can be obtained.
45
Q.27(b)
3C
*
2C
1C
46
Q.27(b)
47
1.
Which piece of evidence suggests that
the reaction is a chain reaction ?
C
For each photon of light absorbed, many
thousands of molecules of chloromethane
are formed.
48
2.
Which of the following is the first step of

the mechanism?
CH4 CH3 + H
Cl2 2Cl
CH4 CH3+ + H
CH4 CH3 + H+
homolytic
heterolytic
Cl2 Cl+ + Cl
49
For elementary steps, the structure of the

transition state resembles that of the final
products.
the stability of the transition state is
determined by the stability of the final
products.
step
the activation energy can be estimated by

the enthalpy change of the elementary
The more endothermic reaction proceeds
more slowly.
50
CH4 CH3 + H
H = +435 kJ mol1
Cl2 2Cl
H = +242 kJ mol1
51
CH4
+435
CH3+ + H
+949
78
CH3 + H
H = +435 + 949 -78 = +1306 kJ mol1
52
CH4
+435
CH3 + H+
-7.7
+1310
CH3 + H
H = +435 -7.7 +1310 = +1737.3 kJ mol1
53
Cl2
+242
Cl+ + Cl
+1260
355
Cl + Cl
H = +242 + 1260 -355 = +1147 kJ mol1
54
Cl2 2Cl
H = +242 kJ mol
First step of the mechanism
55
3.
Second step of the mechanism

Cl + CH4 CH3Cl + H
Cl + CH4 CH3 + HCl
56
H
Cl + CH4 CH3Cl + H
+435
350
Cl + CH3 + H
H = +435 -350 = +85 kJ mol1
57
H
Cl + CH4 CH3 + HCl
+435
431
Cl + H + CH3
H = +435 -431 = +4 kJ mol1
Less endothermic and

does not lead to formation of H2
58
4.
The 3rd step of the mechanism
It gives the other product CH3Cl

It gives another Cl to complete the chain
cycle.
CH3 + Cl2 CH3Cl + Cl
59
5.
Termination steps
CH3 + CH3 CH3CH3
Cl + Cl ClCl
CH3 + Cl CH3Cl
60
ReactionMechanism:
Mechanism:Free
FreeRadical
RadicalSubstitution
Substitution
Reaction
Reaction
Reaction
1. Chain initiation
Homolytic fission of a chlorine molecule
Two chlorine radicals are formed
61
ReactionMechanism:
Mechanism:Free
FreeRadical
RadicalSubstitution
Substitution
Reaction
Reaction
Reaction
2. Chain propagation
62
ReactionMechanism:
Mechanism:Free
FreeRadical
RadicalSubstitution
Substitution
Reaction
Reaction
Reaction
3. Chain termination
63
7.
Which step is rate-determining ?
The propagation stage is the most timeconsuming.

Cl + CH4 CH3 + HCl
H = +4 kJ mol1

+242
350
CH3 + Cl + Cl
H = +242 -350 = 108 kJ mol1

64
7.
Which step is rate-determining ?
The propagation stage is the most timeconsuming.

1.
Cl + CH4 CH3 + HCl
2.
Or, E(C H)
>
E(Cl Cl)
435 kJ mol1
242 kJ mol1
Step 1 has higher Ea rate-determining
65
Example 27-5A
66
Stabilityof
ofAlkyl
AlkylRadicals
Radicals
Stability
According to the number of alkyl
groups directly attached to the carbon
that bears the unpaired electron
alkyl radicals are classified as
primary, secondary or tertiary
67
Stabilityof
ofAlkyl
AlkylRadicals
Radicals
Stability
Methyl radical
(no alkyl group
attached to the
carbon that
bears the
unpaired
electron)
68
Primary
radical
(one alkyl
group attached
to the carbon
that bears the
unpaired
electron)
Secondary
radical
(two alkyl groups
attached to the
carbon that bears
the unpaired
electron)
Tertiary radical
(three alkyl
groups attached
to the carbon
that bears the
unpaired
electron)
Stabilityof
ofAlkyl
AlkylRadicals
Radicals
Stability
The stability of the alkyl radicals
decreases in the order:
R2CH
RCH2
R 3C
CH3
Tertiary > Secondary > Primary > Methyl
alkyl
alkyl
alkyl
radical
radical
radical
radical
69
Stabilityof
ofAlkyl
AlkylRadicals
Radicals
Stability
Alkyl radical has an unpaired electron
Electron-deficient
Stabilized by substituents (e.g. alkyl
groups)
release electrons to the carbon
atom bearing the unpaired electron
70
Electron-donating property of alkyl groups

arises from the polarization of C H bonds
+H
+
+H
71
Electron-donating groups(e.g. alkyl groups)

cause positive inductive effect on adjacent
groups.
Electron-withdrawing groups(e.g. -F) cause
negative inductive effect on adjacent groups.
Inductive effect arises from polarization of
bonds.
72
Q.28(a)
Cl
Cl
73
No. of reaction sites

Cl
Cl
2
reaction
sites
6
reaction
sites
Stability of free radical intermediates is more

important than the no. of reaction sites available
74
Q.28(a)
Cl
Cl
Stability : H
C
H3C
75
CH3
>
H2
C
H3C
CH2
Q.28(b)
Cl
Cl
76
No. of reaction sites

Cl
Cl
9
reaction
sites
1
reaction
site
Stability of free radical intermediates is more

important than the no. of reaction sites available
77
Q.28(b)
Cl
Cl
Stability : CH2
CH3
H3C
78
<
CH
CH3
H3C
CH3
Example 27-5B
79
Check Point 27-5B
The END
80
27.2 Nomenclature of Alkanes (SB p.148)
Draw the structures of the following

compounds. Are the names provided correct or
incorrect? If they are incorrect, give the
correct name.
(a) 2,4-Dimethylpentane
(a)
The name is correct.
81
Answer

correct name.
(b) 1,3-Dimethylpentane
Answer
(b)
The name is incorrect.
The correct name is
3-methylhexane.
82
Back

correct name.
(c) 4-Ethyl-1-methylheptane
Answer
(c)
The name is incorrect.
The correct name is
4-ethyloctane.
83
Back
Draw the structures of all the isomers of C 6H14,

and give the IUPAC names for all the
Answer
structures drawn.
84
27.4 Preparation of Alkanes (SB p.155)
Define each of the following terms and give an

example of each:
(a) Catalytic cracking
Answer
(a) Catalytic cracking is the process in which a mixture of

alkanes from the heavier fractions is heated at very high
temperatures, in the presence of catalysts and the
absence of air. Smaller and highly branched
hydrocarbons are formed.
For example,
C8H18 C5H12 + C3H6
85

example of each:
(b) Thermal cracking
Answer
(b) Thermal cracking is the breakdown of large alkane

molecules in the heavier fractions into lighter fractions of
smaller molecules in the absence of catalysts and air.
Straight-chain alkanes are usually formed in this process.
For example,
C14H30 C8H18 + 2CH2 = CH2 + 2C + 2H2
86
Back

example of each:
(c) Reforming
Answer
(c) Reforming is a process in which straight-chain alkanes

are heated under pressure in the presence of a platinum
catalyst. The chains break up and reform to give
branched-chain molecules. For example,
87
27.5 Reactions of Alkanes (SB p.161)
(a) Explain why cracking has to be carried out

in the absence of air.
Answer
(a) Cracking must be carried out in the absence of

air because combustion occurs instead of
cracking in the presence of air.
88
(b) An alkane has a relative molecular mass of

72 and produces one product only on
monochlorination. Deduce its structure.
Answer
89
Back
(b) Let the molecular formula of the alkane be CnH2n+2.
Relative molecular mass of the alkane = 72
12.0 n + 1.0 (2n + 2) = 72
n=5
The alkane has the molecular formula of C5H12.
As the alkane produces one product only on monochlorination,
all hydrogen atoms of the alkane molecule must be equivalent.
It must be
90
Two isomeric compounds A and B have the molecular

formula C3H7Cl. Chlorination of A gave a mixture of two
dichlorides of formula C3H6Cl2. Chlorination of B
gave three different compounds of formula C3H6Cl2
(they may not all be different from the dichlorides
from A). What are the structural formulae of A and B
and the dichlorides obtained from each?
Answer
91
A:
B:
Dichlorides formed from A:
92
Back
Dichlorides formed from B:
93
The chlorination of butane gives a mixture of

products as shown below:
Explain their formation and also their relative

abundances.
Answer
94
The two products arise because in one of the propagation steps of the
reaction, a chlorine atom may abstract a hydrogen atom from either C1
or C2 of butane to give two different radicals.
95
The resulting free radicals react with chlorine in a succeeding

propagation step to give the corresponding haloalkane. Butyl radical
gives only 1-chlorobutane while secondary butyl radical gives only 2chlorobutane.
Since the more stable secondary radical is formed at a higher
rate, 2-chlorobutane is formed as the major product of the reaction.
Back
96
Give the structure of the major product

formed by free radical bromination of each of
the following:
Answer
(a) Methylcyclopentane
(a)
Bromomethylcyclopentane
97
Back
Give the structure of the major product
formed by free radical bromination of each of
the following:
(b) 2,2,4-Trimethylpentane
Answer
(b)
4-Bromo-2,2,4-trimethylpentane
98

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Alkanes

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

Crude Oil as a Source of Alkanes

The first step is fractional distillation

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

A simplified diagram of a fractionating tower

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

Typical fractions obtained by fractional distillation

Fuel for motor

For making town

Fuel for trucks,

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

Typical fractions obtained by fractional distillation

Fuel for cargo

Lubricating oil for

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

C8H18 + 2CH2=CH2 + 2C + 2H2

New Way Chemistry for Hong Kong A-Level Book 3A

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

Unbranched petrol is not a good motor fuel

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

Methods 2 and 3 below are specific to the

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

Na2CO3 + RCH3 + other CxHy

Not easy to separate mixture into individual

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

3. Heating aluminium carbide with HCl

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

Reduction of halogenoalkanes (optional)

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

C and H have nearly the same

H bonds are only slightly polarized

not easily attacked by charged particles

Alkanes paraffin little affinity