10.

1 Calculate the heat of reaction, H, for the following reactions:

(a) H2 +F2 2HF
(b) CH4+F2 CH3F+HF
(c) CH4 +Cl2 CH3Cl+HCl
(d) CH4+Br2 CH3Br+HBr
(e) CH4 +I2 CH3 I+HI
(f) CH3CH3+Cl2 CH3 CH2Cl+HCl
(g) CH3CH2CH3+Cl2 CH3CHClCH3+HCl
(h) (CH3)3 CH+Cl2 (CH3 )CCl+HCl

Answer: H H DH=435KJmol-1 H3C H DH=435KJmol-1

F F DH=159KJmol-1 H3CH2C H DH=410KJmol-1
Cl Cl DH=243KJmol-1 (H3C)2HC H DH=395KJmol-1
Br Br DH=192KJmol-1 (H3 C)3C H DH=381KJmol-1
I I DH=151KJmol-1 H3C F DH=452KJmol-1
H3 CH2C Cl DH=341KJmol-1 H3C Cl DH=349KJmol-1
(H3C)2HC Cl DH=339KJmol-1 H3C Br DH=293KJmol-1
(H3C)3C Cl DH=328KJmol-1 H3C I DH=234KJmol-1
(a)H = 435+159-2*569 = - 544 KJ / mol
(b)H = 435+159-452-569 = - 427 KJ / mol
(c)H = 435+243-349-431 = - 102 KJ / mol
(d)H = 435+192-293-366 = - 32 KJ / mol
(e)H = 435+151-234-297 = 55 KJ / mol
(f)H = 410+243-341-431= - 119 KJ / mol
(g)H = 395+243-339-431 = - 132 KJ / mol
(h)H = 381+243-328-431 = - 135 KJ / mol

10.2. List the following radicals in order of decreasing stability:

CH3 ,(CH3)2CHCH2 ,(CH3)2CCH2CH3 ,CH3 CH2 CHCH3

CH3 < (CH3)2CHCH2 < CH3 CH2 CHCH3 < (CH3)2CCH2CH3

10.3 Suggest a method for separating the mixture of CH4, CH3Cl, CH2Cl2, CHCl3, and CCl4 that is
formed when methane is chlorinated. (You may want to consult a handbook.) What analytical method
could be used to separate this mixture and give structural information about each component? How
would the molecular ion peaks in their respective mass spectra differ on basis of the number of
chlorines (remember that chlorine has two predominant isotopes, 35Cl and37Cl)?

Answer:
The compounds all have different boiling points. They could, therefore, be separated by careful
fractional distillation. Or, because the compounds have different vapor pressures, they could easily be
separated by Gas Chromatography. GC / MS could be used to separate the compounds as well as
provide structural information from their mass spectra. Their mass spectra would show contributions
from naturally occurring 35Cl and 37Cl isotopes. The natural abundance of 35Cl is approximately 75%
and that of 37Cl is approximately 25%. Thus, for CH3Cl, containing only one chlorine atom, there will
be an M+. peak and M+2 peak in roughly a 3:1 ratio of intensities. For CH2Cl2, there will be M+.,
M+.+2, M+.+4 peaks in roughly 9:6:1 ratio. For CHCl3, there will be M+., M+.+2, M+.+4, M+.+6 peaks
in roughly 27:27:9:1 ratio. For CCl4, there will be M+., M+.+2, M+.+4, M+.+6, M+.+8 peaks in roughly
81:108:54:12:1 ratio, respectively.

10.4 When methane is chlorinated, among the products found are traces of chloroethane. How is it
formed? Of what significance is its formation?

Answer:

A small amount of ethane is formed by the combination of two methyl radicals:

2 CH3 H3C CH3

This ethane then reacts with chlorine in a substitution reaction (see Section 10.6) to form chloroethane.
The significance if this observation is that it is the evidence for the proposal that the combination of
methyl radicals is one of the chain-terminating steps in the chlorination of methane.

10.5 If our goal is to synthesize CCl4 in maximum yield, this can be accomplished by using a large
excess of chlorine. Explain.

Answer: The use of a large excess of chlorine allows all of the chlorinated methanes (CHCl3, CH2Cl2,
CH3Cl) to react with chlorine.

10.6 Assuming the same mechanism applies, calculate Hfor the chain-initiating, chain-propagating,
and chain-terminating steps involved in the fluorination of methane.

Answer:

Chain-Initiation

F F 2F. H= + 159 KJ / mol

H=159
Chain-Propagation
H 3C H + F CH3 + H F
H =-134KJ/mol
H=435 DH=569

CH3 + F F H3C F + F H=-297KJ/mol

H=159 H=452
Chain-Termination
CH3 + F H3C F H=-452KJ/mol
 H=452
CH3 + CH3 H3C CH3
H=-368KJ/mol

H=368

F + F F F H=-159KJ/mol
H=159

10.7 Show how you can use the chain-propagating steps (see problem 10.6) to calculate the overall
value of H for the fluorination of methane?

Answer: Chain Initiation

Step1 F F 2 F H=+159kJ/mol
(H=159)
Chain Propagation
Step2 CH3 H+F CH3+HF
(H=435) (H=569) H=-134kJ/mol

Step3 CH3+ F F CH3F+ F H=-293 kJ/mol

(H=159) (H=452)

Step2&Step3 H=-427 kJ/mol

10.8 When pentane is heated to a very high temperature, radical reactions take place that produce
(among other products) methane, ethane, propane, and butane. This type of change is called thermal
cracking. Among the reactions that place are the following:

(1)CH3 CH2 CH2CH2CH3 CH3 + CH3CH2CH2CH2

(2)CH3 CH2CH2CH2CH3 CH3 CH2 + CH3 CH2 CH2

(3)CH3 + CH3 CH3CH3

(4)CH3 + CH3 CH2CH2CH2CH3 CH4 +CH3CH2 CH2 CH2CH2

(5)CH3 +CH3CH2 CH3 CH2 CH3

(6)CH3CH2 +CH3 CH2 CH3CH2CH2CH3

(a) For which of those reactions would you expect Eact to equal zero
(b) To be greater than zero?
 (c) To equal H?

Aswer: (a) 3,5,6 reactions Eact is equal zero

(b) 1,2,4 reactions Eact is greater than zero
(c) 1,2 reactions Eact is equal H

10.9 The energy of activation for the first chain-propagating step in the fluorination of methane (cf.
Problem 10.6) is known to to be 5 kJ / mol. The energy of activation for the second chain-propagation
step is known to be very small. Assuming that it is 1.0 kJ / mol then (a) and (b) sketch potential energy
diagrams for this two chain-propagating steps. (c) Sketch potential energy diagram for the
chain-initiating step in the fluorination of methane (d) for the chain-termination step that produce CH3F
(e) sketch a potential energy diagram for the following reaction:

CH3. + HF CH4 + F.
Answer:

F H CH3

E act = + 5.0 kJ / mol

(a)
F + CH4
H = - 134 kJ / mol

CH3 + F

E act = + 4.2 kJ / mol

(b)

H = - 239 kJ / mol
 (c)
H o = E act = + 159 kJ / mol

(d)

Ho = - 452 kJ / mol

(e)

Eact = + 139kJ / mol

Ho = + 134 kJ / mol

10.10 The energy of activation for the hydrogen atom-abstraction step in the chlorination of ethane
is 4.2 kJ mol-1. (a) Use the homolytic bond dissociation energies in Table 10.1 to calculate for this step.
(b) Sketch a potential energy diagram for the hydrogen atom-abstraction step in the chlorination of
ethane similar to that for the chlorination of methane show in Fig.10.3a. (c) When an equimolar
mixture of methane and ethane is chlorinated ,the reaction yields far more ethyl chloride than methyl
chloride (~400 molecules of ethyl chloride for every molecule of methyl chloride). Explain this greater
yield of ethyl chloride.

Answer

(a) CH3CH2 H + Cl H Cl + CH3CH2

(DH0 =410KJmol-1 ) (DH0 =431KJmol-1)

0 = 410 KJ mol + (- 431 KJ mol ) = - 21 KJ mol

-1 -1 -1

(b)

PE

Ho = - 21 kJ / mol

(c) The activation energy for the hydrogen abstraction step in ethane is about 4.2 kJ / mol, much more
lower than that for methane, 21 kJ / mol. Therefore, the ethyl radical form much more rapidly in
mixture than methyl radicals, and this leads to the more rapid formation of ethyl chloride.

10.11 When ethane is chlorinated, 1,1-dichloroethane and 1,2-dichloroethane, as well as more highly
chlorinated ethanes, are formed in the mixture. Write chain mechanisms accounting for the formation
of 1,1-dichloroethane and 1,2-dichloroethane.
Answer:
Chain mechanisms accounting for the formation of 1,2-dichloroethane:
Chain initiation:
light
Cl2 2Cl
or
heat
Chain propagation:
 CH3 CH2 H + Cl CH3CH2 + H Cl

CH3CH2 + Cl Cl CH3CH2 Cl + Cl

ClCH2CH2 H + Cl ClCH2 CH2 + H Cl

ClCH2CH2 + Cl Cl ClCH2 CH2 Cl + Cl

Chain termination:

Cl + Cl Cl Cl

CH3CH2 + Cl CH3 CH2 Cl

CH3CH2 + CH2CH3 CH3CH2 CH2CH3

ClCH2CH2 + CH2 CH2 Cl ClCH2CH2CH2CH2Cl

ClCH2CH2 + Cl ClCH2CH2Cl

ClCH2CH2 + CH2CH3 ClCH2CH2CH2CH3

Chain mechanisms accounting for the formation of 1,1-dichloroethane

Chain initiation:
light
Cl2 2Cl
or
heat

Chain propagation:

CH3 CH2 H + Cl CH3CH2 + H Cl

CH3CH2 + Cl Cl CH3CH2 Cl + Cl

Cl Cl

CH3CH H + Cl CH3 CH + H Cl
 Cl

CH3CH +Cl Cl CH3 CHCl2 + Cl

Chain termination:

Cl + Cl Cl Cl

CH3CH2 + Cl CH3 CH2 Cl

CH3CH2 + CH2CH3 CH3CH2 CH2CH3

Cl Cl Cl Cl

CH3 CH + CHCH3 CH3C CHCH3

H
Cl Cl

CH3CH + Cl CH3C Cl

H
Cl Cl

CH3CH + CH2CH3 CH3C CH2CH3

H
10.12 (a) What percentages of propyl chloride and isopropyl chloride would you expect to obtain from
the chlorination of propane if 1 and 2 hydrogen atoms were equally reactive? (b) What percentages of
isobutyl chloride and tert-butyl chloride would you expect to obtain from the chlorination of isobutane
if 1 and 3 hydrogen atoms were equally reactive? (c) Compare these calculated answers with the
results actually obtained (above) and justify the assertion that the order of reactivity of the hydrogen
atoms is 3>2>1.

Answer:

(a) propyl chloride 75%, iso propyl chloride 25%

(b) isobutyl chloride 90%, tert-butyl chloride 10%
(c) the percentages of propyl chloride and isobutyl chloride is lower than calculated answers .
so the order of reactivity of the hydrogen atoms is 3>2>1.

10.13 Chlorination reactions of certain alkanes can be used for laboratory preparation. Examples are
preparation of cyclopropyl chloride from cyclopropane and cyclobutyl chloride from cyclobutane.
What structural feature of these molecules makes this possible?
Answer: The molecule only has one kind of hydrogen (1o ,2or3). So that the chlorine atom has
only one way to take place of the hydrogen atom, which means we only gets one product. So this kind
of reaction is possible for laboratory preparation.

10.14 Each of the following alkanes reacts with chlorine to give a single monochloro substitution
product. On the basis of this information deduce the structure of each alkane.
(a) C5H10 (b) C8H18 (c) C5H12

Answers: (a) Cyclopentane ;

(b) (CH3)3C C(CH3)3 2,2,3,3 tetromethylbutane ;

(c) C(CH3)4 2,2 dimethylpropane.

10.15 Why is temperature an important variable to consider when using isomers distribution to evaluate
the reactivity of the hydrogens of an alkane toward radical chlorination?

Answer: At low temperature, isomer distribution accurately reflects the inherent reactivities of the
hydrogens of the alkanes. As the temperature is raised, chlorine atoms become more active, and hence
less discriminating. If the temperature is high enough, hydrogens are replaced by chlorine on a purely
statistical basis.

10.16 Consider the chlorination of (s)-2-chloropentane at C4. (a) Write stereochemical structures for
the products that would be obtained and give each its proper (R-S) designation. (b) What is the
stereoisomeric relationship between these products? (c) Are both products chiral? (d) Are both products
optically active? (e) Could the products be separated by conventional means? (f) What other
dichloropentanes would be obtained by chlorination of (S)-2-chloropentane? (g) Which of these are
optically active?
Answer:
(a)

CH3 CH3 CH3

H Cl H Cl H Cl

Cl2
CH2 CH2 + CH2
light
CH2 H C Cl Cl C H

CH3 CH3 CH3

(2S, 4R)-2,4-dichloropentane (2S, 4S)-2,4-dichloropentane

(b) They are diastereomers.
(c) The first one is achiral, the second one is chiral.
(d) The first one is not optically active, the second one is optically active.
(e) Yes
(f)

CH3 CH2Cl CH3 CH3 CH3

Cl Cl H Cl H Cl H Cl H Cl

CH2 CH2 H C Cl Cl C H CH2

CH2 CH2 CH2 CH2 CH2

CH3 CH3 CH3 CH3 CH2Cl

optically inactive optically active optically active optically active optically active

10.17 Consider the bromination of butane using sufficient bromine to cause dibromination. After the
reaction is over, you isolate all of the dibromo isomers by gas chromatography or by fractional
distillation.
(a) How many fractions would you obtain?
(b) What compound (or compounds) would the individual fractions contain?
(c) Which, if any, of the fractions would show optical activity?
(d) Knowing that the bromine isotopes 79Br and 81Br are almost equally abundant in nature, what
mass-to-charge peaks would predominate in the mass spectra of these dibromo isomers?

Answer:
(a) We can obtain 7 fractions.
(b)
CH3 CHBr 2 CH3 CH2Br CH2Br CH2Br CH2Br

CH2 Br2 CH2 CBr2 H C Br Br C H CH2 CH2

+ + +
+ +
CH2 light CH2 CH2 CH2 H C Br Br C H
CH2

CH3 CH3 CH3 CH3 CH3 CH3 CH3

1 2 3 4

CH2Br CH3 CH3 CH3

CH2 H C Br Br C H H C Br
+ + + +
CH2 H C Br H C Br Br C H

CH2Br CH3 CH3 CH3

7
5 6
(c) None of fractions would show optical activity, fractions 3, 4, and 7 are racemic forms, while
fraction 6 is meso compound.
(d) M, M+2 and M+4 will be in a ratio of 1 : 2 : 1.

10.18 The chlorination of 2-methylbutane yields 1-chloro-2-methlbutane, 2-chloro-2-methylbutane,

2-chloro-3-methylbutane, and 1-chloto-3methylbutane. (a) Assuming that these compounds were
separated after the reaction by fractional distillation, tell whether any fractions would show optical
activity. (b) Would any of these fractions be resolvable into enantiomers? (c) How would the 1H NMR
spectra of these compounds differ at position where the chlorine is bonded? Could each fraction from
the distillation be identified on the basis of 1H NMR spectroscopy?

ANSWER:
(a) No, the only fractions that would contain chiral molecules (as enantiomers) would be that
containing 1-chloro-2-methylbutane and the one containing 2-chloro-3-methylbutane. These fractions
would not show optical activity, however, because they would contain racemic forms of the
enantiomers. (b) Yes, the fraction containing 1-chloro-2-methylbutane and the one containing
2-chloro-3-methylbutane. (c) Yes, each fraction from the distillation could be identified on the basis of
1
H NMR.

10.19 The radical reaction of propane with chlorine yields (in addition to more highly halogenated
compounds) 1-chloropropane and 2-chloropropane. Write chain-initiating and chain-propagating steps
showing how each compound is formed.
Answer:
Chain-initiating:
light
Cl2 2 Cl
or heat

Chain-propagation:

(1) CH3CH2CH3 + Cl CH3CH2CH2 + HCl

CH3CH2CH2 + Cl2 CH3CH2CH2Cl + Cl

(2) CH3CH2CH3 + Cl CH3CHCH3 + HCl

CH3CHCH3 + Cl2 CH3CHClCH3 + Cl

10.20 In addition to more highly chlorinated products, chlorination of butane yields a mixture of
compounds with the formula C4H9Cl. (a) Taking stereochemistry into account, how many different
isomers with the formula C4H9Cl would you expect to be produced? (b) If the mixture of C4H9Cl
isomers were subjected to fractional distillation or gas chromatography, how many fractions would you
expect to obtain? (c) Which fractions would be optically inactive? (d) Which would you be able to
resolve into enantiomers? (e) Predict the features in their 1H and 13
C DEPT NMR spectra that would
differentiate among the isomers separated by GC or distillation. (f) How could fragmentation in their
mass spectra be used to differentiate the isomers?

Answer:
(a)
CH3 CH2Cl CH3 CH3

CH2 Cl2 CH2 H C Cl Cl C H

+ +
CH2 light CH2 CH2 CH2

CH3 CH3 CH3 CH3

racemic form
(b) Only two, one fraction is 1-chlorobutane and the other is the racemic form.
(c) Both of them.
(d) The fraction containing the enantiomers.
13
(e) The fractions can be distinguished by DEPT C NMR, and 1H NMR. To the 1-chlorobutane,
proton NMR will give four peaks with one triplet, two mutiplets and one triplet. DEPT Carbon
NMR will give three triplets and one quartet. To the racemic form, proton NMR will give a doublet,
two multiplet and one triplet. DEPT Carbon NMR will give you two quartet, one doublet and one
triplet.
(f) The only difference in mass spectrum is the fragmentation. The possible fragment species of
-CH2Cl will be observed in the 1-chlorobutane.

10.21 Chlorination of (R)-2-chlorobutane yields a mixture of isomers with the formula C4H8Cl2. (a)
How many different isomers would you expect to be produced? Write their structures. (b) If the
mixture of C4H8Cl2 isomers were subjected to fractional distillation, how many fractions would you
expect to obtain? (C) Which of these fractions would be optically active?

Answer:
(a) Five
CH3 CH3 CH3
CH3 CH2Cl CH3

Cl C H Cl C H Cl C H
Cl C H Cl C H Cl C Cl
Cl2 +
+ + +
Cl C H H C Cl CH2
CH2 light CH2 CH2

CH3 CH3 CH2Cl

CH3 CH3 CH3

(b) Five, none of the fractions would be a racemic form.

(c) Fractions 1, 4 and 5 would be optically active.

10.22 Peroxides are often used to initiate radical chain reaction such as alkane halogenations. (a)
Examine the bond energies in Table 10.1 and give reasons that explain why peroxides are especially
effective as radical initiators, (b) Illustrate your answer by outlining how di-tert-butyl peroxide,
(CH3)3CO-OC(CH3)3, might initiate an alkane halogenation.
Answer:
Oxygen-Oxygen bond are easily to be broken, alkyloxy radical could be generated. That is the chain
initiation step. As soon as the alkyloxy radical formed in the reaction progress, it will abstract the
proton the alkane molecule to form the alkyl radical. The alkyl radical will react with the chlorine to
form the chlorine radical. That would be the chain propagation step.

10.23 List in order of decreasing stability all of the radicals that can be obtained by abstraction of a
hydrogen atom from 2-methylbutane.
Answer:

10.24 Show below is an alternative mechanism for the chlorination of methane.

(1) Cl2 2 Cl
(2) Cl + CH4 CH3 Cl + H

(3) H + Cl2 HCl + Cl

0
Calculate H for each step of this mechanism and then explain whether this
mechanism is likely to compete with the one discussed in Sections 10.4 and 10.5.
Answer:
(1) H0 = + 243 KJ mol-1
(2) H0= - 349 + 435 = + 86 KJ mol-1
(3) H0= - 431 + 243 = - 188 KJ mol-1

The mechanism discussed in Sections 10.4 and 10.5 is what shown below.

(1) Cl2 H0=243KJ mol-1

2 Cl
(2) Cl + CH4 CH3 + HCl H0=4KJ mol-1

(3) CH3 + Cl2 CH3Cl + Cl H0=-106KJ mol-1

The cause of the difference between the two mechanism is in the second step.
H0 is 86 KJ mol-1 which is much too larger than 4 KJ mol-1 in the second step.
Obviously, it is more difficult for the second step in the question to take place
than the one shown in the discussion As a result, this mechanism is unlikely to compete
with the one discussed in Sections 10.4 and 10.5.

10.25 Staring with the compound or compounds indicated in each part and using any other needed
reagents, outline syntheses of each of the following compounds.(You need not repeat steps carried
out in earlier part of this problem.)
(a)Ethyl iodide from ethane
(b)Diethyl ether from ethane
(c)Cyclopentene from cyclopentane
(d)2-bromo-3-methylbutane from 2-methylbutane
(e)2-butyne from methane and acetylene
(f)2-butanol from ethane and acetylene
(g)Ethyl azide from ethane
Answer:
(a)
heat
CH3CH3 + I2 CH3CH2I +HI
(b)
light
CH3CH3 + Cl2 CH3CH2Cl +HCl
CH3CH2Cl OH CH3CH2 OH
140C
2CH3CH2OH CH3CH2OCH2CH3
H2SO4
(C)

light
+ Cl2 Cl + HCl

OH
Cl OH

H2SO4
OH + H2O

(d)
Br

+ Br2

Br
CH3CH2 OH
+ CH3 CH2Na

Br

R2O2
+ HBr
 (e)
CH4 + Br2 CH3Br
NaNH2
HC CH HC CNa

HC CNa + CH3Br HC CCH3

NaNH2
HC CCH3 NaC CCH3

NaC CCH3 + CH3Br

(f)
NaNH2
HC CH HC CNa
CH3CH3 + Br2 CH3CH2Br

HC CNa + CH3CH2Br HC CCH2CH3

HC CCH2CH3 + H2 H 2C CHCH2CH3

H2C CHCH2 CH3 + H2O CH3CHCH2CH3

OH
(G)
CH3CH3 + Cl2 CH3CH2Cl

CH3CH2 Cl + NaN3 CH3CH2N3

10.26 Consider the relative rates of chlorination at the various positions in 1-fluorobutane:

H3C CH2 CH2 CH2 F

1.0 3.7 1.7 0.9
Explain this order of reactivity.
Answer:
To the secondary hydrogens, those are more reactive than primary hydrogen, at the meanwhile, F
atom has large electronegativity, reduces the electron density in proportion to methylene groups
attached. Overall, hydrogens at C-3 position have the highest reactivity.

10.27 In the radical chlorination of 2,2-dimethylhexane, chlorine substitution occurs much more
rapidly at C5 than it does at a typical secondary carbon (e.g., C2 in butane). Review the discussion
on radical polymerization and then suggest an explanation for the enhanced rate of substitution of
C5 in 2,2-dimethylhexane.
Answer
 H2 H2
C CH3 C CH3
H2C CH H2C C
H

H
CH2 CH3
H3 C H3C
CH3 CH3

Besides the direct proton abstraction from C5, there would be many proton abstraction from
methyl groups, leading to the back biting proton from C5.

10.28 Hydrogen peroxide and ferrous sulfate react to produce hydroxyl radical (HO) as reported
in 1894 by English chemist H. J. H. Fenton. When tert-butyl alcohol is treated with
HO generated this way, it affords a crystalline reaction product X, m. p. 92, which has these
spectral properties:
MS: heaviest-mass peak is at 131 m/z
IR: 3620, 3350(broad), 2980, 2940, 1385, 1370 cm-1
HNMR: sharp singlets at 1.22, 1.58, and 2.95 (6:2:1 area ratio)
1

CNMR: 28 (CH3), 35 (CH2), 68 (C)

13

Draw the structure of X and write a mechanism for its formation.