FOCUS 11

ORGANIC CHEMISTRY

11A.2 (a) C6 H12 , alkane; (b) C5H6, alkene; (c) C3H6, alkene; (d) C4H6, alkyne

11A.4 (a) Nonane; (b) Hexane; (c) Undecane; (d) Dodecane

11A.6 (a) Nonyl; (b) Pentyl; (c) Ethyl; (d) Heptyl

11A.8 (a) 3-Methylpentane; (b) 2,3-Dimethylpentane;

(c) 2,2,6-Trimethylheptane; (d) 2,2,3,3-Tetramethylbutane

11A.10(a) 4-phenyl-1-nonene or Non-1-en-4-ylbenzene

(b) 4-Chloro-5,6-dimethylhept-2-yne
or 4-Chloro-5,6-dimethyl-2-heptyne

11A.12(a) CH3C(CH3)2CH2CH(CH2CH3)CH2CH3
(b) CH2=CHCH(CH2CH3)CH(CH3)CH3
(c) cis-CH3CH2CH=C(CH2CH3)(CH2)2CH3
(d) trans-CH3CH=CHCH(CH3)CH2CH3

11A.14(a)
506 Focus 11 Organic Chemistry

(b)

(c)

(d)

11A.16(a) (b)

+
(c)
 Focus 11 Organic Chemistry 507

11A.18 (a) Four tetrahedral sp3-hybrid orbitals with σ-bonds

(b) Three trigonal planar sp2-hybrid orbitals with σ-bonds;
one unhybridized p-orbital (perpendicular to the hybridized orbitals) with
a π-bond
(c) Two linear sp-hybrid orbitals with σ-bonds;
two unhybridized p-orbitals (perpendicular to the hybridized orbitals) with
two π-bonds

11A.20 H H
H H
C C
C C C
H
H H H

H H

C C
H H

C C C

H H H H

All carbon atoms are sp2-hybridized except for the carbon on the far right
side of the molecule, which is bonded to three hydrogen atoms and is sp3-
hybridized.

C C

C C C C

Pi-bonds form the second bond in the C=C double bonds.

11A.22(a) C4H8 CH2 CH3 H3C CH3

H2C CH C C
1-Butene H H
cis-2-Butene
508 Focus 11 Organic Chemistry

CH3
H CH3
H2C C
C C
H3C H CH3
trans-2-Butene 2-Methyl-1-propene

(b) C5H10
H H H3C CH2 CH3
C C C C
H CH2 CH2 CH3 H H

1-Pentene cis-2-Pentene

H CH2 CH3
H2C CH CH CH3
C C
H3C H CH3
trans-2-Pentene
3-Methyl-1-butene

11A.24(a) H H H H H H
H Cl
Cl C C C C C C H H H
C
H H H H H H H C C H
1-Chlorohexane
H C C H
C6H13Cl
C
H H
H H
Different formula, not isomers Chlorocyclohexane
C6H11Cl
 Focus 11 Organic Chemistry 509

(b) Same formula, C4 H8 , but different bonding arrangements: structural

isomers
(c) Same formula, C2 H2 Cl2 , same bonding arrangement, but different
geometry: geometrical isomers

11A.26(a) H H

H3C C C CH3

CH3 CH3

(b) Cl H H H H

H3C C C CH3 Cl C C C CH3

CH3 CH3 H CH3 CH3

Both H’s and all four methyl groups are equivalent in the hydrocarbon.

11A.28 (a) and (d) display optical activity.

(a) (d)

11B.2 CH4(g) + 2F2(g) → CF2H2(g) + 2HF(g)

Break 2 C-H bonds
Break 2 F-F bonds
Form 2 C-F bonds
Form 2 H-F bonds
Total
2(+412 kJ.mol–1)
2(+158 kJ.mol–1)
2(–484 kJ.mol–1)
2(–565 kJ.mol–1)
–958 kJ.mol–1


* Indicates the chiral carbon atoms.
510 Focus 11 Organic Chemistry

The corresponding reaction with chlorine is much less exothermic for two
reasons. First, it requires much less energy to break the F—F bond, and
second, the bonds formed between F and C or H are stronger than the
corresponding bonds to Cl. For this reason, direct fluorinations of
hydrocarbons are extremely hazardous: they may lead to fires and
explosions. Chlorinations are also hazardous but are more easily done than
fluorinations.

11B.4 Optically active molecules are indicated by and asterisk.

H H
One monochlorocylopropane: Cl
C C

H C H
H
Three dichlorocyclopropanes:
H H H Cl H H
Cl Cl Cl
C C C C C C*

H C H H C H H C Cl
Cl H H

Three trichlorocyclopropanes:
Cl Cl H Cl H Cl
Cl Cl Cl
C C C C C C*

H C H Cl C H H C H
H H Cl

Three tetrachlorocyclopropanes:
Cl Cl H Cl H Cl
Cl Cl Cl
C C C C C C*

H C Cl H C Cl Cl C H
H Cl Cl

One pentachlorocyclopropane: One hexachlorocyclopropane:

Cl Cl Cl Cl
Cl Cl
C C C C
C Cl C Cl
H Cl
Cl Cl
 Focus 11 Organic Chemistry 511

11B.6

Addition reaction

H H H H
H CH2 CH3
11B.8 (a) H C C C C Br
NaOCH2CH3
C C

H H
H H H H

H H Br H
H H
NaOCH2CH3
H C C C C H C C
(b)
H3C CH3
H H H H

H CH3
C C

H3C H

H CH2 CH3
C C

H H

11B.10 C 2 H 4  HX 
 C2 H5 X

We will break one H—X bond and form one C—H bond and one C—X
bond. Using bond enthalpies:
Halogen Cl Br I

H—X bond breakage kJ  mol1   +431 +366 +299

C—H bond formation kJ  mol1   –412 –412 –412

C—X bond formation kJ  mol1   –338 –276 –238


Total kJ  mol1  –319 –322 –351
512 Focus 11 Organic Chemistry

A general trend in the exothermicity of these reactions is less obvious, as

two opposing factors are involved. Although it requires less energy
to break H—X bond as one descends the periodic table, there is also
less energy released from the formation of a C—X bond.

11C.2 (a) 2,4-Diethyl-1-propylbenzene; (b) 1-Ethyl-4-propylbenzene

11C.4 (a) CH3 (b) Br (c) H2C CH CH2 (d) H2C CH3
Br CH3

H3C
CH3

11C.6 (a), (b)

NH2 NH2 Cl

H2N Cl H2N

Cl H2N H2N

Cl Cl Cl
1,2-Diamino-3,4-dichlorobenzene 1,3-Diamino-2,4-dichlorobenzene 2,3-Diamino-1,4-dichlorobenzene

NH2

Cl Cl NH2 Cl NH2

Cl H2N Cl Cl NH2
1,4-Diamino-2,5-dichlorobenzene 1,2-Diamino-4,5-dichlorobenzene
NH2
1,4-Diamino-2,3-dichlorobenzene

Cl Cl NH2
NH2

H2N Cl

H2N NH2
1,5-Diamino-2,4-dichlorobenzene
Cl Cl H2N Cl
1,2-Diamino-3,5-dichlorobenzene 1,3-Diamino-2,5-dichlorobenzene

Cl Cl

H2N Cl

Cl NH2 H2N NH2

2,5-Diamino-1,3-dichlorobenzene 1,5-Diamino-2,3-dichlorobenzene
 Focus 11 Organic Chemistry 513

All these molecules will be at least slightly polar except for the 1,4-
diamino-2,5-dichlorbenzene, which will be nonpolar.

11C.8 C6 H 5 NO 2  Br2 
?

C6 H 5 Br  NO 2  
?

The two reactions will give different product distributions because the
directing influences of the groups attached to the ring are different. A nitro
group is a metadirecting substituent; a bromo group is ortho- and para-
directing. Thus, the dominant products in the nitration reaction are a
mixture of 1-bromo-2-nitrobenzene and 1-bromo-4-nitrobenzene, whereas
for the bromination reaction, the product is primarily 1-bromo-3-
nitrobenzene.

11C.10 Like the nitro group, the aldehyde group is electron-withdrawing: it forms
resonance structures that place positive charge on the ortho and para
positions. This group is therefore a meta-directing substituent.

11C.12(a) C4H8, alkane

(b) C10 H8 , aromatic hydrocarbon
(c) C5H8, alkene
(d) C6H12, alkane

11C.14 (a) C2H2, alkyne

(b) C9H12, aromatic hydrocarbon
(c) C8H6, alkene
(d) C7H12, alkane

11D.2 (a) R—O—R; (b) R—CO—R; (c) R—CO—OR; (d) R—CO—NHR

11D.4 (a) aldehyde; (b) carboxylic acid; (c) amide; (d) alcohol
514 Focus 11 Organic Chemistry

11D.6 (a) 2,2-Dichloropropane

(b) 1-Bromobut-3-ene

(c) Hex-4-yn-2-ol

(d) Methyl butyl ether

11D.8 (a) CH3(CH2)4CH2OH, primary alcohol

(b) secondary alcohol

(c) phenol

(d) tertiary alcohol

11D.10 (a) CH3OCHCH2CH2

(b) CH3CH2CH2CH2OCH2CH2CH2CH3

(c) CH3CH2OCH2CH2CH2CH2CH3

11D.12 (a) Methyl pentyl ether

(b) Ethyl butyl ether
(c) Dipropyl ether
 Focus 11 Organic Chemistry 515

11D.14 (a) Aldehyde, 2-methylbutanal

(b) Aldehyde, 4-methylbenzaldehyde
(c) Ketone, 5-ethyl-3-heptanone

11D.16

(a) (b)

(c)

11D.18 (a) 3-Methylbutanoic acid

(b) 3-Chloropropanoic acid
(c) Nonanoic acid

11D.20
516 Focus 11 Organic Chemistry

11D.22 (a) Propylamine; (b) Tetraethylammonium ion;

(c) p-Chloroaniline or 4-Chloroaniline

11D.24
 Focus 11 Organic Chemistry 517

11D.26 (a), (c) and (d) may function as nucleophiles. All these molecules have
lone pairs of electrons that will be attracted to a positively charged carbon
center. NH4+ does not have lone pairs of electrons and is positively
charged, which makes it unable to function as a nucleophile. If it is
deprotonated first to give NH3, it could function as a nucleophile.

11D.28 (a) CH3CH2CH2OH

(b) CH3CH(OH)CH2CH2CH3
(c) CH3(CH2)3CH(CH2CH3)CH2CH(OH)CH2CH3
Use an oxidant that is not too strong to avoid over-oxidation and the
formation of carboxylic acids. For example, the salt pyridinium
chlorochromate (PCC), C5H5NH[CrO3Cl].

11D.30

11D.32 (a) condensation

(b) Because the sodium hydroxide is concentrated, the elimination
reaction should dominate; however, nucleophilic substitution may also
occur.
(c) nucleophilic substitution
(d) condensation
(e) electrophilic substitution
518 Focus 11 Organic Chemistry

base (aq)
11D.34 (1) CH3CH2CH2OH   (dissolves)
(2) CH3(CH2)3CH3 
base (aq)
 (does not dissolve)
base (aq)
(3) CH3COOH   (dissolves)
indicator
(4) CH3CH2CH2OH   no color change
indicator
(5) CH3COOH   color change to acidic
(1), (2), and (3) distinguish pentane from the others; (4) and (5) distinguish
propanol from ethanoic acid.

11D.36 The weakest base is methylamine, followed by dimethylamine. The

strongest base is diethylamine. The basicity of amines increases with
increased substitution on the nitrogen atom. In acting as a base, the
nitrogen atom develops a positive charge, which is stabilized by the
electron-donating alkyl groups. Hence the primary amine, methylamine,
is a weaker base than the two secondary amines. Diethylamine is a
stronger base than dimethylamine because the larger ethyl group is a better
electron donor than the smaller methyl group.

11E.2 (a)

(b)
 Focus 11 Organic Chemistry 519

(c)

F3 C

F 3C

CF3

11E.4 The information in the question does not narrow down whether the two
groups should be ortho, meta, or para to each other, and therefore all three
are possible.

HO
OH O O
O

OH OH
OH

HO

11E.6
(a) HO C(CH 3)2 COOH (b) CH CH2 (c) NH2CH2COOH

CH3

11E.8
O O O O
(a) C C N (CH2)2 N C C N (CH2)2 N

H H H H

O O

(b) C O C O

11E.10 Random copolymer

520 Focus 11 Organic Chemistry

11E.12 Polyalkenes < polyesters < polyamides, because of the increasing strength
of intermolecular forces between the chains. The three types of polymer have
about the same London forces if their chains are about the same length. However,
polyesters also have dipole forces contributing to the strength of intermolecular
forces, and polyamides form very strong hydrogen bonds between their chains.

11E.14 (a) Polymerization of the monomer H2C=CHCONH2 results in the

polymer (—CH2CH(CONH2) —)n, and for n = 3:
—CH2CH(CONH2)CH2CH(CONH2)CH2CH(CONH2) —
It is easier to see when drawn:

(b) The side chains (CONH2) form H-bonds.

11E.16 The more polar functional groups present, the stronger the intermolecular
forces. Stronger intermolecular forces result in a:
higher softening point; greater viscosity; and greater mechanical strength

11E.18 When polymer chains are cross-linked, the polymer does not soften as
much as it otherwise would as the temperature is raised. It is also more
resistant to deformation on stretching, because the cross-links pull it back.
However, extensive cross-linking can produce a rigid network that resists
stretching.

OH
H
11E.20 (a) OH
O H
HO H
H H O
O H
OH H H
HO H H
OH
HO OH
 Focus 11 Organic Chemistry 521

(b) The functional group formed acetal linkage.

(c) The polymerization is a condensation reaction.

11E.22 Glycine, alanine, phenylalanine, valine, leucine, isoleucine, tryptophan,

proline, and methionine contain nonpolar side groups.

11E.24
O NH2 O

H
N
HO OH

11E.26 (a) The functional groups include primary and secondary amines, an
alkene, and a carboxylic acid. Histidine is an essential amino acid.
There is one chiral carbon atom (*).

11E.28 (a) TAATCTAGTA

(b) CTGATCCTAGA
522 Focus 11 Organic Chemistry

11.2 C(CH3 )4 (9.5C)  CH3 CH2 CH(CH3 )2 (28C)

 CH3 CH2 CH2 CH2 CH3 (36C)

Because the molecular formulas are all identical, the compounds will have
the same molar mass. The difference in boiling points can then be
attributed to the degree of branching; the more highly branched
compounds have the lower boiling points.

11.4 Ni
(a) CH 3 CH=CHCH 2 CH 3  H 2   CH 3 CH 2 CH 2 CH 2 CH 3 , addition

reaction
(b) CH 2 =CHCH 3  HCl 
 CH 3 CHClCH 3 and an isomer,

CH2 ClCH2 CH3 , addition reaction

11.6 (a) The intermediate is positively charged.

The charge is eliminated by nucleophilic attack of the carbocation by Cl-.
(b)

Cl Cl
Cl H H H

11.8 (a) cis-2-pentene, trans-2-pentene (b) 2-methyl-2-butene

(c) 2-methyl-2-pentene (d) 4-methyl-1-heptyne
(e) 5-methyl-3-heptyne

11.10 (a) (i) 2-methypropane; (ii) 2-methylbutane; (b) iso- is added as a

prefix to denote the isomer of a straight chain hydrocarbon in which the
end CH3 group has been moved from the end of the chain to a position one
carbon unit inward. The systematic name for isohexane will thus be
2-methylpentane.
 Focus 11 Organic Chemistry 523

11.12 (a) (b)

11.14 (a) Ethane can form no chiral products. (b) Propane can form no chiral
products. (c) 2-Bromobutane is chiral. (d) 2-Bromopentane is chiral.

11.16 Assume a 100. g sample.

1 mol C
Amount (moles) of C  90 g C   7.5 mol C
12.01 g C

1 mol H
Amount (moles) of H  10 g H   9.9 mol H
1.01 g H
9.9 mol H 1.3 mol H 4 mol H
 
7.5 mol C 1 mol C 3 mol C

The empirical formula is C3 H 4 , which has a molar mass of 40 g  mol1 .

Because 40.06 g  mol1 is the molar mass of the compound, the molecular

formula is C3 H4 as well. The compound could be a cyclic alkene,

dialkene, or alkyne. See the structures of the possible isomers below.
1.46 g
Amount (moles) C3 H 4  1
 3.6  102 mol
40.06 g.mol
PV 1.0 atm  1.600 L
Amount (moles) H 2  nH2  
RT 0.082 06 L  atm  K 1  mol1  273 K
 7.2  102 mol

nH2 7.2  102 mol

Thus  2
nC3H4 3.6  102 mol
524 Focus 11 Organic Chemistry

There are two  - bonds across which H 2 can add. This is consistent with
the compound’s being an alkyne or a dialkene. No definite identification
of the hydrocarbon can be made on the basis of the data provided. The
three possible isomers consistent with the formula C3 H4 :

(1) HC C CH3

(2) H2C C CH2

(3) HC CH

CH2

Structure 3 is inconsistent with the hydrogenation data.

11.18 The question here is twofold:

(1) Which ring will be nitrated?
(2) Which position of that ring will be the site of electrophilic
substitution?

The OH group is an activating function because it donates electrons to the

aromatic ring, whereas the aldehyde, CHO, group is electron-withdrawing
and therefore deactivating. We thus expect the ring with the OH group
attached to be the one that is substituted. Because OH is an ortho-, para-
directing group, we expect the substitution to occur at one of those sites.
Because the para position is already substituted, this leaves only the
position ortho to the OH group for the substitution. The expected product
is therefore:
 Focus 11 Organic Chemistry 525

11.20 (a) 2,4,6-Trinitrotoluene.

(b) The methyl group on the toluene directs electrophilic aromatic
substitution toward the ortho and para positions because the methyl group
is slightly electron-donating. A nitro group, however, is electron-
withdrawing and will tend to cause electrophilic substitution meta to its
position. The result is that, once a nitro group has substituted onto the ring,
it reinforces the directing influence of the methyl group.
For example, in 2-nitrotoluene (ortho-nitrotoluene) the methyl group will
cause preferential substitution at the 4 position. The position is also the
meta position relative to the nitro group, so that group enhances
substitution at this location as well.

11.22 (a)(i) 1 mol of cyclohexene will react with 1 mol of H2 to form 1 mol of
cyclohexane:
C6H10 + H2 → C6H12
The volume of one mole of H2 at 298 K and 1.00 atm is:

n  R  T 1 mol   0.082057 L  atm  K  mol  (298 K)

1 1

V    22.5 L
P 1 atm

(a)(ii) 3 mol of H2 is needed for a complete reaction with 1 mole of

benzene:
C6H6 + 3H2 → C6H12
Therefore, the volume of H2 needed is three times that needed to react
with one mole, or 67.5 L, of cyclohexene.

(b) For the reaction of cyclohexene with H2:

526 Focus 11 Organic Chemistry

Break 1 C=C bond +612 kJ·mol‾1

Break 1 H—H bond +436 kJ·mol‾1
Form 1 C—C bond −348 kJ·mol‾1
Form 2 C—H bonds 2(−412 kJ·mol‾1)
Total −124 kJ·mol‾1

For the reaction of benzene with H2:

Break 6 C C bonds 6(+518 kJ·mol‾1)
Break 3 H—H bond 3(+436 kJ·mol‾1)
Form 6 C—C bonds 6(−348 kJ·mol‾1)
Form 6 C—H bonds 6(−412 kJ·mol‾1)
Total −144 kJ·mol‾1

(c) Hydrogenation of benzene is not three times more exothermic than the
hydrogenation of hexane; this is because of resonance stabilization of the
C C bonds in benzene. The resonance stabilization of benzene makes
the C C bonds more stable, reducing the overall amount of energy
released during the reaction.

11.24 (a) C3H7NO2S

(b) C5H5N5
(c) C9H10O2
 Focus 11 Organic Chemistry 527

11.26
(a)
O
CH3O
CH3

HO

ether ( OCH3), alcohol ( OH), ketone C O aromatic ring

(b)
HN OH
O C
CH3

amide R C N R' , phenol ( OH), aromatic ring

NH2

(c) NH2

CH2CH3

N 2CH3
CH
O O CH2CH3
N
O O CH2CH3
CH2CH3
amine ( NH2), ester , tertiary amine H2C N
O O CH2CH3

aromatic ring
528 Focus 11 Organic Chemistry

11.28
(a) CH3 (b) CH3 OH

* *
*
* *
* *
OH *

HO
CH3 CH3

11.30

11.32
 Focus 11 Organic Chemistry 529

11.34 (a)

Hexane, alkane

1-Hexene, alkene

1-Pentanol, alcohol

Pentanal, aldehyde

Butanoic acid, carboxylic acid

Methyl propanoate, ester

530 Focus 11 Organic Chemistry

3-Pentanone, ketone

Butyl methyl ether, ether

(b) 1-Pentanol and butyl methyl ether are isomers. Pentanal and 3-
pentanone are isomers. Butanoic acid and methyl propanoate are isomers.
None of these molecules are chiral.

(c) Hexane: London forces

1-Hexene: London forces
1-Pentanol: hydrogen bonding, diploledipole interactions, London forces
Pentanal: dipoledipole interactions, London forces
Butanoic acid:hydrogen bonding, London forces, dipoledipole
interactions
Methyl propanoate: London forces, dipoledipole interactions
3-Pentanone: London forces, dipoledipole interactions
Butyl methyl ether: London forces, weak dipoledipole forces

(d) We can classify the molecules in the list into three categories by their
intermolecular interactions: (1) those with London forces only, (2) those
with London forces and dipoledipole interactions, and (3) those with
London forces, dipoledipole interactions, and hydrogen bonding. The
boiling point should increase with the increase in the types of
intermolecular forces available, so compounds of type 1 will boil at a
 Focus 11 Organic Chemistry 531

lower temperature than compounds of type 2, which will in turn boil at a

lower temperature than compounds of type 3.
Type 1 molecules: hexane and 1-hexene
Type 2 molecules: pentanal, methyl propanoate, 3-pentanone, and butyl
methyl ether
Type 3 molecules: pentanol and butanoic acid
Within these classifications, it is more difficult to order the molecules;
however, we can make some generalizations. The C=O in an aldehyde or a
ketone will have a larger dipole moment than the C—O—C linkage in an
ether because of the geometry around the O atom. Thus we expect the
ether to boil at a lower temperature. Among the molecules of type 3,
carboxylic acids generally exhibit stronger H-bonding than alcohols, so we
expect butanoic acid to boil at a higher temperature than pentanol.

Compound Observed Boiling Point (°C)

Hexane 69
1-Hexene 64
Pentanol 136–138
Butanoic acid 164
Methyl propanoate 80
3-Pentanone 102
Butyl methyl ether 70–71

11.36 (a) HOCH2 CH2 OH  2 CH3 (CH2 )16 COOH 

CH3 (CH2 )16 COOCH2 CH2 OOC(CH2 )16 CH3  2 H2 O

(b)
2 CH3 CH2 OH  HOOCCOOH  CH3 CH2 OOCCOOCH2 CH3  2 H2 O

(c) CH 3 CH 2 CH 2 CH 2 OH  CH 3 CH 2 COOH 


CH3 CH2 COOCH2 CH2 CH2 CH3  H2 O
532 Focus 11 Organic Chemistry

11.38 Resonance forms:

The nitro group in general is an electron-withdrawing group, hence would

normally be expected to enhance the acidity of the phenol simply by
pulling electron density away from the phenol oxygen atom. This happens
by two processes. One is the simple inductive effect of having the
electronegative groups attached to the aromatic ring. The second effect is
through the resonance interaction of the nitro group with the aromatic ring,
which reinforces the resonance interaction with the oxygen atom for the o-
and p-isomers. The m-isomer, however, does not have a reinforcing
resonance interaction.

11.40 (a)   iRT  molarity

Assuming i  1

0.0112 atm   0.0821 L  atm  K -1  mol   298 K 

-1
 3.16 g
X
0.500 L
-1
X  13 800 g  mol  molar mass of the polymer
 Focus 11 Organic Chemistry 533

(b) The molecular mass of CH3CHCH2 is 42.08 g mol-1.

Dividing the molar mass of the polymer by the molar mass of the
monomer ( 13800 g  mol-1 / 42.08 g  mol-1  328 ) indicates that there are
approximately 328 monomers in the average polymer.

(c)  308 pm  monomer -1  (328 monomers)  101000 pm or 101 nm

11.42 (a)

(b) Substitution will be favored over elimination if the hydroxide solution

is dilute.
534 Focus 11 Organic Chemistry

11.44 (a)

(b) As shown in the resonance structure on the right, there is a double

bond along the C=N backbone. Since double bonds restrict rotation, the C,
N, and O atoms in the amide group are in the same plane.

11.46 There is one nucleotide every 340 pm, or 3.40 × 10–10 m. Over the course
of 0.299 m, there will be 8.79 × 108 nucleotides. Each nucleotide has a
molar mass of 625 g·mol–1 on average, so the molar mass of the DNA
molecule will be 5.50 × 1011 g·mol–1.

11.48 The silicone polymer is more hydrophilic as the oxygen atoms in the
– O – SiR2 – O – SiR2 – main chain can interact with water molecules via
the two lone pairs per oxygen atom. It is for this reason that silicones are
used to waterproof fabrics: the oxygen interacts with the fabric while the
hydrophobic part of the silicone polymer forms the outer water-repelling
(waterproofing) surface. A polyphosphazine with methyl side groups will
be more hydrophobic, as there is only one lone pair on the nitrogen atom
of the – PR2 = N – main chain. Of course they could be made more
hydrophilic by replacing the methyl side groups with halogen atoms such
as chlorine.
 Focus 11 Organic Chemistry 535

11.50 (a) The nitrogen atoms as drawn are sp3-hybridized.

(b) The polymer absorbs light because of the long chain of alternating
single bonds and double bonds in the structure.

11.52 These hydrocarbons are too volatile (they are all gases at room
temperature) and would not remain in the liquid state.

11.54 CH2CHCH3 + CH3CH2CH2CH3  CH3(CH2)5CH3

11.56 (a) Byproduct is H2, another valuable fuel.

(b) C7H16 → C7H8 + 4H2

11.58 (a) Moles of C can be determined from moles of CO2.

0.352 g
 0.008 mol CO 2
44.01g.mol -1 CO 2
0.008 mol C × 12.01 g.mol-1 = 0.096 g C
Moles of H can be determined from moles of H2O.
0.109g
= 0.006 mol H 2 O
18.01g.mol -1 H 2 O

0.012 mol H × 1.008 g.mol-1 = 0.012 g H

Find out whether there is oxygen in the compound.
Total sample mass – (mass of C + mass of H)
0.108 g – (0.096 g + 0.012) = 0
Only C and H in the compound.
To find empirical formula divide by smallest number of moles:
0.008 mole
C: =1
0.008 mole

0.012 mole
H: = 1.5
0.008 mole
Multiple by 2 to get the nearest integer. C2H3
536 Focus 11 Organic Chemistry

(b) The molecular formula is x times the empirical formula.

mass of molecular formula 54.09 g.mol -1
x= = 2
mass of empirical formula 27.035g.mol -1

molecular formula = (2)(C2 H 3 )

molecular formula = (C4 H 6 )

(c) Possible structures:

(d) Each of the first four compounds in (c) can add 4 H’s, which is what
happens in a catalytic hydrogenation with a triple or double bond, and all
four compounds would give butane (58.12 g.mol-1). The last three
compounds (cyclobutene, 1-methylcyclopropene, 3-methylcyclopropene)
would add 2 H’s to give cyclobutane (56.11 g.mol-1) and
methylcyclopropane (56.11 g.mol-1), and they can be eliminated.
(e) Remember that the total pressure of a mixture of gases is the sum of
the partial pressures of its components. Partial pressure of the compound is
1.0 atm. Total pressure after adding HBr is 5.0 atm. Therefore, partial
pressure of HBr before the reaction is 4.0 atm, and after the reaction it is
2.0 atm. Since the initial pressure of the compound was 1.0 atm and the
pressure of HBr decreased by 2.0 atm, there is a 1:2 molar ratio between
the reactants. We have determined that the product is the addition of 2 mol
of HBr to the compound.
C4H6(g) + 2HBr(g) → C4H8Br2(g)
The molecular formula is C4H8Br2.
 Focus 11 Organic Chemistry 537

(f) Since optical isomers are formed, the HBr is reacting with

1,3-butadiene, . Since addition of HBr occurs across each double

bond, there are three possible isomers, and as indicated (*), the chiral
centers will also generate optical isomers.

*
Br Br
1,3-Dibromobutane

(g) All the carbons in the reactants are sp2-hybridized.

(h) 1,3-Butadiene