Alkanes and

Cycloalkanes

Chapter 2

2-1
What are Alkanes
 Hydrocarbon: A compound composed only of
carbon and hydrogen.
 Saturated hydrocarbon: A hydrocarbon containing
only single bonds.
 Unsaturated hydrocarbon: A hydrocarbon that
contains one or more carbon-carbon double or
triple bonds.
 Alkane: A saturated hydrocarbon whose carbons
are arranged in an open chain.
 Aliphatic hydrocarbon: Another name for an
alkane.

2-2
The Four Classes of Hydrocarbons

Hydrocarbons

Saturated Unsaturated

Alkanes Alkenes Alkynes Arenes

Class (Chapter 2) (Chapters 5-6) (Chapter 7) (Chapter 21-22)

Carbon- Only carbon- One or more One or more One or more

carbon carbon single carbon-carbon carbon-carbon benzenelike
bonding bonds double bonds triple bonds rings
HH H H
Example H-C-C-H C C H-C C-H
H H H H
Name Ethane Ethene Ethyne Benzene
(Ethylene) (Acetylene

2-3
Structure of Alkanes
 Shape
 Tetrahedral about carbon.
 All bond angles are approximately 109.5°.

109.5°

2-4
Drawing Alkanes
 Line-angle formulas:
 An abbreviated way to draw structural formulas.
 Each vertex and line ending represents a carbon atom.

Ball-and-
stick
model

Line-angle
formula

Structural CH3 CH2 CH3 CH3 CH2 CH2 CH3 CH3CH2CH2 CH2 CH3
formula
Propane Butane Pentane

2-5
Constitutional Isomerism
 Constitutional isomers: Compounds with the
same molecular formula but a different
connectivity of their atoms.
 example: C4H10

CH3
CH3 CH2CH2CH3 CH3 CHCH3
Butane 2-Methylpropane
(bp -0.5°C) (bp -11.6°C)

2-6
Constitutional Isomerism
 Question: Do these formulas represent constitutional
isomers?
CH3 CH3 CH3
CH3 CHCH2 CH and CH3 CH2 CHCHCH3 (each is C7H16)
CH3 CH3
 Write the molecular formula of each.
 Find the longest carbon chain.
 Number each chain from the end nearest the first
branch.
 Compare the chain lengths as well as the identity and
location of branches. They are constitutional isomers.
5
CH3 CH3 5 4 3
CH3 4
4 5 3
CH3 CHCH2 CH 2 4 and CH3 CH2 CHCHCH3 2
1 2 3 1 3 5 2 1 1
CH3 CH3
2-7
Constitutional Isomerism
 The ability of carbon to form strong bonds with
other carbon atoms results in a staggering
number of constitutional isomers.
MolecularConstitutional
Formula Isomers
CH4 1
C5 H12 3
C10 H22 75
C15 H32 4,347
C25 H52 36,797,588
C30 H62 4,111,846,763

2-8
Nomenclature - IUPAC
 Suffix -ane specifies an alkane, e.g. ethane.
 Prefix tells the number of carbon atoms.
Number of Number of
Prefix carbons Prefix carbons
meth- 1 undec- 11
eth- 2 dodec- 12
prop- 3 tridec- 13
but- 4 tetradec- 14
pent- 5 pentadec- 15
hex- 6 hexadec- 16
hept- 7 heptadec- 17
oct- 8 octadec- 18
non- 9 nonadec- 19
dec- 10 eicos- 20

2-9
Nomenclature - IUPAC
 Parent (root) name: The longest carbon chain.
 Substituent: A group bonded to the parent chain.
 Alkyl group: A substituent derived by removal of a
hydrogen from an alkane; given the symbol R-.

Alkane Name Alkyl groupName

CH4 Methane CH3 - Methyl group

CH3 CH3 Ethane CH3 CH2 - Ethyl group

2-10
Nomenclature - IUPAC
[Link] name of a saturated hydrocarbon with an
unbranched chain consists of a prefix and suffix.
2. The parent chain is the longest chain of carbon atoms.
3. Each substituent is given a name and a number. Use a
hyphen to connect the number to the name.
CH3
2
CH3 CHCH3 1 3

2-Methylpropane

4. If there is one substituent, number the chain from the

end that gives it the lower number.
CH3
4 2
CH3 CH2 CH2 CHCH3 5 32 1 1 34 5
2-Methylpentane(not 4-methylpentane)
2-11
Nomenclature - IUPAC
5. If there are two or more identical substituents, number
the chain from the end that gives the lower number to
the substituent encountered first.
 Indicate the number of times the substituent appears
by a prefix di-, tri-, tetra-, and so on.
 Use commas to separate position numbers.

6 4 2 1 3 5
5 3 1 2 4 6
2,4-Dimethylhexane
(not 3,5-dimethylhexane)

2-12
Nomenclature - IUPAC
6. If there are two or more different substituents,
 list them in alphabetical order.
 number from the end of the chain that gives the
substituent encountered first the lower number.
2 4 6 6 4 2
1 3 5 7 7 5 3 1

3-Ethyl-5-methylheptane
(not 3-methyl-5-ethylheptane)

2-13
Nomenclature - IUPAC
7. The prefixes di-, tri-, tetra-, and so on are not included
in alphabetization.
 Alphabetize the names of substituents first and then
insert these prefixes.

4 6
1 5
2 3
4-Ethyl-2,2-dimethylhexane
(not 2,2-dimethyl-4-ethylhexane)

2-14
Nomenclature-IUPAC
 8. Where there are two or more parent chains of
identical length, choose the parent chain with the
greater number of substituents.

2-15
Nomenclature - IUPAC

2-16
Nomenclature - Common
 The number of carbons in the alkane determines
the name.
 All alkanes with four carbons are butanes, those with
five carbons are pentanes, etc.
 iso- indicates the chain terminates in -CH(CH3)2 .
 neo- indicates that the chain terminates in -C(CH3)3.
CH3
CH3CH2CH2CH3 CH3CHCH3
Butane Isobutane

CH3 CH3
CH3 CH2CH2CH2 CH3 CH3 CH2CHCH3 CH3 CCH3
CH3
Pentane Isopentane Neopentane 2-17
Classification of C & H
 Primary (1°) C: A carbon bonded to one other
carbon.
 1° H: a hydrogen bonded to a 1° carbon
 Secondary (2°) C: A carbon bonded to two other
carbons.
 2° H: a hydrogen bonded to a 2° carbon
 Tertiary (3°) C: A carbon bonded to three other
carbons.
 3° H: a hydrogen bonded to a 3° carbon
 Quaternary (4°) C: A carbon bonded to four other
carbons.

2-18
Classification of C & H

2-19
IUPAC - General
 prefix-infix-suffix
 Prefix:Tells the number of carbon atoms in the parent
chain.
 Infix: Tells the nature of the carbon-carbon bonds in the
parent chain.
 Suffix: Tells the class of the compound.

Nature of Carbon-Carbon Suffix Class

Infix Bonds in the Parent Chain
-e hydrocarbon
-an- all single bonds -ol alcohol
-en- one or more double bonds-al aldehyde
-yn- one or more triple bonds -amine amine
-one ketone
-oic acid carboxylic acid
2-20
IUPAC - General
prop-en-e = propene CH3 CH=CH2
eth-an-ol = ethanol CH3 CH2 OH
O
but-an-one = butanone CH3 CCH2 CH3
O
but-an-al = butanal CH3 CH2 CH2 CH
O
pent-an-oic acid = pentanoic acid CH3 CH2 CH2 CH2 COH
OH
cyclohex-an-ol = cyclohexanol

eth-yn-e = ethyne
HC CH
eth-an-amine = ethanamine
CH3 CH2 NH2
2-21
Cycloalkanes
 General formula CnH2n
 Five- and six-membered rings are the most common.
 Structure and nomenclature
 Add the prefix cyclo- to the name of the open-chain
alkane containing the same number of carbons.
 If only one substituent, no need to give it a number.
 If two substituents, number from the substituent of
lower alphabetical order.
 If three or more substituents, number to give them the
lowest set of numbers and then list substituents in
alphabetical order.

2-22
Cycloalkanes
 Line-angle drawings
 Each line represents a carbon-carbon single bond.
 Each vertices and line ending represents a C.
 Represent a ring by a regular polygon that has the
same number of sides as there are carbon atoms
in the ring.
CH2 CH3
C C H2 C
C
= C C = CH CH
C H2 C
C C CH2 CH3

C8 H16

2-23
Cycloalkanes
 Example: Name these cycloalkanes.

(a) (b)

(c) (d)

2-24
Bicycloalkanes
 Bicycloalkane: An alkane that contains two rings
that share two carbons.
 We will refer to the most common of these by
their common names rather than their systematic
(IUPAC) names.

2-25
Conformations
 Conformation: Any three-dimensional
arrangement of atoms in a molecule that results
from rotation about a single bond.

2-26
Conformations
 Staggered conformation: A conformation about a
carbon-carbon single bond in which the atoms or
groups on one carbon are as far apart as
possible from the atoms or groups on an adjacent
carbon so that interactions in terms of energetics
are minimized.
 Newman projection: A way to view a molecule by
looking along a carbon-carbon single bond.
H
H H

H H
H
2-27
Conformations
 Eclipsed conformation: A conformation about a
carbon-carbon single bond in which the atoms or
groups of atoms on one carbon are as close as
possible to the atoms or groups of atoms on an
adjacent carbon. The strain in an eclipsed
conformation is from steric interactions from
atoms that are forced nearer each other
H
H

H
H HH

2-28
Conformations
 Torsional strain
 Strain that arises when nonbonded atoms separated
by three bonds are forced from a staggered
conformation to an eclipsed conformation.
 Also called eclipsed interaction strain.
 The torsional strain between eclipsed and staggered
ethane is approximately 12.6 kJ (3.0 kcal)/mol.

+12.6 kJ/mol

2-29
Conformations
 Dihedral angle Q (Greek theta): The angle
created by two intersecting planes.
 Figure 2.7 Dihedral angles in ethane.

2-30
Conformations
 Figure 2.8 The energy of ethane as a function of
dihedral angle.

2-31
Conformations
 The origin of torsional strain in ethane:
 Originally thought to be caused by repulsion between
eclipsed hydrogen nuclei.
 Alternatively, caused by repulsion between electron
clouds of eclipsed C-H bonds.
 Theoretical molecular orbital calculations suggest that
the energy difference is not caused by destabilization
of the eclipsed conformation but rather by stabilization
of the staggered conformation.
 This stabilization arises from the small donor-acceptor
interaction between a C-H bonding MO of one carbon
and the C-H antibonding MO on an adjacent carbon.
Stabilization is lost when a staggered conformation is
converted to an eclipsed conformation.

2-32
Conformations
 Strain energy The increase in energy resulting
from distortion of bond angles and bond lengths
from their optimal values.
 Steric strain (nonbonded interaction strain) The
strain that arises when nonbonded atoms
separated by four or more bonds are forced
closer to each other than their atomic (contact)
radii will allow.
 Angle strain The strain that arises when a bond
angle is either compressed or expanded
compared to its optimal value.

2-33
Conformations
 Anti conformation: A conformation about a single
bond in which the groups on adjacent carbons lie
at a dihedral angle of 180°, as seen here for
butane.

CH3
H H

H H
CH3

2-34
Anti Butane
 Energy-minimized anti conformation (computed)
 the C-C-C bond angle is 111.9° and all H-C-H bond
angles are between 107.4° and 107.9°.
 the calculated strain is 9.2 kJ (2.2 kcal)/mol.

2-35
Eclipsed Butane
 The calculated energy difference between (a) the non-
energy-minimized and (b) the energy-minimized
eclipsed conformations is 5.6 kJ (0.86 kcal)/mol.

2-36
Gauche Butane
 Gauche conformation: A conformation about a
single bond of an alkane in which two groups on
adjacent carbons lie at a dihedral angle of 60°.
 Here is one of two energy-minimized gauche
conformations of butane. The second one has equal
energy.

2-37
Conformations
 Figure 2.9 The energy of butane as a function of the
dihedral angle about the bond between carbons 2 and 3.

2-38
Cyclopropane
 Angle strain: The C-C-C bond angles are compressed
from 109.5° to 60°.
 Torsional strain: There are 6 sets of eclipsed hydrogen
interactions.
 Strain energy is about 116 kJ (27.7 kcal)/mol.
H H
H

H H
H

2-39
Cyclobutane
 Puckering from planar cyclobutane reduces torsional strain but
increases angle strain.
 The conformation of minimum energy is a puckered “butterfly”
conformation.
 Strain energy is about 110 kJ (26.3 kcal)/mol.

2-40
Cyclopentane
 Puckering from planar cyclopentane reduces torsional strain, but
increases angle stain.
 The conformation of minimum energy is a puckered “envelope”
conformation.
 Strain energy is about 42 kJ (6.5 kcal)/mol.
 Figure 2.13 Conformations of cyclobutane.

2-41
Cyclohexane
 Chair conformation: The most stable puckered
conformation of a cyclohexane ring.
 All bond C-C-C bond angles are 110.9°.
 All bonds on adjacent carbons are staggered.
 Figure 2.15 A chair conformation of cyclohexane.

2-42
Cyclohexane
 Figure 2.16 A chair conformation of cyclohexane showing
axial and equatorial bonds.

2-43
Cyclohexane
 In a chair conformation, six H are equatorial and
six are axial.

2-44
Cyclohexane
 For cyclohexane, there are two equivalent chair
conformations.
 All C-H bonds equatorial in one chair are axial in the
alternative chair and vice versa.

2-45
Cyclohexane
 Boat conformation: A puckered conformation of a
cyclohexane ring in which carbons 1 and 4 are
bent toward each other.
 There are four sets of eclipsed C-H interactions and
one flagpole interaction (flagpole H green).
 A boat conformation is less stable than a chair
conformation by 27 kJ (6.5 kcal)/mol.

2-46
Cyclohexane
 Twist-boat conformation
 Approximately 41.8 kJ (5.5 kcal)/mol less stable than a chair
conformation.
 Approximately 6.3 kJ (1.5 kcal)/mol more stable than a boat
conformation.

2-47
Cyclohexane
 Figure 2.19 Energy diagram for the
interconversion of chair, twist-boat, and boat
conformations of cyclohexane.

2-48
Methylcyclohexane
 Figure 2.21 Two chair conformations of
methylcyclohexane. The steric strain introduced
by two diaxial interactions makes the diaxial
conformation less stable by approximately 7.28
kJ(1.74 kcal)/mol.

2-49
G0 axial ---> equatorial
 Given the difference in strain energy between axial and
equatorial conformations, it is possible to calculate the
ratio of alternative conformations using the following
relationship. G0 =-RT ln K
eq
axial equatorial

 G°  G°
Group (kJ/mol) Group (kJ/mol)
C N 0.8 NH2 5.9
F 1.0 COOH 5.9
C CH 1.7 CH=CH2 7.1
I 1.9 CH3 7.28
Cl 2.2 CH2 CH3 7.3
Br 2.4 CH(CH3) 2 9.0
OH 3.9 C(CH3 ) 3 21.0
2-50
Cis,Trans Isomerism
 Stereoisomers: Compounds that have
 the same molecular formula.
 the same connectivity.
 a different orientation of their atoms in space.
 Cis,trans isomers: Stereoisomers that are the
result of the relative orientation of groups bound
either to a ring (this chapter) or to a carbon-
carbon double bond (Chapter 5).

2-51
Isomers
 Figure 2.22 Relationship between stereoisomers
and constitutional isomers.

2-52
Cis,Trans Isomers
 1,2-Dimethylcyclopentane
H H
H H H H
H H H H HH3 C
H H H H
CH3 CH3 CH3 H

H3 C CH3 H3 C CH3

cis-1,2-Dimethyl- trans
-1,2-Dimethyl-
cyclopentane cyclopentane

2-53
Cis-Trans Isomers
 Stereocenter: An atom, most commonly carbon,
about which exchange of two groups produces a
different stereoisomer.
 example: 1,2-dimethylcyclobutane has two
stereocenters.
 Configuration: Refers to the arrangement of
atoms about stereocenter.

2-54
Cis,Trans Isomerism
 1,4-Dimethylcyclohexane
H3 C H H H

H CH3 H3 C CH3
CH3 CH3

H3 C H3 C

trans
-1,4-Dimethyl- cis-1,4-Dimethyl-
cyclohexane cyclohexane
CH3 CH3
H3 C

CH3
The more stable chair conformation of each isome
2-55
Cis,Trans Isomerism
 trans-1,4-Dimethylcyclohexane
 the diequatorial-methyl chair conformation is more
stable by approximately 2 x (7.28) = 14.56 kJ/mol
CH3 H
H H3 C
H CH3
CH3 H
(less stable) (more stable)

2-56
Cis,Trans Isomerism
 cis-1,4-Dimethylcyclohexane
H H
CH3 H3 C
H H
CH3 conformations are of equal stability CH3

2-57
Cis,Trans Isomerism
 The decalins
H H

A B
H H
trans-Decalin

H
H
A B H
H
cis-Decalin

2-58
 Steroids
 The steroid nucleus C D
A B

 Cholestanol
CH3
CH3 H
H
H H HO
H H
HO H
H

Cholestanol

2-59
Bicycloalkanes
 Norbornane drawn from three different
perspectives
one carbon bridge between carbons
1 and 4 of the six-membered ring
1
6 2 6
1
O
1 4 1
2

5 3 3
5
4
4 4
(a) (b) (c) Camphor

2-60
Bicycloalkanes
 Adamantane join the three axial
add three
axial bonds bonds to a CH group

Cyclohexane Adamantane

NH2

Amantadine
(antiviral agent)

2-61
Physical Properties of Alkanes
 Intermolecular forces of attraction (example)
 ion-ion (Na+ and Cl- in NaCl)
 ion-dipole (Na+…..OH2 and Cl-…..H-O-H solvated in
aqueous solution)
 dipole-dipole and hydrogen bonding
 dispersion forces (very weak electrostatic attraction
between temporary dipoles)

2-62
Physical Properties
 Low-molecular-weight alkanes (methane to
butane) are gases at room temperature.
 Higher molecular-weight alkanes (pentane,
decane, gasoline, and kerosene) are liquids at
room temperature.
 High-molecular-weight alkanes (paraffin wax) are
semisolids or solids at room temperature.

2-63
Physical Properties
 Constitutional isomers have different physical
properties.
mp bp Density
Name (°C) (°C) (g/mL)
hexane -95 68.7 0.659
2-methylpentane -154 60.3 0.653 Hexane
3-methylpentane -118 63.3 0.664
2,3-dimethylbutane
-129 58.0 0.661
2,2-dimethylbutane
-98 49.7 0.649 2,2-Dimethylbutane

2-64
Oxidation of Alkanes
 Oxidation is the basis for the use of alkanes as
energy sources for heat and power.
 heat of combustion: The heat released when one mole
of a substance in its standard state is oxidized to
carbon dioxide and water. 0
H
kJ (kcal)/mol

+ 2O2
CH4 CO2 + 2H2 O -890.4 (-212.8)
Methane
+ 5O2
CH3 CH2 CH3 3CO2 + 4H2 O -2220 (-530.6)
Propane

2-65
Heat of Combustion
 Table 2.7 Heat of combustion for constitutional
isomers of C8H18
H0
Hydrocarbon Structural formula [kJ (kcal)/mol]

Octane -5470.6 (-1307.5)

2-Methyl- -5465.6 (-1306.3)

heptane

2,2-Dimethyl- -5458.4 (1304.6)

hexane

2,2,3,3-Tetramethyl-
butane -5451.8 (1303.0)

2-66
Heats of Combustion
 Figure 2.24 Heats of combustion [kJ (kcal)/mol]
for isomeric alkanes with the molecular formula
C8H18.

-5470.6 (-1307.5)
-5465.6 (-1306.3)
-5458.4 (1304.6)
-5451.8 (1303.0

8CO2 + 9H2 O
2-67
Heat of Combustion
 Figure 2.25 Strain energy of cycloalkanes as a
function of ring size.

2-68
Sources of Alkanes
 Natural gas
 90-95% methane
 Petroleum
 gases (bp below 20°C)
 naphthas, including gasoline (bp 20 - 200°C)
 kerosene (bp 175 - 275°C)
 fuel oil (bp 250 - 400°C)
 lubricating oils (bp above 350°C)
 asphalt (residue after distillation)
 Coal

2-69
Petroleum
 Figure 2.26 Fractional distillation of petroleum.

2-70
Gasoline
 Octane rating: The percent 2,2,4-trimethylpentane
(isooctane) in a mixture of isooctane and heptane that has
equivalent antiknock properties.

Heptane 2,2,4-Trimethylpentane
(octane rating 0) (octane rating 100)

2-71
Synthesis Gas
 Synthesis gas: A mixture of carbon monoxide
and hydrogen in varying proportions which
depend on how it is produced.
C + H2 O heat CO + H2
Coal

1 catalyst
CH4 + 2 O2 CO + 2H2
Methane

2-72
Synthesis Gas
 Synthesis gas is a feedstock for the industrial
production of methanol and acetic acid.
catalyst
CO + 2H2 CH3 OH
Methanol
O
catalyst
CH3 OH + CO CH3 COH
Methanol Acetic acid
 It is likely that industrial routes to other organic
chemicals from coal via methanol will also be
developed.

2-73
Problem 2.63
 On the left is a stereorepresentation of glucose.
 (a) Convert the stereorepresentation on the left to a
planar hexagon representation.
 (b) Convert the stereorepresentation on the left to a chair
conformation.

2-74
Problem 2.63
 (a) Convert the stereorepresentation on the left to
a planar hexagon representation.

2-75
Problem 2.63
 (b) Convert the stereorepresentation on the left to a chair
conformation. Which groups in the chair conformation are
equatorial and which are axial?

 All substituents in this chair conformation are equatorial,

making it a particularly stable chair.

2-76
Alkanes and
Cycloalkanes

End Chapter 2

2-77