Chapter 2.

Alkanes and Cycloalkanes: Introduction to

Hydrocarbons
2.1: Classes of Hydrocarbons
molecules that are made up of carbon and hydrogen
1. Aliphatic
a. alkanes - contain C-C single bonds - CnH(2n+2)
saturated hydrocarbons
b. alkenes - contain C=C double bonds - CnH(2n)
c. alkynes - contain CΞC triple bonds - CnH(2n-2)
Arenes (aromatics) - cyclic hydrocarbons with alternating
C-C single and double bonds

1
2.2: Electron Waves and Chemical Bonds (please read)
2.3: Bonding in H2: The Valence Bond Model
electrons in atomic orbitals combine to form electron pairs in
molecular orbitals

H H H H + 435 KJ/mol

Sigma () bond -

orbital overlap is
along internuclear
axis

(Figure 2.1, p. 00) 2

Principle of maximum overlap (L. Pauling) - the strength of a
bond is directly proportional to the amount of orbital overlap
2.4: Bonding in H2: The Molecular Orbital Model - Molecular
orbitals (MOs) are linear combinations of atomic orbitals (AOs)
LCAO: # of MOs = # of AOs
nodal plane
- +
* one node

+ 436 KJ/mol H

- 436 KJ/mol

+ + 
no nodes 3
(Figure 2.6, p. 64)
2.5: Introduction to Alkanes: Methane, Ethane, and Propane
Alkanes have the general formula CnH2n+2

Methane Ethane Propane

(CH4) (C2H6) (C3H8)
CH4 CH3CH3 CH3CH2CH3
bp= -160° C bp= -89° C bp= -42° C

C-C bond length = 153 pm

C-H bond length = 111 pm
Bond angles between 109 - 112 ° (tetrahedral geometry)

(Figure 2.7, p. 64) 4

2.6: sp3 Hybridization and Bonding in Methane

Energy 2p 2p 2p 2p 2p 2p

2s 2s

All four C-H bond of

methane are identical

sp3 sp3 sp3 sp3

All four sp3 hybrid orbital

are equivalent

5
sp3 Hybridized Orbitals = 1 part s-orbital + 3 parts p-orbitals
(Figure 2.9, p. 66)

- +

6
C-H bond strength = 435 KJ/mol
sp3 hybridized orbital are more directional allowing for greater
orbital overlap and strong bonds compared to unhybridized orbitals
2.7: Bonding in Ethane (Figure 2.11, p. 68)

H H
~111° H
C C
H
153 pm
H H

H°C-C = 376 KJ/mol 7

2.8: Isomeric Alkanes: The butanes
2.9: Higher n-Alkanes (please read)
2.10: The C5H12 Isomers

Isomers: compounds with the same chemical formula, but

different arrangement of atoms
Constitutional isomer: have different connectivities
(not limited to alkanes)
C4H10 C5H12

n-butane isobutane n-pentane isopentane neopentane

C2H6O
O
OH
buta nol die thyl e the r

straight-chain or normal hydrocarbons branched hydrocarbons

n-pentane 8
n-butane
2.11 - 2.15: Systematic Nomenclature (IUPAC System)
Prefix-Parent-Suffix
Parent- number of carbons
Prefix- substituents
Suffix- functional groups
Naming Alkanes General Formula: CnH(2n+2)
suffix: -ane
Parent Names: (Table 2.2, p. 71)
1 CH4 Methane CH4
2 CH3CH3 Ethane C2H6
3 CH3CH2CH3 Propane C3H8
4 CH3(CH2)2CH3 Butane C4H10
5 CH3(CH2)3CH3 Pentane C5H12
6 CH3(CH2)4CH3 Hexane C6H14
7 CH3(CH2)5CH3 Heptane C7H16
8 CH3(CH2)6CH3 Octane C8H18 9
9 CH (CH ) CH Nonane CH
Alkyl substituents (group): carbon chains which are a
substructure of a molecule
one carbon group
off a main chain

R= Rest of the molecule (mainchain)

1 CH3-R Methyl
2 CH3CH2-R Ethyl
3 CH3CH2CH2-R Propyl
4 CH3(CH2)2CH2-R Butyl
5 CH3(CH2)3CH2-R Pentyl
6 CH3(CH2)4CH2-R Hexyl
7 CH3(CH2)5CH2-R Heptyl
8 CH3(CH2)6CH2-R Octyl
10
9 CH3(CH2)7CH2-R Nonyl
les for Systematic Nomenclature of Alkanes
Find the parent chain
a. Identify the longest continuous carbon chain as the
parent chain.
CH3
CH2
7carbons=hept-
CH3 CH HC CH2 CH3
CH2 CH2 CH3
b. If more than one different chains are of equal length
(number of carbons), choose the one with the greater
number of branch points (substituents) as the parent.
CH3 CH3
CH3 CH H C CH2 CH2 CH3 CH3 CH CH CH2 CH2 CH3
CH2 CH3 CH2 CH3
2branchpts. 1branchpt. 11
Numbering the carbons of the parent chain
a. Number the carbon atoms of the parent chain so that any
branch points have the lowest possible number
1 CH 7 CH3
3

2 CH2 6 CH2

H H
CH3 CH C CH2 CH3 CH3 CH C CH2 CH3
3 4 5 4
CH2 CH2 CH3 CH2 CH2 CH3
5 6 7 3 2 1

branch pts. at carbons 3 and 4 branch pts. at carbons 4 and 5

b. If there is branching equidistant from both ends of the

parent chain, number so the second branch point has the
lowest number.
1 2 9 8
CH3 CH2 H3C CH2 CH3 CH3 CH2 H3C CH2 CH3

CH3 CH CH2 CH2 CH CH CH2 CH3 CH3 CH CH2 CH2 CH CH CH2 CH3
9 7 6 5 4 3 2 1
3 4 5 6 7 8

branch pts. at carbons 3, 6, 7 branch pts. at carbons 3,4,7 12

3. Substituents
a. Identify and number the substituents and list
them in alphabetical order.
9 8
Parent C-9 = nonane
CH3 CH2 H3C CH2 CH3
3- ethyl
4-methyl 4,7-dimethyl
CH3 CH CH2 CH2 CH CH CH2 CH3 7-methyl
7 6 5 4 3 2 1

b. If there are two substituents on the same carbon,

assign them the same number.
4. Write out the name
a. Write out the name as a single word:
hyphens (-) separate prefixes
commas (,) separate numbers
b. Substituents are listed in alphabetical order
c. If two or more identical substituents are present use the
prefixes: di- for two
tri- for three 13
tetra- for four
note: these prefixes (di-, tri-, tetra-, etc.) are not used for
alphabetizing purposes
9 8
CH3 CH2 H 3C CH2 CH3
3- ethyl-4,7-dimethylnonane
CH3 CH CH2 CH2 CH CH CH2 CH3
7 6 5 4 3 2 1

Complex Substituents (substituents with branching)

a. Named by applying the four previous rules with some
modification
b. Number the complex substituent separately from the parent.
Begin numbering at the point of attachment to the parent
chain
c. Complex substituents are set off by parenthesis.
CH3 CH2
1 2 3 4 5 6 7 8 9 10
CH3 CH CH2 CH2 CH CH CH2 CH2 CH2 CH3

H2C CH2 CH3

1 2 3 2,6-dimethyl-5-(1-methylpropyl)decane
14
CH3
Nonsystematic (trivial) Names:
3-carbons: HC 3

CH Parent
Chain
H3C
Isopropyl-

4-Carbons:
(1-methylethyl)
H3 C CH3
CH Parent Parent
H3 C CH CH2 Parent
Chain Chain H3 C C Chain
H3 C CH2
CH3
CH3
sec-butyl- Isobutyl- tert-butyl-
(1-methylpropyl) (2-methylpropyl) (1,1-dimethylethyl)

5- Carbons: H3 C
CH3 CH3

Parent Parent Parent

CH CH2 CH2 H3 C C CH2 H3 C CH2 C
Chain Chain Chain
H3 C
CH3 CH3
Isopentyl-, isoamyl neopentyl- tert-pentyl-, tert-amyl
(3-methylbutyl) (2,2-dimethylpropyl) (1,1-dimethylpropyl)
Alphabetizing trivial names:
Iso- and neo are part of the alkyl group name and are used for alphabetizing.
sec- and tert- are not included in the alphabetical order.

4-(1-methylethyl)heptane 2-methyl-6-(2-methylpropyl)decane
-or-
4-Isopropylheptane
-or- 15
6-Isobutyl-2-methyldecane
 Cycloalkanes

Parent Parent
Chain Chain

Propane Cyclopropane cyclopropyl Heptane Cycloheptane Cycloheptyl

Parent
Chain
Parent
Butane Cyclobutane Cyclobutyl Chain

Octane Cyclooctane Cyclooctyl

Parent
Chain

Pentane Cyclopentane Cyclopentyl Parent

Chain

Parent Nonane Cyclononane Cyclononyl

Chain

Hexane Cyclohexane Cyclohexyl Parent

Chain

Decane Cyclodecane Cyclodecyl

16
aming Cycloalkanes General Formula: CnH(2n)
Parent Chain
a. Use the cycloalkane as the parent chain if it has a greater number of
carbons than any alkyl substituent.
b. If an alkyl chain off the cycloalkane has a greater number of carbons,
then use the alkyl chain as the parent and the cycloalkane as a
cycloalkyl- substituent.
CH3

Methylcyclopentane 2-Cyclopropylbutane

2. Numbering the Cycloalkane

a. When numbering the carbons of a cycloalkane, start with a substituted
carbon so that the substituted carbons have the lowest numbers (sum).
CH3 CH3 CH3
CH3
1 1 CH3 4 CH3
1 6 5
6 2 2 6 2 3
5 6
5 3 3 2
3 CH3 5 CH3 4 1
4 4 CH3 CH3
-not- -not-
1,3-Dimethylcyclohexane 1,5-Dimethylcyclohexane 1,2,4-Trimethylcyclohexane 1,3,4-Trimethylcyclohexane 17
(1 + 2 + 4 = 7) (1 + 3 + 4 = 8)
 2. b. When two or more different substituents are present, number according
to alphabetical order.
2 1

1 2
-not-
1-Ethyl-2-methylcyclohexane 2-Ethyl-1-methylcyclohexane

. Halogen Substituents
Halogen substituents are treated exactly like alkyl groups:
-F fluoro-
-Cl chloro-
-Br bromo-
-I iodo-

CH3
1-Chloro-2-methylcyclobutane

Cl

18
Degrees of Substitution
Primary (1°) Carbon: carbon that is bonded to only one other carbon
Secondary (2°) Carbon: carbon that is bonded to two other carbons
Tertiary (3°) Carbon: carbon that is bonded to three other carbons
Quarternary (4°) Carbon: carbon that is bonded to four other carbons

Primary (1°ˇ)
secondary Secondary (2°ˇ)
alcohol Tertiary (3°ˇ)
HO Quarternary (4°ˇ)

1° Hydrogens- hydrogens on a primary carbon. -CH3 (methyl group)

2° Hydrogens- hydrogens on a secondary carbon. -CH2- (methylene group)
3° Hydrogens- hydrogens on a tertiary carbon. CH (methine group)
CH3 CH3
methyl group: 1° hydrogens
H3C CH2 CH CH2 C CH3 methylene group: 2° hydrogens
CH3
methine group: 3° hydrogens

19
2.16: Sources of Alkanes and Cycloalkanes (please read)
2.17: Physical Properties of Alkanes and Cycloalkanes
Non-nonbonding intermolecular attractive forces
(van der Waals forces)
1. Dipole – Dipole
2. Dipole – Induced-dipole
3. Induced-dipole – Induced-dipole : small instantaneous dipoles
that result from a distortion of the electron clouds. There
is an attraction between molecules as result of these
temporary dipoles

20
Alkanes show: regular increase in bp and mp as the molecular
weight increase. Branching lowers the bp or alkanes
n-pentane bp= 36.1 °C
iso-pentane bp= 27.9 °C
neo-pentane bp= 9.5°C pentane 2-methylbutane 2,2-dimethylpropane

Alkanes have low polarity and are hydrophobic (low water

solubility). Solubility deceases are the number of carbons
increase
21
2.18: Chemical Properties: Combustion of Alkanes
Hydrocarbons (C-H bonds) are weak to extremely weak acids
Combustion of hydrocarbons (Oxidation)
CnH2n+2 + O2 n CO2 + (n+1) H2O + heat
Heat (ΔH°) of combustion = H°(products) − H°(reactants)
Measure of relative stability
2.19: Oxidation-Reduction in Organic Chemistry
Oxidation [O]: the loss of electrons.
Increase in the number of C-X bonds, where X is an atom
more electronegative than carbon. Decrease in H content.
Reduction [H]: the gain of electrons.
Increase in number of C-Y bonds, where Y is an atom
less electronegative than carbon. Increase on H content.

22
 Increasing oxidation state

C C C C C C

Cl Cl Cl
C Cl C Cl C Cl C Cl
Cl
Cl Cl

O
C OH C O C
CO2
OR

C NH2 C NH C N

23
2.20: sp2 Hybridization and Bonding in Ethylene

hybridize one s-orbital

120 °
and two p-orbitals

leave one p-orbital

unhybridized

Three sp2 hybrid orbitals and

(Figure 2.19, p. 89) one unhybridized p-orbital 24
C=C double bonds- ethylene (C2H4) (Figure 2.20, p. 90)

ΔHC=C° = 611 KJ/mol

ΔHC-C° = 376 KJ/mol

ΔHπ-bond°= 235 KJ/mol

25
Molecular Orbitals of C=C

σ-antibonding MO
σ-bond
+ 376 KJ/mol
π-antibonding MO

π-bond
+ 235 KJ/mol

π-bond
- 235 KJ/mol

π-bonding MO

σ-bond
- 376 KJ/mol
σ-bonding MO

26
2.21: sp Hybridization and Bonding in Acetylene
(Figure 2.22, p. 91)

hybridize one s-orbital

and one p-orbitals

two sp hybrid orbitals and

leave two p-orbital
two unhybridized p-orbital 27
unhybridized
 CΞC triple bonds- acetylene (C2H2)
one C-C σ-bond and two C-C π-bonds (Figure 2.23, p. 92)

ΔHCΞC° = 835 KJ/mol

ΔHC-C° = 376 KJ/mol
ΔH1st π-bond° = 235 KJ/mol

ΔH2nd π-bond° = 224 KJ/mol

28