John E.

McMurry

www.cengage.com/chemistry/mcmurry

Chapter 2
Alkanes

Credits to Paul D. Adams • University of Arkansas

Why this Chapter?
 Alkanes are unreactive, but provide a useful vehicle to
introduce important ideas about organic compounds

 Alkanes - the simplest family of organic chemicals.

But before looking at alkanes, let’s get familiar with some

basics….
2.1 Functional Groups
General Chemistry 2

What are functional groups?

 Is part of a larger molecule
 Composed of an atom or group of atoms that have a
characteristic chemical behaviour
 Behaves in nearly the same chemical way in every molecule it’s
a part of.

e.g. C=C
Functional Groups with Multiple
Carbon–Carbon Bonds General Chemistry 2

 Alkenes have a C-C double bond

 Alkynes have a C-C triple bond
 Arenes have special bonds that are represented as
alternating single and double C-C bonds in a six-
membered ring
Functional Groups with Carbon Singly
Bonded to an Electronegative Atom
General Chemistry 2
Functional Groups with a Carbon–Oxygen
Double Bond (Carbonyl Groups)
General Chemistry 2
Survey of Functional Groups
General Chemistry 2
Survey of Functional Groups
General Chemistry 2
2.2 Alkanes and Alkane
Isomers General Chemistry 2

 Alkanes: Compounds with C-C single bonds and C-H bonds only (no
functional groups)
 Connecting carbons can lead to large or small molecules
 The formula for an alkane with no rings in it must be CnH2n+2 where
the number of C’s is n
 Alkanes are saturated with hydrogen (no more can be added
(that’s why it’s a.k.a. saturated hydrocarbons!)
 They are also called aliphatic compounds
Alkane Isomers
General Chemistry 2

 CH4 = methane, C2H6 = ethane, C3H8= propane

 The molecular formula of an alkane with more than
three carbons can give more than one structure
 C4 (butane) = butane and isobutane
 C5 (pentane) = pentane, 2-methylbutane, and 2,2-
dimethylpropane
 Alkanes with C’s connected to no more than 2 other C’s
are straight-chain or normal alkanes
 Alkanes with one or more C’s connected to 3 or 4 C’s
are branched-chain alkanes
Constitutional Isomers
General Chemistry 2

 Isomers that differ in how their atoms are arranged in

chains (but have same chemical formula) are called
constitutional isomers
 Compounds other than alkanes can be constitutional
isomers of one another
Condensed Structures of
Alkanes General Chemistry 2

 We can represent an alkane in a brief form or in many types

of extended form
 A condensed structure does not show bonds but lists atoms,
such as
 CH3CH2CH2CH3 (butane)
 CH3(CH2)2CH3 (butane)

Structural formulas
Naming Straight Chain
Alkanes General Chemistry 2
2.3 Alkyl Groups
General Chemistry 2

 Alkyl group – remove one H from an alkane (a part of a

structure)
 Name: replace -ane ending of alkane with –yl ending
 -CH3 is “methyl” (from methane)
 -CH2CH3 is “ethyl” from ethane
Alkyl Groups (Continued)
General Chemistry 2
Types of Alkyl Groups
General Chemistry 2

 Classified by the connection site (See Figure 3.3)

 a carbon at the end of a chain (primary alkyl group)
 a carbon in the middle of a chain (secondary alkyl group)
 a carbon with three carbons attached to it (tertiary alkyl
group)
Alkyl Groups (Continued)
General Chemistry 2

* There is no 4˚ hydrogen here.

2.4 Naming Alkanes
General Chemistry 2

 Compounds are given systematic names* by a process that uses

*Naming system devised by International Union of Pure and Applied Chemistry (IUPAC)
 Steps to naming alkanes:
Step 1: Find parent hydrocarbon chain
- find the longest continuous carbon chain
- if got 2 different chains of equal length, choose the one with
larger no. of branch point as parent chain.
Naming Alkanes (Continued)
General Chemistry 2

Step 2: Carbons in the parent chain are numbered in

sequence

Step 3: Substituents (or branch points) are

identified and numbered
Naming Alkanes (Continued)
General Chemistry 2

Step 4: Write compound name as a single word

- hyphens to separate prefixes
- commas to separate numbers
- cite substituents in alphabetical order
- if got same substituents on parent chain, use di-, tri-,
tetra- prefixes (but don’t use prefixes for
alphabetizing)
Naming Alkanes (Continued)
General Chemistry 2

Step 5: Name a complex substituent (or branch) as

though it is a compound by itself
- this step applies if a substituent has sub-branching.
CH3 CH3
1 2 3 4 5 6
CH3CHCHCH2CH2CH —CH2CH—CH3 2,3-dimethyl -6-(2-methylpropyl)decane
1 2 3

CH3 CH2CH2CH2CH3
7 8 9 10

CH3 CH3
9 8 7 6 5
CH3CH2CH2CH2CH—CH—CHCH3
1 2 3

4 CH2 CH3
2-methyl-5-(1,2-dimethylpropyl)nonane
CH2—CH—CH3
3 2 1
 Naming Alkanes (Continued)
General Chemistry 2
 For historical reasons, some simpler branched-chain
alkyl groups also have non-systematic or common
names: 2. Four-carbon 3. Five-carbon alkyl
alkyl groups groups
1. Three-carbon CH3CHCH2CH2—
alkyl group
CH3CH2CHCH3 CH3
sec-Butyl Isopentyl (a.k.a. isoamyl)
CH3
CH3CHCH3
CH3
CH3—C—CH2—
Isopropyl CH3CHCH2—
CH3
Isobutyl Neopentyl
CH3 CH3
CH3—C— CH3CH2—C—
CH3 CH3
tert-Butyl
tert-Pentyl (a.k.a. tert-amyl)
Naming Alkanes (Continued)
General Chemistry 2

 E.g. of using common name alkyl groups to

name alkanes
1 2
CH3CHCH3

CH3CH2CH2CHCH2CH2CH3
1 2 3 4 5 6 7

4-isopropylheptane or 4-(1-methylethyl)heptane

Reminders!!
• The prefix iso- and neo- is considered part of the alkyl group name
for alphabetizing purpose (e.g. isopropyl and isobutyl are listed
alphabetically under i), BUT….
• Hyphenated prefixes sec- and tert- are not considered for
alphabetizing purpose (e.g. sec-butyl and tert-butyl are listed under b).
2.5 Reactivity of Alkanes
General Chemistry 2

 Called paraffins (low affinity compounds) because they

do not react as most chemicals
 They will burn in a flame, producing carbon dioxide,
water, and heat
 They react with Cl2 in the presence of light to replace H’s
with Cl’s (not controlled)
Physical Properties of
Alkanes General Chemistry 2

 Boiling points and melting points increase as size of alkane increases

 Dispersion forces increase as molecule size increases, resulting in higher
melting and boiling points
2.6 Conformations of Ethane
General Chemistry 2

 Stereochemistry concerned with the 3-D

aspects of molecules
  bonds are cylindrically symmetrical
 Rotation is possible around C-C bonds in open-
chain molecules
Conformers (a.k.a molecules in a certain
conformation)
General Chemistry 2

 Conformation- Different arrangement of atoms

resulting from bond rotation
 Conformations can be represented in 2 ways:
Conformer (continued)
General Chemistry 2

 We do not observe perfectly free rotation

 There is a barrier to rotation, and some
conformers are more stable than others
 Staggered conformation- most stable: all 6 C-
H bonds are as far away as possible
 Eclipsed conformation- least stable: all 6 C-H
bonds are as close as possible to each other
thus creating torsional strain* (i.e., the extra
energy present in the eclipsed conformation)

* Most chemists believe that torsional strain is the result of slight repulsion
of electron clouds in C—H bonds when they come too near each other in
eclipsed conformation.
Energies Associated with Staggered

or Eclipsed Conformations in Ethane

General Chemistry 2
2.7 Conformations of Other
Alkanes General Chemistry 2

 The eclipsed conformer of propane has 3 interactions:

two ethane-type H-H interactions, and one H-CH3
interaction
Conformations of Other
Alkanes General Chemistry 2

 Conformational situation is more complex for larger

alkanes
 Not all staggered conformations have same energy, and
not all eclipsed conformations have same energy
Conformations of Butane
General Chemistry 2

 Anti conformation- methyl groups are 180˚ apart

 Gauche conformation- methyl groups are 60˚ apart

Which is the most energetically stable?

Steric Strain
General Chemistry 2

 Steric strain- repulsive interaction between atoms that are forced

closer together than their atomic radii allow.
Conformational Energy Costs
General Chemistry 2
Let’s Work a Problem
General Chemistry 2

Draw as many compounds as you can that are

alcohols with the formula, C4H10O:
Answer
General Chemistry 2

The safest approach to answer this question would

be to draw out all straight-chain isomers, then
proceed next to the simplest branched structures
and so on.

1-butanol 2-butanol isobutyl alcohol tert-butyl alcohol

 Self-test Problems
General Chemistry 2

1. What is the IUPAC name of this alkane?

CH2CH3 CH3

CH3CHCH2CH2CH2CHCH3

2. Draw structural formula of 4-isopropyl-3-methylheptane.

3. Make a graph of potential energy vs. angle of bond rotation

for propane, and assign values to the energy maxima.

4. Sight along the C2—C3 bond of 2,3-dimethylbutane, and

draw a Newman projection of the most stable conformation.