Classes of

Hydrocarbons
 Hydrocarbons

Aliphatic Aromatic
 Hydrocarbons

Aliphatic Aromatic

Alkanes Alkenes Alkynes

 Hydrocarbons

Alkanes are
hydrocarbons in which
Aliphatic all of the bonds are
single bonds.

H H
Alkanes H C C H

H H
 Hydrocarbons

Alkenes are
hydrocarbons that
Aliphatic contain a carbon-
carbon double bond.

H H
Alkenes C C
H H
 Hydrocarbons

Alkynes are
hydrocarbons that
Aliphatic contain a carbon-
carbon triple bond.

Alkynes

HC CH
 Hydrocarbons

The most common

aromatic hydrocarbons
are those that contain a
benzene ring.
Aromatic
H
H H

H H

H
Reactive Sites in Hydrocarbons
The Functional Group
Concept
 Functional Group

a structural unit in a molecule responsible for i

characteristic chemical behavior and its
spectroscopic characteristics
 Alkanes

R—H R—X

functional group is a hydrogen atom

the reaction that takes place is
termed a substitution
one of the hydrogens is substituted
by some other atom or group, X
 Alkanes

R—H R—X
functional group is a hydrogen
the reaction that takes place is substitution
one of the hydrogens is substituted
by some other atom or group

H H H H

H C C H + Cl2 H C C Cl + HCl

H H H H
 Functional Groups in Hydrocarbons

alkanes RH
alkenes RH, double bond
alkynes RH, triple bond
aromatics ArH, double bond
Some Key Functional Groups
 Families of organic compounds and
their functional groups

Alcohols ROH
Alkyl halides RX (X = F, Cl, Br, I)

Amines primary amine: RNH2

secondary amine: R2NH

tertiary amine: R3N

Ethers ROR
 Many classes of organic compounds
contain a carbonyl group

O O

C C
R

Carbonyl group Acyl group

 Many classes of organic compounds
contain a carbonyl group

O O

C C
R H

Carbonyl group Aldehyde

 Many classes of organic compounds
contain a carbonyl group

O O

C C
R R'

Carbonyl group Ketone

 Many classes of organic compounds
contain a carbonyl group

O O

C C
R OH

Carbonyl group Carboxylic acid

 Many classes of organic compounds
contain a carbonyl group

O O

C C
R OR'

Carbonyl group Ester

 Many classes of organic compounds
contain a carbonyl group

O O

C C
R NH2

Carbonyl group Amide

General formula for an alkane

CnH2n+2
Introduction to Alkanes:
Methane, CH4
Ethane, C2H6
Propane, C3H8
 The simplest alkanes

Methane (CH4) CH4

Ethane (C2H6) CH3CH3
Propane (C3H8) CH3CH2CH3

bp -160°C bp -89°C bp -42°C

No isomers possible for C1, C2, C3 hydrocarbons
 Isomeric Alkanes:
The Butanes

C4H10
General formula for any butane
n-Butane
C4H10
Isobutane

CH3CH2CH2CH3 (CH3)3CH

bp -0.4°C bp -10.2°C
 Higher n-Alkanes
Pentane (C5H12) and Beyond

CnH2n+2
n>4
 CnH2n+2
CH3CH2CH2CH2CH3 n>4
n-Pentane

CH3CH2CH2CH2CH2CH3
n-Hexane

CH3CH2CH2CH2CH2CH2CH3
n-Heptane
The C5H12 Isomers
 C5H12

CH3CH2CH2CH2CH3 (CH3)2CHCH2CH3
n-Pentane Isopentane

(CH3)4C

Neopentane
 How many isomers?

The number of isomeric alkanes

increases as the number of carbons
increase.
There is no simple way to predict
how many isomers there are for a
particular molecular formula.
Table 2.3
Number of Constitutionally Isomeric Alkanes

CH4 1
C2H6 1
C3H8 1
C4H10 2
C5H12 3
C6H14 5
C7H16 9
Table 2.3
Number of Constitutionally Isomeric Alkanes

CH4 1 C8H18 18
C2H6 1 C9H20 35
C3H8 1 C10H22 75
C4H10 2 C15H32 4,347
C5H12 3 C20H42 366,319
C6H14 5 C40H82 62,491,178,805,831
C7H16 9
C6H6 Isomers

How many isomers

with the
composition
C6H6 can you draw?
C6H6 Isomers: How many isomers with
the composition
C6H6 can you draw?
Structure and Bonding in
Alkenes
 Structure of Ethylene

bond angles: H-C-H = 117°

H-C-C = 121°
bond distances: C—H = 110 pm
C=C = 134 pm

planar
Bonding in Ethylene

s
s

s s
s

Framework of s bonds
Each carbon is sp2 hybridized
Bonding in Ethylene

Each carbon has a half-filled p

orbital
Bonding in Ethylene

Side-by-side overlap of half-filled

p orbitals gives a p bond
Isomerism in Alkenes
 Isomers

Isomers are different compounds that

have the same molecular formula
(composition).
 Isomers

Constitutional isomers Stereoisomers

 Isomers

Constitutional isomers Stereoisomers

same connectivity;
different connectivity different arrangement
of atoms in space
 Isomers

Constitutional isomers Stereoisomers

consider the isomeric alkenes of

molecular formula C4H8
 H CH2CH3 H3C H
C C C C
H H H3C H

1-Butene 2-Methylpropene

H3C CH3 H3C H

C C C C
H H H CH3

cis-2-Butene trans-2-Butene
 H CH2CH3 H3C H
C C C C
H H H3C H

1-Butene 2-Methylpropene

H3C CH3

C C Constitutional isomers
H H

cis-2-Butene
 H CH2CH3 H3C H
C C C C
H H H3C H

1-Butene 2-Methylpropene

H3C H

Constitutional isomers C C
H CH3

trans-2-Butene
 Stereoisomers

H3C CH3 H3C H

C C C C
H H H CH3

cis-2-Butene trans-2-Butene
Molecular Chirality:
Enantiomers
 Chirality

A molecule is chiral if its two mirror image

forms are not superposable upon one another.

A molecule is achiral if its two mirror image

forms are superposable.
 Bromochlorofluoromethane is chiral

Cl
It cannot be
Br superposed point
H for point on its
mirror image.

F
 Bromochlorofluoromethane is chiral

Cl Cl
Br Br
H H

F F
To show nonsuperposability, rotate this
model 180° around a vertical axis.
 Bromochlorofluoromethane is chiral

Cl Br
Br Cl
H H

F F
Another look
 Enantiomers

nonsuperposable mirror images are

called enantiomers

and

are enantiomers with respect to each other

 Isomers

constitutional
stereoisomers
isomers
 Isomers

constitutional
stereoisomers
isomers

enantiomers geometric isomers

(optical) (cis/trans)
Chlorodifluoromethane
is achiral
Chlorodifluoromethane
is achiral

The two
structures are
mirror images,
but are not
enantiomers,
because they can
be superposed on
each other.
Symmetry in Achiral
Structures
Symmetry tests for achiral structures

Any molecule with a plane of symmetry

must be achiral.
 Plane of symmetry

A plane of symmetry bisects a molecule into two

mirror image halves. Chlorodifluoromethane
has a plane of symmetry.
 Plane of symmetry

A plane of symmetry bisects a molecule into two

mirror image halves. Chlorodifluoromethane
has a plane of symmetry.
 Plane of symmetry

A plane of symmetry bisects a molecule into two

mirror image halves.
1-Bromo-1-chloro-2-fluoroethene has a plane
of symmetry.
 Plane of symmetry

A plane of symmetry bisects a molecule into two

mirror image halves.
1-Bromo-1-chloro-2-fluoroethene has a plane
of symmetry.
 Physical Properties of
Alkanes and Cycloalkanes
 Boiling Points

increase with increasing number of carbons

more atoms, more electrons, more
opportunities for induced dipole-induced
dipole forces
decrease with chain branching
branched molecules are more compact with
smaller surface area—fewer points of contact
with other molecules
 Boiling Points

increase with increasing number of carbons

more atoms, more electrons, more

opportunities for induced dipole-induced
dipole forces

Heptane Octane Nonane

bp 98°C bp 125°C bp 150°C
 Boiling Points

decrease with chain branching

branched molecules are more compact with
smaller surface area—fewer points of contact
with other molecules

Octane: bp 125°C

2-Methylheptane: bp 118°C

2,2,3,3-Tetramethylbutane: bp 107°C
 Boiling Points of Alkanes

governed by strength of intermolecular

attractive forces
alkanes are nonpolar, so dipole-dipole and
dipole-induced dipole forces are absent
only forces of intermolecular attraction are
induced dipole-induced dipole forces
Induced dipole-Induced dipole attractive forces

+– +–

two nonpolar molecules

center of positive charge and center of
negative charge coincide in each
Induced dipole-Induced dipole attractive forces

+– +–

movement of electrons creates an

instantaneous dipole in one molecule (left)
Induced dipole-Induced dipole attractive forces

–
+ +–

temporary dipole in one molecule (left)

induces a complementary dipole in other
molecule (right)
Induced dipole-Induced dipole attractive forces

– –
+ +

temporary dipole in one molecule (left)

induces a complementary dipole in other
molecule (right)
Induced dipole-Induced dipole attractive forces

– –
+ +

the result is a small attractive force between

the two molecules
Induced dipole-Induced dipole attractive forces

– –
+ +

the result is a small attractive force between

the two molecules
Straight chain hydrocarbon Branched hydrocarbon

Lots of intermolecular Fewer intermolecular

contacts contacts