Ch 24 From Petroleum to

Pharmaceuticals
Classes of Hydrocarbons

Hydrocarbons
Hydrocarbons

Aliphatic
Aliphatic

Aromatic
Aromatic

Hydrocarbons
Hydrocarbons

Aliphatic
Aliphatic

Alkanes
Alkanes

Aromatic
Aromatic

Alkenes
Alkenes

Alkynes
Alkynes

Hydrocarbons
Hydrocarbons

Aliphatic
Aliphatic

Alkanes
Alkanes

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

Hydrocarbons
Hydrocarbons

Aliphatic
Aliphatic

Alkenes are
hydrocarbons that
contain a carboncarbon double bond.
H

H
C

Alkenes
Alkenes
H

C
H

Hydrocarbons
Hydrocarbons

Aliphatic
Aliphatic

Alkynes are
hydrocarbons that
contain a carboncarbon triple bond.

Alkynes
Alkynes
HC

CH

Hydrocarbons
Hydrocarbons
The most common
aromatic hydrocarbons
are those that contain
a benzene ring.

Aromatic
Aromatic

H
H

Reactive Sites in Hydrocarbons

The Functional Group
Concept

Functional
FunctionalGroup
Group
a structural unit in a molecule responsible for its
characteristic chemical behavior and its
spectroscopic characteristics

Alkanes
Alkanes
RH

RX

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
Alkanes
RH

RX

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 + Cl2

Cl + HCl

Functional
FunctionalGroups
GroupsininHydrocarbons
Hydrocarbons

alkanes

RH

alkenes

RH, double bond

alkynes

RH, triple bond

aromatics

ArH, double bond

Some Key Functional Groups

Families
Familiesof
oforganic
organiccompounds
compoundsand
and
their
theirfunctional
functionalgroups
groups
Alcohols

ROH

Alkyl halides

RX (X = F, Cl, Br, I)

Amines

primary amine: RNH2

secondary amine: R2NH
tertiary amine: R3N

Ethers

ROR

Many
Manyclasses
classesof
oforganic
organiccompounds
compounds
contain
containaacarbonyl
carbonylgroup
group

Carbonyl group

Acyl group

Many
Manyclasses
classesof
oforganic
organiccompounds
compounds
contain
containaacarbonyl
carbonylgroup
group

Carbonyl group

Aldehyde

Many
Manyclasses
classesof
oforganic
organiccompounds
compounds
contain
containaacarbonyl
carbonylgroup
group

Carbonyl group

Ketone

R'

Many
Manyclasses
classesof
oforganic
organiccompounds
compounds
contain
containaacarbonyl
carbonylgroup
group

Carbonyl group

OH

Carboxylic acid

Many
Manyclasses
classesof
oforganic
organiccompounds
compounds
contain
containaacarbonyl
carbonylgroup
group

Carbonyl group

Ester

OR'

Many
Manyclasses
classesof
oforganic
organiccompounds
compounds
contain
containaacarbonyl
carbonylgroup
group

Carbonyl group

Amide

NH2

General formula for an alkane

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

The
Thesimplest
simplestalkanes
alkanes
Methane (CH4)

CH4

Ethane (C2H6)

CH3CH3

Propane (C3H8)

CH3CH2CH3

bp -160C

bp -89C

bp -42C

No isomers possible for C1, C2, C3 hydrocarbons

Isomeric Alkanes:
The Butanes

C4H10
General formula for any butane

n-Butane
CH3CH2CH2CH3

bp -0.4C

C
H
4
Isobutane10
(CH3)3CH

bp -10.2C

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
Howmany
manyisomers?
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
Table2.3
2.3
Number
Numberof
ofConstitutionally
ConstitutionallyIsomeric
IsomericAlkanes
Alkanes

CH4
C2H6

1
1

C3H8
C4H10

1
2

C5H12
C6H14

3
5

C7H16

Table
Table2.3
2.3
Number
Numberof
ofConstitutionally
ConstitutionallyIsomeric
IsomericAlkanes
Alkanes

CH4
C2H6

1
1

C8H18
C9H20

18
35

C3H8
C4H10

1
2

C10H22
C15H32

75
4,347

C5H12
C6H14

3
5

C20H42
C40H82

366,319
62,491,178,805,831

C7H16

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
Structureof
ofEthylene
Ethylene
bond angles:

H-C-H = 117
H-C-C = 121

bond distances:

CH = 110 pm
C=C = 134 pm

planar

Bonding
BondingininEthylene
Ethylene

Framework of bonds
Each carbon is sp2 hybridized

Bonding
BondingininEthylene
Ethylene

Each carbon has a half-filled p

orbital

Bonding
BondingininEthylene
Ethylene

Side-by-side overlap of half-filled p

orbitals gives a bond

Isomerism in Alkenes

Isomers
Isomers

Isomers are different compounds that

have the same molecular formula
(composition).

Isomers
Isomers

Constitutional
Constitutionalisomers
isomers

Stereoisomers
Stereoisomers

Isomers
Isomers

Constitutional
Constitutionalisomers
isomers

different connectivity

Stereoisomers
Stereoisomers
same connectivity;
different arrangement
of atoms in space

Isomers
Isomers

Constitutional
Constitutionalisomers
isomers

Stereoisomers
Stereoisomers

consider the isomeric alkenes of

molecular formula C4H8

CH2CH3

H
C

H
1-Butene

H3C

H
C

H3C

2-Methylpropene
CH3

H3C

H3C

H
C

C
H

cis-2-Butene

C
CH3

trans-2-Butene

CH2CH3

H
C

H
1-Butene

H3C

H
C

H3C

C
H

2-Methylpropene
CH3

C
H

H3C

Constitutional isomers
H

cis-2-Butene

CH2CH3

H
C

H3C
C

H
1-Butene

H3C

2-Methylpropene
H3C

H
C

Constitutional isomers
H

C
CH3

trans-2-Butene

Stereoisomers
H3C

CH3
C

H3C

H
C

C
H

cis-2-Butene

C
CH3

trans-2-Butene

Molecular Chirality:
Enantiomers

Chirality
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
Br
H
F

It cannot be
superposed point
for point on its
mirror image.

Bromochlorofluoromethane is chiral

Cl

Cl

Br

Br
H
F

H
F
To show nonsuperposability,
rotate this model 180
around a vertical axis.

Bromochlorofluoromethane is chiral

Cl
Cl

Br

Br

H
F

H
F

Another
Anotherlook
look

Enantiomers
Enantiomers

nonsuperposable mirror images are

called enantiomers

and

are enantiomers with respect to each other

Isomers
constitutional
isomers

stereoisomers

Isomers
constitutional
isomers

enantiomers
(optical)

stereoisomers

geometric isomers
(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
Symmetrytests
testsfor
forachiral
achiralstructures
structures

Any molecule with a plane of symmetry

must be achiral.

Plane
Planeofofsymmetry
symmetry

A plane of symmetry bisects a molecule into two

mirror image halves. Chlorodifluoromethane
has a plane of symmetry.

Plane
Planeofofsymmetry
symmetry

A plane of symmetry bisects a molecule into two

mirror image halves. Chlorodifluoromethane
has a plane of symmetry.

Plane
Planeofofsymmetry
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
Planeofofsymmetry
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
BoilingPoints
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 areafewer points of contact
with other molecules

Boiling
BoilingPoints
Points
increase with increasing number of carbons
more atoms, more electrons, more
opportunities for induced dipole-induced
dipole forces

Heptane
bp 98C

Octane
bp 125C

Nonane
bp 150C

Boiling
BoilingPoints
Points
decrease with chain branching
branched molecules are more compact with
smaller surface areafewer points of contact
with other molecules

Octane: bp 125C

2-Methylheptane: bp 118C
2,2,3,3-Tetramethylbutane: bp 107C

Boiling
BoilingPoints
Pointsof
ofAlkanes
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
Induceddipole-Induced
dipole-Induceddipole
dipoleattractive
attractiveforces
forces

two nonpolar molecules

center of positive charge and center of negative
charge coincide in each

Induced
Induceddipole-Induced
dipole-Induceddipole
dipoleattractive
attractiveforces
forces

movement of electrons creates an

instantaneous dipole in one molecule (left)

Induced
Induceddipole-Induced
dipole-Induceddipole
dipoleattractive
attractiveforces
forces

temporary dipole in one molecule (left) induces

a complementary dipole in other molecule
(right)

Induced
Induceddipole-Induced
dipole-Induceddipole
dipoleattractive
attractiveforces
forces

temporary dipole in one molecule (left) induces

a complementary dipole in other molecule
(right)

Induced
Induceddipole-Induced
dipole-Induceddipole
dipoleattractive
attractiveforces
forces

the result is a small attractive force between

the two molecules

Induced
Induceddipole-Induced
dipole-Induceddipole
dipoleattractive
attractiveforces
forces

the result is a small attractive force between

the two molecules

Straight chain hydrocarbon Branched hydrocarbon

Lots of intermolecular
contacts

Fewer intermolecular
contacts