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Ch 24 From Petroleum to

Pharmaceuticals
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 its


characteristic chemical behavior and its

spectroscopic characteristics
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

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 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 -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
C4H10 Isobutane

CH3CH2CH2CH3 (CH3)3CH

bp -0.4C 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 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
C2 H6 1
C3 H8 1
C4H10 2
C5H12 3
C6H14 5
C7H16 9
Table 2.3
Number of Constitutionally Isomeric Alkanes

CH4 1 C8H18 18
C2 H6 1 C9H20 35
C3 H8 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: CH = 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 areafewer 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 98C bp 125C bp 150C
Boiling 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 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