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Ch 24 From Petroleum to Pharmaceuticals Classes of Hydrocarbons

Hydrocarbons

Aliphatic

Aromatic

Hydrocarbons

Aliphatic

Aromatic

Alkanes

Alkenes

Alkynes

Hydrocarbons

Aliphatic

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

H
Alkanes H

H C H

C
H

H

Hydrocarbons

Aliphatic

Alkenes are hydrocarbons that contain a carboncarbon double bond.

H Alkenes
H C C

H

H

Hydrocarbons

Aliphatic

Alkynes are hydrocarbons that contain a carboncarbon triple bond.

Alkynes HC

CH

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

Aromatic

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 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 C H C H H + Cl2 H

H
C H

H C Cl + HCl

H

H

Functional Groups in Hydrocarbons

alkanes alkenes alkynes aromatics

RH RH, double bond RH, triple bond ArH, double bond

Some Key Functional Groups

Families of organic compounds and their functional groups Alcohols Alkyl halides Amines ROH RX (X = F, Cl, Br, I) primary amine: RNH2 secondary amine: R2NH tertiary amine: R3N Ethers ROR

Many classes of organic compounds contain a carbonyl group

O C Carbonyl group R

O C

Acyl group

Many classes of organic compounds contain a carbonyl group

O C Carbonyl group R

O C

H

Aldehyde

Many classes of organic compounds contain a carbonyl group

O C Carbonyl group R

O C Ketone

R'

Many classes of organic compounds contain a carbonyl group

O C Carbonyl group R

O C

OH

Carboxylic acid

Many classes of organic compounds contain a carbonyl group

O C Carbonyl group R

O C Ester

OR'

Many classes of organic compounds contain a carbonyl group

O C Carbonyl group R

O C Amide

NH2

General formula for an alkane

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

The simplest alkanes Methane (CH4) Ethane (C2H6) Propane (C3H8) CH4 CH3CH3 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 CH3CH2CH2CH3

C4H10

Isobutane (CH3)3CH

bp -0.4°C

bp -10.2°C

Higher n-Alkanes Pentane (C5H12) and Beyond

CnH2n+2
n>4

CH3CH2CH2CH2CH3 n-Pentane

CnH2n+2
n>4

CH3CH2CH2CH2CH2CH3 n-Hexane

CH3CH2CH2CH2CH2CH2CH3 n-Heptane

The C5H12 Isomers

C5H12

CH3CH2CH2CH2CH3 n-Pentane

(CH3)2CHCH2CH3
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 C 2 H6 C 3 H8 C4H10 C5H12 C6H14 C7H16

1 1 1 2 3 5 9

Table 2.3 Number of Constitutionally Isomeric Alkanes

CH4 C 2 H6 C 3 H8 C4H10 C5H12 C6H14 C7H16

1 1 1 2 3 5 9

C8H18 18 C9H20 35 C10H22 75 C15H32 4,347 C20H42 366,319 C40H82 62,491,178,805,831

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 arrangement of atoms in space

different connectivity

Isomers

Constitutional isomers

Stereoisomers

consider the isomeric alkenes of molecular formula C4H8

H C H 1-Butene C

CH2CH3

H3C C C

H

H

H3C

H

2-Methylpropene

H3C C
H C

CH3

H3C C

H

C
CH3

H

H

cis-2-Butene

trans-2-Butene

H C H 1-Butene C

CH2CH3

H3C C C

H

H

H3C

H

2-Methylpropene

H3C C
H C

CH3
Constitutional isomers H

cis-2-Butene

H C H 1-Butene C

CH2CH3

H3C C C

H

H

H3C

H

2-Methylpropene H3C H C H

Constitutional isomers

C
CH3

trans-2-Butene

Stereoisomers

H3C C
H C

CH3

H3C C

H

C
CH3

H

H

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 Br H F

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

Bromochlorofluoromethane is chiral

Cl Br H F H

Cl Br

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

Bromochlorofluoromethane is chiral

Cl Br H F Cl

Br
H

F

Another look

Enantiomers

nonsuperposable mirror images are called enantiomers

and

are enantiomers with respect to each other

Isomers
constitutional isomers

stereoisomers

Isomers
constitutional isomers

stereoisomers

enantiomers (optical)

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 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 bp 98°C

Octane bp 125°C

Nonane 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 contacts Fewer intermolecular contacts