Introduction

Classification of Hydrocarbon
Hydrocarbon Aliphatic Alkanes Alkenes Alkynes Aromatic

Hydrocarbon
Chapter 2.0

Cycloalkanes

Cycloalkenes

Saturated

Unsaturated

Introduction to Hydrocarbons
Hydrocarbons Hydrocarbons

Aliphatic Aliphatic Aromatic

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

Hydrocarbons simplest organic compounds contain only carbon and hydrogen

Alkanes

Hydrocarbons

Hydrocarbons

Aliphatic

Alkanes whose carbon atoms are joined in rings are called cycloalkanes. They have the general formula CnH2n where n = 3,4,

Aliphatic

Alkenes are hydrocarbons that contain a carboncarbon double bond. H H

C H C H

CycloAlkanes

Alkenes

Hydrocarbons

Hydrocarbons

Aliphatic

Alkynes are hydrocarbons that contain a carboncarbon triple bond.

Alkynes HC CH

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

Aromatic

Alkanes
Simplest members of hydrocarbon family Contain only hydrogen and carbon Only have single bonds Saturated compound All members have general formula of

Hydrocarbon Alkanes
Chapter 2.1
Alkanes Alkanes nomenclature system Structural isomers Cycloalkanes Synthesis of alkanes Reaction of alkanes Sources of alkanes and cycloalkanes

CnH2n + 2
Twice as many hydrogen as carbon + 2

Alkane Nomenclature

24.2

Alkyl Groups
Alkyl group is a group which is derived from
unbranched-chain alkanes by removing 1 H atom from the end C atom General formula : CnH2n + 1 Represented by R symbol suffix : - yl
H

Names of some common alkyl groups

Alkane
methane ethane

Alkyl
methyl ethyl propyl

Structure
- CH3 - CH2 CH3
H H C H H C H H C H

propane
H C H H C H C H

10 H

H C

H C H H

isopropyl

C H

20

Alkane
butane
H H C H H C H H C H C H

Alkyl
H

Structure
H C H
H C H

Alkane
H C

Alkyl
H H C H

Structure
H C H H C H H C H H C H

H C H
H C

butyl
10
H

pentane
H H C H H C H H C H H C H
10

C H
H

pentyl

H
H C H H

C H

20

sec-butyl

C H

H H C H
H H C H

H C

H C

H C H

CH3 H C H C H

isopentyl

isobutyl
H H C H CH3 H C
H

C H

10
H

CH3 H
CH3 H C C

C H
30

H
H

CH 3 H C C H H

CH3 H C C

tert-butyl

C H

neopentyl

C H

CH3 H

CH3 H

Naming of organic compound according to IUPAC system.

Step 1) Find the longest continuous carbon chain and use the IUPAC name of the unbranched alkane as the basis. Add name of substituent as a prefix. Use base name with yl ending. Use replicating prefixes (di-, tri-, tetra-, etc.) according to the number of substituents attached to the main chain. Number the chain from the end nearest the substituent, and identify the carbon to which the substituent is attached by number. List substituents in alphabetical order. order.

Carbon Chain Length and Prefixes Used in the I.U.P.A.C Nomenclature System

Step 2)

Step 3)

Step 4)

Naming Alkanes
C-C-C-CCC Six carbon atoms in longest chain used base name of

Practice Exercise
(CH3)2CHCH(CH3)2

All carbon and hydrogen with single bonds use ending Name of compound is

Use replicating prefixes (di-, tri-, tetra-, etc.) according to the number of identical substituents attached to the main chain.

H3C

H C

H C

Practice Exercise
Give IUPAC name for the following compound
CH3 H 3C
1 2
6

CH3

CH3 CH3
Longest C chain has 4 carbon use but All C and H with single bonds use Parent name:

CH 2 CH 3 CH CH
3

C CH3

CH 2

CH 2

ane
Continuous C chain : Prefix : Suffix Substituent Locant : : :

CH3 - on 2nd and 3rd carbon - dimethyl IUPAC name: 2,3-dimethylbutane

Draw the structure of 3,5,5 - trimethyl heptane

Start by drawing the longest carbon chain: CCCCCCC

When 2 or more of different kind of substituents present : the substituents are listed alphabetically prefixes di, tri, tert are ignored in alphabetising 2 3
CH CH2

Answer: C
1 2 3 4

CH3

except iso and neo 5 4 6

CH CH2 CH3 CH2 CH3

C
5 6 7

methyl CH3

ethyl

CCCCCCC C

4-ethyl-2-methyl.

Practice Exercise
CH3 H3C
1 2 3 4 5 6 5

C CH3

CH2

CH CH2 CH3

CH2

CH3

When 2 chains of equal length compete for selection as parent chain, choose the chain with the greater number of substituents

Continuous C chain : Prefix : Suffix : Substituent :

6C hex 4-ethyl-2,2-dimethylhexane - ane dimethyl& ethyl

CH3 H3C CH2 CH CH CH2 CH2 CH3

CH3 CH

CH3 CH CH3

When first branching occurs at an equal distance from either end of the longest chain, choose the
CH3 CH3 CH CH2 CH2 CH3 CH CH3 CH CH3

name that gives the lower number at the first point of different

H3C

CH2

CH

CH3 H 3C
6 5

CH CH3

CH2

CH CH3

CH

CH3

Polyfunctional organic compounds contain many different kinds of functional groups The proper suffix is determined by :
CH3
i.

identifying all the functional groups present then choose the principal group of

H 3C

CH CH3

CH2

CH CH3

CH

CH3

ii.

highest

priority

Name for polyfunctional groups consist of 4 parts:

i.

Example of Polyfunctional Groups

parent
1 2 3 4 5

Suffix : identifies the principal functional group class to which the molecule belongs Parent : identifies the size of the main chain/ring

ii.

prefix

iii.

Prefix : identifies what substituents are located on the main chain/ring Locants : tells where substituents are located on the main chain/ring

Higher priority
suffix

iv.

amino5- aminopentan-2-ol @ 5-amino-2-pentanol

Practice Exercise
suffix

H3C CH CH3 CH3

prefix

CH2 CH3

Methylpropane
suffix H3C CH CH2 CH3 prefix

Ethyl cyclohexane

Structural Isomer

Cyclopropylbutane

Structural Isomer
All have same formula but different structures and properties

Structural Isomer
C5H12

C4H10
H3C
CH3 H C CH3

H2 C

C H2

CH3

butane

CH3 2-methylpropane

Number of Constitutionally Isomeric Alkanes

CH4 C2 H6 C3 H8 C4H10 C5H12 C6H14 C7H16 1 1 1 2 3 5 9 C8H18 C9H20 C10H22 C15H32 C20H42 C40H82 18 35 75 4,347 366,319 62,491,178,805,831
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.

Cycloalkanes

Naming of Cycloalkanes
Name any alkyl groups on the ring in the usual way. CH2CH3 Ethylcyclopentane

List substituents in alphabetical order and count in the direction that gives the lowest number. H3C CH3 3-Ethyl- 1,1-dimethylcyclohexane Ethyl- 1,1CH2CH3

IUPAC Nomenclature of Cycloalkanes

Named by placing the prefix corresponding alkanes

If only one substituent present : to designate its position

not necessary

cyclo to the

Example
suffix
prefix

Examples

CH 2

H 2C

CH 2

6C

CH3

H 2C

CH 2

H 2C

CH 2

hexane Methyl cyclo hexane

Cyclopropane

Cyclobutane

Example 1
3 2

Methyl

CH 3
1

When 2 substituents present :

i.

1-ethyl-2-methyl cyclohexane ethyl-

4 5 6

Numbered the C beginning with substituent according to the alphabetical order Numbered in the way that gives the next substituent the lowest number possible
4 3 2 5 6

CH 2 CH 3
Ethyl

ii.

CH 3
1

CH 2 CH 3

1-ethyl-6-methylcyclohexane ethyl-

Practice Exercise
Give IUPAC names for the following cycloalkanes : CH3 HC
3

When single ring is attached to a chain with greater no. of C atoms : named as

cycloalkylalkane
5 C chain
CH2 CH2 CH2 CH2 CH3
1 2 3 4 5

H3C

CH3

parent

CH2CH3

4C chain substituent

1- cyclobutyl pentane

CH3

When more than 1 ring is attached to a single chain : also named as

Alkane
Physical Properties Non polar molecules Not soluble in water Low density Low melting point Low boiling point
These goes up as the number of carbons increase

cycloalkylalkane
parent

straight chain

CH2CH2CH2 3 1 2

substituent groups 1,31,3- di cyclo hexyl propane

Practice Exercise
Arrange the following compounds in order of increasing boiling point CH3CH2CH3
propane

CH3CH2CH2CH2CH3
n-pentane

CH3( CH2)7 CH3

n-nonane

Hydrogenation of alkenes
An example of addition reaction

H C C H
alkene hydrogen

H + H2
Pt / Pd / Ni

H C H H

Synthesis of alkanes

C H

alkane

Example: C2H4 + H2 C2H6

ethene ethane
Ni

Hydrolysis of Grignard reagent (alkylmagnesium halide)

RMgX + H2O RH + Mg(OH)X
alkylmagnesium halide alkane
H+

Wurtz reaction (Reduction of alkyl halide)

2RX + Na R-R + 2NaX

alkyl halide reducing agent alkane

Example:
CH3CH2CH2MgCl + H2O Propylmagnesium chloride
H+

Example:
CH3CH2CH3 + Mg(OH)Cl Propane 2CH3CH2CH2Br + 2Na CH3CH2CH2CH2CH2CH3 + 2NaBr bromopropane hexane

Reaction of Alkanes

and cycloalkane
Light/heat

Composition of Crude Oil

Naphtha (bp 95-150 C) C5-C12 Light gasoline (bp: 25-95 C) Kerosene (bp: 150-230 C)
CRUDE OIL

C12-C15

HYDROCARBONS
ALIPHATICS AROMATICS
17%

NON-HYDROCARBONS
NAPHTHENES
50%
CYCLOALKANES

SULFURS
<8%

NITROGENS
<1%

OXYGENS
<3% O

METALLICS
<100PPM

Crude oil

25%

C15-C25 Gas oil (bp: 230-340 C)

C1 - C60

(C6H5)n

SH
N H COOH

Refinery gas C1-C4 Residue

10

Industrial Fractioning Column

Petroleum refining
Cracking
converts high molecular weight hydrocarbons to more useful, low molecular weight ones i) thermal cracking (by heat) ii) catalytic cracking (with the aid of catalyst)

Reforming
increases branching of hydrocarbon chains branched hydrocarbons have better burning characteristics for automobile engines

Petroleum Refining
GAS
C1-C4 bp < 50 oF C5 - C? bp 50-200oF C? - C12 bp 200-400oF

Petroleum Reforming
GAS FUEL GAS TREATER GASOLINE HEAVY NAPHTHA KEROSENE
HYDROTREATER

CRUDE

DESALTER

FURNACE

T O W E R

LIGHT NAPHTHA HEAVY NAPHTHA KEROSENE

C12 - C16 bp 400-500oF C15 - C18 bp 500-650oC > C20 bp >650oF

T O W E R

LIGHT NAPHTHA

REFORMER

AROMATIC EXTRACTION

HYDROTREATER

AROMATICS JET FUELS/KEROSENE CATALYTIC CRACKER

ATM. GAS OIL

HYDROTREATER

DIESEL & FUEL OILS

ATM. GAS OIL

RESIDUUM VACUUM GAS OIL Vacuum Distillation LUBRICATING OIL ASPHALT COKER COKE CATALYTIC CRACKER

RESIDUUM

Distillation separation by boiling point

Conversion Reactions
THERMAL

Catalytic Reforming Conversion Reactions

Dehydrogenation of cycloalkanes to aromatics CH3
C 7H 16 +
ga soline

CH3 3H2

CRACK

C 7 H 1 5 .C 1 5 H 3 0 .C 7 H 1 5

C 7 H1 4 +

C 1 5 H3 0
recycle

ga soline add itive

CATALYTIC
Dehydroisomerization of cyclopentanes to aromatics

ALKYLATION

C H 3C H2 C H3

CH2 CH

C H2 C H3

C H3 C H2C H 2

C H 2C H2 C H 2C H3

CH3 3H2

COMBINE
POLYMERIZATION
Isomerization of alkanes

CH3

REFORMIING

Dehydrogenation Dehydroisomerization Isomerization

CH3CH2CH2CH2 CH3 Dehdrocyclization of alkanes

H3C CH CH2 CH3

REARRANGE
ISOMERIZATION

CH3 4 H2

Dehydrocyclization Hydrocracking

CH3 CH2CH2 CH2CH2 CH2CH3 Hydrocracking of alkanes

CH3CH2CH2CH2CH2 CH2CH3

CH3 CH2CH3

CH3 CH2CH2 CH3

11

Catalytic cracking in laboratory scale

Conversion Reactions
THERMAL

CRACK

C 7 H 1 5 .C 1 5 H 3 0 .C 7 H 1 5

C 7H 16 +
ga soline

C 7 H1 4 +

C 1 5 H3 0
recycle

ga soline add itive

CATALYTIC

ALKYLATION

C H 3C H2 C H3

CH2 CH

C H2 C H3

C H3 C H2C H 2

C H 2C H2 C H 2C H3

COMBINE
POLYMERIZATION

REFORMIING

Dehydrogenation Dehydroisomerization Isomerization

REARRANGE
ISOMERIZATION

Dehydrocyclization Hydrocracking

12