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ALKANE AND

CYCLOALKANES
SITI HAJAR ANAZIAH MUHAMAD

C OURSE O UTCOME

Ability to explain the relationship between the structure,


physical and chemical properties of the different bonds and
functional groups in organic compounds (CO2)

Course Learning Outcome


The student should be able to:
Name alkanes.

Explain aliphatic properties.

Predict, draw and name the products of functional group reactions.

Draw the mechanistic pathway.

Fossil Fuels:
Many alkanes occur in
nature, primarily in
natural gas and
petroleum.
Natural gas is com-posed
largely of methane, with
lesser amounts of ethane,
propane and butane.

Petroleum is a complex mixture of compounds, most of which are hydrocarbons


containing one to forty carbon atoms. Distilling crude petroleum (called refining),
separates it into usable fractions that differ in boiling point.
gasoline: C5H12C12H26
kerosene: C12H26C16H34
diesel fuel: C15H32C18H38

Sources of Alkanes: Petroleum and Natural Gas

Petroleum is the source of alkanes. It is a complex mixture of


mostly alkanes and aromatic hydrocarbons with smaller amounts
of oxygen-, nitrogen-, and sulfur-containing compounds.
Natural gas is a gaseous mixture of hydrocarbons recovered from
natural sources. It is mostly methane (CH4, BP -162oC) with small
amounts of ethane (C2H6, BP -88oC) and propane (C3H8, BP -42o).
Petroleum Refining

Liquid petroleum and natural gas are usually separated at the


wellhead and shipped independently to processing (refining) plants.
The liquid petroleum (crude) is separated by distillation according to
the volatility (BPs) of the different size hydrocarbons. The fractions
collected by refining are still mixtures of hydrocarbons that have
commercial value.

Refining crude petroleum into usable fuel and other petroleum products.
(a) An oil refinery. At an oil refinery, crude petroleum is separated into
fractions of similar boiling point by the process of distillation.
(b) Schematic of a refinery tower. As crude petroleum is heated, the lowerboiling, more volatile components distill first, followed by fractions of
progressively higher boiling point.

Hydrocarbon Fractions from Petroleum


boiling range
of fraction (o C)

size range

name and use

below 20

C1 to C4

20 to 60

C5 to C6

60 to 100

C6 to C7

natural gas, bottled


gas, petrochemicals
petroleum "ether".
solvents
ligroin, solvents

40 to 200

C5 to C10

straight-run gasoline

175 to 325

C12 to C18

kerosene and jet fuel

250 to 400

C12 and higher

gas oil, fuel oil


and diesel oil

nonvolatile
liquids

C20 and higher

nonvolatile
solids

C20 and higher

mineral oil,
lubricating oil
paraffin w ax,
asphalt, tar

Petroleum Technologies

Technologies exist to interconvert the various hydrocarbons using


catalysts.
Cracking is a process for breaking down larger alkanes into
smaller alkanes by heating. The mixture of larger alkanes is
heated in the absence of oxygen at high temperatures (~500oC) for
only a few minutes in the presence of catalysts. By this method,
alkanes of size C12 and larger can be turned into gasoline-size
alkanes (C5 to C10).
Isomerization
Since the 1920s, it has been known that highly branched alkanes
perform better in the internal combustion engine than straightchain alkanes. Catalytic isomerization changes straight-chain
alkanes into the more useful branched alkanes.

CH3CH2CH2CH2CH2CH3
hexane

acid catalyst

CH3CH2CH2CHCH3
CH3
+
CH3CH2CHCH2CH3
CH3
branched alkanes

Catalytic Reforming

Alkanes are transformed into cycloalkanes and aromatic


hydrocarbons by catalytic reforming.

silica-alumina
CH3CH2CH2CH2CH2CH2CH3
catalyst, 500oC
heptane
20 atm H2

CH3
+ 4H2

The aromatic hydrocarbons produced by catalytic reforming


are used as additives in gasoline and as starting materials for
the petrochemical industry. Production of these aromatics is in
the billions of pounds per year in the United States.

Petroleum Products
Daily consumption of petroleum in the United States is over 17
million barrels which amounts to close to one billion tons per year.
Of this total, approximately 43% goes into gasoline, another 25%
into fuel oil, and approximately 7.5% into jet fuel. Thus, about
75% of all the petroleum consumed is burned as a source of
energy. The remainder is used as "feedstock" for polymers (~4%)
and the chemical industry (~3%), and the many other products
used in our society such as oils, lubricants and asphalt.

An Overview of Petroleum Refining


smaller alkanes

Crude
Petroleum

Refining

straightchain
alkanes
of
different
sizes
branched alkanes

Cracking
Isomerization
Reforming

aromatics

Combustion
All hydrocarbons undergo combustion, the reaction with oxygen
that liberates energy. Thus, all hydrocarbons are potential "fuels",
materials that burn in oxygen releasing energy.

Heat of Combustion
The heat of combustion (Hcomb) is the amount of heat liberated
when one mole of material undergoes combustion at 1 atm pressure
to produce gaseous CO2 and liquid water.
CO2(g) + 2H2O(l)
CH4 + 2O2
methane
Hcomb = -882 kJ/mol (or -55.1 kJ/g)
For a gasoline-size hydrocarbon::

2C8H18 + 25O2

16CO2(g) + 18H2O(l)

Hcomb = -5452 kJ/mol (or -47.8 kJ/g)


Note, the total amount of heat liberated increases with the size of
the hydrocarbon, but that doesn't make it a better fuel. On a per
weight basis, methane is a better fuel than the octane.

Gasoline Performance: The Octane Rating


The combustion of alkanes is a complicated reaction probably
involving free radicals. Much attention has been directed towards
the combustion of hydrocarbons in the internal combustion engine.
Since the 1920s, it has been known that some hydrocarbons tend to
give better performance during combustion. Some fuels cause
"knocking", the premature ignition of the fuel before the piston is
in the firing position for a power stroke. Knocking causes loss of
power.

Branched hydrocarbons were found to perform better than straightchain alkanes in the internal combustion engine. In 1927, an
arbitrary engineering performance standard was developed called
"the octane rating." The performance of the branched alkane
"isooctane" (actually 2,2,4-trimethylpentane) in a specific internal
combustion engine was given a rating of 100. Heptane, which
causes severe knocking, was given a rating of 0.
CH3 CH3
CH3CCH2CHCH3
CH3
"isooctane"
100

CH3CH2CH2CH2CH2CH2CH3
heptane
0

A fuel with a
performance equivalent
to a mixture of 75%
isooctane and 25%
heptane is given an
octane rating of 75.

Octane Boosters
It is common practice to add octane boosters to gasoline to
improve the performance of the fuel. Many years ago,
tetraethyllead, (C2H5)4Pb, was an important additive for this
purpose. It is now illegal to use "leaded" gasoline in an
automobile in the United States. Aromatics and "oxygenated
fuels" are blended into gasoline to raise the octane rating.
Some Octane Ratings of
Hydrocarbons and Additives
Octane Rating
heptane
0
1-pentene
91
2,2,4-trimethylpentane 100
benzene
106
methanol
107
ethanol
108
methyl t-butyl ether
116
toluene
118

Methyl t-butyl ether (MTBE) is an


oxygenated fuel blended into
gasoline to improve performance
and reduce air pollution.
Production of MTBE increased over
the past 10 years to many billions of
pounds per year in the United
States. However, MTBE is being
phased out because of
environmental and health concerns.

P HYSICAL P ROPERTIES OF
A LKANES

14

A LKANES AND A LKANE


I SOMERS

Alkanes: Compounds with C-C single bonds and C-H bonds only (no
functional groups)

Connecting carbons can lead to large or small molecules

The formula for an alkane with no rings in it must be CnH2n+2 where the
number of Cs is n

Alkanes are saturated with hydrogen (no more can be added)

They are also called aliphatic compounds

A LKANE I SOMERS

CH4 = methane, C2H6 = ethane, C3H8= propane

The molecular formula of an alkane with more than three


carbons can give more than one structure

C4 (butane) = butane and isobutane

C5 (pentane) = pentane, 2-methylbutane, and 2,2dimethylpropane

Alkanes with Cs connected to no more than 2 other Cs are


straight-chain or normal alkanes

Alkanes with one or more Cs connected to 3 or 4 Cs are


branched-chain alkanes

C ONSTITUTIONAL I SOMERS

Isomers that differ in how their atoms are arranged in chains are called
constitutional isomers

Compounds other than alkanes can be constitutional isomers of one


another

They must have the same molecular formula to be isomers

C ONDENSED S TRUCTURES OF
A LKANES

We can represent an alkane in a brief form or in many types of extended


form

A condensed structure does not show bonds but lists atoms, such as

CH3CH2CH2CH3 (butane)

CH3(CH2)2CH3 (butane)
Structural formulas

N AMING S TRAIGHT C HAIN


A LKANES

A LKYL G ROUPS

Alkyl group remove one H from an alkane (a part of a structure)

General abbreviation R (for Radical, an incomplete species or the rest


of the molecule)
Name: replace -ane ending of alkane with yl ending
-CH3 is methyl (from methane)
-CH2CH3 is ethyl from ethane

A LKYL G ROUPS
(C ONTINUED )

T YPES

OF

Classified by the connection site

A LKYL G ROUPS

A LKYL G ROUPS
(C ONTINUED )

* There is no 4 hydrogenWhy or why not? Lets talk about


this

Hydrogen atoms are classified as primary (10), secondary (20), or


tertiary (30) depending on the type of carbon atom to which they are
bonded

C YCLOALKANES
Cycloalkanes have molecular formula CnH2n and contain carbon atoms
arranged in a ring. Simple cycloalkanes are named by adding the prefix
cyclo- to the name of the acyclic alkane having the same number of
carbons.

N AMING A LKANES

Compounds are given systematic names by a process that uses

Follows specific rules

Find parent hydrocarbon chain

IUPAC systematic Nomenclature Alkanes


1. Find the parent carbon chain and add the suffix.

Note that it does not matter if the chain is straight or it bends.

Also note that if there are two chains of equal length, pick the
chain with more substituents. In the following example, two
different chains in the same alkane have seven C atoms. We
circle the longest continuous chain as shown in the diagram
on the left, since this results in the greater number of
substituents.

N AMING A LKANES
(C ONT..)
2. Number the atoms in the carbon chain to give the first substituent the
lowest number.

N AMING A LKANES
(C ONTINUED )
If the first substituent is the same distance from both ends, number the
chain to give the second substituent the lower number.

N AMING A LKANES
(C ONTINUED )
When numbering a carbon chain results in the same numbers from either
end of the chain, assign the lower number alphabetically to the first
substituent.

N AMING A LKANES
(C ONTINUED )
3. Name and number the substituents.
Name the substituents as alkyl groups.
Every carbon belongs to either the longest chain or a substituent, not
both.
Each substituent needs its own number
If two or more identical substituents are bonded to the longest chain, use
prefixes to indicate how many: di- for two groups, tri- for three groups,
tetra- for four groups, and so forth.

N AMING A LKANES
(C ONTINUED )
4. Combine substituent names and numbers + parent and
suffix.
Precede the name of the parent by the names of the substituents.
Alphabetize the names of the substituents, ignoring all prefixes except
iso, as in isopropyl and isobutyl.
Precede the name of each substituent by the number that indicates its
location.
Separate numbers by commas and separate numbers from letters by
hyphens. The name of an alkane is a single word, with no spaces after
hyphens and commas.

N AMING A LKANES
(C ONTINUED )

N AMING A LKANES
(C ONTINUED )

A)

B)

Substituents are identified and numbered

CYCLOALKANES
NAMING
Cycloalkanes are named by using similar rules, but the prefix cycloimmediately precedes the name of the parent.

1. Find the parent cycloalkane.

CYCLOALKANES NAMING
(C ONT..)
2. Name and number the substituents. No number is needed to
indicate the location of a single substituent.

For rings with more than one substituent, begin numbering at one
substituent and proceed around the ring to give the second substituent the
lowest number.

CYCLOALKANES NAMING
(C ONT..)
With two different substituents, number the ring to assign the
lower number to the substituents alphabetically.

Note the special case of an alkane composed of both a ring and a long
chain. If the number of carbons in the ring is greater than or equal to the
number of carbons in the longest chain, the compound is named as a
cycloalkane.

CYCLOALKANES NAMING
(C ONT..)

CYCLOALKANES NAMING
(C ONT..)

CYCLOALKANES NAMING
(C ONT..)
NomenclatureCommon Names

Some organic compounds are identified using common names that do not
follow the IUPAC system of nomenclature. Many of these names were
given long ago before the IUPAC system was adopted, and are still widely
used. Additionally, some names are descriptive of shape and structure, like
those below:

REACTION OF ALKANES
Combustion of Alkanes
Alkanes undergo combustionthat is, they burn in the presence of
oxygen to form carbon dioxide and water.

This is an example of oxidation. Every CH and CC bond in the


starting material is converted to a CO bond in the product.

REACTION OF ALKANES
(C ONT..)
Halogenation of Alkanes
250-400 o
C H + X2

Reactivity:-

or h

C X + HX

X2 : F2 > Cl2 > Br2 (> I2)


H : 3o > 2o > 1o > H3C-H

Chlorination - a substitution reaction


h
CH4 + Cl2
CH3Cl + HCl
or

REACTION OF ALKANES
(C ONT..)
Polychlorination
CH3Cl + Cl2

CH2Cl2 + HCl

dichloromethane
methylene chloride

CH2Cl2 + Cl2

CHCl3 + HCl

trichloromethane
chloroform

CHCl3 + Cl2

CCl4 + HCl

tetrachloromethane
carbon tetrachloride

Iodination and fluorination


iodine does not react while, fluorine reacts very readily

order of halogen reactivity:

F2 > Cl 2 > Br 2 (> I 2)

E. G:

C HLORINATION OF M ETHANE

Requires heat or light for initiation.

The most effective wavelength is blue, which is absorbed


by chlorine gas.

Many molecules of product are formed from absorption


of only one photon of light (chain reaction).
CHAPTER 4

45

T HE F REE -R ADICAL C HAIN R EACTION

Initiation: Generates a radical intermediate.

Propagation: The intermediate reacts with a stable molecule to


produce another reactive intermediate (and a product molecule).

Termination: Side reactions that destroy the reactive intermediate.

I NITIATION S TEP : F ORMATION OF


C HLORINE ATOM

A chlorine molecule splits homolytically into


chlorine atoms (free radicals).

L EWIS S TRUCTURES OF F REE R ADICALS

Free radicals are reactive species with odd numbers of


electrons.

P ROPAGATION S TEP : C ARBON R ADICAL

The chlorine atom collides with a methane molecule


and abstracts (removes) an H, forming another free
radical and one of the products (HCl).

P ROPAGATION S TEP : P RODUCT


F ORMATION

The methyl free radical collides with another


chlorine molecule, producing the organic product
(methyl chloride) and regenerating the chlorine
radical.

T ERMINATION S TEPS

O VERALL R EACTION

O VERALL R EACTION
( CONT..)

54

The intermediate alkyl radical


The nature of the intermediate free radical determines the product:
CH 4
methane

CH 3CH 3
ethane

CH3CH2CH3
propane

CH 3
methyl radical

CH 3CH 2
ethyl radical
CH3CH2CH2
n-propyl radical

CH3CHCH 3
isopropyl radical

X2

X2

X2

X2

CH 3X
halomethane

CH3CH2X
haloethane
CH3CH2CH2X
1-halopropane

CH 3CHXCH 3
2-halopropane

S YNTHESIS

OF ALKANES AND
CYCLOALKANES

Hydrogenation of alkenes and alkynes

H2
CnH2n

H2/Ni

CnH2n+2

C2H5OH
25o, 50 atm

Pt, Pd or Ni
alkene

alkane

+ 2 H2

+ H2

Pt

Pd

(CH3)3CH

Reduction of alkyl halides


i.

Hydrolysis with Grignard reagent


R-X + Mg

R Mg X

RMgX + HOH

R-H + Mg(OH)X

CH3CH2CH2MgBr + H2O
ii.

Reduction of alkyl halide with metal and acid


(Zn in CH3COOH or HBr)

R-X
R-H
CH3CHBrCH2CH3
iii.

CH3CH2CH3 + Mg(OH)Br

CH3CH2CH2CH3

Reaction with LiAlH4


C9H19CH2-Br

C9H19CH3

Alkylation of terminal alkynes


An acetylenic hydrogen is weakly acidic:

Na
R C C H
NH3

(CH3)2CHC C H

R C C Na+ + 1/2H2
a sodium
acetylide

NaNH 2
ether

(CH3)2CHC C
+ NH3

Na+

Alkylation of terminal alkynes (cont..)


The anion formed will react with a primary halide:

R C C- Na + + CH 3X

1. NaNH2
2. CH3Br
H2/Pt

R C CCH 3 + NaX

Corey Posner Whitesides - House Synthesis


R-X + 2Li
1o, 2o,
or 3o

diethyl ether

2RLi + CuI

R2CuLi + R'X
1o alkyl or 2o
cycloalkyl halide

RLi + LiX
alkyllithium
R2CuLi + LiI
lithium
dialkylcuprate
a Gilman reagent
R-R' + RCu +LiX