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CHAPTER 3

ALKANES

ALKANES AND CYCLOALKANES

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Course Outcome
 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.

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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: C5H12—C12H26
kerosene: C12H26—C16H34
diesel fuel: C15H32—C18H38 3
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. 4
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 lower-
boiling, more volatile components distill first, followed by fractions of
progressively higher boiling point.

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Hydrocarbon Fractions from Petroleum

boiling range size range name and use


of fraction (oC)

below 20 C1 to C4 natural gas, bottled


gas, petrochemicals
20 to 60 C5 to C6 petroleum "ether".
solvents
60 to 100 C6 to C7 ligroin, solvents

40 to 200 C5 to C10 straight-run gasoline

175 to 325 C12 to C18 kerosene and jet fuel


gas oil, fuel oil
250 to 400 C12 and higher
and diesel oil
nonvolatile mineral oil,
liquids C20 and higher
lubricating oil
nonvolatile C20 and higher paraffin wax,
solids asphalt, tar
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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 straight-
chain alkanes. Catalytic isomerization changes straight-chain
alkanes into the more useful branched alkanes.

acid catalyst CH3CH2CH2CHCH3


CH3CH2CH2CH2CH2CH3 CH3
+
hexane CH3CH2CHCH2CH3
CH3
branched alkanes
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Catalytic Reforming

Alkanes are transformed into cycloalkanes and aromatic


hydrocarbons by catalytic reforming.

CH3
silica-alumina
CH3CH2CH2CH2CH2CH2CH3
catalyst, 500oC + 4H2
heptane
20 atm H2

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.

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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

straight-
chain Cracking
Crude
alkanes Isomerization
Petroleum Refining
of Reforming
different
sizes

branched alkanes aromatics


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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.

CH4 + 2O2 CO2(g) + 2H2O(l)


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. 10
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 straight-
chain 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.
A fuel with a
CH3 CH3 performance equivalent
CH3CCH2CHCH3 CH3CH2CH2CH2CH2CH2CH3 to a mixture of 75%
CH3 isooctane and 25%
"isooctane" heptane
heptane is given an
100 0 octane rating of 75.
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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 Methyl t-butyl ether (MTBE) is an


Hydrocarbons and Additives oxygenated fuel blended into
Octane Rating gasoline to improve performance
heptane 0 and reduce air pollution.
1-pentene 91 Production of MTBE increased over
2,2,4-trimethylpentane 100 the past 10 years to many billions of
benzene 106 pounds per year in the United
methanol 107 States. However, MTBE is being
ethanol 108 phased out because of
methyl t-butyl ether 116 environmental and health concerns.
toluene 118

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Physical Properties of Alkanes

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Nomenclature
 Recall that alkanes are aliphatic hydrocarbons having C—C and C—H  bonds.
They can be categorized as acyclic or cyclic.

 Acyclic alkanes have the molecular formula CnH2n+2 (where n = an integer) and
contain only linear and branched chains of carbon atoms. They are also called
saturated hydrocarbons because they have the maximum number of
hydrogen atoms per carbon.

 Cycloalkanes contain carbons joined in one or more rings. Because their


general formula is CnH2n, they have two fewer H atoms than an acyclic alkane
with the same number of carbons

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 All C atoms in an alkane are surrounded by four groups, making them sp3
hybridized and tetrahedral, and all bond angles are 109.50.

 The 3-D representations and ball-and-stick models for these alkanes


indicate the tetrahedral geometry around each C atom. In contrast, the
Lewis structures are not meant to imply any 3-D arrangement. Additionally,
in propane and higher molecular weight alkanes, the carbon skeleton can
be drawn in a variety of ways and still represent the same molecule.

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• The three-carbon alkane CH3CH2CH3, called propane, has a molecular
formula C3H8. Note in the 3-D drawing that each C atom has two bonds
in the plane (solid lines), one bond in front (on a wedge) and one bond
behind the plane (on a dashed line).

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 In a Lewis structure, the bends in a carbon chain don’t matter.

 There are two different ways to arrange four carbons, giving two compounds
with molecular formula C4H10, named butane and isobutane.
 Butane and isobutane are isomers, two different compounds with the same
molecular formula. Specifically, they are constitutional or structural isomers.
 Constitutional isomers differ in the way the atoms are connected to each other.

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 Carbon atoms in alkanes and other organic compounds are classified by the
number of other carbons directly bonded to them.

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 Hydrogen atoms are classified as primary (10), secondary (20), or tertiary (30) depending on the type of carbon atom to which they are bonded

 The maximum number of possible constitutional isomers increases dramatically as the number of carbon atoms in the alkane increases. For example, there are 75 possible isomers for an alkane having 10 carbon atoms, but 366,319 possible isomers for one having 20 carbons.

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Cycloalkanes

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.

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Nomenclature

The name of every organic molecule has 3 parts:


1. The parent name indicates the number of carbons in the longest
continuous chain.
2. The suffix indicates what functional group is present.
3. The prefix tells us the identity, location, and number of substituents
attached to the carbon chain.

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• Carbon substituents bonded to a long carbon chain are called alkyl
groups.
• An alkyl group is formed by removing one H atom from an alkane.
• To name an alkyl group, change the –ane ending of the parent alkane
to –yl. Thus, methane (CH4) becomes methyl (CH3-) and ethane
(CH3CH3) becomes ethyl (CH3CH2-).
• Naming three- or four-carbon alkyl groups is more complicated because
the parent hydrocarbons have more than one type of hydrogen atom.

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For example, propane has both 10 and 20 H atoms, and
removal of each of these H atoms forms a different alkyl
group with a different name, propyl or isopropyl.

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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.

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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.

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2. Number the atoms in the carbon chain to give the first substituent the
lowest number.

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If the first substituent is the same distance from both ends, number the
chain to give the second substituent the lower number.

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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.

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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.

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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.

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Cycloalkanes are named by using similar rules, but the prefix cyclo-
immediately precedes the name of the parent.

1. Find the parent cycloalkane.

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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.

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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.
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Nomenclature—Common 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:

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Synthesis of alkanes and cycloalkanes
Hydrogenation of alkenes and alkynes

H2 H2/Ni
CnH2n C nH2n+2 (CH3)3CH
Pt, Pd or Ni C2H5OH
25o, 50 atm
alkene alkane

Pt
+ 2 H2

Pd
+ H2

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Reduction of alkyl halides
i. Hydrolysis with Grignard reagent
Ether (THF)
R-X + Mg R – Mg –X
RMgX + HOH R-H + Mg(OH)X
CH3CH2CH2MgBr + H2O CH3CH2CH3 + Mg(OH)Br

ii. Reduction of alkyl halide with metal and acid


(Zn in CH3COOH or HBr)
R-X R-H
CH3CHBrCH2CH3 CH3CH2CH2CH3

iii. Reaction with LiAlH4

C9H19CH2-Br C9H19CH3 41
Alkylation of terminal alkynes
An acetylenic hydrogen is weakly acidic:

Na -
R C C H R C C Na+ + 1/2H2
NH3
a sodium
acetylide

NaNH2 -
(CH3)2CHC C H (CH3)2CHC C Na+
ether
+ NH3

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Alkylation of terminal alkynes
The anion formed will react with a primary halide:

R C C- Na + + CH 3X R C CCH 3 + NaX

1. NaNH2
2. CH3Br
H2/Pt

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Corey – Posner – Whitesides - House Synthesis
diethyl ether
R-X + 2Li RLi + LiX
1o, 2o, alkyllithium
or 3o

2RLi + CuI R2CuLi + LiI


lithium
dialkylcuprate
a Gilman reagent

R2CuLi + R'X R-R' + RCu +LiX

1o alkyl or 2o
cycloalkyl halide
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Oxidation / combustion of Alkanes

• Since alkanes are the only family of organic molecules that have
no functional group, they undergo very few reactions.
• One reaction that alkanes undergo is combustion.
• Combustion is an oxidation-reduction reaction
• Recall that oxidation is the loss of electrons and reduction is the
gain of electrons.
• To determine if an organic compound undergoes oxidation or
reduction, we concentrate on the carbon atoms of the starting
material and the product, and compare the relative number of C—
H and C—Z bonds, where Z = an element more electronegative
than carbon (usually O, N, or X).

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Reaction of Alkanes
Oxidation of Alkanes
• Oxidation results in an increase in the number of C—Z bonds; or
• Oxidation results in a decrease in the number of C—H bonds.
• Reduction results in a decrease in the number of C—Z bonds; or
• Reduction results in an increase in the number of C—H bonds.

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Combustion of Alkanes
• Alkanes undergo combustion—that is, they burn in the presence of
oxygen to form carbon dioxide and water.
• This is an example of oxidation. Every C—H and C—C bond in the
starting material is converted to a C—O bond in the product.

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Reactions of alkanes with halogens

250-400 o
C H + X2 C X + HX
or h

Reactivity:- X2 : F2 > Cl2 > Br2 (> I2)


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

Chlorination - a substitution reaction


h
CH4 + Cl2 CH3Cl + HCl
or
 48
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: F 2 > Cl 2 > Br 2 (> I 2)


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A Mechanism
• a detailed, step by step, description of the transformation of reagents
into products

• it must explain all experimental facts


• the mechanism should be tested by devising appropriate
experiments - mechanistic predictions must be tested in the lab

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Mechanism of the chlorination of methane
The experimental facts
1. No reaction occurs at room temperature in the absence of light.
2. Reaction readily occurs, in the absence of light, at
temperatures above 250C.
3. Reaction occurs at room temperature in the presence of light of
a wavelength absorbed by chlorine.

4. When the reaction is initiated by light, a large number of


chloromethane molecules are produced for each photon of light
absorbed by the system.

5. The presence of even a small quantity of oxygen slows down


the reaction.
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Mechanism of the halogenation

250-400o
1. X2 2X initiation
or h

2. X + RH HX + R

propagation
3. R + X2 RX + X

2, 3, 2, 3, 2, 3....etc.
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Chain Reaction Refer ( CH10; pg 435)

Chain initiation:
Cl-Cl 2Cl

Chain propagation:
Cl + CH4 CH3 + HCl
CH3 + Cl2 CH3Cl + Cl

Chain termination:
2Cl Cl2
2CH3 C2H6 (ethane)
Cl + CH3 CH3Cl 53
The intermediate alkyl radical
The nature of the intermediate free radical determines the product:
X X2
CH 4 CH 3 CH 3X
methane methyl radical halomethane

X X2
CH 3CH 3 CH 3CH 2 CH3CH2X
ethane ethyl radical haloethane

X2
CH3CH2CH2 CH3CH2CH2X
n-propyl radical 1-halopropane
X
CH3CH2CH3
propane X2
CH3CHCH3 CH 3CHXCH 3
isopropyl radical 2-halopropane
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EXERCISE 2
In the presence of light, methane (1 mol) reacts with chlorine (1
mol) to form which product(s)?

A) CH3Cl
B) CH2Cl2
C) CHCl3
D) CCl4
E) All of these 

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Lipids
• Lipids are biomolecules that are soluble in organic solvents and
insoluble in water.
• Lipids have varied sizes and shapes, and a diverse number of
functional groups.
• Lipids are composed of many nonpolar C—H and C—C bonds, and
have few polar functional groups.
• The metabolism of lipids provides energy for our bodies.

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Lipids—Cholesterol
• Cholesterol is a member of the steroid family, a group of lipids having
four rings joined together. Because it has just one polar OH group, it is
insoluble in the aqueous medium of the blood.

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