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ALKANES
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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)
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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 Refining
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Hydrocarbon Fractions from Petroleum
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.
CH3
silica-alumina
CH3CH2CH2CH2CH2CH2CH3
catalyst, 500oC + 4H2
heptane
20 atm H2
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Petroleum Products
smaller alkanes
straight-
chain Cracking
Crude
alkanes Isomerization
Petroleum Refining
of Reforming
different
sizes
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
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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.
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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.
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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
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Nomenclature
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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
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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.
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4. Combine substituent names and numbers + parent and
suffix.
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Cycloalkanes are named by using similar rules, but the prefix cyclo-
immediately precedes the name of the parent.
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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
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
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
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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.
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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