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Chapter 2Alkanes
Hydrocarbon: a compound composed of only carbon and hydrogen.
Alkanes: hydrocarbons containing only carbon-carbon single bonds.
H-C C-HH-C-C-HH
H
H
H HC C
H
H H
Hydrocarbons
Alkanes(Chapter 11)
Alkenes(Chapter 12)
Alkynes(Chapter 12)
Arenes(Chapter 13)
Only carbon-carbon single
bonds
One or more carbon-carbondouble bonds
One or morecarbon-carbontriple bonds
One or morebenzene-like
rings
Ethane Ethene(Ethylene)
Ethyne(Acetylene)
Benzene
The first two alkanes are methane and ethane.
H-C-HH
HH-C-C-HH
H
H
H
Methane Ethane
• Table 2.1 The first 10 alkanes with unbranched chains
CH4 CH4C2H6 CH3CH3C3H8 CH3CH2CH3C4H10 CH3(CH2)2CH3C5H12 CH3(CH2)3CH3
C6H14 CH3(CH2)4CH3C7H16 CH3(CH2)5CH3C8H18 CH3(CH2)6CH3C9H20 CH3(CH2)7CH3C10H22 CH3(CH2)8CH3
CH4 CH4C2H6 CH3CH3C3H8 CH3CH2CH3C4H10 CH3(CH2)2CH3C5H12 CH3(CH2)3CH3
C6H14 CH3(CH2)4CH3C7H16 CH3(CH2)5CH3C8H18C9H20C10H22
CondensedStructural Formula
MolecularFormulaName
decane
nonane
octane
heptane
hexane
pentane
butane
propane
ethanemethane
CondensedStructural Formula
MolecularFormulaName
CondensedStructural Formula
MolecularFormulaName
decane
nonane
octane
heptane
hexane
pentane
butane
propane
ethanemethane
CondensedStructural FormulaName
The IUPAC name of an alkane with an unbranched chain of carbon atoms consists of two parts: (1) a prefix: the number of carbon atoms in
the chain.(2) the suffix -ane: shows that the compound
is a saturated hydrocarbon.
Prefixmeth-eth-prop-but-pent-
hex-
oct-non-dec-
12345
67hept-8910
Number ofCarbon Atoms
Number ofCarbon AtomsPrefix
The name of an alkane with a branched chain of carbon atom consists of:a parent name: the longest chain of carbon
atomssubstituent names: the groups bonded to the
parent chain
CH3
CH3CH2CH2CHCH2CH2CH2CH38
substituent
4-Methyloctane
1 2 3 4 5 6 7 8
parent chain
12
34
5
6
7
Alkyl group: a substituent group derived from an alkane by removal of a hydrogen atom.commonly represented by the symbol R-.named by dropping the -ane from the name of
the parent alkane and adding the suffix -yl.
-CH2CH3
-CH3
-CH2CH2CH3
-CHCH3CH3
-CH2CH2CH2CH3
-CH2CHCH3CH3
-CHCH2CH3CH3
-CCH3
CH3
CH3
tert-butyl
sec-butyl
isobutyl
butyl
isopropyl
propyl
ethyl
methylName
CondensedStructural Formula
CondensedStructural FormulaName
If there is one substituent, number the parent chain from the end that gives the substituent the lower number.
CH3
CH3CH2CH2CHCH35
2-Methylpentane(not 4-methylpentane)
123
4
If the same substituent occurs more than once:Number the parent chain from the end that
gives the lower number to the substituent encountered first.
Indicate the number of times the substituent occurs by a prefix di-, tri-, tetra-, penta-, hexa-and so on.
Use a comma to separate position numbers.
CH3CH2CHCH2CHCH3
CH3 CH3
2,4-Dimethylhexane(not 3,5-dimethylhexane)
12
34
56
If there are two or more different substituents: list them in alphabetical order.number the chain from the end that gives the
lower number to the substituent encountered first.
If there are different substituents in equivalent positions on opposite ends of the parent chain, give the substituent of lower alphabetical order the lower number.
CH3CH2CHCH2CHCH2CH3
CH3
CH2CH3
12
34
56
7
3-Ethyl-5-methylheptane(not 3-methyl-5-ethylheptane)
Do not include the prefixes di-, tri-, tetra-, and so on, or the hyphenated prefixes sec- and tert- in alphabetizing; alphabetize the names of substituents first,
and then insert these prefixes
CH2CH3
CH3CCH2CHCH2CH3
CH3
CH34-Ethyl-2,2-dimethylhexane
(not 2,2-dimethyl-4-ethylhexane)
23
45
61
Halogens as substituent groupsSame priority as alkyl groupsFluoro, chloro, bromo, iodo
Common names; in this older system, • The number of carbon atoms determines the
name.• The first three alkanes are methane, ethane,
and propane.
• All alkanes of formula C4H10 are called butanes, all those of formula C5H12 are called pentanes, etc.
• For alkanes beyond propane, iso shows that one end of an otherwise unbranched chain terminates in (CH3)2CH-
• For more complex alkanes, use the IUPAC system.
Cycloalkanes
Cyclic hydrocarbon: a hydrocarbon that contains carbon atoms joined to form a ring.
Cycloalkane: a cyclic hydrocarbon in which all carbons of the ring are saturated. Cycloalkanes of ring sizes ranging from 3 to
over 30 carbon atoms are found in nature.
• Five-membered (cyclopentane) and six-membered (cyclohexane) rings are especially abundant in nature.
Cyclopentane Cyclohexane
NomenclatureTo name a cycloalkane, prefix the name of the
corresponding open-chain alkane with cyclo-, and name each substituent on the ring.
• If there is only one substituent on the ring, there is no need to give it a location number.
• If there are two substituents, number the ring beginning with the substituent of lower alphabetical order.
Isopropylcyclopentane1-tert-Butyl-4-methylcyclohexane
1 4
Conformation: any three-dimensional arrangement of atoms in a molecule that results by rotation about a single bond.
• following are three conformations for a butane molecule.
Most crowdedconformation
rotate by 120°
rotate by 60°
Least crowdedconformation
Intermediatecrowding
Cyclopentane The most stable conformation of a
cyclopentane ring is an envelope conformation.
Cyclohexane
The most stable conformation of a cyclohexane ring is the chair conformation.all bond angles are approximately 109.5°.
In a chair conformation,six C-H bonds are equatorial.six C-H bonds are axial.
HHH
HHH
(a) Ball-and-stick modelshowing all 12 hydrogens
axis through thecenter of the ring
H H
H
H
H
H
(b) The six equatorialC-H bonds
(c) The six axial C-H bonds
• The more stable conformation of a substituted cyclohexane ring has substituent group(s) equatorial rather than axial.
CH3
Equatorial methylcyclohexane
CH3
Axial methylcyclohexane
Cis-trans isomers
Cis: on the same side. Trans: across from each other.
Same molecular formula, same connectivity—different orientation of atoms in space. Stereoisomers.
Viewing a cyclopentane ring edge-on:
trans-1,2-Dimethyl-cyclopentane
cis-1,2-Dimethyl-cyclopentane
CH3
H
CH3
H
H
HH
H
HH
H
H
CH3
H3C
H
HH
HH
H
View from above:
CH3trans-1,2-Dimethyl-
cyclopentanecis-1,2-Dimethyl-
cyclopentane
H3C CH3 H3C
View of the cyclohexane ring as a planar hexagon:
trans-1,4-Dimethylcyclohexane cis-1,4-Dimethylcyclohexane
H
H3C
CH3
H
H
H3C
H
CH3
or or
CH3
CH3
CH3
CH3
Physical Properties
The most important physical property of alkanes and cycloalkanes is their almost complete lack of polarity.
• The electronegativity difference between carbon and hydrogen is 2.5 - 2.1 = 0.4 on the Pauling scale.
• Given this small difference, we classify a C-H bond as nonpolar covalent.
• Alkanes are nonpolar compounds and the only interaction between their molecules are the very weak London dispersion forces.
Melting and boiling pointsBoiling points of alkanes are lower than those
of almost any other type of compound of the same molecular weight.
In general, both boiling and melting points of alkanes increase with increasing molecular weight.
CH4CH3CH3CH3CH2CH3CH3(CH2)2CH3
CH3(CH2)3CH3CH3(CH2)4CH3CH3(CH2)5CH3CH3(CH2)6CH3CH3(CH2)7CH3CH3(CH2)8CH3
methane
ethanepropane
butane
pentane
hexane
heptane
octanenonane
decane
Name
CondensedStructrualFormula
mp(°C)
bp(°C)
-182
-183
-190-138
-130
-95
-90
-57-51
-30
-164
-88
-420
36
69
98
126151
174
(a gas)
(a gas)
(a gas)(a gas)
0.626
0.659
0.684
0.7030.718
0.730
*For comparison, the density of H2O is 1 g/mL at 4°C.
Mol wt(amu)
16.0
30.144.1
58.1
72.2
86.2
100.2
114.2128.3142.3
Density of Liquid
(g/mL at 0° C)*
• Alkanes that are constitutional isomers are different compounds and have different physical and chemical properties.
bp (°C)Namehexane
2-methylpentane3-methylpentane
2,3-dimethylbutane
2,2-dimethylbutane
68.7
60.363.3
58.0
49.7
Hexane
2,2-Dimethylbutane
Solubility: a case of “like dissolves like”.Alkanes are not soluble in water; they are
unable to form hydrogen bonds with water.Alkanes are soluble in each other.Alkanes are also soluble in other nonpolar
organic compounds, such as toluene and diethyl ether.
Reactions
Oxidation (combustion)Oxidation of hydrocarbons, including alkanes
and cycloalkanes, is the basis for their use as energy sources for heat [natural gas, liquefied petroleum gas (LPG), and fuel oil] and power (gasoline, diesel fuel, and aviation fuel).
CH3CH2CH3 5O2 3CO2 4H2O++Propane
530 kcal/mol+
CH4 2O2 CO2 2H2OMethane
++ 212 kcal/mol+
Reaction with halogens (halogenation)Halogenation of an alkane is a substitution
reaction.
CH4 Cl2 CH3Cl HCl+ heator light
+Methane Chloromethane
(Methyl chloride)
CH3Cl Cl2 CH2Cl2 HCl+heat
+Dichloromethane
(Methylene chloride)
CH2Cl2Cl2
CHCl3Cl2
CCl4heat heatTrichloromethane
(Chloroform)Tetrachloromethane
(Carbon tetrachloride)
Summary of Topics: Chapter 2
NomenclatureCis-trans isomers
Conformations—particularly cyclohexane Properties (mp/bp; solubility) Reactions:
CombustionRadical halogenation