Lecture 2&3: Alkane

Introduction
In this chapter, we begin our study of organic compounds with the alkanes, the simplest type of organic compounds. Actually, alkanes are members of a larger class of organic compounds called hydrocarbons. A hydrocarbon is a compound composed of only carbon and hydrogen.

Alkanes are saturated hydrocarbons; that is, they contain only carbon-carbon single bonds. In this context, saturated means that each carbon has the maximum number of hydrogens bonded to it. We often refer to alkanes as aliphatic hydrocarbons, because the physical properties of the higher members of this class resemble those of the long carbon-chain molecules we find in animal fats and plant oils (Greek: aleiphar, fat or oil)
A hydrocarbon that contains one or more carbon-carbon double bonds, triple bonds, or benzene rings is classified as an unsaturated hydrocarbon.
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Structure of Alkanes
Shape tetrahedral about carbon all bond angles are approximately 109.5

Representing Alkanes

d-stick BallBall-an and stick model model

Line angle (line Line-angle bond) formula formula Condensed Stru ctural structural formula formula

CH3 CH2 CH2 CH3 Butane

CH3 CH2 CH2 CH2 CH3 Pen tane

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Nomenclature
Alkanes have the general formula CnH2n+2
names of unbranched chain alkanes

N am e

M ol ecul ar Form ul a

N am e nonane decan e dodecan e

m ethane CH 4 C2 H 6 ethan e propane C H

3 8

M ol ecul ar Form ul a C9 H2 0 C1 0 H 2 2 C1 2 H 2 6

bu tane
hexan e

C4 H 1 0
C6 H 1 4

pen tane C5 H 1 2

tetrad ecane C1 4 H 3 0 hexadecane C1 6 H 3 4

octadecan e C1 8 H 3 8

hep tane C7 H 1 6 octane C8 H1 8

ei cosane

C2 0 H 4 2
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Constitutional Isomerism in Alkanes

Constitutional isomers: compounds with the same molecular formula but a different connectivity (arrangement) of their atoms there are two constitutional isomers with molecular formula C4H10

CH3 CH3 CH2 CH2 CH3 Butane (bp -0.5C) CH3 CHCH3 2-Meth ylp ropan e (bp -11.6C)
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the potential for constitutional isomerism is enormous

Molecular Formula CH4 C5 H1 2 C1 0 H2 2 C1 5 H3 2 C2 5 H5 2 C3 0 H6 2

Constitutional Isomers 1 3 75 4,347 36,797,588 4,111,846,763

Nomenclature of Alkane
In the older system of common nomenclature, the total number of carbon atoms in an alkane, regardless of their arrangement, determines the name. The first three alkanes are methane, ethane, and propane. All alkanes of formula C4H10 are called butanes, all C5H12 are called pentanes, all C6H14 are called hexane. For those beyond propane, iso indicates a (CH3)2CH group Ideally, every organic compound should have a name from which its structural formula can be drawn. For this purpose, chemists have adopted a set of rules established by an organization called the International Union of Pure and Applied Chemistry (IUPAC). In this class, we concentrate on IUPAC names. However, we also use common names, especially when the common name is used almost exclusively in the everyday discussions of chemists.
The IUPAC name of an alkane with an unbranched chain of carbon atoms consists of two parts: (1) a prefix that indicates the number of carbon atoms in the chain and (2) the ending ane to show that the compound is a saturated hydrocarbon.
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Prefixes used in the IUPAC system to show the presence of 1 to 20 carbons in an unbranched chain
Pref i x Carbons meth1 eth 2 prop3 but4 pent5 hex6 hept7 oct8 non 9 dec10

C arb on s Pref i x undec11 dod ec12 tri dec13 tetradec14 pentadec- 15 hexadec16 heptadec- 17 octad ec18 non adec- 19 eicos20
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 Parent name: the longest carbon chain

Substituent: a group bonded to the parent chain

alkyl group: a substituent derived by removal of a hydrogen from an alkane; commonly represented by the symbol RCH4 becomes CH3- (methyl) CH3CH3 becomes CH3CH2- (ethyl)

parent chain
2 4

subs tituent

6 7

4-Meth yloctan e
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Names of the most common alkyl groups

Con dens ed Structu ral Formula -CH3 -CH2 CH3 -CH2 CH2 CH3 sec- butyl Con dens ed Structu ral Formula -CH2 CHCH3 CH3 -CHCH2 CH3 CH3

N ame methyl ethyl propyl

N ame isobu tyl

isopropyl -CHCH3 CH3 bu tyl -CH2 CH2 CH2 CH3

CH3 t ert- bu tyl -CCH3 CH3

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IUPAC Nomenclature for Alkanes

1. The name of an alkane with an unbranched chain of carbon atoms consists of a prefix showing the number of carbon atoms in the chain and the ending ane.
2. For branched alkanes, take the longest chain of carbon atoms as the parent chain, and its name becomes the root name. 3. Give each substituent on the parent chain a name and a number. The number shows the carbon atom of the parent chain to which the substituent is bonded. Use a hyphen to connect the number to the name. 4. If there is one substituent, number the parent chain from the end that gives it the lower number 5. If there are two or more identical substituents, number the parent chain from the end that gives the lower number to the substituent encountered first. The number of times the substituent occurs is indicated by the prefix di, tri, tetra, penta, hexa, and so on. A comma is used to separate position numbers.
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IUPAC Nomenclature for Alkanes Continue

6. If there are two or more different substituents allow numbering from both ends of the parent chain, number the chain using the direction that gives the lowest series of numbers, (if the number is also the same, the alphabetical order of the substituents names is used to determine the direction). Note: all alkyl groups as well as halo (fluoro, chloro, bromo and iodo) groups have the same precedence, and they are listed in alphabetical order. 7. The prefixes di, tri, tetra, and so on are not included in the alphabetizing. Neither are the hyphenated prefixes sec and tert. However, unhyphenated prefix iso is traditionally included in the alphabetizing. Alphabetize the name of the substituents first, and then insert the prefix.

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Examples
CH3 CH3 CH2 CHCH2 CHCH2 CH3 CH2 CH3 3-Ethyl-5-meth ylh eptane
not 3-methyl-5-ethylheptane
2 1 4 3 5 6 7

CH3 CH2 CH3 CH3 CCH2 CHCH2 CH3 CH3 4-Ethyl-2,2-dimeth ylh exane
not 2,2-dimethyl-4-ethylhexane, not 3-ethyl-5,5-dimethylhexane
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6 5

Classification of Carbons and Hydrogen Atoms

Primary (1): a C bonded to one other carbon
Secondary (2): a C bonded to two other carbons Tertiary (3): a C bonded to three other carbons

Quaternary (4): a C bonded to four other carbons

a 2 carb on a 4 carb on CH3 CH3 -C-CH2 -CH-CH3 a 1 carb on CH3 CH3 a 1 carb on 2,2,4-Trimeth ylp entane
The hydrogens bonded to a primary carbon are classified as primary hydrogens, those on a secondary carbon are secondary hydrogens, and those on a tertiary carbon are tertiary hydrogens.
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a 3 carb on

Cycloalkanes
A hydrocarbon that contains carbon atoms joined to form a ring is called a cyclic hydrocarbon. When all carbons of the ring are saturated, we call the hydrocarbon a cycloalkane. Cycloalkanes of ring sizes ranging from 3 to over 30 abound in nature, and in principle, there is no limit to ring size. Five-membered (cyclopentane) and sixmembered (cyclohexane) rings are especially abundant in nature and received special attention.

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Cycloalkanes
General formula CnH2n

five- and six-membered rings are the most common

Structure and nomenclature to name, prefix the name of the corresponding openchain alkane with cyclo-, and name each substituent on the ring

if only one substituent, no need to give it a number

if two substituents, number from the substituent of lower alphabetical order if three or more substituents, number to give them the lowest set of numbers, and then list substituents in alphabetical order
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Examples
Cyclic hydrocarbons are commonly written as line-angle formulas

Isopropylcyclopentan e

1-tert -Bu tyl-4-methylcycloh exane

1-Isobutyl-2-meth ylcyclohexan e

1-Ethyl-1-methylcyclopropane
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The IUPAC System: A General System of Nomenclature

prefix-infix-suffix
prefix tells the number of carbon atoms in the parent

infix tells the nature of the carbon-carbon bonds

suffix tells the class of compound
Nature of Carbon-Carbon Bonds in the Parent Chain all single bonds one or more double bonds one or more triple bonds S uffix -e -ol -al -amine -one -oic acid Class hydrocarbon alcohol aldehyde amine ketone carboxylic acid
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Infix -an-en-yn-

Examples
prop-en-e = propene eth-an-ol = ethanol but-an-one = butanone but-an-al = butanal pent-an-oic acid = pentanoic acid cyclohex-an-ol = cyclohexanol eth-yn-e = ethyne eth-an-amine = ethanamine
CH 3 CH=CH
2

CH 3 CH 2 OH

OH
HC CH

O
CH3 CH2 NH 2
O H

O OH
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Cis-Trans Isomerism in Cycloalkanes

Cis-trans isomers have
the same molecular formula the same connectivity of their atoms

an arrangement of atoms in space that cannot be interconverted by rotation about sigma bonds
H H H H H CH3 CH3 H H H CH3 H H H H H H3 C H H H

H3 C

CH3

H3 C

CH3
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cis-1,2-D imethylcyclopentan e

t rans-1,2-D imeth ylcyclopentane

Physical Properties of Alkanes and Cycloalkanes

Alkanes are nonpolar compounds and have only

weak interactions between their molecules

Dispersion forces: weak intermolecular forces of

attraction resulting from interaction of temporary induced dipoles

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 Boiling point

low-molecular-weight alkanes (1 to 4 carbons) are gases at room temperature; e.g., methane, propane, butane
higher-molecular-weight alkanes (5 to 17 carbons) are liquids at room temperature (e.g., hexane, decane, gasoline, kerosene) high-molecular-weight alkanes (18 or more carbons) are white, waxy semisolids or solids at room temperature; e.g., paraffin wax
Density

average density is about 0.7 g/mL

liquid and solid alkanes float on water
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Constitutional isomers are different compounds and have different physical (and chemical) properties

N ame hexan e 3-methylp entane 2-methylp entane

Meltin g Boiling Point Point D en sity (C) (C) (g/mL) -95 69 64 62 58 50 0.659 0.664 0.653 0.662 0.649
2,2-Dimethylbutane
Hexane

-6 -23 2,3-dimethylbutan e -129 2,2-dimethylbutan e -100

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Reactions of Alkanes
Carbon-carbon single bonds are difficult to break, which makes alkanes and cycloalkanes the least reactive family of organic compound. However, alkanes and cycloalkanes burn readily in oxygen and will undergo substitution reactions with halogen.
Oxidation is the basis for the use of alkanes as energy

sources for heat and power

heat of combustion: heat released when one mole of a substance is oxidized to carbon dioxide and water
CH4 + 2 O2 Methan e CH3 CH2 CH3 + 5 O2 Propan e CO2 + 2 H2 O H = -212 kcal/mol

3 CO2 + 4 H2 O H = -530 kcal/mol

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Halogenation of Alkane (Substitution) Alkanes react with halogen to produce a mixture of halogenated compounds. In a halogenation reaction, atoms of a halogen bond to a carbon atom. This type of reaction is also called substitution reaction because halogen atoms replace one or more hydrogen atoms in an alkane. When halogenation uses chlorine, it is called chlorination, and with bromine, it is called bromination. Halogenation can take place when a mixture of an alkane and halogen are heated or exposed to strong light.
Light or heat

Alkane + Halogen

Haloalkane + Hydrogen Halide

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Example
H H C H + Cl2 H
Light or heat

H H C Cl + HCl H

+ Cl2

H ClC Cl H
+ HCl + Cl2

Cl ClC Cl
H + HCl + Cl2

Cl ClC Cl Cl
+ HCl
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When halogenation occurs with larger alkanes, the halogen atoms may substitute for any of the hydrogen atoms. However, tertiary hydrogen is more reactive than secondary hydrogen, and secondary hydrogen is more reactive than primary hydrogen. Question: In the following molecule, which hydrogen is the most reactive?

CH3

CH3

CH3CHCH2CCH3 CH3
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Sources of Alkanes
Natural gas

90-95% methane, 5-10% ethane

Petroleum

gases (bp below 20C)

naphthas, including gasoline (bp 20 - 200C) kerosene (bp 175 - 275C) fuel oil (bp 250 - 400C)
lubricating oils (bp above 350C) asphalt (residue after distillation)
Coal
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Synthesis Gas
a mixture of carbon monoxide and hydrogen in varying proportions, depending on how it is produced
C + H2 O Coal CH4 + 1 O2 2 Methan e heat catalyst CO + H2 CO + 2 H2

methanol and acetic acid are produced from synthesis gas

CO + 2 H2 catalyst CH3 OH Methan ol O CH3 COH Acetic acid
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CH3 OH + CO Methan ol

catalyst