Chapter 12

12.1 Alkanes

Alkanes

Alkanes
Alkanes: Contain only C and H. Have only single CC bonds. Have a general formula of CnH2n +2.
C Atoms 1 3 6
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H Atoms 2(1) + 2 = 4 2(3) + 2 = 8 2(6) + 2 = 14

Formula CH4 C3H8 C6H14

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Structural Formulas
Structural formulas show the arrangement of atoms in an organic compound. In expanded structural formulas, all the individual bonds are drawn. In condensed structural formulas, each carbon is written with the H atoms connected to it. H H | | HC = CH3 C = CH2 | | H H
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Line-Bond Formulas

Because each C atom has a tetrahedral arrangement, the geometrical arrangement of carbon atoms is not a straight line. A line-bond formula abbreviates the carbon chain and shows only the zigzag pattern of bonds from carbon atom to carbon atom.

Summary of Formulas

IUPAC System of Naming Alkanes

The IUPAC (International Union of Pure and Applied Chemistry) establishes the rules for naming organic compounds. Alkanes are named with ane endings. The first four alkanes are methane, ethane, propane, and butane. The names of longer carbon chains use Greek prefixes such as pent- for 5 C atoms and hex- for 6 C atoms.
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Names of Continuous-Chain Alkanes

Learning Check
A. Give the name of each compound: 1) CH3CH3 2) CH3CH2CH3 3) CH3CH2CH2CH2CH2CH3 B. Write the condensed structural formula of pentane.

Solution
A. Give the name of each compound: ethane 1) CH3CH3 2) CH3CH2CH3 propane 3) CH3CH2CH2CH2CH2CH3 hexane B. Write the condensed structural formula of pentane. CH3CH2CH2CH2CH3
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Learning Check
A. What is the condensed formula for H H H H | | | | H CCCCH | | | | H H H H B. What is its molecular formula? C. What is its name?
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Solution
A. CH3CH2CH2CH3 B. C4H10 C. butane

Conformations
As the groups attached to a C-C single bond rotate around the bond, their relative arrangements has different conformations.

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Conformations of Butane

Drawing Structures for Butane

Rotation of the end CH3- provides different conformations for butane.

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Learning Check
For propane, write the: 1) Molecular formula 2) Expanded structural formula 3) Condensed structural formula (two conformations) 4) Line-bond formula

Solution
1) Molecular formula C3H8 2) Expanded structural formula
H H H | | | H CCCH | | | H H H

3) Condensed structural formula (two conformations)

CH3CH2CH3 CH3 | CH3CH2

4) Line-bond formula
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or
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Chapter 12 Alkanes
12.2 IUPAC Naming System for Alkanes 12.3 Drawing Structural Formulas
CH3 CH3 | | CH3CHCH2CHCH3 2,4-dimethylpentane
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Branched-Chain Alkanes

In a branchedchain alkane, a side group called a branch or a branch substituent is attached to a carbon chain.

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Classification of Carbon Atoms

Carbon atoms are classified according to the number of attached carbon atoms. Primary (1) bonds to one carbon atom. Secondary (2) bonds to two carbon atoms. Tertiary (3) bonds to three carbon atoms. CH3 | CH3 CH2CH2CH3 CH3CHCH3
secondary primary tertiary

Alkyl Groups
An alkyl group: Is composed of one or more carbon atoms attached to a carbon chain. Is derived from the corresponding alkane by removing one hydrogen. Is named by replacing the ane ending of the corresponding alkane with yl. Derived from methane is methyl and from ethane is ethyl.
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Alkyl Groups

Naming Branched-Chain Alkanes

The names of branched-chain alkanes indicate the groups bonded to the longest carbon chain. CH3 methyl group on C-3 | CH3CH2CH2CHCH2CH3 hexane 6 5 4 3 2 1 3-Methylhexane
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Naming Summary
In the IUPAC system: The longest chain is named as the main chain. Any carbon branches use their alkyl names. Each branch is numbered by counting the main chain from the end nearest the first side group. Branches are listed in alphabetical order.
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Learning Check
Give the IUPAC name for each alkane. A. CH3 CH3 | | CH3CHCH2CHCH3 B. CH2CH3 CH3 | | CH3CH2CHCH2CCH2CH3 | CH3
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Solution
A. CH3 CH3 | | CH3CHCH2CHCH3 2,4-dimethylpentane CH2CH3 CH3 | | CH3CH2CHCH2CCH2CH3 | CH3 5-ethyl-3,3-dimethylheptane
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What Is In A Name?
The structural formula is drawn from the IUPAC name. 2, 4-dimethylhexane

B.

2, 4
Location of branches on main chain

dimethyl
Two CH3- groups attached

hexane
6 carbon main chain with single C-C bonds

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Drawing Structural Formulas

Draw the condensed formula of 2-methylpentane 1. Draw the main chain of 5 carbon atoms. CCCCC 2. Add a CH3 branch to C-2 on the main chain. CH3 | CCCCC 3. Add hydrogen atoms to give 4 bonds to each C. CH3 | CH3CHCH2CH2CH3
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Learning Check
Draw the condensed structural formula for A. 2, 3-dimethylbutane

B. 2, 3, 4-trimethylpentane

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Solution
Write the condensed structural formula for A. 2, 3-dimethylbutane CH3 CH3 | | CH3CHCHCH3 B. 2, 3, 4-trimethylpentane CH3 CH3 CH3 | | | CH3CHCHCHCH3
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Writing Isomers
The constitutional isomers for C4H10 can be written by first writing the continuous chain. Then remove one CH3 and attach it as a branch. CH3 | CH3CHCH3 CH3CH2CH2CH3 Butane 2-Methylpropane

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Learning Check
Write 3 constitutional isomers of C5H12 and name each.

Solution
CH3CH2CH2CH2CH3 pentane CH3 | CH3CHCH2CH3 2-methylbutane CH3 | CH3CCH3 | CH3
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2,2-dimethylpropane

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Chapter 12

Alkanes

Haloalkanes
In a haloalkane, one or more H atoms in an alkane is replaced by a halogen atom. Simple haloalkanes are named alkyl halides. In IUPAC names, a halogen is named as fluoro, chloro, bromo, or iodo. CH3Br bromomethane (methyl bromide) Cl | CH3CHCH2CH3 2-chlorobutane (sec-butyl chloride)
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12.4 Haloalkanes

Substituents

Naming of Haloalkanes

Two or more substituents are named in alphabetical order. Cl Br | | CH3CHCH2CHCH2CH3 4-bromo-2-chlorohexane

Methane compounds with two or more chlorine atoms are sometimes named by common names that do not reflect their structures.

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Learning Check
The name of this compound is: Cl CH3 | | CH3CH2CHCH2CHCH3 1) 2,4-dimethylhexane 2) 3-chloro-5-methylhexane 3) 4-chloro-2-methylhexane

Solution
The name of this compound is: Cl CH3 | | CH3CH2CHCH2CHCH3 3) 4-chloro-2-methylhexane

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Learning Check
Give the IUPAC name for each. A. CH3CH2F Br Cl | | B. CH3CHCHCH3

Solution
Give the IUPAC name for each. A. CH3CH2F fluoroethane Br Cl | | B. CH3CHCHCH3 2-bromo-3-chlorobutane

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Learning Check
Halothane is widely used as an anesthetic, which is a compound that decreases the ability of the nerve cells to conduct pain. What is the IUPAC name of halothane? F Br | | FCCCl | | F H
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Solution
The IUPAC name is 2-bromo-2-chloro-1,1,1-trifluoroethane. F Br | | FCCCl | | F H

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Chlorofluorocarbons (CFCs)
The ozone (O3) layer in the atmosphere absorbs most of the suns harmful radiation. Chlorofluorocarbons (CFCs) cause reactions that destroy the ozone layer. CFCs such as Freon-12 (CF2Cl2) have been used in refrigeration, air conditioning, and foam insulation. The use of CFCs in spray cans is no longer allowed.
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Chlorofluorocarbons and Ozone

In the stratosphere, the CFCs are cleaved by the high-energy UV radiation from the sun.
UV light

CF2Cl2 CF2Cl + Cl The Cl reacts with ozone (O3). The ClO produced destroys another O3 forming additional Cl. Thus one Cl can destroy many O3 molecules. Cl + O3 ClO + O2 ClO + O3 Cl + 2O2
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Impact of Loss of Ozone

Chapter 12

Alkanes

According to the National Academy of Sciences, each 1% loss of ozone (O3) increases the amount of UV radiation reaching the earth by 2%. More UV radiation means more skin cancer and cataracts in humans, more intense photochemical smog, and lower crop yields.
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12.5 Cycloalkanes

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Cycloalkanes
Cycloalkanes: Are rings of carbons that can be drawn as geometric figures. Have a general formula of CnH2n or 2 H less than the alkane. propane C3H8 cyclopropane C3H6. butane C4H10 cyclobutane C4H8. Are named with the prefix cyclo- in front of the corresponding alkane name.
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Formulas of Cycloalkanes

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Naming Cycloalkanes
A cycloalkane with: One substitutuent is named by placing the name of the substituent in front of the cycloalkane name. Two or more substitutuents is named by numbering the ring in the direction that gives the lower numbers to the substituents.

Cycloalkanes with Side Groups

CH3 methylcyclopentane CH3 CH3 1,2-dimethylcyclopentane CH3 CH3 1,2,4-trimethylcyclohexane CH3
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Learning Check
Name each of the following cycloalkanes.
CH3

Solution
Name each of the following cycloalkanes.
CH3

1,2-dimethylcyclobutane
CH3 Cl Cl CH3

chlorocyclopentane

Cl

Cl

1-chloro-3-methylcyclohexane
CH3
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CH3

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Constitutional Isomers

Cis-Trans Isomers

The rigid ring in a cyclic structure prevents rotation of substitutuents bonded to the ring. A cyclic structure with two substituents has two isomers called cis-trans isomers. The cis isomer, has two substituents on the same side of the ring. The trans isomer, has two substituents on opposite sides of the ring.
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The compound 1,2-dichlorocyclopropane has cis-trans isomers. Cl atoms on Cl atoms on same side opposite sides

Cl

Cl

Cl Cl

cis-1,2-dichlorocyclopropane

` -1,2-dichlorocyclopropane trans
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Learning Check
Name each as a cis or trans isomer.
Br Br Cl
Br

Solution
Name each as a cis or trans isomer.
Br Cl

trans-1,2-dibromocyclopropane cis-1,3-dichlorocyclobutane

Cl

Cl

Cl

Cl

trans-1-bromo-3-chlorocyclopentane
Br
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Br

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Chapter 12

Alkanes

Physical Properties of Alkanes

Alkanes, including cycloalkanes: Are nonpolar and insoluble in water. Have densities between 0.65 0.70 g/mL; they float on water. Have low melting and boiling points compared to other families of organic compounds.

12.6 Physical Properties of Alkanes and Cycloalkanes 12.7 Chemical Properties of Alkanes and Cycloalkanes

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Boiling Points of Alkanes

Boiling points: Increase in larger alkane molecules due to increased dispersion forces. Are lower for branched alkanes because they have fewer contact points. Are higher for cycloalkanes because their rigid structures allow more contact and attraction between molecules.

Boiling Points of Pentanes

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Uses of Alkanes

Crude Oil

Methane, ethane, propane, and butane are gases at room temperature and used as fuels. Alkanes with 5-17 carbon atoms are liquids and found in gasoline, diesel, and jet fuels. Alkanes with 18 or more carbon atoms are solids and found in the waxy coatings of fruits and vegetables.
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The differences in boiling points are used to separate hydrocarbons in crude oil. Heating to higher temperatures produces gases that are removed and cooled.
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Chemical Properties of Alkanes

Combustion
A fuel such as propane reacts with oxygen and burns, producing CO2 and H2O. Propane is burned to obtain energy and heat for cooking or warming a room. 3CO2 + 4H2O C3H8 + 5O2

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Alkanes are typically not very reactive due to strong C-C single bonds. The most typical reaction is combustion, where an alkane reacts with oxygen to produce carbon dioxide, water, and energy. alkane + O2 CO2 + H2O + energy

Steps in Balancing a Combustion Equation

Step 1 Write the reactants and products. CO2 + H2O C3H8 + O2 Step 2 Balance C. C3H8 + O2 3CO2 + H2O Step 3 Balance H. C3H8 + O2 3CO2 + 4H2O Step 4 Balance O with O2. C3H8 + 5O2 3 CO2 + 4H2O
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Learning Check
Complete and balance the reaction for the complete combustion of C7H16.

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Solution
Step 1 C7H16 + O2 Step 2 and 3 C7H16 + O2 Step 4 C7H16 + 11O2 7CO2 + 8H2O
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Learning Check
CO2 + H2O Write the combustion reaction for ethane and balance.

7CO2 + 8H2O

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Solution
Write the combustion reaction for ethane and balance. ethane CH3CH3 = C2H6 C2H6 + 7/2 O2 2CO2 + 3H2O Multiply through by 2 to clear 7/2 2C2H6 + 7O2 4CO2 + 6H2O

Halogenation of Alkanes (Substitution)

When alkanes react with halogens, a mixture of halogenated products is produced. In a reaction called substitution, one or more H atoms are replaced with a halogen usually Cl or Br. The equation for the reaction of ethane and chlorine to give the monosubstituted product is CH3CH3 + Cl2 CH3CH2Cl
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Learning Check
Give the structures and names of the monosubstituted products for the reaction of propane with bromine in the presence of light.

Solution
Give the structures and names of the monosubstituted products for the reaction of propane with bromine in the presence of light. CH3CH2CH2 Br 1-bromopropane; propyl bromide Br | CH3CHCH3 2-bromopropane; isopropyl bromide
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