ALKANES AND CYCLOALKANES

Alkanes are hydrocarbons in which the carbon atoms are held together by single bonds. Their general formula is CnH2n+2 .
Example: Methane odorless, nontoxic, flammable gas, which has a boiling point of 164.0C.

Ethane -an odorless, nontoxic, flammable gas, which has a boiling point of -88.6C. -a minor component of natural gas (10%-30%, depending on the location of the source).

Propane is used as an industrial fuel, and in home heating and cooking. Both propane and butane are used as LPG fuels (liquefied petroleum gas) for outdoor cooking.

Butane, like propane, burns cleanly, and is used in LPG fuels (liquefied petroleum gas) for outdoor cooking. In liquid form, it is used in cigarette lighters and lighter sticks.

When the atoms of butane are connected differently, another structure results: methylpropane

Butane and methylpropane are isomers.

WHAT ARE ISOMERS?

ISOMERISM in Organic Compounds

The term ISOMERS come from the Greek words isos and meros which mean made of the same parts.

ISOMERS are compounds that have the same formula but with different structures.

TYPES OF ISOMERS
I. STRUCTURAL ISOMERS OR CONSTITUTIONAL ISOMERS Compounds that have the same composition but their atoms are connected differently. A. chain isomers B. position isomers C. functional isomers

TYPES OF ISOMERS
II. STEREOISOMERS Structures in which the atoms have the same connectivity but differ in orientation of the atoms in space A. conformational isomers These are different arrangements that can be converted into one another by rotation about single bonds. B. geometric isomers Exhibited by some alkenes and substituted cycloalkanes. C. optical isomers Exhibited by molecules that contain an asymmetric carbon.

Chain isomers

C5H12

Position isomers

Position isomers

2-pentanol

3-pentanol

Functional isomers

C 3H 6O

Functional isomers

1-hexene

cyclohexane

C6H12

Conformations of Alkanes and Cycloalkanes Conformations refer to different arrangement of atoms that result from rotation around a C-C single bond. They readily interconvert. They are NOT different compounds, rather they show different projections of atoms in space.

Conformational Isomers of ethane

Staggered conformation of ethane

Eclipsed conformation of ethane

Newman projection formulas

The two extreme arrangements are the eclipsed and the staggered. The staggered is the most stable conformation. The eclipsed is less stable due to 1. electrostatic repulsion between bonding orbitals, described as torsional strain. 2. interaction between nonbonded atoms, known as steric effect which becomes evident when there are bulky groups like a t-butyl group.

Conformations of cycloalkanes Lets consider cyclohexane:

Chair conformation of cyclohexane

This is the more stable conformation

Boat conformation of cyclohexane

This conformation is less stable due to: 1. Torsional strain 2. Steric effect between flagpole Hs

How to draw the chair conformation of cyclohexane

Geometric isomers

Also exhibited by some substituted cycloalkanes

Optical isomers

Tartaric acid

ALKANES Contain C and H only Contain single C C bonds Have 4 bonds to every carbon atom Are nonpolar

SOURCES OF ALKANES
fossil fuels: natural gas petroleum coal petroleum is a complex mixture of hydrocarbons 1. solvents 2. fuels 3. raw materials for chemical syntheses separated into fractions by fractional distillation in an oil refinery

products from fractional distillation of petroleum: fraction natural gas petroleum ether ligroin raw gasoline kerosene gas oil lube oil asphalt coke b.pt. range below 20o 20 60o 60 100o 40 205o 175 325o above 275o non-volaltile liquids non-volatile solids solid carbon no. of carbons C1 C4 C5 C6 C6 C7 C5 C10 C12 C18 C12 & up

Physical Properties 1. Boiling Points of Alkanes

Molecular Formula CH4 C2H6 C3H8 C4H10 C5H12 C6H14 Melting Point (oC) -183 -183 -190 -138 -130 -95 Boiling Point (oC) -164 -89 -42 -0.5 36 69 State at 25oC gas

Name methane ethane propane butane pentane hexane

2. Solubility of Alkanes
Alkanes are insoluble in water because the polar water molecules are not attracted to the non-polar alkane molecules. However alkanes are soluble in non-polar solvents such as carbon tetrachloride,CCl4. Generally speaking, non-polar substances will be insoluble in polar solvents such as water, but they will be soluble in non-polar solvents such as CCl4 (like dissolves in like).

Reactions of Alkanes 1. Combustion CH4

methane

2O2

CO2

2H2O + heat

2C8H18

25O2

16CO2

18H2O + heat

octane (gasoline)

2. Pyrolysis (Cracking)
alkane, 400-600oC smaller alkanes + alkenes + H2

Used to increase the yield of gasoline from petroleum. Higher boiling fractions are cracked into lower boiling fractions that are added to the raw gasoline. The alkenes can be separated and used in to make plastics.

3. Halogenation

Example: CH4 + Cl2

CH3 Cl + HCl

Mechanism for Bromination of Methane with Br2 (Free Radical Substitution) Step 1 (Initiation) Heat or uv light cause the weak halogen bond to undergo homolytic cleavage to generate two bromine radicals.

Step 2 (Propagation) (a) A bromine radical abstracts a hydrogen to form HBr and a methyl radical, then (b) The methyl radical abstracts a bromine atom from another molecule of Br2 to form the methyl bromide product and another bromine radical, which can then itself undergo reaction, creating a cycle that can repeat. (a) (b)

Step 3 (Termination) Various reactions between the possible pairs of radicals allow for the formation of ethane, Br2 or the product, methyl bromide. These reactions remove radicals and do not perpetuate the cycle.

(ethane)

Summary When treated with Br2 or Cl2, radical substitution of R-H generates the alkyl halide and HX. Alkane R-H relative reactivity order : tertiary > secondary > primary > methyl. Halogen reactivity F2 > Cl2 > Br2 > I2 Only chlorination and bromination are useful in the laboratory.

Summary
Bromination is selective for the R-H that gives the most stable radical. Chlorination is less selective Reaction proceeds via a free radical substitution mechanism which involves free radical intermediates.

EXAMPLES OF CHLORINATION OF ALKANES A. CH3CH3 B. + Cl2 > CH3CH2Cl + HCl

CH3-CH2-CH3 + Cl2 > CH3-CH2-CH2Cl + CH3-CHCl-CH3 45% 55% C. (CH3)3CH + Cl2 (CH3)3CCl + (CH3)2CHCH2Cl 65% 35%

Energy of transition state

Energy Diagram

Relative Stability of Alkyl Free Radicals

Alkyl radical stability increases in the order: primary (1) < secondary (2) < tertiary (3) < allyl benzyl