Physical properties of alkanes & cycloalkanes

Physical state

Boiling Point

Solubility

Physical state At room temperature (25oC) and atmospheric pressure (1 atm), for unbranched alkanes, C1 C4 : gases C5 C17 : liquids C18 - more : solids

Boiling points The boiling points of the straight alkanes show a regular increase with increasing molecular weight. weight. Branching of the alkanes chain, lower the boiling point.

Mr

boiling point

C-H is non polar bond  Intermolecular forces exist London dispersion The London dispersion forces increase :  As molecular weight increases,  Molecular size increases  Molecular surface area increase


Therefore, more energy is required to separate molecules from one another Result - a higher boiling point.

Mr

boiling point

Chain branching :  makes a molecule more compact  Surface area reduces  The strength of the London dispersion forces reduce  Lower boiling points.

Isomeric Alkanes Have different boiling point due to branching

Pentane 2-methylbutane 2,22,2dimethylpropane CH3 CH3CCH3 CH3 9oC

CH3CH2CH2CH2CH3

CH3CHCH2CH CH3 28.5oC

37oC

For example, butane and 2-methylpropane both have a molecular formula C4H10, but the atoms are arranged differently CH3CH2CH2CH3 CH3CH2CH2CH3 butane

CH3CHCH3 CH3

CH3CHCH3 CH3

2-methylpropane

In butane the C atoms are arranged in a single chain, but 2-methylpropane is a shorter chain with a branch

Name

Molecular structure

Boiling point

Butane has a higher boiling point because the dispersion forces are greater. The molecules are longer (and so set up bigger temporary dipoles) and can lie closer together than the shorter, fatter 2-methylpropane molecules.

Cycloalkanes The boiling points of cycloalkanes are 10oC to 15oC higher than the corresponding straight chain alkanes. Cycloalkane Cyclobutane Cyclopentane Boiling point 13oC 49oC alkane Butane Pentane Boiling point -0.5oC 36..3oC

Solubility
Alkanes less dense than water Alkanes and cycloalkanes are almost totally insoluble in water
 

They are non-polar molecule nonUnable to form hydrogen bond with H2O

Liquid alkanes and cycloalkanes are soluble in one another, and they generally dissolve in non-polar solvents. nonGood solvents for alkanes are benzene, carbon tetrachloride, chloroform, and other hydrocarbons.

Nature sources of alkanes; Natural gas oil Natural gas contains primarily methane and ethane, with some propane and butane Oil is a mixture of liquid alkanes and other hydrocarbons

CHEMICAL REACTION OF ALKANES

Non-reactivity of alkanes Alkanes are generally inert towards many chemical reagents (bases, acids, dehydrating agents and aqueous oxidizing agents)

C and H has nearly the same electronegativity, the C-H bonds of alkanes are only slightly Cpolarised (non polar)

Reaction of alkanes
 

Combustion Halogenation

Combustion of alkanes


Alkanes burnt in air ( oxygen ) to give carbon dioxide gas, water and heat.

y CxHy+ x  O2 4

+ Heat

y x CO2 + H2O 2

Examples:
Combustion of alkane in excess oxygen

C4H8+ 3O2

4CO2 + + Heat

4H2O

Examples:
Combustion of alkane in limited oxygen

C4H8+ 4O2

4CO + 4H2O + Heat

Alkanes are unreactive towards polar or ionic reagents but can react with nonpolar reagents such as oxygen and bromine.

The low reactivity of alkanes toward many reagents explain why alkanes were originally called paraffins. paraffins. (Latin : parum affinis= low affinity). affinity).

Halogenation: a free radical substitution reaction

Alkanes react with halogen (chlorine & bromine) to produce haloalkanes in the presence of light or temperature >> 100 oC. RH + X2

hv RX + HX p

With methane, the reaction produces a mixture of halomethane and a hydrogen halide.

Examples:
i. CH4 + Cl2

hv p

CH3Cl + CH2Cl2 + CHCl3 + CCl4 + HCl

ii.

hv CH3CH3 + Cl2 p CH3CH2Cl + HCl

CH3 CH3 | | hv CH CCH Cl + iii. CH3 CCH3 + Cl2 p 3 2 HCl | | CH3 CH3 (ii) & (iii): 1 product only because all the hydrogen atoms are identical

iv.

hv CH3CH2CH3 + Br2 p

CH3CH2CH2Br ( minor) + CH3CHCH3 | Br ( major) + HBr

Reaction mechanism
CH4 + Cl2 i.

hv p CH3Cl + HCl

Chain initiation step hv p

Cl Cl

2Cl

ii. Chain propagation steps H H-C H

3HC

H + Cl p CH3 + HCl + Cl Cl_ p CH3Cl + Cl

iii. Chain termination step. Cl + Cl p Cl2

Cl + CH3 p CH3Cl CH3 + CH3 p CH3CH3

Example
The bromination of 2-methylbutane yields a 2mixture of isomers.
CH2Br CH3 C H CH2 CH3 CH3 CH3 C H CHBr CH3
CH3 CH3 C Br CH2 CH3

Increasing % yield

Exercise


Chlorination reaction of certain alkanes can be used for laboratory preparations, for example in the preparation of chlorocyclopentane from cyclopentane. cyclopentane. Give the mechanism for the reaction. reaction.