13.2.3 Properties

Physical properties

Alkanes are almost non-polar molecules because of the covalent nature of C-C and C-H bonds and due to very little difference of electronegativity between carbon and hydrogen atoms.

They possess weak van der Waals forces. Due to the weak forces, the first four members, C1 to C4 are gases, C5 to C17 are liquids and those containing 18 carbon atoms or more are solids at 298 K. They are colourless and odourless. What do you think about solubility of alkanes in water based upon nonpolar nature of alkanes?

Petrol is a mixture of hydrocarbons and is used as a fuel for automobiles. Petrol and lower fractions of petroleum are also used for dry cleaning of clothes to remove grease stains. On the basis of this observation, what do you think about the nature of the greasy substance?

You are correct if you say that grease (mixture of higher alkanes) is non-polar and, hence, hydrophobic in nature. It is generally observed that in relation to solubility of substances in solvents, polar substances are soluble in polar solvents, whereas the non-polar ones in non-polar solvents i.e., like dissolves like.

There is a steady increase in boiling point with increase in molecular mass. This is due to the fact that the intermolecular van der Waals forces increase with increase of the molecular size or the surface area of the molecule.

You can make an interesting observation by having a look on the boiling points of three isomeric pentanes viz., (pentane, 2-methylbutane and 2,2-dimethylpropane). It is observed that pentane having a continuous chain of five carbon atoms has the highest boiling point (309.1K) whereas 2,2 – dimethylpropane boils at 282.5K.

With increase in number of branched chains, the molecule attains the shape of a sphere. This results in smaller area of contact and therefore weak intermolecular forces between spherical molecules, which are overcome at relatively lower temperatures.

Chemical properties

As already mentioned, alkanes are generally inert towards acids, bases, oxidising and reducing agents. However, they undergo the following reactions under certain conditions.

1. Substitution reactions

One or more hydrogen atoms of alkanes can be replaced by halogens, nitro group and sulphonic acid group. Halogenation takes place either at higher temperature (573-773 K) or in the presence of diffused sunlight or ultraviolet light. Lower alkanes do not undergo nitration and sulphonation reactions.

These reactions in which hydrogen atoms of alkanes are substituted are known as substitution reactions. As an example, chlorination of methane is given below:

Halogenation

It is found that the rate of reaction of alkanes with halogens is F2 > Cl2 > Br2 > I2. Rate of replacement of hydrogens of alkanes is : 3° > 2° > 1°. Fluorination is too violent to be controlled. Iodination is very slow and a reversible reaction. It can be carried out in the presence of oxidizing agents like HIO3 or HNO3.

Halogenation is supposed to proceed via free radical chain mechanism involving three steps namely initiation, propagation and termination as given below:

Mechanism

(i) Initiation : The reaction is initiated by homolysis of chlorine molecule in the presence of light or heat. The Cl–Cl bond is weaker than the C–C and C–H bond and hence, is easiest to break.

(ii) Propagation : Chlorine free radical attacks the methane molecule and takes the reaction in the forward direction by breaking the C-H bond to generate methyl free radical with the formation of H-Cl.

The methyl radical thus obtained attacks the second molecule of chlorine to form CH3 – Cl with the liberation of another chlorine free radical by homolysis of chlorine molecule.

The chlorine and methyl free radicals generated above repeat steps (a) and (b) respectively and thereby setup a chain of reactions.

The propagation steps (a) and (b) are those which directly give principal products, but many other propagation steps are possible and may occur. Two such steps given below explain how more highly haloginated products are formed.

(iii) Termination: The reaction stops after some time due to consumption of reactants and / or due to the following side reactions :

The possible chain terminating steps are

Though in (c), CH3 – Cl, the one of the products is formed but free radicals are consumed and the chain is terminated. The above mechanism helps us to understand the reason for the formation of ethane as a byproduct during chlorination of methane.

2. Combustion

Alkanes on heating in the presence of air or dioxygen are completely oxidized to carbon dioxide and water with the evolution of large amount of heat.

Due to the evolution of large amount of heat during combustion, alkanes are used as fuels. During incomplete combustion of alkanes with insufficient amount of air or dioxygen, carbon black is formed which is used in the manufacture of ink, printer ink, black pigments and as filters.

3. Controlled oxidation

Alkanes on heating with a regulated supply of dioxygen or air at high pressure and in the presence of suitable catalysts give a variety of oxidation products.

4. Isomerisation

n-Alkanes on heating in the presence of anhydrous aluminium chloride and hydrogen chloride gas isomerise to branched chain alkanes. Major products are given below. Some minor products are also possible which you can think over. Minor products are generally not reported in organic reactions.

5. Aromatization

n-Alkanes having six or more carbon atoms on heating to 773K at 10-20 atmospheric pressure in the presence of oxides of vanadium, molybdenum or chromium supported over alumina get dehydrogenated and cyclised to benzene and its homologues. This reaction is known as aromatization or reforming.

Toluene (C7H8) is methyl derivative of benzene.

6. Reaction with steam

Methane reacts with steam at 1273 K in the presence of nickel catalyst to form carbon monoxide and dihydrogen. This method is used for industrial preparation of dihydrogen gas

7. Pyrolysis

Higher alkanes on heating to higher temperature decompose into lower alkanes, alkenes etc. Such a decomposition reaction into smaller fragments by the application of heat is called pyrolysis or cracking.

Pyrolysis of alkanes is believed to be a free radical reaction. Preparation of oil gas or petrol gas from kerosene oil or petrol involves the principle of pyrolysis. For example, dodecane, a constituent of kerosene oil on heating to 973K in the presence of platinum, palladium or nickel gives a mixture of heptane and pentene.

 

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