Chemical properties of Alkanes

         (i) Substitution reactions of Alkanes

         (a) Halogenation : R-H + X-X → R-X +HX

         The reactivity of halogen is : F₂ > Cl₂ > Br₂ > I₂

• Fluorine can react in dark Cl₂, Br₂ require light energy.I₂ does not show any reaction at room temperature, but on heating it presents iodination.
• Iodination of methane is completed in presence of oxidising agent such as HNO₃/HIO₃/HgO which neutralizes HI.
• Chlorination of methane :

         (ii) Reaction based on free radical mechanism

         (a) Nitration : 

         Nitrating mixture : (i) (Conc. HNO₃ + Conc. H₂SO₄) at 250⁰ C

         (ii) (HNO₃ vapour at 400^o - 500^o C).

         (b) Sulphonation : Free radical mechanism 

• Lower alkanes mainly ethane, methane do not give this reaction.

         (iii) Oxidation

         (a) Complete Oxidation or combustion :

• This is exothermic reaction.

         (b) Incomplete oxidation or combustion  

         (c) Catalytic Oxidation :  

         This is the industrial process for the developer of methyl alcohol.

•   Higher alkanes are oxidised to fatty acids in presence of manganese stearate.

         (d) Chemical oxidation :

         (iv) Thermal decomposition or cracking or pyrolysis or fragmentation

         q This reaction is of great importance to petroleum industry.

         (v) Isomerisation :

         (vi) Aromatisation : 

         (vii) Step up reaction

         (a) Reaction with CH₂N₂ (Diazo methane) :

         (b) Reaction with CH₃Cl/NaOH :

         (c) Reaction with   

         (viii) HCN formation :

         (ix) Chloro sulphonation/Reaction with SO₂+Cl₂

         This reaction is called as reed's reaction.

         q This is needed in the commercial formation of detergent.

         (x) Action of steam :      

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