Neither positive ions nor negative ions are attracted to a nonpolar molecule. In fact, the alkanes undergo so few reactions that they are sometimes called paraffins, from the Latin parum affinis, meaning “little affinity.”

Two important reactions that the alkanes do undergo are combustion and halogenation. Nothing happens when alkanes are merely mixed with oxygen (O₂) at room temperature, but when a flame or spark provides the activation energy, a highly exothermic combustion reaction proceeds vigorously. For methane (CH₄), the reaction is as follows:

CH₄ + 2O₂ → CO₂ + 2H₂O + heat

If the reactants are adequately mixed and there is sufficient oxygen, the only products are carbon dioxide (CO₂), water (H₂O), and heat—heat for cooking foods, heating homes, and drying clothes. Because conditions are rarely ideal, however, other products are frequently formed. When the oxygen supply is limited, carbon monoxide (CO) is a by-product:

2CH₄ + 3O₂ → 2CO + 4H₂O

This reaction is responsible for dozens of deaths each year from unventilated or improperly adjusted gas heaters. (Similar reactions with similar results occur with kerosene heaters.)

Alkanes also react with the halogens chlorine (Cl₂) and bromine (Br₂) in the presence of ultraviolet light or at high temperatures to yield chlorinated and brominated alkanes. For example, chlorine reacts with excess methane (CH₄) to give methyl chloride (CH₃Cl).

CH₄ + Cl₂ → CH₃Cl + HCl

With more chlorine, a mixture of products is obtained: CH₃Cl, CH₂Cl₂, CHCl₃, and CCl₄.

Fluorine (F₂), the lightest halogen, combines explosively with most hydrocarbons. Iodine (I₂) is relatively unreactive. Fluorinated and iodinated alkanes are produced by indirect methods. We will discuss the names and uses of halogenated hydrocarbons in Section 12.8 “Halogenated Hydrocarbons”.