Halogenation of Alkanes

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What is Halogenation Reaction?

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Halogenation is the term, which can be defined as a chemical reaction that involves the addition of either one or more halogens either to material or compound. The halogenation's stoichiometry and pathway depend on the functional groups and structural features of the organic substrate and the specific halogen. Also, inorganic compounds like metals undergo halogenation.

What is Halogenation of Alkanes?

Halogenation of an alkane that produces a hydrocarbon derivative, where either one or more halogen atoms have been substituted for the hydrogen atoms.

Notoriously, alkanes are unreactive compounds only because they are non-polar and lack the functional groups, where the reactions can occur. Therefore, free-radical halogenation provides a method by which alkanes are functionalized.

However, a severe limitation of radical halogenation is the count of similar C-H bonds, present in all but the simplest alkanes, so the selective reactions are difficult to achieve.

General Reaction of Alkanes

Alkane halogenation is given as an example of a substitution reaction, which is a type of reaction that often takes place in organic chemistry. A substitution reaction is a chemical reaction, where a part of a small reacting molecule replaces either an atom or the atom's group on a hydrocarbon or its derivative.

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The general equation substituting a single halogen atom for one of the hydrogen atoms of an alkane can be given as follows.

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General Features of Halogenation of Alkanes

The features of halogenation of alkanes can be listed as follows.

  • The R-H notation is the alkane's general formula. In this case, 'R' represents an alkyl group. At the same time, the addition of a hydrogen atom to an alkyl group forms the alkyl group's parent hydrocarbon.

  • The R-X notation on the product side can be represented as the general formula for a halogenated alkane. Where, in this case, 'X' is the general symbol for a halogen atom.

  • The reaction conditions can be noted by placing these conditions on the equation arrow, which separates the reactants from products. Halogenation of an alkane needs the presence of light or heat.

Chlorination of Methane by Substitution

In the halogenation of an alkane, the alkane is stated to undergo either chlorination, fluorination, iodination, or bromination depending on the identity of the halogen reactant. Bromination and Chlorination are the alkane halogenation reactions that are used widely. In general, the fluorination reactions proceed too quickly to be useful, whereas iodination reactions go too slowly.

Usually, halogenations result in the formation of a mixture of products instead of a single product. Also, there results in more than one product because here, more than one alkane or one hydrogen atom can be replaced with the halogen atoms.

When chlorine and methane are heated to a high temperature in the presence of light, they react as follows.

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Mechanism of Halogenation of Alkanes

This halogenation of alkanes mechanism takes place in three steps as given below.

  1. Initiation Step

The Cl-Cl bond of the elemental chlorine undergoes hemolysis when irradiated with UV light. This process yields two chlorine atoms, which are also called chlorine radicals.

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  1. Propagation Step

One of the chlorine radicals abstracts a hydrogen atom from methane to form the methyl radical. In turn, the methyl radical abstracts a chlorine atom from one of the chlorine molecules, and then, the formation of chloromethane takes place. Also, the second step of the propagation regenerates a chlorine atom, and these steps repeat several times until the termination happens.

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  1. Termination Step

The termination happens when a chlorine atom either reacts with the other chlorine atom to generate Cl2, or a chlorine atom reacts with a methyl radical to produce chloromethane, which constitutes a minor pathway, where, how the product is made. Also, two methyl radicals can combine to form ethane, which is a minor by-product of this reaction.

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At this step, this reaction does not stop. But, however, since the chlorinated methane product can be allowed to react with additional chlorine to form polychlorinated products.

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By controlling the reaction conditions, including the ratio of chlorine to methane, it can be possible to favor the formation of either one or another possible chlorinated methane product.

Organic Compounds Halogenation

Halogenation by Reaction Type

There exist many pathways to halogenate organic compounds, like ketone halogenation, free radical halogenation, electrophilic halogenation, and the halogen addition reaction. These enzymatic halogenation reactions on the organic molecule are also popular, which either follow electrophilic, nucleophilic, or free radical mechanisms. The structure substrate is one factor, which determines the pathway.

Halogenation by the Halogen Type

The halogen influences the halogenation facility. Chlorine and Fluorine are more electrophilic and also aggressive halogenating agents. In comparison, bromine is a weaker halogenating agent compared to both chlorine and fluorine. At the same time, iodine can be given as the least reactive of them all. The dehydrohalogenation facility follows the reverse trend, where the iodine can be removed most easily from organic compounds, and the organofluorine compounds are highly stable.

Nature of the Mechanism of Alkanes' Halogenation

In the presence of either heat or ultraviolet light (UV), the halogen reaction with an alkane results in a haloalkane formation (which is an alkyl halide). This phenomenon can be explained using the reaction mechanism - A mechanism to halogenate. In the methane molecule, the carbon‐hydrogen bonds are the low-polarity covalent bonds.

Did You Know?

  • Electrophiles, which attach to the double bond of alkenes, weaken the ÿ bond. In contrast to the alkene hydrogenation, catalysts do not allow adding chlorine or molecular bromine to generate nearby dichalcogenides.

FAQ (Frequently Asked Questions)

1. What is the halogenation reaction of alkanes?

Halogenation can be described as a reaction that occurs with the addition of either one or more halogens to a substance. In the periodic table, Halogens form the 17th group, and they comprise compounds such as chlorine, fluorine, bromine, astatine, and iodine. The substance resulting from a halogenation reaction of alkanes is referred to as a halogenated compound.

2. Can halogenation of alkanes be given as a rearrangement reaction?

Generally, the alkanes' halogenation regiochemistry is determined by the available C – H bonds' relative weakness. Whereas, for the industrial processing of chlorinated methane, a free radical halogenation of alkanes can be used. It can be expressed as, CH4 + Cl2 → CH3Cl + HCl. Also, these free radical reactions can go with a rearrangement.

3. Explain the reaction of alkanes.

Alkanes (which are one of the essential organic compounds) are subjected to very few reactions. The two important reactions of alkanes are halogenation and combustion (which is, the substitution for a single halogen of single hydrogen on the alkane).