In organic chemistry, Markovnikov’s rule is a principle that governs the addition of a proton (H+) or a Lewis acid to an alkene or alkyne, the proton or Lewis acid will add to the carbon atom that has more hydrogen atoms, For example, adding hydrogen halide to the alkenes follows this rule. It is given by Vladimir Markovnikov (Russian chemist) in 1870.

For example, when unsymmetrical reagents are added to the unsymmetrical alkenes. The negative part is added to carbon with fewer hydrogen atoms as shown below:

addition of hydrogen halide to alkenes

Examples of Markovnikov’s Rule

Addition of hydrogen halide to alkenes

The addition of hydrogen halide to the alkenes is a highly regioselective reaction. In this reaction, two isomeric alkyl halides are formed. However, one is formed in preference to the other.

addition of hydrogen halide to alkenes


mechanism for the additon of hydrogen bromide to 2methylpropene

In the above mechanism, the first step is the rate-determining step. The regioselectivity occurs in the second step. The stabilities of two carbocation control the product of this reaction.

  • Addition, according to Markovnikov’s rule

  • Addition, Based on Hoffman’s rule

addition of hydrogen halide to alkenes

Hydration of alkenes

The addition of water to the unsymmetrical alkenes follows Markownikov’s rule. According to this rule, the hydroxyl group of water attaches to the carbon of alkenes. Which has fewer hydrogens whereas hydrogen adds to the carbon with greater hydrogens.

Markovnikov's Rule example

Addition of hydrogen halide to the alkynes

The reaction of hydrogen halide to alkynes follows Markovnikov’s rule. This reaction is catalyzed by metallic halides.

addition of hydrogen bromide to alkynes

Related Resources

Concepts Berg

Why Does “Markovnikov’s Rule” Work?

This rule works on the basis of the formation of the most stable carbonium ion. However, it does not work in the presence of unsymmetrical alkene.

What are some exceptions to Markownikov’s rule?

Anti-Markovnikov is the exception to Markovnikov’s rule. These are the reactions following the free radical mechanism, instead of the electrophilic addition as suggested by Markovnikov.

What is the peroxide effect?

The addition of HBr to the unsymmetrical alkenes against Markovnikov’s rule is known as the peroxide effect or Anti Markovnikov’s rule. It follows a free radical mechanism.

Is Markownioff’s rule applicable when HBr is added to pent-2-ene?

The pent-2-ene is an unsymmetriocal alkene. Therefore Markovnikov’s is applicable to this reaction.

What is the product formed when pent 1 ene is reacted with HBr in the presence of H2O2?

When HBr is reacted with pent-1-ene in the presence of H2O2 1-bromopentane is formed.


  • Organic Chemistry tenth edition by Francis A. Carey (University of Virginia) and Robert M. Guiliano ( University of Villanova)
  • A textbook of Organic Chemistry by M.Younas (University of Punjab)
  • Anti-Markovnikov addition reaction (