This is an empirical rule based on Markovnikov's experimental observations on the addition of hydrogen halides to alkenes.
The rule states that : "when an unsymmetrical alkene reacts with a hydrogen halide to give an alkyl halide, the hydrogen adds to the carbon of the alkene that has the greater number of hydrogen substituents, and the halogen to the carbon of the alkene with the fewer number of hydrogen substituents"
Courtesy: Dr. Ian Hunt, Department of Chemistry, University of Calgary
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