IB Chemistry R3.4 R3.4.8
R3.4.8 HL

Electrophilic Addition Mechanisms

Mechanism of HBr addition to alkenes and Markovnikov’s rule.

📘 IB Understanding

Electrophilic addition involves an electrophile (electron-pair acceptor) attacking the electron-rich C=C double bond. The π-bond breaks and two new σ-bonds form.

Mechanism: Addition of HBr to Propene

Step 1

The π-electrons of the C=C attack the Hδ⁺ of H–Br (the electrophile). The H–Br bond breaks heterolytically, forming a carbocation and Br⁻.

Step 2

The Br⁻ ion (nucleophile) attacks the carbocation, forming the haloalkane product.

Markovnikov’s Rule

Markovnikov’s Rule

When HX adds to an unsymmetrical alkene, the hydrogen atom bonds to the carbon that already has more hydrogen atoms. This produces the more stable (more substituted) carbocation intermediate.

Carbocation Stability

Tertiary > Secondary > Primary > Methyl

More alkyl groups stabilise the positive charge via the inductive effect (electron donation)

📋 Exam Tip

Always show curly arrows from the electron-rich region to the electron-poor region. In step 1, draw the arrow from the C=C bond to the H of HBr. In step 2, draw from the lone pair on Br⁻ to the C⁺.

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