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Electrophilic Addition Mechanism

A concise revision guide to addition reactions of alkenes, electrophiles, electron-rich π bonds and why the carbon-carbon double bond is the reactive centre in alkene chemistry.

Paper 2
Topic 6: Organic Chemistry I
9CH0/02
Dr. Mohammed Al-Fatah

Written by: Dr. Mohammed Al-Fatah

Chemistry specialist revision notes for A Level Chemistry.

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1

Addition Reactions of Alkenes

An addition reaction is a reaction in which two reactant molecules combine to form a single product molecule.

Alkenes commonly undergo addition reactions because their carbon-carbon double bond can be broken and replaced by new single bonds.

This is why the C=C bond is the functional group that controls the characteristic reactions of alkenes.

Key idea: In an alkene addition reaction, atoms add across the C=C double bond and only one organic product molecule is formed.

Addition across a double bond

The double bond opens up, allowing new atoms or groups to attach to the two carbon atoms from the original C=C bond.

2

Why the π Bond Reacts

In an alkene, the π bond is weaker than the σ bond, so it requires less energy to break during a reaction.

The π bond also contains a region of high electron density. This exposed electron density is especially attractive to electron-seeking species.

Because the π bond is both weaker and more exposed than a σ bond, it is particularly susceptible to attack by electrophiles.

Exam focus: Link alkene reactivity to the exposed, electron-rich π bond rather than simply saying that alkenes have a double bond.

Electron-rich π bond

The π bond forms exposed electron density above and below the molecular plane, making the alkene attractive to electrophiles.

3

Electrophiles

An electrophile is an electron pair acceptor.

Electrophiles are attracted to regions of high electron density. In alkenes, this means the electrophile is drawn towards the electron-rich π bond.

This attraction begins the electrophilic addition mechanism.

E⁺

Electrophile: A species that accepts an electron pair from an electron-rich region during a chemical reaction.

4

The Electrophilic Addition Mechanism

In electrophilic addition, the π bond breaks and new single bonds are formed. The electrophile accepts an electron pair from the alkene.

At this stage, students must be careful with curly arrows. A curly arrow shows the movement of an electron pair, so the arrow should start from a bond or lone pair, not from a positive charge.

1. Attraction

The electrophile is attracted to the high electron density in the π bond.

2. Bond breaking

The π bond breaks because it is weaker than the σ bond.

3. New bonds form

New single bonds form to give an addition product.

Remember: Electrophilic addition happens because the π bond is electron-rich, exposed and relatively easy to break.

5

Exam Link: Why Alkenes React This Way

Exam answers should connect three ideas: the alkene contains a C=C bond, the π bond has high electron density, and electrophiles are attracted to this electron-rich region.

It is not enough to write that alkenes are reactive because they have a double bond. The explanation needs to identify the role of the π bond and the electrophile.

Exam phraseWhy it mattersCommon mistake to avoid
π bond has high electron densityExplains why an electrophile is attracted to the alkene.Only saying that the double bond is reactive.
Electrophile accepts an electron pairLinks the definition of electrophile to the mechanism.Calling the electrophile an electron donor.
π bond breaks and new single bonds formExplains why the reaction is an addition reaction.Describing substitution instead of addition.

Check Your Understanding

Use these short activities to check the key ideas before moving on to reactions of alkenes.

Electrophilic addition reaction explained visually.
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Copyright notice: This OLS revision content, including the explanations, layout, diagrams, tables and embedded learning structure, is authored for Online Learning System by Dr. Mohammed Al-Fatah. It may not be copied, reproduced, redistributed or adapted without written permission.