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.
GCSE Recap: What Alkenes Do
Three quick questions on the reactions of alkenes that you met at GCSE.
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.
Quick Check: Addition or Not?
Decide quickly whether each equation shows an addition reaction.
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.
Quick Check: Spot the Errors
Click the five wrong words in a student's description of the π bond.
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.
Electrophile: A species that accepts an electron pair from an electron-rich region during a chemical reaction.
Quick Check: Find the Electrophile
Identify the electrophile in a reagent that this page has not used.
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.
Quick Check: Order the Mechanism
Put the events of an electrophilic addition you have not seen into the correct order.
Quick Check: Hydrogen Iodide and Cyclohexene
In each round, pick the one accurate statement about this addition.
The Inductive Effect and Markovnikov Addition
This section is the summary; the full explanation with worked examples is on the Markovnikov Addition and the Inductive Effect page.
Cambridge asks you to describe and explain the inductive effect of alkyl groups on the stability of the carbocations formed during electrophilic addition, and to use this to explain Markovnikov addition.
An alkyl group is electron-releasing: it pushes electron density along the σ bond towards the positively charged carbon. This spreads out and reduces the positive charge, which stabilises the carbocation. The more alkyl groups attached to the positive carbon, the greater the stabilisation.
| Carbocation | Alkyl groups on C+ | Inductive stabilisation | Relative stability |
|---|---|---|---|
| Primary | one | least | lowest |
| Secondary | two | more | intermediate |
| Tertiary | three | most | highest |
When a hydrogen halide such as HBr adds to an unsymmetrical alkene such as propene, two carbocations are possible. The reaction proceeds mainly through the more stable secondary carbocation, so the hydrogen atom ends up on the carbon that already carried more hydrogen atoms and bromine adds to the other carbon. This is Markovnikov addition, and 2-bromopropane is the major product.
Exam focus: Explain the major product by comparing carbocation stability and naming the inductive effect of the alkyl groups. Cambridge expects the mechanism to be drawn for bromine with ethene and for hydrogen bromide with propene.
Quick Check: Predict the Major Product
Use carbocation stability to predict the products from alkenes other than propene.
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 phrase | Why it matters | Common mistake to avoid |
|---|---|---|
| π bond has high electron density | Explains why an electrophile is attracted to the alkene. | Only saying that the double bond is reactive. |
| Electrophile accepts an electron pair | Links the definition of electrophile to the mechanism. | Calling the electrophile an electron donor. |
| π bond breaks and new single bonds form | Explains why the reaction is an addition reaction. | Describing substitution instead of addition. |
Quick Check: Explain Why the Alkene Reacts
Write a short explanation, then compare it with the mark points and the model answer.
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Some ionic radii are shown.
| Ion | Ionic radius / nm |
|---|---|
| Na+ | 0.102 |
| K+ | 0.138 |
| F− | 0.133 |
| Cl− | 0.180 |
Which compound has the strongest ionic bonding?
Explain why the metallic bonding in magnesium is much stronger than that in sodium.
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.
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