Reactions of Alkenes with Hydrogen Halides
A concise revision guide to the addition reaction of alkenes with hydrogen halides, including HBr and HCl, the electrophilic addition mechanism, carbocation formation and why one product may form in greater amount with unsymmetrical alkenes.
- 5.4iii
- 5.6i-b
- 5.6ii-a
- 5.6ii-c
What these spec points say
- 5.4iii be able to describe the reactions of alkenes, limited to: the addition of hydrogen halides to produce mono-substituted halogenoalkanes
- 5.6i-b be able to describe the electrophilic addition mechanism of hydrogen bromide to ethene, including diagrams and evidence where possible
- 5.6ii-a be able to describe the electrophilic addition mechanism of hydrogen bromide to propene, including diagrams and evidence where possible
- 5.6ii-c know the relative stability of primary, secondary and tertiary carbocation intermediates
Before You Start
This page builds on GCSE work on covalent bonding, acids and the addition reactions of alkenes.
- A covalent bond is a shared pair of electrons between two atoms.
- Acids release hydrogen ions, H+, in solution; hydrogen bromide and hydrogen chloride dissolve in water to form acids.
- Alkenes undergo addition reactions: atoms add across the C=C double bond to give one product.
GCSE Recap: Covalent Molecules and Acids
Four quick GCSE questions on covalent bonds, acids and addition before you meet the hydrogen halides.
The Overall Reaction
Alkenes react with hydrogen halides such as hydrogen bromide, HBr, or hydrogen chloride, HCl, in an addition reaction.
The C=C double bond opens. The hydrogen atom adds to one carbon atom from the original double bond, and the halogen atom adds to the other carbon atom.
The functional group changes from an alkene to a halogenoalkane.
Key idea: This is addition because two atoms are added across the C=C double bond and the alkene becomes a saturated halogenoalkane.
Quick Check: Formula and Reaction Type
Work out the product of an addition that this page does not show.
Why HBr and HCl Act as Electrophiles
In hydrogen bromide, bromine is more electronegative than hydrogen. This means the H-Br bond is polar, with an uneven distribution of electron density.
The hydrogen atom carries a partial positive charge, Hδ+, while the bromine atom carries a partial negative charge, Brδ–.
The electron-rich π bond in the alkene is attracted to Hδ+. The hydrogen atom acts as the electrophile because it accepts electron density from the alkene π bond.
Electrophile: An electron-pair acceptor. In this reaction, Hδ+ is attracted to the electron-rich π bond and begins the electrophilic addition mechanism.
Exam focus: The electrophile is the Hδ+ atom of HBr, not Br–. The π bond attacks the hydrogen atom first.
Bromine pulls the bonding pair towards itself, so the Hδ+ end of H–Br is attracted to the π bond and acts as the electrophile.
Quick Check: Which End Attacks?
Decide whether the statement about hydrogen iodide is true or false.
Watch: one alkene, two different products
But-1-ene and HBr give two different products. Both form, but one forms far more. Which one, and why?
The Electrophilic Addition Mechanism
The π bond donates electron density to Hδ+, forming a new C-H bond. At the same time, the H-Br bond breaks by heterolytic fission, producing Br–.
After H+ has added, one carbon atom from the original C=C double bond becomes positively charged. This produces a carbocation intermediate.
The bromide ion, Br–, then donates a lone pair to the carbocation, forming the final bromoalkane product.
Step 1: The π bond attacks Hδ+
The alkene π bond is electron-rich, so it is attracted to the partially positive hydrogen atom in HBr.
Step 2: H-Br breaks heterolytically
Both electrons from the H-Br bond move to bromine, forming Br– and leaving a carbocation on the organic molecule.
Step 3: Br– attacks the carbocation
The bromide ion donates a lone pair to the positively charged carbon, forming a new C-Br bond.
The π bond reacts with Hδ+ first, then Br- attacks the carbocation intermediate to form the halogenoalkane.
Quick Check: Run the Mechanism
Follow hydrogen iodide and oct-4-ene through the mechanism, one step at a time.
Unsymmetrical Alkenes Can Form More Than One Product
When an alkene is unsymmetrical, HBr or HCl can add in two different ways. This is because H+ can add to either carbon atom of the C=C double bond.
Each possible route forms a different carbocation intermediate. These carbocations can have different stabilities, so the products are not always formed in equal amounts.
Route 1
H+ adds to one carbon atom of the C=C bond, forming one possible carbocation intermediate.
Route 2
H+ adds to the other carbon atom of the C=C bond, forming a different carbocation intermediate.
Key idea: The major product usually forms from the pathway that produces the more stable carbocation intermediate.
Quick Check: Compare the Two Routes
Drag the words and numbers into place to compare the two carbocations.
Why One Product Forms in Greater Amount
A carbocation is an organic ion with a positively charged carbon atom. Carbocations are stabilised when alkyl groups are attached to the positively charged carbon.
Alkyl groups are electron-releasing. They help spread out and reduce the positive charge, making the carbocation less reactive and more stable.
Because the more stable carbocation is formed more readily, the reaction proceeds mainly through that pathway. This leads to a higher yield of the corresponding product.
| Carbocation type | Alkyl groups attached to C+ | Relative stability |
|---|---|---|
| Primary | One alkyl group | Less stable |
| Secondary | Two alkyl groups | More stable |
| Tertiary | Three alkyl groups | Most stable |
Exam focus: Explain the major product by comparing carbocation stability, not just by stating which product forms.
Alkyl groups stabilise carbocations by releasing electron density towards the positively charged carbon.
The major product comes from the more stable carbocation: the one with more alkyl groups attached to the positive carbon.
HBr and Propene: Major and Minor Products
Choose a step to watch HBr add to propene by two routes, compare the two carbocations and see why 2-bromopropane is the major product.
© Dr. Mohammed Al-Fatah – onlinelearningsystem.net
Quick Check: Explain the Major Product
Write a short explanation, then compare it with the mark points and the model answer.
Quick Check: Pick the Accurate Statement
In each round, choose the one statement that is accurate.
FAQs
These questions secure the electrophile and major-product reasoning that HX questions reward.
Why does the hydrogen atom, not the bromine atom, react with the π bond first?
Bromine is more electronegative than hydrogen, so H-Br is polar with Hδ+. The electron-rich π bond is attracted to Hδ+ and donates its electron pair to it. Br– only attacks once the carbocation has formed.
Does but-2-ene give a major and a minor product with HBr?
No. But-2-ene is symmetrical, so adding H+ to either carbon of the C=C bond gives the same secondary carbocation. Only one product forms: 2-bromobutane.
Why is a tertiary carbocation more stable than a primary one?
A tertiary carbocation has three alkyl groups on the positive carbon, and each releases electron density towards it. This spreads out and reduces the positive charge more than the single alkyl group of a primary carbocation.
Is the minor product formed at all?
Yes, in a small amount. The less stable carbocation still forms some of the time, so a mixture results. For an unsymmetrical alkene, name both the major and the minor product.
Does HCl add to alkenes in the same way as HBr?
Yes. H-Cl is polar with Hδ+, so it adds by the same electrophilic addition mechanism through a carbocation. Ethene and HCl give chloroethane, a halogenoalkane.
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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