IB Chemistry R3.4 R3.4.3
R3.4.3 SL

Heterolytic Fission and Curly Arrows

Key Definition

Heterolytic fission is the breaking of a covalent bond where both bonding electrons remain with one of the two fragments formed. This produces two oppositely charged ions.

Heterolytic vs Homolytic Fission

There are two ways a covalent bond can break. In R3.4 we focus on heterolytic fission, where electron pairs stay together.

Heterolytic Fission

Both electrons go to one fragment.

A:B → A⁺ + :B⁻

Produces ions. Shown with a double-headed curly arrow.

Homolytic Fission

One electron goes to each fragment.

A:B → A· + ·B

Produces radicals. Shown with single-headed fish-hook arrows (R3.3).

Forming Ions by Heterolytic Fission

When a bond between two atoms of different electronegativity breaks heterolytically, the more electronegative atom takes both electrons.

Heterolytic Fission of C-Br Bond Heterolytic Fission of C-Br Bond CH₃ Br Both electrons move to Br CH₃⁺ Carbocation (lost both electrons) + Br⁻ Bromide ion (gained both electrons) Br is more electronegative than C, so the bonding pair moves to Br

Curly Arrow Rules

A curly arrow (double-headed) represents the movement of an electron pair. You must follow these rules when drawing them.

Rules for Drawing Curly Arrows

  1. The arrow starts from the source of the electron pair (a lone pair or the centre of a bond)
  2. The arrow points to the destination (the atom accepting the electron pair)
  3. The arrow must be double-headed (showing a pair of electrons, not a single electron)
  4. Do not confuse with fish-hook arrows (single-headed), which show single electron movement in radical reactions (R3.3)

Examples of Ion Formation

Bond Heterolytic fission produces Why?
C-ClC⁺ + Cl⁻Cl is more electronegative
C-BrC⁺ + Br⁻Br is more electronegative
C-IC⁺ + I⁻I is more electronegative
H-ClH⁺ + Cl⁻Cl is more electronegative

Think About It

How do you know which fragment ends up with the negative charge after heterolytic fission?

The more electronegative atom takes both bonding electrons. Since it gains the electron pair, it becomes the negatively charged ion. The atom that loses the electrons becomes positively charged.

Common Exam Mistakes

  • Using fish-hook (single-headed) arrows instead of curly (double-headed) arrows. Heterolytic fission involves pairs of electrons.
  • Drawing the curly arrow pointing the wrong way. It must go from the bond to the more electronegative atom.
  • Confusing heterolytic fission (produces ions) with homolytic fission (produces radicals).
Study this topic on the go

Get flashcards and quizzes in ChemEasy, or plan your revision with ChemPlan IB.

See our apps →
← R3.4.2 Nucleophilic Sub.R3.4.4 Electrophiles →