Sn1 Versus Sn2 Competition
For the hydrolysis of a secondary alkyl bromide, switching from aqueous ethanol to pure water as solvent is expected to favour which pathway and for what reason?
Select the correct option:
Solution
SN1, because the more polar protic solvent stabilises the developing carbocation and halide ion
The rate-determining step of an SN1 reaction is heterolytic ionisation of the carbon-halogen bond, which generates a carbocation and a halide ion in the transition state. A highly polar protic solvent like water solvates and stabilises both of these developing charges far better than a less polar mixed solvent, lowering the energy of the ionisation transition state and accelerating the SN1 path. Moving from aqueous ethanol to pure water therefore increases solvent polarity and shifts a borderline secondary substrate toward SN1. The SN2 nucleophile-concentration option is wrong because increased solvation of charges, not concentration, dominates here, and stronger solvation actually hampers the SN2 nucleophile. The claim that water lowers the SN2 backside-attack barrier is incorrect since SN2 is disfavoured by strongly solvating protic media. The reduced-polarity SN2 option is internally contradictory because water is more polar, not less. The secondary substrate is significant here because it lies at the SN1/SN2 borderline, so changing the solvent is enough to tip the balance, whereas a clearly primary or clearly tertiary halide would stay committed to one mechanism. This illustrates the general principle that protic solvents of high dielectric constant accelerate reactions whose rate-determining step creates separated charges. This matches the NCERT discussion of solvent effects. Sanity check: more polar protic solvent stabilises ions, so the ion-forming SN1 route is favoured.
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About This Question
- Subject
- chemistry
- Chapter
- organic compounds containing halogens
- Topic
- sn1 versus sn2 competition
- Difficulty
- Hard
- Year
- 2025
Solution
Correct Answer:
SN1, because the more polar protic solvent stabilises the developing carbocation and halide ion
The rate-determining step of an SN1 reaction is heterolytic ionisation of the carbon-halogen bond, which generates a carbocation and a halide ion in the transition state. A highly polar protic solvent like water solvates and stabilises both of these developing charges far better than a less polar mixed solvent, lowering the energy of the ionisation transition state and accelerating the SN1 path. Moving from aqueous ethanol to pure water therefore increases solvent polarity and shifts a borderline secondary substrate toward SN1. The SN2 nucleophile-concentration option is wrong because increased solvation of charges, not concentration, dominates here, and stronger solvation actually hampers the SN2 nucleophile. The claim that water lowers the SN2 backside-attack barrier is incorrect since SN2 is disfavoured by strongly solvating protic media. The reduced-polarity SN2 option is internally contradictory because water is more polar, not less. The secondary substrate is significant here because it lies at the SN1/SN2 borderline, so changing the solvent is enough to tip the balance, whereas a clearly primary or clearly tertiary halide would stay committed to one mechanism. This illustrates the general principle that protic solvents of high dielectric constant accelerate reactions whose rate-determining step creates separated charges. This matches the NCERT discussion of solvent effects. Sanity check: more polar protic solvent stabilises ions, so the ion-forming SN1 route is favoured.
This hard difficulty chemistry question is from the chapter organic compounds containing halogens, covering the topic of sn1 versus sn2 competition. It appeared in the 2025 exam.
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