
Concept explainers
(a)
Interpretation: The rate constant for first order solvolysis reaction of
Concept introduction:
Tertiary or secondary halides undergo fastest unimolecuar substitution as they can readily form the tertiary carbocation followed by secondary and least reactive are primary.
(b)
Interpretation: The rate constant for first order solvolysis reaction of
Concept introduction: Haloalkane solvolysis with ethanol, methanol or water is a typical example for unimolecuar substitution. It proceeds via two-step mechanism. The first slow step that determines rate is the removal of leaving group from the substrate haloalkane and generates a carbocation. Since the rate is only governed by substrate alone and no other nucleophile or solvent it is termed as unimolecuar substitution. The final step is attack of nucleophile on carbocation generated and formation of racemic products.
Tertiary or secondary halides undergo fastest unimolecuar substitution as they can readily form the tertiary carbocation followed by secondary and least reactive are primary.
(c)
Interpretation: The rate constant for first order solvolysis reaction of
Concept introduction: Haloalkane solvolysis with ethanol, methanol or water is a typical example for unimolecuar substitution. It proceeds via two-step mechanism. The first slow step that determines rate is the removal of leaving group from the substrate haloalkane and generates a carbocation. Since the rate is only governed by substrate alone and no other nucleophile or solvent it is termed as unimolecuar substitution. The final step is attack of nucleophile on carbocation generated and formation of racemic products.
Tertiary or secondary halides undergo fastest unimolecuar substitution as they can readily form the tertiary carbocation followed by secondary and least reactive are primary.

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Chapter 7 Solutions
ORGANIC CHEMISTRY (LL)-PACKAGE
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- Consider the following decomposition reaction of N2O5(g): For the reaction 2 N2O5(g) → 4 NO2(g) + O2(g), the following mechanism has been proposed: N2O5 → NO2 + NO3 (K1) NO2 + NO3 → N2O5 (k-1) NO2 + NO3 → NO2 + O2 + NO (K2) NO + N2O5 → NO2 + NO2 + NO2 (K3) Indicate whether the following rate expression is acceptable: d[N2O5] = -k₁[N₂O₂] + K¸₁[NO₂][NO3] - K¸[NO₂]³ dtarrow_forwardIn a reaction of A + B to give C, another compound other than A, B or C may appear in the kinetic equation.arrow_forwardFor the reaction 2 N2O5(g) → 4 NO2(g) + O2(g), the following mechanism has been proposed: N2O5 →> NO₂+ NO3_(K1) NO2 + NO3 → N2O5 (k-1) NO2 + NO3 → → NO2 + O2 + NO (K2) NO + N2O5- NO2 + NO2 + NO2 (K3) d[N₂O5] __2k‚k₂[N2O5] Indicate whether the following rate expression is acceptable: dt k₁₁+ k₂arrow_forward
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