Advices For Studying Organic Chemistry

(Wang) #1

  1. The first step is highly endothermic and has high free energy of activation.

    1. It involves heterolytic cleavage of the C–Cl bond and there is no other bonds are
      formed in this step.

    2. The free energy of activation is about 630 kJ mol–1 (150.6 kcal mol–1) in the gas
      phase; the free energy of activation is much lower in aqueous solution –– about
      84 kJ mol–1 (20 kcal mol–1).



  2. A free-energy diagram for the SN1 reaction of tert-butyl chloride with water:


Figure 6.7 A free-energy diagram for the SN1 reaction of tert-butyl chloride with
water. The free energy of activation for the first step, ∆G‡(1), is much
larger than ∆G‡(2) or ∆G‡(3). TS(1) represents transition state (1),
and so on.



  1. The C–Cl bond of tert-butyl chloride is largely broken and ions are beginning to
    develop in the transition state of the rate-determining step:


Cδ+

CH 3

CH 3

CH 3 Clδ−
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