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Kinetic and Organic Reaction Mechanism

Chapter 5

Thermodynamics and kinetics as a mean of

investigating the mechanisms of chemical reactions.
Relationship for Gibbs Energy (LFER). Hammett's
equation. Taft's equation. Grunwald-Winstein Equation.
Swain-Scott equation


1. Relate the substituent constant values of table:Hammett constants, to
the electron donating or -withdrawing character of each substituent. How
does this compare with qualitative predictions of substituent effects on
acidity? Why might you expect σm and σp values for the same substituent
to be different
2. Match the ρ values with the appropriate reactions. Explain your reasoning.
Reaction constants: +2.45, +0.75, -2.39, -7.29.
a) nitration of substituted benzenes
b) ionization of substituted benzenthiols
c) ionization of substituted benzenephosphonic acids
d) reaction of substituted N,N-dimethylanilines with methyl iodide
3. Determine the value of ρ for the reaction shown from the data given:
4. The basicity of a series of substituted benzyldimethylamines has been
measured. Determine whether these basicity data are correlated by the
Hammet equation. What is the value of ρ ? What interpretation do you put
on its sign?
5. Under strongly alkaline conditions (methoxide ion) HCl is eliminated from
2-chloro-2-methyl-1-phenylpropane to give 2-methyl-1-phenylprop-1-ene.

From the following results for the effect of substituents in the phenyl ring on
the rate of the reaction, determine the Hammett value for this reaction
6. The following partial rate factors(kf) were obtained for the bromination of
monosubstituated benzenes hy hypobromous acid in 50 % aqueous dioxan
containing perchloric acid.

Show that the values of kf fit a Hammet equation using σ+ values and
determine the value of ρ. Predict the kf value for p-fluorobenzene.
Do these results allow you to distinguish between H2+OBr and Br + as the
brominated spieces?
7. The mechanism of semicarbazone formation from benzaldehyde involves
condensation, followed by elimination of water:

The second step ( k2) is acid-catalysed. The effect of substituents in the

benzene ring of benzaldehyde upon the rate of reaction depends upon the
pH, as shown by the following figures.

Calculate the Hammett ρ value at both pH's and explain the difference in
terms of a change in the rate determining step.
8. The reaction between ethyl chloroformate and aniline is a two-step
process, involving addition followed by elimination

The following kinetic data were obtained for the effect of substituents in the
aniline on the rate of reaction:

What may be deduced about the rate determining step in this reaction from
the plot of log kobs against σ-.
Suggest an experimental check on the proposed mechanism.
9. In the presence of a base (potassiun t-butoxide in t-butanol) 2-phenyl-
ethylbenzene sulphonate undergoes elimination to give styrene and the
mechanism of the reaction is E2.

A kinetic study of the effect of substituents in ring B, with same substituent

in ring A, on the rate of reaction gives a good Hammett plot with slope of ρ.
Values of ρ have been determined as a function of the substituent in ring A,
with following results.

(A more positive ρ value indicates greater accumulation of negative

charge.) How does the trend in the values of ρ reflect changes in the
transtion state with different substituents in ring A?
10. Arrange the following substituted benzoate esters in order of their rate
of hydrolysis under basic conditions. Does this correlate to the substituent
values used for Hammett plots?