CHM311:PhysicalOrganicChemistryProblemSet1

Instructions:

You have a choice of submitting electronically to harinath@iiserpune.ac.in; or a neatly written hard copy with attached graphs.
The last date for submission is Friday, Sep 13, 2013
You can discuss and collaborate but the final submitted version must be yours and written (or typed) in your own words
Be prepared to make a presentation in class to defend your answer
Each problem is worth 15 marks
Use values from Clayden

1. The acidity of a series of substituted benzyldimethylammonium ions has been measured. Determine whether these data are
correlated by the Hammett equation. What is the value of?

2. The following pKas of a series of phenyl-tetramethyl-guanidinium structures are listed below. Using the Hammett relationship,
decipher whether there is a correlation between pKa and substituents? Explain. (for 4-CF3 =0.54)
X
H
NO2
CN
CF3
Cl
Br
CH3
OCH3

pKa
12.2
9.8
10.9
11.4
11.7
11.6
12.4
12.6

3.
a)

b)

The equilibrium between a carbonyl compound such as cyclopentanone (see below) and its hydrate usually favors the
aldehyde or ketone. Propose an arrow pushing mechanism for this equilibrium. Draw an energy profile to express this and
mark the difference between the free energy. In a similar experiment, cycopropanone shows an entirely different
equilibrium that is in favor of the product. Comment on this observation.

The equilibrium constants for cyanohydrin formation K1 and K2 are measured. Assume that the K1 is 5 and K2 is 200.
Calculate G1 & G2 for the two equilibria at 25 C. Rationalize the differences in the position of these equilibria.

4. For the ionization equilibrium given below, calculate G and S at 298 K. Draw a Hammett plot for this equilibrium and calculate
. Comment on the sign and magnitude of .

5. For the following equilibrium, the value of equilibrium constant was determined over a range of temperatures. Graphically
determine H and S.

Ar
S
S
Ar

Ar

Ar

-4
6. The rate constant for this reaction was found to be 1.56 x 10 s1. When the hydrogen atoms marked in bold are replaced by
-4
deuterium, the rate constant for this reaction was found to be 1.34 x 10 s1. Calculate the kinetic isotope effect. For the following
reaction, propose a reasonable mechanism and clearly label the rate determining step.

HO

H
conc. H2SO4

H
O

7. The following data was obtained when the reaction described below was conducted. Derive a rate law for this reaction. What is
the order of the reaction? Can you propose a mechanism that accounts for this rate law?

Time (h)

[OH]

[ketone]

10

10

2.31

3.68

1.3

1.35

0.91

0.498

0.7

0.183

0.57

0.067

0.48

0.025

8. Sulfonylation of naphthalene proceeds to produce two products:

Temperature
%A
%B

80C
95
5

180C
10
90

(a) Propose a reasonable arrow-pushing mechanism for the formation of A and B.

(b) Draw out an energy profile that is consistent with the above observations with clear labels for relative energies for each product
(c) If A is the preferred product at low temperatures, how would you account for the formation of B as the major product at higher
temperature?
(d) What strategy should one adopt if we want to get exclusively (>99%) of A?
9. Assume that the first step is an equilibrium and the second step is the rate-determining step, write out a rate law for the reaction.
Draw out an energy profile for the reaction and clearly label the rate determining step.

10.
a)

Reaction of the following bromides with tBuOK in tert-butanol favors elimination reaction. The rate constant for one was
found as 4.1 x 10-3 Lmol-1s-1 while the other was 8.0 x 10-6 Lmol-1s-1. Draw out the two compounds in the respective chair
conformations and explain the rate differences. Identify which bromide would react slower.

b)

Rationalize the observation that A forms an acetal much slower than B