CHEMISTRY 2410

First Examination
Fall, 2012
Name:
Pledge:

10

15

30

25

20

TOTAL

100

PROBLEM 1.

Provide answers for each of the following:

A.

The pKas for acetic acid (CH3CO2H) and hydrochloric acid (HCl) are 5 and -7, respectively. Determine
the equilibrium constant (K) for the equation given below showing briefly how you came to your
conclusion.
K
HCl + CH3CO2

Cl

+ CH3CO2H

B.

Correlate the structures with the listed boiling points. Provide a rationalization for the observed
differences in physical properties.

: A. X = O

Observed boiling points: i. 80.7 C

B. X =CH2

ii. 88 C

C. X = NH

iii. 106 C

(5 points each, 10 points total)

PROBLEM 2.

Examine each of the pairs of compounds below and determine their relationship to each other as:
A.
Identical compounds (i.e., superimposable without bond rotation)
B.
Conformational isomers
C.
Constitutional isomers
D.
Different compounds
I.
CH3

CH3

H 3C

CH3

CH3
H

and CH3
H

II.
CH3

and CH3

CH3

CH3

III.
H

CH3

Br

and

Br

CH3

H
Br

H
H

Br

IV.
H
H

and

V.
H
CH3

H
CH3
CH3

CH3 H

CH3

and CH3 H

H
CH3

CH3

(3 points each, 15 points total)

PROBLEM 3.

Order the following compounds from most stable to least stable. Give the calculated destabilizing
energy in each case to support your ordering. A table of relevant energies is given at the end of the
problem.
A.

Consider the following trimethylcyclohexanes:

CH3

CH3

CH3

CH3

CH3

CH3
H3C

CH3

CH3

B.

II

III

Examine the conformations depicted:

CH3 H
CH3

CH3

CH3 H

CH3 H
CH3

CH3

CH3 H

II

CH3

H
CH3

CH3

CH3

III

C.

Evaluate these substituted decalins:

H

CH3
CH3

CH3
CH3

II

CH3
CH3

III

Useful Conformational Energies

1,3-diaxial CH3/H

0.9 kcal/mol

1,3-diaxial CH3/CH3

3.2 kcal/mol

CH3,CH3 gauche

0.9 kcal/mol

H,H eclipsed

0.1 kcal/mol

CH3,H eclipse

1.4 kcal/mol

CH3,CH3 eclipsed

2.5 kcal/mol

(10 points each, 30 points total)

PROBLEM 4.

Consider the substitution reaction below:

A.

Supply a clear, stepwise mechanism for this unimolecular reaction (SN1). Show all movement of
electrons and charges that accompany the transformation of the starting materials into products.
Br

OH
CH3 + HBr

B.

CH3 + H2O

Consider subjecting the following compounds to the reaction conditions given in part A and rank
them from most reactive to least reactive. Give a reason for your selections.
OH

CH3

OH

CH3
HO

C.

Draw an energy diagram (reaction energy versus reaction coordinate) consistent with your
supplied mechanism (in part A).

(25 points total)

PROBLEM 5.
Calculate the overall heats of reaction (H) for each of the transformations given below. Informed by
these calculations, decide the order of reactivity for these reactions from most likely to least likely.
(NOTE: See useful bond dissociation energies on the next page.)
OH

Br

+ H-Br

Reaction 1

OH

Cl

+ H-Cl

Reaction 2

+ H2O

Br

+ Br2

Reaction 3

+ H-Br

Cl

Reaction 4

+ H2O

+ Cl2

+ H-Cl

Useful Bond Dissociation Energies

H-Br
H-Cl
Br-Br
Cl-Cl
H-OH
Primary C-H
Primary C-Br
Primary C-Cl
Primary C-OH
Secondary C-H
Secondary C-Br
Secondary C-Cl
Secondary C-OH
Tertiary C-H
Tertiary C-Br
Tertiary C-Cl
Tertiary C-OH

87.5 kcal/mol
103 kcal/mol
46 kcal/mol
58 kcal/mol
119 kcal/mol
101kcal/mol
71 kcal/mol
84 kcal/mol
95 kcal/mol
98 kcal/mol
72 kcal/mol
84 kcal/mol
96 kcal/mol
96 kcal/mol
70 kcal/mol
84 kcal/mol
96 kcal/mol
(20 points)