CHM 4411 F15

Exam III 3 December 15

Name:
UFID:
INSTRUCTIONS: Read through the entire exam before you begin. Answer all of the questions.
For questions involving calculations, show all of your work HOW YOU DO THE
CALCULATIONS IS JUST AS IMPORTANT AS OBTAINING THE CORRECT
ANSWER. Read all questions carefully and watch units.
No points will be deducted for propagation of errors. If the answer to an earlier section is
incorrect, and a later section relies on that answer, the latter problem will be graded as if the
former section were correct.
The entire exam is worth a total of 100 points. The last page contains a list of equations and
potentially useful information for reference.

Good Luck!

Question
1
2
3
4
5
6
7
Bonus
Total

CHM 4411 F15

Exam III

Possible
points
24
10
10
15
14
7
20
3
100

Points
earned

Page 1 of 10

1. (2 pts each) Multiple Choice: Circle the best response.

(a) In the derivation of Transition State Theory, an assumption is made that the reactants are:
Unstable relative to the products

In equilibrium with the products

Hard sphere molecules

In equilibrium with an activated complex

(b) The rate constant in the rate law

Rate =

k[H 2 ][Br2 ]1/2

[HBr]

has units of:

M-1 s-1

M-1/2 s-1

M1/2 s-1

s-1

(c) Which of the following reactions must occur via a multiple-step reaction pathway:

BaCO3 ! !
BaO + CO2
3I + H 2O2 + 2H + ! !
I 3 + 2H 2O
Cl2 + C2O4 H 2 ! !
2CO2 + 2Cl + 2H +
2N 2O5 ! !
4NO2 + O2

(d) The rate of a chemical reaction depends on the total number of collisions between reactant
molecules. The total number of collisions is favored by:
smaller collision cross section and low molecular velocities
smaller collision cross section and high molecular velocities
larger collision cross section and low molecular velocities
larger collision cross section and high molecular velocities

CHM 4411 F15

Exam III

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(e) The half life of the overall reaction A B which is zero order in A is:

1/ (k[A]o )

[A]o / (2k)

k[A]o

[A]o / (4k)

!!
!
C + D , the relaxation time which characterizes
(f) For an equilibrium reaction A + B
!
the return of the perturbed system to equilibrium is given by:

1 = k1{[A]eq +[B]eq }+ k1{[C]eq +[D]eq }

If is measured at several different values of [A]eq and [B]eq, then from this experimental
data, what parameters can be evaluated?
k1 only

k-1 only

k1 and Keq only

k1, k-1 and Keq

(g) Compare two reactions with activation energies Ea1 and Ea2, and pre-exponential factors
A1 and A2. The rate constant for reaction 2 is always greater than the rate constant for
reaction 1 when:

Ea1 > Ea2

and

A1 > A2

Ea1 < Ea2

and

A1 > A2

Ea1 > Ea2

and

A1 < A2

Ea1 < Ea2

and

A1 < A2

(h) All of the following are TRUE statements about kinetic studies EXCEPT:
It is not always possible to determine reaction order with respect to each reactant in a
chemical reaction
Reaction mechanisms inferred from experimental results can not be proven
The initial rate method can not be used to determine rate laws if a product acts to inhibit
or accelerate the reaction
The method of flooding can be used to determine reaction orders when there are several
reactant species

CHM 4411 F15

Exam III

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2. (10 pts) Consider a reaction with an activation energy of 83.1 kJ/mol running at room
temperature (300 K). If you wanted to double the rate of this reaction (using the same initial
concentration of reactants,) at what temperature should you run the reaction?

CHM 4411 F15

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3. (10 pts) Consider the acid-catalyzed polyesterification reaction. Show that the time required
to go from p = 0.98 to p = 0.99 is very close to the time to reach p = 0.98 from the start of the
polymerization, assuming the reaction is externally catalyzed and contains an equimolar
mixture of diacid and diol.

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4. (15 pts) Consider the following reaction mechanism:

!!

!!

!!

If ! = ! = 100! , sketch the concentration dependence of [A], [B], [C], and [D] as a
function of time using one set of axes. Describe in words what your graph illustrates.

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5. (14 pts) One mechanism for the decomposition of N2O5 has been proposed:
1
N 2O5 !k!
NO2 + NO3

k2
NO2 + NO3
NO2 + O2 + NO
3
NO2 + NO3 !k!
N 2O5
4
NO + NO3 !k!
2NO2

Derive an expression for the rate of disappearance of N2O5 using the steady-state
approximation.

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6. (7 pts) Derive the rate law for the formation of product F in the process represented by the
following mechanism:
k

1
""
"
B+ X
A
k "

( fast equilibrium)

2
""
"
E
X + D
k "

( fast equilibrium)

3
E !k!
F

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(slow)

Exam III

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7. (20 pts) Consider the concentration behavior of reactant A in each of the situations below. On
the line to the right, write the numbers of ALL graphs that could represent the time
dependence of [A]. You will receive 2 points for each correct answer, but you will have 1
point deducted for each incorrect answer.
(a) An elementary reaction
(b) A reaction whose rate law is zero-order in reactant A
(c) An elementary reaction whose rate law is first order in reactants A and B,
which is studied using a kinetic trial where [A]o = 100[B]o
(d) An elementary reaction + + which is studied using a kinetic
trial where [A]o = [B]o
(e) A reaction whose rate law is first order in reactant A and which is given by
!!
!
C + D
A + B
the equilibrium
!
(f) A system at equilibrium and characterized by the exothermic elementary
!!
!
B that is perturbed by a temperature jump
reaction A
!
(g) An elementary reaction + 2 where [Y]o = 100[A]o

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Bonus: (3 pts) Describe three (3) differences between chain-growth and step-growth
polymerizations.

Equations
[ A]0
[ A]
ln
+ k ([ A]0 [ B]0 ) t
= ln
[ B]
[ B]0

Michaelis-Menten
R [S]
rate = max
K m +[S]

Guggenheim Analysis:
ln zt+ zt = kt + ln #$ z z0 1 e k %&

)(

1/ 2

zt = z (1 ek ) + zt + ek

8k T
Z AB = B N av2 [ A][ B]

kT
kobs = B eS / R eH / RT

k = Ae Ea / RT

K eq = e G/ RT

Kezdy-Swinbourne Analysis:

Step-growth polymerization:
1
'
DPn =
= !" M #$ kobs
t +1
o
1 p

For consecutive reactions:

[ A] = [ A]0 e k1t
k [ A]
[ B] = 1 0 e k1t e k2t
k2 k1

Chain growth polymerization:

1/2
! fk ! I # $
"
$
d
&
Rate = k p !" M #$#
# k &
t
"
%
k p !" M #$
=
1/2
2 fkd kt !" I #$

CHM 4411 F15

k e k1t k1e k2t

[C ] = [ A]0 1 2

k2 k1

R = 8.314 J/mol K = 0.08206 L atm/mol K

Exam III

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