CHEM 311 (191) Second Major Exam 2 HOURS

Monday November 4, 2019

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Test Code (00 )

(16 Questions)

R= 8.314 J mol-1 K-1

NA =6.022 x 1023 mol-1
h = 6.626 x 10-34 J s
kB = 1.38 x 10-23 J K-1
1uM = 1 x 10-6 M
1 cm3 = 1 x 10-3 dm3

Read the questions with clarity, and understand the questions before answering

Dr. Tarek Kandiel Section 1

Dr. Ali Rinaldi Section 2
Dr. M.A. Morsy Section 3
Dr. M.R. Janjua Section 4

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1. The rate constant k of the following complex reaction is 2.5 x 10-2 s-1:

2N2O5 → 4NO2 + O2

The reaction is first order. What would be the rate of NO2 formation when N2O5
concentration is 0.0100 M?

A) 1.0 x 10-3 M s-1

B) 2.5 x 10-4 M s-1
C) 2.5 x 10-5 M s-1
D) 5.0 x 10-3 M s-1
E) No enough information to estimate the NO2-Rate of formation.

2. The half-life of radioactive 222Rn is 3.8 days. A sample of 222Rn is allowed to

decay for 15.2 days and after this time, 5.6 mmol remained. What was the initial
amount of 222Rn ?

A) 90 mmol
B) 25 mmol
C) 45 mmol
D) 11 mmol
E) 35 mmol

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3. An complex reaction, A + 2B C, shows the following rate equation:

It was performed with [A]o >> [B]o and [C]o =0. The following plots are obtained
from two runs at 300 K where for run-1 [A]o = 0.50 M and for run-2 [A]o = 0.70 M.
What is the value?

A) 0.50 M-2.2 s-1

B) 0.15 M-3 s-1
C) 1.5 M-2.2 s-1
D) 0.050 M-2 s-1
E) 0.75 M-2 s-1

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4. Apply the steady state approximation to the intermediates and in the
following sequential reaction

to obtain an expression for the concentration [ ] as function of time, when

initially [A]o = ao, and [ ]o = [ ]o = [ ]o = 0.
[Note: , where C is the integration constant]

A) [ ] = ao (1 - )
B) [ ] = (k3/k2) (1 - )
C) [ ] = (k1/k2) ao ( - 1)
D) [ ] = k3 ao ( - 1)
E) [ ] = (k1/k2) ao ( - )

5. Reactant A is converted to B and C in two parallel elementary reactions:

where k1 is 0.10 s-1 and k2 is 5.0 x 10-3 s-1.

If the initial concentration of A is 0.500 M, what will be the value of [B] after 10
seconds (assuming constant volume throughout the reaction)

A) 0.31 M
B) 0.18 M
C) 0.0080 M
D) 0.0012 M
E) 0.45 M

6. The reaction rate constant of an elementary reaction will decrease if :..

[Note, higher “stability” means lower internal energy of materials]

A) the “stability” of the transition state molecule decreases.

B) the reaction entropy of activation increases.
C) the reaction temperature increases.
D) the “stability” of the reactants decrease.
E) the “stability” of the transition state molecule increases.

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7. For the elementary reaction :
2A C

the effective rate constant at 500 K is 1.66 x 10-3 M-1 s-1. The half-life period
of this reaction at 700 K is found to be 200 seconds when [A]o is 0.50 M. What
is the calculated activation energy of this reaction? (Assume the Arrhenius pre-
exponential factor is constant at both temperatures)

A) 26.1 kJ mol-1
B) 11.0 kJ mol-1
C) -5.5 kJ mol-1
D) 300 J mol-1
E) 65.5 kJ mol-1

8. The kinetic results of the following bimolecular reaction with two different types
of catalysts at 500 K are,
CO + O CO2

Catalyst-I, k1 = 2.1 x 1012 M-1 s-1 and Ea1= 30 kJ mol-1

Catalyst-II, k2 = 2.1 x 1012 M-1 s-1 and Ea2= 25 kJ mol-1

What is the possible difference in the entropy of activation between catalyst-I

and catalyst-II processes?

A) 10 J K-1 mol-1
B) -20 J K-1 mol-1
C) ≈0
D) 0.010 J K-1 mol-1
E) -0.010 J K-1 mol-1

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 9. Which of the following reaction is diffusion-limited:

Reaction I: H2(aq) + ½ O2(aq) H2O(l) k = 5.1 x 103 M-1 s-1

Reaction II: H2(aq) + O2(aq) H2O2(aq) k = 1.1 x 106 M-1 s-1

Reaction III: H2(aq) + O2(aq) H2O2(aq) k = 1.4 x 1010 M-1 s-1

if the diffusion coefficient (in water at 25 oC), and radius of each gas are as
follows:
DO2 = 2.2 x 10-5 cm2 s-1 and DH2 = 3.2 x 10-5 cm2 s-1
rO2 = 2.0 x 10-8 cm and rH2 = 1.5 x 10-8 cm

(all rate constants are obtained at 25 oC)

A) Reaction III
B) Reaction I and III
C) Reaction I and II
D) Reaction I
E) Reaction II

10. The reaction

2NO + 2H2 → N2 + 2H2O
is proposed to occur through the following two elementary steps :

By using the steady state approximation, what would be its rate

expression?

A) R = k1[H2][NO]2
B) R = k1[H2][NO]
C) R = k1 k2 [H2][NO]2
D) R =(k1/k2) [H2][NO]2
E) R = k1[H2]2[NO]2

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11. Using the pre-equilibrium approximation, derive the predicted rate law
expression for the following mechanism:
k1
A3 3A
k-1
k2
A+B P

A)

B)

C)

D)

E)

12. The given figure represents the experimental rate constant of gas-phase
isomerization of cyclopropane at different pressures.

Assuming that the data is consistent with the Lindemann mechanism,

what is the order of the reaction at pressure values greater than 40 Torr?

A) 1
B) 2
C) 3
D) Zero
E) 4

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13. For an enzymatic reaction, the variation of initial reaction rate against the initial
substrate concentration in the form 1/Ro vs. 1/[S]o for systems without and with

u
inhibitor (at 10.0 M inhibitor concentration) produce linear plots of slopes 3.00
s and 15.0 s, respectively.
If both experiments performed with the same enzyme concentration and
producing same maximum rate (Rmax) of 9.00 x 10-4 M s-1, what would be the
Michaelis-Menten constants of both systems; without inhibitor (Km), with 10.0
u

M inhibitor (K*m), and the Ki for this enzyme-inhibitor system, respectively?

A) 2.70 x 10-3 M, 1.35 x 10-2 M, and 2.50 x 10-6 M.

B) 1.35 x 10-3 M, 2.70 x 10-3 M, and 2.50 x 10-6 M
C) 1.10 x 10-3 M, 2.70 x 10-2 M, and 3.20 x 10-6 M
D) 1.10 x 10-2 M, 2.70 x 10-3 M, and 3.20 x 10-6 M
E) 2.70 x 10-3 M, 1.35 x 10-2 M, and 3.20 x 10-6 M

14. The enzyme fumarase catalyzes the hydrolysis of fumarate:

Fumarate(aq) + H2O(l) → L-malate(aq)

The turnover number (rate constant of enzyme-substrate intermediate into

product) for this enzyme is 2.5 x 103 s–1, and the Michaelis constant Km is 4.2 x
10-6 M. What is the initial rate of fumarate hydrolysis if the initial enzyme
concentration is 2.0 x 10-6 M and the fumarate concentration is 2.0 x 10-2 M

A) 5.0 x 10-3 M s-1

B) 1.5 x 10-6 M s-1
C) 2.0 x 10-2 M s-1
D) 2.5 x 10-1 M s-1
E) 4.2 x 10-6 M s-1

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15. The reduction of CO2 catalyzed by metal nanoparticles (M) is proposed to occur
with following steps:

The reaction is limited by the first step where k-1<<k2

Which metal will give the highest rate of CO formation at low pressures of H2?

A) Ni
B) Pt
C) Fe
D) Cu
E) All the same because is limited by the first step

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16. The following plots were obtained on the adsorption of Kr on three different
charcoal adsorbents (1,2,3) with similar surface areas at 194 K. All three plots
show the same intercepts.

Assuming similar desorption rate of Kr for all charcoals, what would be the
correct statement from this graph,

A) the Kr-adsorption rate on Charcoal-3 is the highest

B) the Kr-adsorption rate on Charcoal-1 is the highest
C) The Kr-adsorption rates on the three types of charcoal samples are the
same.
D) The Kr-adsorption monolayer volume is the highest in charcoal 1
E) The Kr-adsorption monolayer volume is the highest in charcoal 3

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Answer Key
1. A
2. A
3. A
4. A
5. A
6. A
7. A
8. A
9. A
10. A
11. A
12. A
13. A
14. A
15. A
16. A

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