Department of Chemistry, King Fahd University of Petroleum and

Minerals

CHEM 311 (182) Second Major Exam 2 HOURS

March 30, 2019 (Saturday)

STUDENT NAME: ..............................................

STUDENT ID NUMBER: ...............................................

Test Code (00 )

(16 Questions)

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

Dr. MRSA Janjua Section 1

Dr. Ali Rinaldi Section 2
Dr. Abdul Rajjak Shaikh Section 3
Dr. Mazen Khaled Section 4

Page 1
Useful Physical constants and Formula

PHYSICAL CONSTANTS:

e = 1.602 × 10
−19
C 1 nm = 1 x 10-9 m
23 −1 1 pm = 1 x 10-12 m
NA = 6.022 x 10 mol 1 amu = 1.6605 x 10-27 kg
−12
ε0 = 8.854 × 10 C2 J-1 m-1 1 dm = 10 cm
−1 −1 1 dm3 = 1 litre
R = 8.314 J mol K
−23 −1
kB = 1.381 x 10 JK
−34
h = 6.626 x 10 Js
−2
g = 9.81 m s
−1
F = 96485 C mol
∆Go = - RT ln K
∆G = ∆H - T∆S

5
1 atm = 1.101325 x 10 Pa
5
1 bar = 10 Pa;

1 Torr = 1 mmHg = 133.322 Pa

2 −2
1 J = 1 kg m s
0 °C = 273.15 K

−3
ρsol = 1 g cm
εr = 78.5 of water at 25 oC
1 C = 1 A s and 1 J = 1 C V

8 −1
c = 2.998 x 10 m s
−2
g = 9.81 m s

Page 2
1. What is the activation energy for the following elementary reaction at 298 K:
eff k
A+B  →C
The half-life is 1.49×10-6 s, the initial concentration of [A] = [B] = 1.0×10-4 M, and
the Arrhenius pre-exponential factor = 1.4×1010 M-1 s-1. (R= 8.314 J mol–1 K–1)
A) 1.8 kJ/mol
B) 1.0 kJ/mol
C) 1.4 kJ/mol
D) 6.7 kJ/mol
E) 1.5 kJ/mol

2. The Steady State Approximation can be applied to a reaction intermediate if it

reaches rapidly a maximum concentration which:
A) is significantly smaller than the reactant concentration, and remains almost
constant.
B) is present in a concentration much smaller than reactant concentration but is not
constant.
C) is not reacting during the course of the reaction.
D) is at equilibrium
E) has constant concentration but large compared to reactant concentrations.

3. The volume of nitrogen gas at 1 atm and 273 K required to cover 1g of the silica gel
is 0.129 dm3. Calculate the surface area of the gel if each nitrogen molecule occupies
an area of 16.2 × 10˗20 m2 (Volume of an ideal gas at Standard Temperature and
Pressure = 22.4 dm3)
A) 562 m2
B) 576 m2
C) 346 m2
D) 162 m2
E) 129 m2

k1 k2
4. For the sequential reaction: A  → I →P the rate constants are k1=
12 -1 10 -1
2.0 × 10 s and k2 = 3.3 × 10 s . At what time does the maximum concentration
of the intermediate I occur?
A) 2.1 × 10-12 s
B) 1.1 × 10-12 s
C) 3.1 × 10-11 s
D) 4.1 × 10-10 s
E) 1.3 × 10-12 s

Page 3
5. For the parallel elementary reactions: A B & A C
The following graph is obtained from experiments:

When only A is present at the beginning, at what temperature will the smallest
A) 350 K
B) 500 K
C) 600 K
D) 650 K
E) 625 K

C2 H6( g ) ↽ ⇀ 2CH3 i ( g )
6. For ethane decomposition reaction:
the transition state for the forward reaction is the elongation of C2H6 molecule with
the entropy of activation of:
C 2 H 6 ↽ ⇀ C 2 H 6‡ ∆S‡ = 43.0 J/K mol
Whereas for the reverse reaction the entropy of activation is:
2CH 3 i ↽ ⇀ C 2 H 6‡ ∆S‡ = -79.0 J/K mol
What is the ratio of the Arrhenius pre-exponential factor of the forward and reverse
reactions?
A) 8.68 × 105
B) 1.15 × 10-6
C) 0.368
D) 2.72
E) 512

Page 4
7. For the reaction: X + Y → P Experiment were performed in various inert solvent
medium. The following experimental rate constant values were obtained:

At which point is the reaction diffusion-controlled.

A) III and IV
B) I and II
C) I
D) II
E) None

8. An enzyme has a turnover number (k2) of 104 min-1. If [S]o=2Km and the molecular
mass of the enzyme is 2.0 x 104 gram mol-1, how many moles of substrates can 1
gram of the enzyme convert every minute in 1.0 liter ? (Assuming the enzyme
reaction follows the Michaelis-Menten law).
A) 0.33 mol of substrate per gram of enzyme
B) 0.50 mol of substrate per gram of enzyme
C) 0.17 mol of substrate per gram of enzyme
D) 1.33 mol of substrate per gram of enzyme
E) 1.01 mol of substrate per gram of enzyme

9. The decomposition mechanism of ozone is

k
O3 ↽ k 1 ⇀ O 2 + O
−1

k2
O3 + O  → 2O 2
If k-1[O2] << k2[O3], then the order of the reaction with respect to ozone is
(Hint: use the rate expression in terms of production of [O2])
A) 1
B) 0
C) 2
D) 2.5
E) 3

Page 5
10. Kuni is the effective first order rate constant of the following unimolecular reaction
k
A + M ↽k 1 ⇀ A∗ + M
−1

k2
A∗  →P
1 1
The slope and y intercept of the plot of K uni versus M are 4 x 106 and 8 x 1011
k-1
respectively. The value of k 2 is
A) 2 x 105
B) 0.5 x 105
C) 32 x 105
D) 2 x 10-5
E) 0.5 x 10-5

11. The net reaction for formation of HI from H2 and I2 is

H2 + I2 ↽ ⇀ 2HI
The following mechanism was proposed for this reaction
k
I 2 ↽ k 1 ⇀ 2I
−1

k
H 2 + I ↽k 2 ⇀ H 2I
−2

k3
H 2 I + I  → 2HI
Using the preequilibrium approximation, derive the predicted rate law expression for
the above mechanism:
A) 2k3K1K2[H2][I2]
B) 2k3K2[H2][I2]
C) 2k3K1K2[H2][I]
D) 3k3K2[H2][I]
E) 2K1K2[H2]

Page 6
12. Illustration of a potential energy contour plot for the AB + C reaction at collinear
geometry (θ=180°) is shown in following Figure. Which of the points represent AB
are far from each other?

A) b
B) d
C) b'
D) a'
E) c

13. Determine the rate of formation of methane.

k1
CH 3OCH 3  → CH 3Oi + iCH 3
k2
iCH 3 + CH 3OCH 3  → CH 4 + iCH 2 OCH 3
k3
iCH 2 OCH 3  → iHCHO + iCH 3
k4
iCH 3 + iCH 3  → C2 H 6
1
 k1  2 3
2
r = k2   [CH 3OCH 3 ]
2
 4k
A)
1
 k1  2 1
2
r = k2   [CH 3OCH 3 ]
2
 4k
B)
1
 k1  2 3
r = k1   [CH3OCH3 ]2
C)  k2 
1
 k1  2 1
2
r = k2   [iCH 3OCH 3 ]
2
 4k
D)
1
 k2  2 3
r = k4   [CH3OCH3 ]2
E)  k4 

Page 7
14. Hydrogen iodide undergoes decomposition into H2 + I2 when irradiated with
radiation having a wavelength of 207 nm. It is found that when 1 J of energy is
absorbed, 440 µg of HI (molar mass = 127.911 g/mol) is decomposed. The
molecularity of the reaction is:
A) 2
B) 1
C) 1/2
D) 3/2
E) 0

15. Consider the following Jablonski diagram:

Which statement is correct?

A) Transition 6 corresponds to electronic absorption
B) Transition 5 corresponds internal conversion
C) Transition 12 and 13 are very slow
D) Transition 4 is faster than transition 3
E) Transition 10 corresponds to intersystem crossing

Page 8
16. Fluorescence decay is the main decay mechanism of tryptophan. Quenching of
tryptophan fluorescence by dissolved O2 gas was monitored by measuring emission
lifetimes at 348 nm in aqueous solutions. Determine the quenching rate constant for
this process from the following data:
[O2] moldm-3 0 0.023 0.055 0.08 0.108
τ (ns) 2.6 1.5 0.92 0.71 0.57
A) 1.22x1010 dm3mol-1s-1
B) 1.22x10-10 dm3mol-1s-1
C) 5.81x1010 dm3mol-1s-1
D) 2.53x1010 dm3mol-1s
E) 1.22x1010 dm3mol-2s-1

Page 9
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

Page 10