Name:

Lab section:

Chemistry 120B

Exam #1 02/10/10

Exam # A___

Instructions:
o Your cell phone must be off and all other materials must be put away
before beginning the exam.
o You are only allowed to use a SINGLE LINE NON-PROGRAMMABLE
CALCULATOR.
o Do not start the exam until you are told to do so.
o Print your name on the top of every page. One point will be removed
from your total score for every page on which you do not write your name.
o Read each problem carefully before you begin.
o Make sure you answer what the problem is asking.
o Answer each problem clearly and legibly.
o Check your work for errors.

Always ask yourself Does this answer make sense?.
o Partial credit will be awarded for partial answers so always try!
o If there is any evidence of cheating (either during the exam or while it is
being graded) you will receive a zero for the exam and you will be
reported to the Dean of Students in the Office of Judicial Affairs.

This exam consists of this cover page, and 7 pages of problems. Make sure that all
8 pages are present.

Sign your name below and include the last four digits of your CWID (student ID
number). Failure to include the last four digits of your CWID will result in an automatic
score of zero.
Your signature indicates that you have read and understand these instructions.

Signature

Last 4 digits of CWID

Question # Points possible Your points

1
18
2
22
3
18
4
14
5
28

Hudson

Chemistry 120B Exam #1A

pg. 1 of 10

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Name:
Watch your units and significant figures.
1) 0.412 mol H3PO4 are initially placed in a 0.750 L volume. H3PO4 decomposes
according to the reaction below. After 32.0 sec, there are 0.148 mol H3PO4 remaining.
(18 points total)
2 H3PO4 (g)  P2O5 (g) + 3 H2O (g)
a) Write the rate expression relating the rates of change of products to the rates of
change of reactants for the reaction above.
(6 points)
Rate =

1 [ H 3 PO 4 ] 1 [ P2 O5 ] 1 [ H 2 O]
=
=
2
t
1 t
3 t

b) Given the information above:

(12 points)

i. Determine the rate of change of H3PO4 concentration over the first 32 sec.

[ H 3 PO4 ]
=
t

(0.148mol 0.412mol )
(32 sec 0 sec)

0.750 L = 0.0110 M / sec

ii. Determine the average rate of reaction over the first 32 sec.
Rate =

Hudson

1 [ H 3 PO4 ]
1
= (0.0110 M / sec) = 5.50 x10 3 M / sec
2
t
2

Chemistry 120B Exam #1A

pg. 2 of 10

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Name:
Watch your units and significant figures.
2) Consider the reaction with the following experimental data:

(22 points total)

CO (g) + Cl2 (g)  COCl2 (g)

Experiment # [CO]0 [Cl2]0 Initial Rate (M/sec)
1

0.080

0.12

0.0213

0.16

0.12

0.0427

0.080

0.36

0.0369

a) Given the experimental data for the above reaction:

(14 points)

i. Determine the rate law. Explain your reasoning.

ii. Calculate the rate constant k. Include the correct units.

i)
Rate = k[CO ] x [Cl 2 ] y

Rate = k[CO ] x [Cl 2 ] y

Rate2 = k[0.16] x [0.12] y = 0.0427
Rate1 = k[0.080] x [0.12] y = 0.0213
[0.16] x
0.0427
=
x
[0.080]
0.0213
2 x = 2 .0
x =1

Rate3 = k [0.080] x [0.36] y = 0.0369

Rate1 = k[0.080] x [0.12] y = 0.0213
[0.36] y 0.0369
=
[0.12] y 0.0213
3 y = 1.73
y ln 3 = ln 1.73
y=

Rate = k[CO]1[Cl2]1/2

ln 1.73
= 0.49 = 0.5
ln 3

ii)
Rate = k[CO ]1 [Cl 2 ]1 / 2

0.0213 = k[0.080]1 [0.12]1 / 2

M
0.0213
1
sec = 0.77
k=
= 0.76 9
1
1/ 2
1/ 2
[0.080] [0.12]
( M )( M )
sec M 1 / 2

Hudson

Chemistry 120B Exam #1A

pg. 3 of 10

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Name:
Watch your units and significant figures.
b) The reaction 2 NO (g) + 2 H2 (g)  N2 (g) + 2 H2O (g) is first order with respect to
H2 and second order with respect to NO.
(8 points)
i. Write the rate law for the above reaction. What are the units of the rate constant k?

Rate = k[H2]1[NO]2
This is a 3rd order reaction overall so the units of k = M-2s-1 = 1/(M2 s1)
ii. If the rate of this reaction at 298 K is 3.6 x 10-4 M/sec, determine the reaction rate if
the concentration of NO is decreased by half and the concentration of H2 is
increased by half. (Hint: Given your rate law, by what factor does the rate change
given these concentration changes? Calculate the new rate.)

If the [NO] is decreased by half then the concentration is multiplied by . Imagine

a concentration starting at 100 and ending at 50 100 * = 50
If the [H2] is increased by half then the concentration is multiplied by 3/2. Imagine
a concentration starting at 100 and ending at 150 100 * 3/2 = 150
Rate1 = k[ NO ]2 [ H 2 ] = 3.6 x10 4 M / s
Rate 2 = k[0.5 NO ]2 [1.5 H 2 ]
Rate 2 = k[ NO ]2 [ H 2 ](.5) 2 (1.5)
Rate 2 = Rate1(0.37 5 ) = (3.6 x10 4 )(0.37 5 ) = 1.35 x10 4 M / s
The new rate will decrease by a factor of 0.375 and will become 1.6 x 10-4 M/s.

Hudson

Chemistry 120B Exam #1A

pg. 4 of 10

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Name:
Watch your units and significant figures.
3) The second order decomposition of NO2 at 1000 K has a rate constant of 0.24 M-1s-1
according to the reaction:
(18 points total)
2 NO2  2 NO + O2
k = 0.24 M-1s-1
a) The initial concentration of NO2 is 0.647 M, and the reaction mixture initially contains
no products.
(10 points)
i. Determine the concentration of NO2 after 12.4 s?

1
1
= kt +
[ NO2 ]t
[ NO2 ]0
1
1
= (0.24 M 1s 1 )(12.4 s ) +
[ NO2 ]t
0.647 M
1
= 4.522 M 1
[ NO2 ]t
[ NO2 ]t =

1
= 0.22 M
4.522 M 1

ii. Determine the concentration of O2 after 12.4 s?

To determine how much O2 formed we need to consider how much NO2 was lost
AND the stoichiometric relationship between the two. Using the rate expression we
can see the relationship (given identical time intervals).
1 [ NO2 ] 1 [O2 ]
=
2 t
1 t
1
[O2 ] = [ NO2 ]
2
1
[O2 ] = (0.22 0.647) = 0.21M
2
[O2 ] = 0.21 0 = 0.21M
Rate =

Hudson

Chemistry 120B Exam #1A

pg. 5 of 10

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Name:
Watch your units and significant figures.
b) Below is a graph of experimental data for the second order decomposition of NO2
at 1000 K.
(8 points)
i) Label the axes that would result in the
straight line shown
ii) What information does the slope and
intercept yield?
Slope = __k__

Slope = k

1
[NO2]
Intercept =

Intercept = ____1/[NO2]0___

T=600K

1
[NO2]0
time

iii) Starting at the same initial concentration, draw a new line representing experimental
data if the temperature were decreased to 600 K. Explain your reasoning.

When temperature decreases, the rate constant decreases (according to the

Arrhenius equation). Therefore, the slope of the line must decrease with decreasing
temperature.

Hudson

Chemistry 120B Exam #1A

pg. 6 of 10

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Name:
Watch your units and significant figures.
4) The rate constant for the reaction 2 N2O5 (g) 4 NO2 (g) + O2 (g) was measured at
several temperatures. According to the Arrhenius equation, a plot of ln k vs 1/T results in
a straight line. The equation of the line is: y = -6.30 x 103 x + 14.5.
(14 points total)

Experiment # Temperature (K) Rate constant, k (s-1)

1

318

5.00 x 10-3

298

1.32 x 10-3

ln k

y = -6.30 103 x + 14.5

1/T
a) Determine the activation energy in kJ/mol

(8 points)

A plot of ln k vs 1/T has a slope of Ea/R and an intercept of ln A following the

linear form of the Arrhenius equation:
Ea 1
ln k =
+ ln A
R T
Ea
slope =
= 6.30 x103 K
R
kJ
Ea = (8.314 J / molK )(6.30 x103 K ) = 5.24 x10 4 J / mol
= 52.4kJ / mol
1000 J
A longer version of solving this problem is to use the two point Arrhenius
equation:
k E 1 1
ln 2 = a
k1 R T1 T2

1.32 x10 3
Ea
1
1
=

ln

3
5.00 x10 8.314 J / molK 318 298
Ea
ln(0.264 ) =
(2.11x10 4 K 1 )
8.314 J / molK
ln (0.264 )
kJ
Ea =
(8.314 J / molK ) = 5.25 x10 4 J / mol
= 52.5kJ / mol
4
1
(2.11x10 K )
1000 J

Hudson

Chemistry 120B Exam #1A

pg. 7 of 10

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Name:
Watch your units and significant figures.
Ea

b) According to collision theory; k = pze RT where p is the orientation factor and z is

(6 points)
the collision frequency. Given the two reactions at the given temperatures:
Reaction 1

NOCl2 + NO  2 NOCl

T = 500 K

Reaction 2

N2 + O2  2 NO

T = 350 K

i) Which reaction has the smaller p? Explain your reasoning.

The smaller orientation factor contains the more complex molecules  reaction
1.

ii) Which reaction the smaller z? Explain your reasoning.

The smaller collision frequency will occur at the lower temperature  reaction
2.

Hudson

Chemistry 120B Exam #1A

pg. 8 of 10

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Name:
Watch your units and significant figures.
5) The general mechanism by which an enzyme (E) binds a substrate (S) and then reacts
to form the products (P) is as follows:
(28 points total)
k1

Step 1)

ES
k

(fast)

ES E + P

(slow)

E+S

k2

Step 2)

a) Given the above reaction mechanism:

i) Write the overall reaction

(14 points)

SP
ii) Define and identify any intermediate species in the reaction

An intermediate species is a compound that is produced in an early step and

then used in a later step. In this mechanism, ES is an intermediate.
iii) Define and identify any catalytic species in the reaction

A catalyst is a compound that increases the rate of the reaction by changing the
reaction mechanism. It is used in an early step and then reformed in a later step.
In this mechanism, E is a catalyst.
iv) Determine the rate law using explicit forms of k (eg. k1, k2 )

The rate law can be determined by expressing the rate law using the stoichiometry
with the slow step and then replacing any intermediate species.
Rate = k2 [ ES ]
ES is an intermediate so we replace it using the fast equilibrium with equivalent
forward and reverse rates.
Rate f = k1[ E ][ S ]
Rater = k1[ ES ]
k1[ E ][ S ] = k1[ ES ]
k1[ E ][ S ]
k1
Substitute the intermediate into the original rate expression:
Rate = k2 [ ES ]
[ ES ] =

[ ES ] =

k1[ E ][ S ]
k1

Rate =

k1k2[ E ][ S ]
k1

Hudson

Chemistry 120B Exam #1A

pg. 9 of 10

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Name:
Watch your units and significant figures.
b) Which of the following statements are true about reaction mechanisms?

(2 points)

I. The final rate law can include intermediates.

II. A rate law can be written from the stoichiometry of the slowest elementary step.
III. The rate of the reaction is dependent on the fastest step in the mechanism.
IV. The final rate law can include catalysts.
A) II, IV

B) I, II, III

C) I, IV

D) I, III

c) Label each of the following in the energy diagram:

(12 points)

activated complexes

i) reactants and products

ii) intermediate(s) and/or catalyst(s)
iii) activated complex(es)
iv) activation energy(ies) (Ea, clearly indicate
magnitude with arrow(s))
v) Which of the following mechanisms could be
represented by this energy diagram?
Explain your reasoning.

Energy

Ea1
Ea2

reactants

intermediate
Reaction progress

A) Step 1: 2 A  D (slow)
Step 2: B + D  E (fast)
Step 3: E  2 C (fast)
B) Step 1: A + B  D (fast equilibrium)
Step 2: A + D  2 C (slow)
C) Step 1: 2 A  D (fast equilibrium)
Step 2: B + D  E (slow)
Step 3: E  2 C (fast)
D) Step 1: A + B  D (slow)
Step 2: A + D  2 C (fast equilibrium)
There are two steps present (2 activation energies). The magnitude of the first
activation energy is smaller than the second therefore the first step is the fast step.

Hudson

Chemistry 120B Exam #1A

pg. 10 of 10

products