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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.
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Hudson
pg. 1 of 10
1 [ H 3 PO 4 ] 1 [ P2 O5 ] 1 [ H 2 O]
=
=
2
t
1 t
3 t
(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)
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
pg. 2 of 10
0.080
0.12
0.0213
0.16
0.12
0.0427
0.080
0.36
0.0369
(14 points)
i)
Rate = k[CO ] x [Cl 2 ] 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
Hudson
pg. 3 of 10
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.)
Hudson
pg. 4 of 10
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
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
pg. 5 of 10
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.
Hudson
pg. 6 of 10
318
5.00 x 10-3
298
1.32 x 10-3
ln k
1/T
a) Determine the activation energy in kJ/mol
(8 points)
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
pg. 7 of 10
NOCl2 + NO 2 NOCl
T = 500 K
Reaction 2
N2 + O2 2 NO
T = 350 K
The smaller orientation factor contains the more complex molecules reaction
1.
The smaller collision frequency will occur at the lower temperature reaction
2.
Hudson
pg. 8 of 10
Step 1)
ES
k
(fast)
ES E + P
(slow)
E+S
k2
Step 2)
(14 points)
SP
ii) Define and identify any intermediate 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
pg. 9 of 10
(2 points)
B) I, II, III
C) I, IV
D) I, III
(12 points)
activated complexes
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
pg. 10 of 10
products