NAME: MUTINY ON THE BOUNTY CHEMISTRY 444, SPRING, 2015

Circle Section Number: 10 11 80 Examination 2, April 11, 2015

Answer each question in the space provided; use back of page if extra space is needed. Answer questions so the grader can READILY
understand your work; only work on the exam sheet will be considered. Write answers, where appropriate, with reasonable numbers of
significant figures. You may use only the "Student Handbook," a calculator, and a straight edge.

1. (15 points) For acetic acid in dilute aqueous solution at 298.15 K, the equilibrium constant for
DO NOT WRITE
the reaction IN THIS SPACE
𝑪𝑯𝟑 𝑪𝑶𝟐 𝑯  𝑪𝑯𝟑 𝑪𝑶− 𝟐 + 𝑯+
Is 1.73 × 10 mol L . In a relaxation experiment, the relaxation time was determined to be 8.5 ns
-5 -1 p. 1_______/15
for a 0.100 M solution. (a) Write an expression for the relaxation constant in terms of the forward,
p. 2_______/10
kf, and reverse, kr, rate constants for this reaction. [Show all steps and explain any
+
approximations you use.] (b) For this initial concentration, what is the concentration, [H ], p. 3_______/10
assuming that the system may be treated as an ideal solution? (c) Calculate the forward and
reverse rate constants. p. 4_______/10

p. 5_______/15
(a) Letting the deviation from equilibrium be x, one has the following equation:
𝑑[𝐻𝐻] p. 6_______/15
= −𝑘𝑓 [𝐻𝐻] + 𝑘𝑟 [𝐴𝐴][𝐻]
𝑑𝑑
p. 7_______/15
which leads to
p. 8_______/10
𝑑�[𝐻𝐻]𝑒𝑒 − 𝑥�
= −𝑘𝑓 �[𝐻𝐻]𝑒𝑒 − 𝑥� + 𝑘𝑟 ��[𝐴𝐴]𝑒𝑒 + 𝑥��[𝐻]𝑒𝑒 + 𝑥�� =============
𝑑𝑑
p. 9 _______/5
This equation can be reduced to one on x, if one remembers that the rate constants and (Extra credit)
equilibrium constant are related: =============
TOTAL PTS
𝑑𝑑 1
= −𝑘𝑓 𝑥 − 𝑘𝑟 �[𝐴𝐴]𝑒𝑒 + [𝐻]𝑒𝑒 �𝑥 = 𝑥
𝑑𝑑 𝜏 /100

1
where 𝜏 = 𝑘𝑓 + 𝑘𝑟 �[𝐴𝐴]𝑒𝑒 + [𝐻]𝑒𝑒 �
. In this equation, I have neglected all terms higher
than first order in x.

(b) Using the equilibrium expression, one finds that

[𝐴𝐴]𝑒𝑒 = [𝐻]𝑒𝑒 = 1.3067 × 10−3 𝑚𝑚𝑚 𝐿−1 .

(c) From the value of the relaxation time, and knowledge of the equilibrium constant, one gets

1
𝑘𝑓 + 𝑘𝑟 �[𝐴𝐴]𝑒𝑒 + [𝐻]𝑒𝑒 � =
𝜏
or
1
𝑘𝑓 + 2.6134 × 10−3 𝑚𝑚𝑚 𝐿−1 𝑘𝑟 =
8.5 × 10−9 𝑠
and
𝑘𝑓
𝐾 = = 1.73 × 10−5 𝑚𝑚𝑚 𝐿−1
𝑘𝑟
Solving these equations simultaneously gives
𝑘𝑓 = 7.737 × 105 𝑠 −1 and 𝑘𝑟 = 4.472 × 1010 𝐿 𝑚𝑚𝑚 −1 𝑠 −1
NAME: CHEM 444, Exam 2, Spring, 2015, page 2

2. (10 points) Sodium succinate, S, is oxidized in the presence of dissolved oxygen to sodium fumarate in the
presence of the enzyme succinoxidase. For a fixed succinoxidase concentration, the initial rate of formation of
sodium fumarate was found to vary with the succinate concentration as shown in the table. From these data,
calculate the Michaelis constant, KM, and the maximum rate for this concentration of enzyme.
[S] (mM) 10.00 2.00 1.00 0.50 0.33
-1
v0 (µM s ) 1.17 0.99 0.79 0.62 0.50

A Lineweaver-Burk plot (1/v0 versus 1/[S] ) for these data is linear, as seen in the plot.

2.5

2
1/v0 = 0.390/[S] + 0.832
R² = 0.9969
1/v0 (s µM-1)

1.5

0.5

0
0 0.5 1 1.5 2 2.5 3 3.5
1/[S] (mM-1)

From the intercept, the maximum velocity for this enzyme concentration is

1 1
𝑣𝑚𝑚𝑚 = = = 1.20 𝜇𝜇 𝑠 −1
𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 0.832 𝑠 𝜇𝜇−1

From the slope, one may find the Michaelis constant:

𝑠 𝑚𝑚 𝜇𝜇
𝐾𝑀 = 𝑠𝑠𝑠𝑠𝑠(𝑣𝑚𝑚𝑚 ) = 0.390 �1.20 � = 0.469 𝑚𝑚
𝜇𝜇 𝑠

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NAME: CHEM 444, Exam 2, Spring, 2015, page 3
𝑑
�=
3. (10 points) Calculate the simplest form of the commutator of the operators 𝐷 , and 𝑋� = 𝑥 2.
𝑑𝑑

The commutator one is looking for is:

� , 𝑋� � = 𝐷
�𝐷 � 𝑋� − 𝑋� 𝐷�
The action of this commutator on a general function of x, f(x) as the following form:

𝑑 2 𝑑
� 𝑋� − 𝑋�𝐷
�𝐷 � �𝑓(𝑥) = [𝑥 𝑓(𝑥)] − 𝑥 2 𝑓(𝑥)
𝑑𝑑 𝑑𝑑

Expanding the derivative gives the following result:

𝑑𝑑 𝑑𝑑
� 𝑋� − 𝑋�𝐷
�𝐷 � �𝑓(𝑥) = 2𝑥𝑥(𝑥) + 𝑥 2 − 𝑥2 = 2𝑥𝑥(𝑥)
𝑑𝑑 𝑑𝑑

Hence, the simplest form of the operator is multiplication by 2x.

� , 𝑋�� = 2𝑥
�𝐷

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NAME: CHEM 444, Exam 2, Spring, 2015, page 4

4. (10 points) Normalize the particle in a two-dimensional box, with the wave function,
𝒏𝒏𝒏 𝒎𝒎𝒎
ψ(𝒙, 𝒚) = 𝑨𝒏,𝒎 𝒔𝒔𝒔 � 𝒂 � 𝒔𝒔𝒔 � 𝒃 �
where a and b are lengths of the box in the x and y directions, and n and m are quantum numbers for the x and y
motion, respectively.

The normalization is given by the requirement:

𝑎𝑎𝑎 ψ 𝑦)ψ(𝑥, 𝑦)𝑑𝑑𝑑𝑑

∗ (𝑥,
∫ = 1
𝑠𝑠𝑠𝑠𝑠

Substituting the function into this equation gives:

𝑎 𝑏
𝑛𝑛𝑛 𝑚𝑚𝑚 𝑛𝑛𝑛 𝑚𝑚𝑚
𝐴2𝑛,𝑚 � � 𝑠𝑠𝑠 � � 𝑠𝑠𝑠 � � 𝑠𝑠𝑠 � � 𝑠𝑠𝑠 � � 𝑑𝑑𝑑𝑑 = 1
𝑎 𝑏 𝑎 𝑏
0 0

This equation can be factored to give:

𝑎 𝑏
𝑛𝑛𝑛 𝑚𝑚𝑚
𝐴2𝑛,𝑚 � 𝑠𝑠𝑠2 � � 𝑑𝑑 � 𝑠𝑠𝑠2 � � 𝑑𝑑 = 1
0 𝑎 0 𝑏

The integrals are found on Table 2.3 in the handbook. The result is

𝑎 1 1 𝑏 1 1
𝐴2𝑛,𝑚 � − 𝑠𝑠𝑠2𝑛𝑛 − 0 + sin(0)� � − 𝑠𝑠𝑠2𝑚𝑚 − 0 + sin(0)� = 1
2 4𝑛𝑛 4𝑛𝑛 2 4𝑚𝑚 4𝑚𝑚

Because n and m are positive integers, this equation simplifies to:\

𝑎 𝑏
𝐴2𝑛,𝑚 � � � � = 1
2 2

Solving by taking the real positive root, one finds the normalization constant:

2
𝐴𝑛,𝑚 =
√𝑎𝑎

Finally, the normalized wave function is:

2 𝑛𝑛𝑛 𝑚𝑚𝑚
ψ(𝑥, 𝑦) = 𝑠𝑠𝑠 � � 𝑠𝑠𝑠 � �
√𝑎𝑎 𝑎 𝑏

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NAME: CHEM 444, Exam 2, Spring, 2015, page 5
-1
5. (15 points) Calculate the difference in cm between the two lowest energy levels of a quantum mechanical
harmonic oscillator, characterized by ν0 = 9 x 10 Hz.
13

E1 − E 0 = hν 0 = 6.626 × 10 −34 J × s × 9 × 1013 s −1 = 59.634 × 10 −21 J

molecules J
Per mole: E1 − E 0 = 59.634 × 10 − 21 J × N A = 59.634 × 10 − 21 J × 6.022 × 10 23 = 35912
mole mol
-1
Using the conversion on page 1 of the handbook 1cm =0.01196266 kJ/mol,

−1
kJ  kJ 
E1 − E 0 = 35.912 ×  0.01196266 −1 
= 3002.023 cm −1
mol  mol × cm 

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NAME: CHEM 444, Exam 2, Spring, 2015, page 6

6. (15 points) For the harmonic oscillator in the first excited state (n = 1), (a) calculate the expectation value of
displacement from the equilibrium position 〈𝒙〉, and (b) the expectation value of the square of the displacement
1
1 4
〈𝒙𝟐 〉. The normalization constant is: 𝐴1 = � � , where the quantity α is defined in the handbook. (c) Calculate
4𝛼 2 𝜋
the uncertainty in the displacement from equilibrium. Your answer should be in terms of α and other constants.
𝑥
The wave function for this state is given, from the handbook by ψ1 (𝑥) = 𝐴1 𝐻1 ( )𝑒𝑒𝑒(−𝑥 2 /2𝛼 2). Using Table 11.1 and
𝛼
1 1/4 2𝑥
normalization constant, one gets the normalized wave function: ψ1 (𝑥) = � � � � 𝑒𝑒𝑒(−𝑥 2 /2𝛼 2). This is an odd
4𝛼 2 𝜋 𝛼
∞
function of x. The expectation value of any function f(x) is given by the integral: 〈𝑓(𝑥)〉 = ∫−∞ ψ1∗ 𝑓(𝑥)ψ1 𝑑𝑑.

∞
(a) The expectation value of the displacement is: 〈𝑥〉 = ∫−∞ ψ1∗ 𝑥ψ1 𝑑𝑑 = 0 because, since ψ1 is odd and x is odd,
the function ψ1∗ 𝑥ψ1 is odd and its integral between these limits is zero.

(b) On the other hand, the expectation value of the square of the displacement is not zero because the integrand is even
and must be evaluated by integration:
∞ ∞ ∞ ∞
4𝑥 2 𝑥2 4 4 −𝑥 22 8𝐴12 𝑥2
4 −𝛼 2
〈𝑥 2 〉 = � ψ1∗ 𝑥 ψ1 𝑑𝑑 =
2
� 𝐴12 2
exp �− 2 � 𝑑𝑑 = 2𝐴1 � 2 𝑥 𝑒 𝛼 𝑑𝑑 = �𝑥 𝑒 𝑑𝑑
𝛼2 𝛼 𝛼 𝛼2
−∞ −∞ 0 0
where the doubling of the integral over the reduced space shows that the two halves are equal. The integral is found on
Table 2.3.
∞
𝑥2 3 5
− 2
� 𝑥 4𝑒 𝛼 𝑑𝑑 = 𝛼 √𝜋
8
0
Substituting this result and the value of the normalization constant into the equation gives
1
8 1 2 3 3 2
〈𝑥 2 〉 = 2
� 2 � � 𝛼 5 √𝜋� = 𝛼
𝛼 4𝛼 𝜋 8 2

(c) The uncertainty in a quantity, such as the position, is defined as:

∆𝑥 = �< 𝑥 2 > − < 𝑥 >2
Substitution from the parts (a) and (b) gives

3 3
∆𝑥 = � 𝛼2 − 0 = � 𝛼
2 2
The uncertainty depends on the length α, which depends on the force constant, the mass and Planck’s constant.

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NAME: CHEM 444, Exam 2, Spring, 2015, page 7

7. (15 points) For a particle in a one-dimensional box along x (stretching from x = 0 to x = a), the system is in a
normalized mixed state, the wave function of which is given by an expansion in the eigenstates of the energy by
the following formula:
𝟏 √𝟑
ψ𝒎𝒎𝒎𝒎𝒎 (𝒙)
ψ𝟏 (𝒙) + = ψ (𝒙)
𝟐 𝟐 𝟐
Calculate the expectation value of the square of the momentum, < 𝒑�𝟐 >, for the system in this state.

𝑑2
The operator for the square of the momentum is 𝑝̂ 2 = −2 . The expectation value is, by definition,
𝑑𝑥 2
𝑎
𝑑2 1 𝑎
√3 ∗ 𝑑2 1 √3
< 𝑝̂ 2 > = −2 � ψ∗𝑚𝑚𝑚𝑚𝑚 (𝑥) ψ (𝑥)𝑑𝑑 = 2
− � � ψ1∗ (𝑥) + ψ2 (𝑥)� 2 � ψ (𝑥) + ψ (𝑥)� 𝑑𝑑
0 𝑑𝑥 2 𝑚𝑚𝑚𝑚𝑚 0 2 2 𝑑𝑥 2 1 2 2
Before continuing with the evaluation, let’s examine the operation of this operator on the general basis wave function:
𝑑2 𝑑2 2 𝑛𝑛𝑛 𝑛 2 𝜋2 2 𝑛𝑛𝑛 𝑛 2 ℎ2 2 𝑛𝑛𝑛 𝑛 2 ℎ2
−2 ψ𝑛 (𝑥) = −2 𝑑𝑥 2 ��𝑎 𝑠𝑠𝑠 � �� = 2 � � � 𝑠𝑠𝑠 � � = � � � 𝑠𝑠𝑠 � � = � � ψ 𝑛 (𝑥)
𝑑𝑥 2 𝑎 𝑎2 𝑎 𝑎 4𝑎2 𝑎 𝑎 4𝑎2

The basis functions are eigenfunctions of this operator. Thus, one can easily evaluate the operations in the expectation
value. Hence,
𝑎
1 √3 ∗ 12 ℎ2 1 22 ℎ2 √3
< 𝑝̂ 2 > = � � ψ1∗ (𝑥) + ψ2 (𝑥)� �� 2 � ψ (𝑥) + � 2 � ψ2 (𝑥)� 𝑑𝑑
0 2 2 4𝑎 2 1 4𝑎 2

Multiplying through gives a sum of terms:

1 12 ℎ 2 𝑎
√3 22 ℎ2 𝑎
√3 12 ℎ2 𝑎
< 𝑝̂ 2 > = � 2 � � ψ1∗ (𝑥)ψ1 (𝑥)𝑑𝑑 + � 2 � � ψ1∗ (𝑥)ψ2 (𝑥)𝑑𝑑 + � 2 � � ψ∗2 (𝑥)ψ1 (𝑥)𝑑𝑑
4 4𝑎 0 4 4𝑎 0 4 4𝑎 0
3 22 ℎ 2 𝑎
+ � 2 � � ψ∗2 (𝑥)ψ2 (𝑥)𝑑𝑑
4 4𝑎 0
Because of the orthonormality of the wave functions, the first and fourth terms have integrals that are 1, and the second and
third terms have integrals that are zero. As a result, one has
1 12 ℎ 2 3 22 ℎ 2 13ℎ2
< 𝑝̂ 2 > = � 2� + � 2� =
4 4𝑎 4 4𝑎 16𝑎2

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NAME: CHEM 444, Exam 2, Spring, 2015, page 8

8. (10 points) True or false. Mark an X in the box with the correct answer. Do not guess. The total number of
points for this problem is graded right – wrong/2.

Statement True False

To every measurable quantity in quantum mechanics, there X

exists a corresponding operator.

Any two functions from a set that is complete are X

orthogonal to each other.

The wave function has to be single-valued in the spatial X

coordinates.

inx 1/2
Every function of the type e , where i=(-1) and n is an X
integer, is an eigenfunction of the linear momentum
operator.

The energy of a particle in a two-dimensional box is X

quantized according to quantum mechanics.

The second lowest energy level of a rigid rotor is doubly X

degenerate.

Quantum tunneling does not play any role in rates of X

chemical reactions.

Heisenberg’s uncertainty principle can be illustrated by X

considering the non-commuting operators of momentum
and kinetic energy.

The degeneracy of a quantum mechanical 1-dimensional X

2
harmonic oscillator is n .

The interaction between two charged particles used in the X

quantum mechanical description of the hydrogen atom is
given by a simple Columbus potential.

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NAME: CHEM 444, Exam 2, Spring, 2015, page 9

� and 𝒑
9. (5 points, extra credit) We have seen that the position and conjugate linear momentum operators (e.g. 𝒙 �𝒙 )
do not commute with each other. But what about some other operators? Do they commute? Determine whether
the component of position, 𝒙 � in one direction and the angular momentum, 𝑳�𝒛 , about another axis commute.

First, we look up on page 11-1 of the handbook the operator for the appropriate angular momentum:

𝜕 𝜕
𝐿�𝑧 = −𝑖 �𝑥 − 𝑦 �
𝜕𝜕 𝜕𝜕

Next, apply the commutator of this with the position operator to a general function 𝑓(𝑥, 𝑦, 𝑧):

𝜕 𝜕 𝜕 𝜕
�𝐿�𝑧 , 𝑥��𝑓 = −𝑖 �𝑥 − 𝑦� 𝑥𝑥 + 𝑖𝑥 �𝑥 − 𝑦 �𝑓
𝜕𝜕 𝜕𝜕 𝜕𝜕 𝜕𝜕
𝜕(𝑥𝑥) 𝜕(𝑥𝑥) 𝜕𝜕 𝜕𝜕
= −𝑖 �𝑥 − 𝑦 � + 𝑖𝑥 �𝑥 − 𝑦 �
𝜕𝜕 𝜕𝜕 𝜕𝜕 𝜕𝜕
𝜕𝜕 𝜕𝜕 𝜕𝜕 𝜕𝜕
= −𝑖 �𝑥𝑥 − 𝑦𝑦 − 𝑥𝑥 � + 𝑖𝑥 �𝑥 − 𝑦 � = 𝑖𝑦𝑦
𝜕𝜕 𝜕𝜕 𝜕𝜕 𝜕𝜕

Thus, one sees that the commutator of these two operators is

�𝐿�𝑧 , 𝑥�� = 𝑖 𝑦�

These two operators do not commute, which means that one cannot have a complete set of simultaneous eigenstates of
the two operators. In fact, this can be used to generate a set of three relations by cyclic permutation of indices:

�𝐿�𝑥 , 𝑦�� = 𝑖 𝑧̂
�𝐿�𝑦 , 𝑧̂ � = 𝑖 𝑥�
�𝐿�𝑧 , 𝑥�� = 𝑖 𝑦�

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