CHEMISTRY 444.

11 Spring, 2011 (11S)

QUIZ 1 Feb. 17, 2011

NAME: Score ______/20

Problem 1 (8 points)

Starting from the continuous probability distribution for one-dimensional diffusion, show how one would
determine the average squared displacement in a model describing isotropic diffusion in two
dimensions.

The 1-dimensional continuous probability distribution is given by:

1 −x 2 / 4 Dt
P(x,t) dx =
4 πDt e dx

For two-dimensional isotropic diffusion, with uncorrelated probabilities, we write:

⎛ 1 −x 2 / 4 Dt ⎞⎛ 1 −y 2 / 4 Dt ⎞
€ P(x, y,t) dx dy = ⎜
⎝ 4 πDt e dx ⎟⎜
⎠⎝ 4 πDt e dy ⎟
⎠
1 −( x +y ) / 4 Dt
2 2
P(x, y,t)dx dy =
4 πDt e dx dy

Transforming to plane polar coordinates, r 2 = x 2 + y 2 :

€ 1 −( r 2 ) / 4 Dt
P(x, y,t) dx dy =
4 πDt e dx dy

1 −( r 2 ) / 4 Dt
P(r, φ,t) dr dφ =
4 πDt e €
r dr dφ

Integrating out the angular part

2π
1 −( r 2 ) / 4 Dt ⎛ 1 −( r 2 ) / 4 Dt ⎞ 2 π
€ P(r,t)dr = ∫ 4 πDt e
r dr d φ =
⎝ 4 πDt e
⎜ r dr ⎟ ∫ dφ
⎠ 0
0

1 −( r 2 ) / 4 Dt
2Dt e
P(r,t)dr = r dr

The average squared displacement is:

€ ∞ ∞
⎛ 1 ⎞ ∞
⎛ 1 3 −( r 2 ) / 4 Dt ⎞
∫ r 2⎜⎝ 2Dt e−( r ) / 4 Dt r dr⎟⎠ =
2
r2 = ∫ r 2 P(r,t)dr = ∫ ⎜⎝ 2Dt r e dr⎟
0 0 0
⎠

Using Table 2.3, the integral is evaluated as:

€ r 2 = 4Dt

€
 Problem 2 (2 Points)

Assuming an ideal gas model for Neon (Ne) and Krypton (Kr) and isotropic, two-dimensional diffusion,
what is the ratio:

r2
Kr

r2
Ne

Solution:
€
r2 DKr 2
σ Ne mNe 2
dNe mNe dNe mNe 0.2382 nm 20.1797 g
Kr
2
= = 2
= 2
= =
r DNe σ Kr mKr dKr mKr dKr mKr 0.3362 nm 83.798 g
Ne

= (0.7085)(0.490727) = 0.348

€
 CHEM444 Section 11/81 Spring 2011 (11S)
QUIZ 2 Feb. 24, 2011

NAME: Score ______/10

Problem 1 (10 points)

Boundary centrifugation is performed on a solution of cytochrome c (M=13,400 gr/mol) in water at

T=20° C (ρ=0.998 gr cm3, η=1.002 cP) using a centrifuge operating at 40000 revolutions per minute
(rpm). The following data are for the position of the boundary layer as a function of time:

Time (hours) Xb (cm)

0 4.00
2.5 4.11
5.2 4.23
12.3 4.57
19.1 4.91

What is the sedimentation coefficient of cytochrome c under these conditions? Show all work and give
your answer in the appropriate units

Solution:

Plot the data as ln(xb/xb,t=0) versus time, t. The

slope is ϖ 2 s . We fit the last 4 data points as a
straight line with the parameters a and b defining
the line y = at + b with a being the slope.

€
Results of Fitting (using gnuplot’s Marquardt-
€ Levenburg algorithm
 The sedimentation coefficient is then

ϖ 2 s = 0.0107 hr −1
0.0107 hr −1 ⎛ 1hr ⎞ 2.97x10 −6 sec −1
s= ⎜ ⎟ =
ϖ2 ⎝ 3600sec ⎠ ϖ2
2.97x10 −6 sec −1
= 2 2 2
⎛ rev ⎞ ⎛ radians ⎞ ⎛ 1 min ⎞
⎜ 40000 ⎟ ⎜2π ⎟ ⎜ ⎟
⎝ min ⎠ ⎝ rev ⎠ ⎝ 60 sec ⎠
= 1.7x10 −13 sec

Problem 2 (5 points)
€
For the following data giving reactant concentration versus time for the following general chemical
transformation:
A  products
Time (sec) [A] (M)
1 0.12
2 0.074
3 0.044
4 0.027
5 0.016
6 0.009
8 0.0036
10 0.0013

determine the order of the reaction (i.e., is this first or second order reaction). Show work and use any
means (i.e., graphical or other) to arrive at your answer. Please give a rationale for your conclusion
regarding the reaction order.

Solution:
Recall that the linearized form of the integrated rate law for first order kinetics is:

ln[A] = ln[A]0 − kt

Recall that the linearized form of the integrated rate law for second order kinetics is

€
1 1
= + 2kt
[A] [A]0

To determine the reaction order (first or second), one plots the data according to the appropriate
linearized form of the integrated rate expressions. For first order, one plots ln([A]) versus time, and for
€ second order, one plots (1/[A]) versus time. The reaction order is determined by the best fit of the data
to one of the models. In this case, the best fit is given by the first order rate expression, thus indicating
that the reaction is first order with respect to species A. In Figure 1, the green line is the fitted line, and
the symbols are
the ln([A])
values
based on the
data given.
Plotting the
inverse

Figure 1. Natural log of concentration versus time. Red points are the
data, green line the best fit linear function to the data.

concentration versus time we obtain nonlinear behavior (Figure 2), thus indicating again that the
reaction is not second order.

Figure 2. Inverse concentration data versus time. The trend is clearly non-
linear, indicating that the reaction is not second order.
 CHEM444 Section 11/81 Spring 2011 (11S)
QUIZ 3 March 10, 2011

NAME: Score ______/10

Problem 1 (2 points). Using your knowledge and conclusions of our discussion of kinetic theory,
3
determine the average of the cube of the x-component of velocity ( v x
) given the Maxwell-Boltzmann
distribution for the x-component of velocity:

⎛ m ⎞1/ 2 −mv 2 / 2k T
f (v x ) = ⎜ ⎟ e x B €
⎝ 2πkB T ⎠

Solution:
Substituting the integrand, we see that the integral is that of an odd function over symmetric limits, thus
€ giving zero.

∞ ⎛ m ⎞1/ 2 −mv 2 / 2k T
v 3
x = ∫ v ⎜
3
x ⎟ e x B dx
−∞ ⎝ 2πk T
B ⎠

⎛ m ⎞1/ 2 ∞ 3 −mv 2 / 2k T
= ⎜ ⎟ ∫ v x e x B dx = 0
⎝ 2 πk T
B ⎠ −∞

€ Problem 2 (8 Points) Given the following mechanism for the transformation of hydrogen and bromine
to HBr,

k
Br2 ⎯⎯1 → 2 Br • __________________
k
Br • + H 2 ⎯⎯2 → HBr + H • __________________
k
H • + Br2 ⎯⎯3 → HBr + Br • __________________
k
H • + HBr ⎯⎯4 → H 2 + Br • __________________
k
2 Br • ⎯⎯5 → Br2 __________________
d [ HBr]
determine the rate expression for in terms of rate constants and measurable concentrations,
dt
not concentrations of intermediates. In the space provided next to each elementary reaction step,
€ whether the step is termination, propagation, initiation, etc.
indicate

€
Solution:
 k
Br2 ⎯⎯1 → 2 Br • ___initiation_______________
k
Br • + H 2 ⎯⎯2 → HBr + H • _____propagation_____________
k
H • + Br2 ⎯⎯3 → HBr + Br • _____propagation_____________
k
H • + HBr ⎯⎯4 → H 2 + Br • _____inhibition_____________
k
2 Br • ⎯⎯5 → Br2 __________termination________

d [ HBr]
= k 2 [ Br • ][ H 2 ] + k 3 [ H •][ Br2 ] − k 4 [ H • ][ HBr] (1)
dt
d [ Br • ] 2
= 2k1 [ Br2 ] − k 2 [ Br • ][ H 2 ] + k 3 [ H •][ Br2 ] + k 4 [ H • ][ HBr] - 2k 5 [ Br • ] (2)
dt
d[ H •]
= k 2 [ Br • ][ H 2 ] − k 3 [ H • ][ Br2 ] - k4 [ H • ][ HBr] (3)
dt

Apply steady state approximation to (2) and (3) by setting them to zero.
Subtract (3) from (1) to get:

d [ HBr]
€ = 2k 3 [ H • ][ Br2 ] (4)
dt

Add (2) and (3) to get:

2
0 = 2k1 [ Br2 ] - 2k 5 [ Br • ]
€
⎛ k1 ⎞1/ 2 1/ 2 1/ 2
[ Br • ] = ⎜ ⎟ [Br2 ] = k [Br2 ] (5)
⎝ k 5 ⎠

Substituting (5) in (3) gives:

1/ 2
0 = k2 k [ Br2 ] [H 2 ] - [H •]{k3 [Br2 ] + k4 [HBr]}
1/ 2
€ k 2 k [ Br2 ] [H2 ]
[ H •] = (6)
{k [Br ] + k [HBr]}
3 2 4

Substituting (6) into (4) gives our result

€
 d [ HBr]
= 2k 3 [ H • ][ Br2 ]
dt
3/2
d [ HBr] 2k 3 k2 k [ Br2 ] [ H 2 ]
=
dt {
k 3 [ Br2 ] + k 4 [ HBr] }
Problem 3 (Bonus 2 Points) In class, we determined that the fractional coverage of a surface for
Langmuir non-dissociative adsorption processes is:

KP
€ θ=
1+ KP

where K is the equilibrium constant defining the equilibrium between adsorption and desorption, and P
is the total pressure for this one component system.
€

Derive the analogous expression for dissociative processes.

The process is written as a molecule A2 dissociating and then adsorbing onto two independent surface
sites (which may not necessarily be adjacent).

k
A2 + 2S ⎯⎯a → 2(S • A)
k
2(S • A) ⎯⎯d → 2S + A2

At equilibrium, the adsorption and desorption rates are equal.

€ ka PA 2 CS2 = k d CS•
2
A

⎛ CS•
2 ⎞ ⎛ CS• A ⎞ 2 ⎛ CS• A ⎞ 2 ⎛ θ S• A ⎞ 2
A
ka PA 2 = k d ⎜ 2 ⎟ = kd ⎜ ⎟ = k d ⎜ ⎟ = kd ⎜ ⎟
⎝ CS ⎠ ⎝ CS ⎠ ⎝ Ctot − CS• A ⎠ ⎝1 − θ S• A ⎠
⎛ θ S• A ⎞ 2
kd ⎜ ⎟ = ka PA 2
⎝1 − θ S• A ⎠

⎛ θ S• A ⎞ 2
⎜ ⎟ = K ad PA 2
⎝1 − θ S• A ⎠
⎛ θ S• A ⎞
⎜ ⎟ = K ad PA 2
⎝1 − θ S• A ⎠
K ad PA 2
θ S• A =
1+ K ad PA 2

€
 CHEM444 Section 11/81 Spring 2011 (11S)
QUIZ 4 March 17, 2011

NAME: Score ______/10

Problem 1 (2 points). Describe perturbation-relaxation approaches in chemical kinetics. Address the
following: 1. Define perturbation-relaxation approaches, 2. Explain why they are needed, 3. Discuss the
major result(s) arising from such analyses and how they are practically useful.

Perturbation-relaxation methods in chemical kinetics are used to extract kinetic rate constants for fast
reactions for which initial rates may not be easily accessible experimentally. Such approaches introduce
small changes, perturbations, to systems at equilibrium. The perturbations can be via temperature
changes (T-jump), pressure changes, fast application of external fields (i.e. NMR). Following the
application of the perturbation, the system’s relaxation to a new equilibrium is monitored. The kinetics of
the relaxation provide information on the relaxation time of the system. This characteristic time, τ relaxation ,
embeds information about the kinetic rate constants. In conjunction with other kinetic data (i.e.,
equilibrium constants), individual rate constants can be extracted.

€
Problem 2 (8 Points). The following data where obtained from K. Bendinskas, C. DiJiacomo, A. Krill,
and E. Vitz, Journal of Chemical Education, 82(7), 1068 (2005). In this study, the enzyme alcohol
dehydrogenase (ADH) is used to catalyze the conversion of ethanol (the substrate) to acetaldehyde (the
product). Eight kinetic trials were carried out in a pH 9.0 buffer; only the concentration of ethanol was
varied from one trial to the next. The reaction was followed spectrophotometrically, Specifically, the
direct conversion of ethanol to acetaldehyde only gives rise to absorbance changes in the UV portion of
the spectrum, which is difficult to follow with standard lab spectrometers and cuvettes. The authors
were able to couple the ethanol reaction to another reaction that gives rise to a color change in the
visible region (through a coupling scheme described in the above reference, dichlorophenolindophenol
undergoes a synchronous redox reaction which causes the solution to go from blue to colorless; the
authors monitored this change at 635 nm).

The initial rate of reaction was defined as the slope of absorbance at 635 nm versus time plot that was
recorded for each trial (these dA/dt values are given in the table below, and represent the rate of
reaction, R). Using the data provided, determine the Michaelis-Menten constant, Km, and the maximum
reaction velocity.

Trial [Ethanol] - (mol/L) Rate - Absorbance change - (dA/dt) - (1/min)

1 0.007 0.06
2 0.015 0.11
3 0.031 0.16
4 0.068 0.21
5 0.100 0.23
6 0.200 0.28
7 0.300 0.29
8 0.400 0.28

Solution:
For this part, we set up the linear form for inverse rate versus inverse substrate concentration
(Michaelis-Menten kinetic model) and then regress the data to find the queried data. Plots of this nature
 are called Lineweaver-Burke plots. In this problem, you are specifically given information that the
absorbance time differential data at the initial reaction times represent the initial reaction rate, so we will
not concern ourselves with converting absorbance to concentration, though one could invoke relations
such as Beer’s relation for converting to more appropriate units. For the present, we use the given data
as initial reaction rate data.

Rmax [ETOH]
Rate =
K M + [ETOH]
1 1 KM
= +
Rate Rmax Rmax [ETOH]

The linearized plot of the raw data (ethanol concentration versus absorbance rate) is:
€ The solid green line is the line of best fit (regression data given below). The symbols are the linearized
data.
 The final fitting to a line of y = a*x + b gives (a = slope, b = intercept). The maximum rate is:

1 1
Rmax = = = 0.31min−1
b 3.23854

Km mol mol
a= − − > K m = aRmax = (0.0930335 min)(0.31min−1 ) = 0.029
Rmax L L

€
 CHEM444 Section 11/81 Spring 2011 (11S)
QUIZ 5 March 24, 2011

NAME: Score ______/10

Problem 1 (5 points). For each pair of functions given, demonstrate whether the pair is orthogonal:

⎛ 8x 3 12x ⎞ ⎛ -x 2 ⎞ ⎛16x 4 48x 2 ⎞ ⎛ -x 2 ⎞

A. ψ1 = A1⎜ 3 − ⎟ exp⎜ 2 ⎟ ψ 2 = A2 ⎜ 4 − 2 +12⎟ exp⎜ 2 ⎟ (-∞ ≤ x ≤ ∞)
⎝ α α ⎠ ⎝ 2α ⎠ ⎝ α α ⎠ ⎝ 2α ⎠

Solution:
To determine if the two functions are orthogonal to one another, we compute the following integral. The
€integrand is odd over the symmetric integration limits, thus allowing us to write the answer immediately.
Since the integral is zero, the pair is orthogonal. One can expand the integrand to obtain a sum of
integrals of odd functions; either way, the integral is zero and the pair is orthogonal. Finally, as we will
see later, these functions are the eigenfunctions for the quantum harmonic oscillator (though this
information is not necessary to solve the current problem).

? ∞ ∞ ⎛ -x 2 ⎞ ⎛ 8x 3 12x ⎞⎛ 16x 4 48x 2 ⎞

0 = ∫ ψ1*ψ 2 dx = A1 A2 ∫ exp⎜ 2 ⎟ ⎜ 3 − ⎟⎜ 4 − 2 + 12⎟ dx
-∞ -∞ ⎝ α ⎠ ⎝ α α ⎠⎝ α α ⎠
∞ ∞
= A1 A2 ∫ (even)(odd)(even) dx = A1 A2 ∫ (odd) dx = 0
-∞ -∞

⎛ πx ⎞ ⎛ 2πx ⎞
€ B. ψ1 = A1 sin⎜ ⎟ ψ 2 = A2 sin⎜ ⎟ (0 ≤ x ≤ a)
⎝ a ⎠ ⎝ a ⎠
Solution:
The functions given are eigenfunctions of the 1-D particle in a box problem, so they should turn out to
be orthogonal.
€
? a a
⎛ πx ⎞ ⎛ 2πx ⎞
0 = ∫ ψ1*ψ 2 dx = A1 A2 ∫ sin⎜ ⎟sin⎜ ⎟ dx
0 0
⎝ a ⎠ ⎝ a ⎠
πx a
let z = - -- > dx = dz
a π
? a ⎛ a ⎞ π
0 = ∫ ψ1*ψ 2 dx = ⎜ ⎟ A1 A2 ∫ sin( z) sin(2z) dz
0
⎝ π ⎠ 0

Use last integral in Table 2.2 (page 2-2) of Handbook (Dybowski and Teplyakov) with m=2 and n=1:

€ ? a π z= π
⎛ a ⎞ ⎛ a ⎞ sin(z) sin(3z)
0
*
0 = ∫ ψ ψ 2 dx = ⎜ ⎟ A1 A2 ∫ sin( z) sin(2z) dz = ⎜ ⎟ A1 A2
1
⎝ π ⎠ 0
⎝ π ⎠ 2
− { 6 } z= 0
=0−0 =0

€ Problem 2 (5 Points) For a particle in a 1-D box of side length “a” (0≤x≤a), what is the expectation
value of the linear momentum?
Solution:
For this problem, we straightforwardly determine the expectation value of linear momentum for a particle
in a box of one dimension. A priori, we might think that since the particle is equally likely to have
momentum in the positive and negative directions of equal magnitude (i.e., the distribution of particle
momenta is symmetric about px=0), the expectation value may reasonably well be zero. Let’s consider
 this explicitly.

⎛ nπx ⎞
ψ n = An sin⎜ ⎟ (0 ≤ x ≤ a)
⎝ a ⎠

∂
pˆ x = −i
∂x
a
⎛ nπx ⎞⎡ ∂ ⎛ ⎛ nπx ⎞⎞⎤ ⎛ −nπi ⎞ a ⎛ nπx ⎞ ⎛ nπx ⎞
∫ An sin⎜ ⎟⎢−i
⎝ a ⎠⎣ ∂x ⎝
A sin
⎜ n ⎜ ⎟⎟⎥
⎝ a ⎠⎠⎦
dx ⎜
⎝ a ⎠ 0
⎟ ∫ sin⎜ ⎟cos⎜
⎝ a ⎠ ⎝ a ⎠
⎟ dx
0
< px >= a
= a
⎛ nπx ⎞ ⎛ nπx ⎞ ⎛ nπx ⎞
∫ n ⎝ a ⎠ n ⎝ a ⎠
A sin⎜ ⎟ A sin⎜ ⎟ dx ∫ sin2⎜⎝ a ⎟⎠ dx
0 0

a
⎡ ⎛ nπx ⎞⎤
(−i)⎢sin 2⎜ ⎟⎥
⎣ ⎝ a ⎠⎦ 0
< px >= a =0
2 ⎛ nπx ⎞
∫ sin ⎜⎝ a ⎟⎠ dx
0

Thus we see that the numerator determines the final result, which indeed shows that the expectation
value of momentum is zero.
€
 CHEM444 Section 11/81 Spring 2011 (11S)
QUIZ 6 April 7, 2011

NAME: Score ______/10

Problem 1 (5 points). For each pair of functions given, demonstrate whether the pair is orthogonal:

⎛ 8x 3 12x ⎞ ⎛ -x 2 ⎞ ⎛16x 4 48x 2 ⎞ ⎛ -x 2 ⎞

ψ1 = A1⎜ 3 − ⎟ exp⎜ 2 ⎟ ψ 2 = A2 ⎜ 4 − 2 +12⎟ exp⎜ 2 ⎟ (-∞ ≤ x ≤ ∞)
⎝ α α ⎠ ⎝ 2α ⎠ ⎝ α α ⎠ ⎝ 2α ⎠

Solution:
To determine if the two functions are orthogonal to one another, we compute the following integral. The
€ integrand is odd over the symmetric integration limits, thus allowing us to write the answer immediately.
Since the integral is zero, the pair is orthogonal. One can expand the integrand to obtain a sum of
integrals of odd functions; either way, the integral is zero and the pair is orthogonal. These functions are
the eigenfunctions for the quantum harmonic oscillator.
? ∞ ∞ ⎛ -x 2 ⎞ ⎛ 8x 3 12x ⎞⎛ 16x 4 48x 2 ⎞
1= ∫ ψ1*ψ 2 dx = A1 A2 ∫ exp⎜ 2 ⎟ ⎜ 3 − ⎟⎜ 4 − 2 + 12⎟ dx
-∞ -∞ ⎝ α ⎠ ⎝ α α ⎠⎝ α α ⎠
∞ ∞
= A1 A2 ∫ (even)(odd)(even) dx = A1 A2 ∫ (odd) dx = 0
-∞ -∞

Problem 2 (5 Points) Can the momentum and potential energy of a quantum particle existing in one-
dimensional space be known simultaneously? Please show your detailed work. Consider that the
€ potential is not constant for all values of position, x.

Solution:

Let’s consider a generic, position-dependent potential, V(x) (one-dimensional). We’ll let the associated
ˆ (x) . In order to test whether the potential energy and linear
operator for this potential energy be V
momentum can be determined simultaneously and exactly, we evaluate the commutator operating on
some general function, f(x).

⎡ € ⎤
[pˆ ,Vˆ (x)] f (x) = ⎢⎣−i dxd ,Vˆ (x)⎥⎦ f (x)
x

d df (x)
= −i (V (x) f (x)) + iV (x)
dx dx
df (x) dV (x) df (x)
= −iV (x) − if (x) + iV (x)
dx dx dx
dV (x)
= −if (x)
dx
Thus, the commutator evaluates to:

€ [pˆ ,Vˆ (x)] = −i dVdx(x) ≠ 0

x

Since the commutator is not zero, the properties cannot be determined simultaneously and exactly.