CHBE 4300 – KINETICS AND REACTOR DESIGN Georgia Institute of Technology Fall 2015

Problem Set #3 – “due” September 21st, 2015

If you have questions regarding these solutions, please contact John Findley (jfindley6@gatech.edu)

Problem 1
The liquid-phase reaction of methanol and triphenyl takes place in a constant-volume batch reactor at
25°C.
𝐶𝐻3 𝑂𝐻 + (𝐶6 𝐻5 )3 𝐶𝐶𝑙 → (𝐶6 𝐻5 )3 𝐶𝑂𝐶𝐻3 + 𝐻𝐶𝑙
𝐴+𝐵 →𝐶+𝐷
The following data are collected for equal initial concentrations of methanol and triphenyl:

𝐶𝐴 (𝑚𝑜𝑙/𝑑𝑚3 ) 1.0 0.95 0.816 0.707 0.50 0.370

time (h) 0 0.278 1.389 2.78 8.33 16.66

The following data are collected for an initial methanol concentration of 0.1 𝑚𝑜𝑙⁄𝑑𝑚3 and an
initial triphenyl concentration of 1 𝑚𝑜𝑙⁄𝑑𝑚3 :

𝐶𝐴 (𝑚𝑜𝑙/𝑑𝑚3 ) 0.1 0.085 0.074 0.053 0.036

time (h) 0 1 2 5 10

Determine the rate law and rate law parameters. If you were to take more data points, what
would be a reasonable choice of conditions (𝐶𝐴0 , 𝐶𝐵0 )? Why?

Solution:
We will assume that we have a rate law of the following form:

𝑟 = −𝑘𝐶𝐴𝑛 𝐶𝐵𝑚
Also, from the 1:1 stoichiometric ratio, we can tell that:
𝑑𝐶𝐴 𝑑𝐶𝐵
= = 𝑟 = −𝑘𝐶𝐴𝑛 𝐶𝐵𝑚
𝑑𝑡 𝑑𝑡
Where we assumed that we were operating a constant volume, isothermal batch reactor with no
concentration gradients.

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We will solve the problem using the integral and differential methods.

Integral Method
For the second set of data, we see that 𝐶𝐵0 ≫ 𝐶𝐴0 so we can assume that the 𝐶𝐵 is relatively
constant for this experiment. This allows us to use the method of excess to calculate the rate
dependence on 𝐶𝐴 .
𝑑𝐶𝐴
= 𝑘′𝐶𝐴𝑛
𝑑𝑡
Next, we can use the integral method iteratively to find the reaction order with respect to A
(𝐶𝐴1−𝑛 − 𝐶𝐴0
1−𝑛 )
= (𝑛 − 1) ∗ 𝑘𝑡

Reaction 2 Integral Method

30
Ca^(1-n)

20

10 y = 1.7789x + 9.9808
R² = 1
0
0 2 4 6 8 10 12
t (h)

t CA CA^(1-n)
0 0.1 10
1 0.085 11.76471
2 0.074 13.51351
5 0.053 18.86792
10 0.036 27.77778

n 2
slope 1.778881
k' 1.778881

Notice how good the fit is for a second order reaction. 𝑅 2 = 1

2
Now, we can return to the first data set. Because 𝐶𝐴0 = 𝐶𝐵0 we know that 𝐶𝐴 = 𝐶𝐵

Now, we can write the rate law as:

𝑑𝐶𝐴
= 𝑘𝐶𝐴𝑚+2
𝑑𝑡

Reaction 2 Integral Method

7
y = 0.2981x + 1.0166
6
R² = 0.9999
5
CA^(1-(2+m))

0
0 2 4 6 8 10 12 14 16 18
t (h)

t CA CA(1-(2+m))
0 1 1
0.278 0.95 1.096724
1.389 0.816 1.441975
2.78 0.707 1.866573
8.33 0.5 3.482202
16.66 0.37 5.987381

m 0.8
slope 0.298105
k 0.165614

Therefore, the rate law according to the integral method is:

𝑑𝐶𝐴 𝑑𝐶𝐵
= = 𝑟 = −0.1656 ∗ 𝐶𝐴2 𝐶𝐵0.8
𝑑𝑡 𝑑𝑡
𝑚𝑜𝑙 −1.8
𝑘 = 0.1656 −1.8
𝐿 ∗ℎ

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Differential Method
To perform the differential method on this set of data, we must first linearize the rate equation:
𝑑𝐶𝐴
ln (− ) = ln(𝑘) + 𝑛 ∗ ln(𝐶𝐴 ) + 𝑚 ∗ ln(𝐶𝐵 )
𝑑𝑡
Once again, we will begin by analyzing experiment 2 (because 𝐶𝐵0 ≫ 𝐶𝐴0 ). The concentration of
B is relatively constant, so we can rewrite our rate equation as follows:
𝑑𝐶𝐴
ln (− ) = ln(𝑘′) + 𝑛 ∗ ln(𝐶𝐴 )
𝑑𝑡
Now, the data is numerically differentiated (this time using the “SLOPE” command in Excel)

Experiment 2 Differential Method

0
-3.5 -3 -2.5 -2 -1.5 -1 -0.5 0
-1

-2
y = 1.5301x - 0.7205
ln(-dCa/dt)

R² = 0.9455
-3

-4

-5

-6

-7
ln(Ca)

t Ca (mol/L) (-dCa/dt) ln(Ca) ln(-dCa/dt)

0 0.1 0.015 -2.30259 -4.19970508
1 0.085 0.013 -2.4651 -4.34280592
2 0.074 0.007769 -2.60369 -4.85758412
5 0.053 0.004612 -2.93746 -5.37904058

For experiment 2, it is shown that the reaction order with respect to species A is
approximately 1.5 (the slope)
For part 2, we use the fact that 𝐶𝐴 = 𝐶𝐵 to get a new rate law:
𝑑𝐶𝐴
ln (− ) = ln(𝑘) + (𝑛 + 𝑚) ∗ ln(𝐶𝐴 )
𝑑𝑡
Notice that k is the y-intercept and the sum on n and m is the slope.

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 Experiment 1 Differential Method
0
-1.2 -1 -0.8 -0.6 -0.4 -0.2 0
-0.5

-1

y = 2.4879x - 1.8112 -1.5

R² = 0.9859 -2

-2.5

-3

-3.5

-4

-4.5

t Ca dC/dt lnCa ln(dC/dt)

0 1 0.179856 0 -1.7156
0.278 0.95 0.150234 -0.05129 -1.89556
1.389 0.816 0.099486 -0.20334 -2.30773
2.78 0.707 0.057829 -0.34672 -2.85026
8.33 0.5 0.026452 -0.69315 -3.63243
16.66 0.37 0.015606 -0.99425 -4.16008

From experiment 1, we see that 𝑚 + 𝑛 = 2.5 so 𝒎 = 𝟏

𝑚𝑜𝑙 −1.5
𝑘 = −0.1634
𝐿−1.5 ∗ ℎ
The rate law is as follows:
𝑑𝐶𝐴 𝑑𝐶𝐵
= = 𝑟 = −0.1634 ∗ 𝐶𝐴1,5 𝐶𝐵1
𝑑𝑡 𝑑𝑡
Notice that although the differential method was easier to use when determining the reaction
order, the fits were slightly off compared to those obtained while using the differential method
(the integral method was more robust but time-consuming). Using more data points would help
the differential method to fit better. Also, a good idea for another experiment is to choose initial
conditions such that 𝐶𝐴0 ≫ 𝐶𝐵0 so that we can easily verify the B dependence.

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Problem 2
Using the kinetic theory of gases, estimate the rate constant for the recombination of two oxygen
atoms at 200 °C assuming a collision diameter oo= 3 Å. For this reaction, would you expect
any dependence of the reaction rate on the orientation of collision? Would you expect that the
collision must have a minimum energy to lead to reaction? Explain.

Solution:
From collision theory, we know that:

2
𝜌(𝜋𝑑𝐴𝐵 ) 8𝑅𝑇 −𝐸 𝑎 1
𝑘=𝐿 √( )𝑒 𝑘𝐵 𝑇 𝑒 2
4 𝐿𝜋𝜇
−𝐸𝑎
8𝑘𝐵 𝑇
𝜌 is the steric ratio, √( ) is the average relative velocity and 𝑒 𝑘𝐵 𝑇 is related to the fraction of
𝜋𝜇
collisions with enough energy to react.

Oxygen radicals recombine readily without approximately 0 energy of activation, so we can say
that
−𝐸𝑎
𝑒 𝑘𝐵 𝑇 = 1
Oxygen radicals do not exhibit steric hindrance (they are small and identical) so we can say that
the steric ratio is 1. This gives us the new rate constant equation:

2
(𝜋𝑑𝐴𝐵 ) 8𝑘𝐵 𝑇 1
𝑘= √( )𝑒 2
4 𝜋𝜇

The collisions are between two identical oxygen radicals (MW = 16 g/mol), so we can calculate
the reduced mass as follows:
𝑚 16 𝑔 1 𝑚𝑜𝑙 𝑘𝑔
𝜇= = ∗ 23
∗ = 1.33 ∗ 10−26 𝑘𝑔
2 2 𝑚𝑜𝑙 6.022 ∗ 10 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 1000 𝑔
The collision cross sectional area is as follows:
2
(𝜋𝑑𝐴𝐵 ) (𝜋3Å2 ) 1 𝑚2
𝜎= = ∗ 20 2 = 7.1 ∗ 10−20 𝑚2
4 4 10 Å

6
Substituting these values into the equation for k, we find:

𝐽
1 8 ∗ 8.314 ∗ (473𝐾)
𝑘 = 6.02 ∗ 1023 ∗ (7.1 ∗ 10−20 𝑚2 ) ∗ 𝑒2 ∗ √( 𝑚𝑜𝑙 ∗𝐾 )
6.02 ∗ 1023 ∗ 𝜋(1.33 ∗ 10−26 𝑘𝑔)

𝑚3
7
𝑘 = 7.88 ∗ 10
𝑚𝑜𝑙 ∗ 𝑠

7
Problem 3

adsorbates confined to a 1-D “trench” defect on a catalyst surface. Assume that N identical
adsorbates exist in the trench. Be sure your final equation yields the appropriate units.

Solution:
This is a 1-D case, so we are looking at the collision frequency along a line (as opposed to a
collision cylinder). Based on this, we can define a “concentration” of adsorbates per unit length
𝑁
as 𝐿 . Analogously to the 3D case described in class, we can define a collision frequency as
follows:
𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛𝑠 𝑁
= ̅̅̅̅̅
𝑣
𝑡𝑖𝑚𝑒 𝐿 𝑟𝑒𝑙
Now, we need to find the average relative velocity, ̅̅̅̅̅
𝑣𝑟𝑒𝑙 of the billiard balls. We will assume that
every ball will be moving at the same average speed, 𝑣̅ .
For balls moving in the same direction, 𝑣𝑟𝑒𝑙 = 0
For balls moving in opposite directions, 𝑣𝑟𝑒𝑙 = 2𝑣̅
We know that the balls are moving to the left and to the right with equal probabilities, so:
𝑣𝑟𝑒𝑙 = 𝑣̅
̅̅̅̅̅
The mean free path is defined as follows:
𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒⁄
𝜆= 𝑡𝑖𝑚𝑒 = 𝑣̅
𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛𝑠⁄ 𝑁
𝑡𝑖𝑚𝑒 𝐿 ̅̅̅̅̅
𝑣𝑟𝑒𝑙

Knowing that ̅̅̅̅̅

𝑣𝑟𝑒𝑙 = 𝑣̅ ,
𝐿
𝜆=
𝑁
This expression has units of length.
8
Problem 4

Solution:
a)
𝑰𝑪𝒍 + 𝑯𝟐 → 𝑯𝑰 + 𝑯𝑪𝒍

𝐻𝐼 + 𝐼𝐶𝑙 → 𝐻𝐶𝑙 + 𝐼2

In the first reaction, a H-H bond is broken, whereas in the second reaction, a H-I bond is broken.
The H-H bond is stronger than a H-I bond, so the energy of activation will be higher for the first
reaction.

b)
𝑪𝑯𝟑 𝑪𝑶𝑪𝑯𝟑 → 𝑪𝑯𝟑 ∗ +𝑪𝑯𝟑 𝑪𝑶 ∗

𝐶𝐻3 ∗ +𝐶𝐻3 𝐶𝑂𝐶𝐻2 ∗→ 𝐶𝑂𝐶2 𝐻5

In the first reaction, 𝐶𝐻3 𝐶𝑂𝐶𝐻3 is split into radicals. In the second reaction, two radicals (which
are inherently unstable) combine, resulting in a very low activation energy. The first reaction has
the higher energy of activation.

c)
𝐻2 + 𝐶2 𝐻4 → 𝐶2 𝐻6

𝑩𝒓𝟐 + 𝑲 → 𝑲𝑩𝒓 + 𝑩𝒓

9
The second reaction will have a higher pre-exponential factor because 𝐻2 + 𝐶2 𝐻4 → 𝐶2 𝐻6 is
limited by the orientation of the 𝐶2 𝐻4 molecule, so there is a smaller number of reactions
oriented in a way such that a reaction can occur.

(𝐶2 𝐻4 )

d)
𝟐𝑶 ∗→ 𝑶𝟐

2𝐶𝐻3 ∗→ 𝐶2 𝐻6

The first reaction will have a higher pre-exponential factor. Although the 𝐶𝐻3 ∗ radical has a
larger diameter (the collision cylinder will be larger), it is limited in the number of orientations in
which it can collide and react (it has more steric restrictions).

10