Errors?

Please direct to Jay Joshi

<jjoshi7@gatech.edu>

CHBE 4300—Homework 1 Solutions

1. Xylene can be produced from toluene, as written schematically

The values of ΔG° were determined at 700 K. What is the equilibrium composition
(including all xylene isomers) at 700 K and 1.0 atm pressure? Propose a method to
manufacture para-xylene without producing significant amounts of either ortho- or meta-
xylene.

Solution

Assume: Ideal gas

We can find the equilibrium constant, K, using the provided Gibbs Free Energies of each reaction
at 700K:

−∆𝐺 ° 𝑖
𝐾𝑖 = 𝑒𝑥𝑝 [ ]
700𝑅
So we find (by numbering each reaction 1 to 3, going down):

K1 = 0.075

K2 = 0.078

K3 = 0.167
 Errors? Please direct to Jay Joshi
<jjoshi7@gatech.edu>

Now, we can construct our “ICE table” to relate the equilibrium constants to composition:
Initial Change Final
Toluene 1 -2ξ1-2ξ2-2ξ3 1-2ξ1-2ξ2-2ξ3
Para 0 ξ1 ξ1
Ortho 0 ξ2 ξ2
Meta 0 ξ3 ξ3
Benzene 0 ξ1+ξ2+ξ3 ξ1+ξ2+ξ3
TOTAL 1
So we can relate our individual equilibrium constants to composition directly, since we made the
ideal gas assumption, and are operating at an assumed standard state pressure of 1 atm:

(𝑦𝑝𝑎𝑟𝑎 )(𝑦𝑏𝑒𝑛𝑧 ) 𝜉1 (𝜉1 + 𝜉2 + 𝜉3 )

𝐾1 = 2
= = 0.075
𝑦𝑡𝑜𝑙 (1 − 2𝜉1 − 2𝜉2 − 2𝜉3 )2
(𝑦𝑜𝑟𝑡ℎ𝑜 )(𝑦𝑏𝑒𝑛𝑧 ) 𝜉2 (𝜉1 + 𝜉2 + 𝜉3 )
𝐾2 = = = 0.078
𝑦𝑡𝑜𝑙 2 (1 − 2𝜉1 − 2𝜉2 − 2𝜉3 )2
(𝑦𝑚𝑒𝑡𝑎 )(𝑦𝑏𝑒𝑛𝑧 ) 𝜉3 (𝜉1 + 𝜉2 + 𝜉3 )
𝐾1 = = = 0.167
𝑦𝑡𝑜𝑙 2 (1 − 2𝜉1 − 2𝜉2 − 2𝜉3 )2
This is a system of three equations and three unknowns. The ξ’s can be solved to find:

ξ1 = 0.062

ξ2 = 0.065

ξ3 = 0.138

Now, the composition can be evaluated:

Toluene: 𝑦𝑡𝑜𝑙 = 1 − 2𝜉1 − 2𝜉2 − 2𝜉3 = 1 − 2 ∗ 0.062 − 2 ∗ 0.065 − 2 ∗ 0.138 = 𝟎. 𝟒𝟕𝟎

Benzene: 𝑦𝑏𝑒𝑛𝑧 = 𝜉1 + 𝜉2 + 𝜉3 = 0.062 + 0.065 + 0.138 = 𝟎. 𝟐𝟔𝟓
Ortho-xylene: 𝑦𝑜𝑟𝑡ℎ𝑜 = 𝜉2 = 𝟎. 𝟎𝟔𝟓
Meta-xylene: 𝑦𝑚𝑒𝑡𝑎 = 𝜉3 = 𝟎. 𝟏𝟑𝟖
Para-xylene: 𝑦𝑝𝑎𝑟𝑎 = 𝜉1 = 𝟎. 𝟎𝟔𝟐

A shape-selective catalyst can be utilized to increase para-xylene selectivity, since para-

xylene has a smaller kinetic diameter than the other isomers. The catalyst could allow mostly
para-xylene to diffuse out of it to shift the product distribution.
 Errors? Please direct to Jay Joshi
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2. Vinyl chloride can be synthesized by reaction of acetylene with hydrochloric acid over a
mercuric chloride catalyst at 500 K and 5.0 atm total pressure. An undesirable side reaction is
the subsequent reaction of vinyl chloride with HCl. These reactions are illustrated below.

The equilibrium constants at 500 K are 6.6 x 103 and 0.88 for reaction 1 and 2, respectively.
Assume ideal behavior.
Solution
a) Find the equilibrium composition at 5.0 atm and 500 K for the case when acetylene
and HCl are present initially as an equimolar mixture. What is the equilibrium
conversion of acetylene?

First, write out the ICE table for the two reactions. Keep in mind, the feed is equimolar:

The respective equilibrium constants can also be broken up into Ky and KP, using the ideal
gas assumption to ignore Kφ:

𝑦𝐶
𝐾𝑎1 = 𝐾𝑦1 𝐾𝑃1 = (𝑦 ) (𝑃−1 )
𝐴 𝑦𝐵
𝑦𝐷
𝐾𝑎2 = 𝐾𝑦2 𝐾𝑃2 = (𝑦 ) (𝑃−1 )
𝐶 𝑦𝐵

You can then substitute in ξ1 and ξ2 for the vapor mole fractions in both equations. Plugging
in the given equilibrium constants at reaction conditions as well transforms the equations:

1 (𝜉1 − ξ2 )(1 − ξ1 − ξ2 )
6.6 × 103 = ∗
5 (0.5 − ξ1 )(0.5 − ξ1 − ξ2 )
1 ξ2 (1 − ξ1 − ξ2 )
0.88 = ∗
5 (ξ1 − ξ2 )(0.5 − ξ1 − ξ2 )
 Errors? Please direct to Jay Joshi
<jjoshi7@gatech.edu>
Solving the system of equations gives ξ1 and ξ2, which are can then be directly plugged in to
the equations found in the ICE table above to find the outlet composition:

To find equilibrium conversion of acetylene, we use the equation:

𝑛𝐴 0.012
𝑓𝐴 = 1 − °
=1− = 𝟎. 𝟗𝟕𝟔
𝑛𝐴 0.5

b) Redo part (a) with a large excess of inert gas. Assume the inert gas constitute 90 vol.
% of the initial gas mixture.

We now have to rewrite the ICE table. To account for the addition of inerts, add 9 moles to
the previous 1 mole basis to obtain 90 vol% of inerts:

Relating the information on the table above to the equilibrium constants, our system of
equations now becomes:

1 (𝜉1 − ξ2 )(10 − ξ1 − ξ2 )
6.6 × 103 = ∗
5 (0.5 − ξ1 )(0.5 − ξ1 − ξ2 )
1 ξ2 (10 − ξ1 − ξ2 )
0.88 = ∗
5 (ξ1 − ξ2 )(0.5 − ξ1 − ξ2 )

Solving for ξ1 and ξ2, we can evaluate the compositions of the final mixture:
 Errors? Please direct to Jay Joshi
<jjoshi7@gatech.edu>

Analogously to part (a), the equilibrium conversion is found using the new final acetylene
amount:

0.0014
𝑓𝐴,𝑛𝑒𝑤 = 1 − = 𝟎. 𝟗𝟗𝟕𝟐
0.5
 Errors? Please direct to Jay Joshi
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3. A first-order homogenous reaction of A going to 3B is carried out in a constant pressure
batch reactor. It is found that starting with pure A, the volume after 12 min is increased by 70
percent at a pressure of 1.8 atm. If the same reaction is to be carried out in a constant volume
reactor and the initial pressure is 1.8 atm, calculate the time required to bring the pressure to
2.5 atm.

Solution

First, we need to solve for the reaction rate constant. Start with the batch reactor design
equation. Remember, we are told the reaction is first-order, so we can write:

𝑑𝑛𝐴
= −𝑘𝐶𝐴 𝑉 = −𝑘𝑛𝐴
𝑑𝑡

Integrate the differential equation to obtain the solution form for a first order reaction:

𝑛𝐴
= 𝑒𝑥𝑝[−𝑘𝑡]
𝑛𝐴 °
𝑛
We do not know 𝑛 𝐴° . However, we can find it through the molar expansion factor. To do this,
𝐴
start by using the ideal gas law to define the ratio of initial and final total moles:

𝑅𝑇𝑛𝑡𝑜𝑡𝑎𝑙 𝑃𝑉
=
𝑅𝑇𝑛𝑡𝑜𝑡𝑎𝑙 ° 𝑃𝑉 °

The vessel is constant pressure, so P does not change. We are also given that there is a 70%
increase in volume after 12 minutes. This information let us simplify our ratio:

𝑛𝑡𝑜𝑡𝑎𝑙 𝑉 0.7𝑉 ° + 𝑉 °
= = = 1.7
𝑛𝑡𝑜𝑡𝑎𝑙 ° 𝑉 ° 𝑉°

We relate this ratio of total moles to conversion using the following equation:

𝑛𝑡𝑜𝑡𝑎𝑙
= 1 + 𝜀𝐴 𝑓𝐴
𝑛𝑡𝑜𝑡𝑎𝑙 °

The expansion factor can be found using the given information

3−1
𝜀𝐴 = (1) ( )=2
|−1|
𝑛
Write conversion in terms of 𝑛 𝐴° . Then, plug in the appropriate numbers and solve:
𝐴
 Errors? Please direct to Jay Joshi
<jjoshi7@gatech.edu>
𝑛𝐴
1.7 = 1 + 2 ∗ (1 − )
𝑛𝐴 °

𝑛𝐴
= 0.65
𝑛𝐴 °

Now, we can plug this into our solution of the batch reactor balance to solve for the reaction
rate constant:

0.65 = 𝑒𝑥𝑝[−𝑘 ∗ 12𝑚𝑖𝑛]

𝑘 = 0.0359 𝑚𝑖𝑛−1

Now, we can start to consider the actual variable pressure case in the problem statement.
𝑛
However, 𝑛 𝐴° from the design equation will not be the same as before. We can still find it
𝐴
using the same method though. So, we write out the ideal gas law again:

𝑅𝑇𝑛𝑡𝑜𝑡𝑎𝑙 𝑃𝑉
=
𝑅𝑇𝑛𝑡𝑜𝑡𝑎𝑙 ° 𝑃° 𝑉

𝑛𝑡𝑜𝑡𝑎𝑙 𝑃 2.5 𝑎𝑡𝑚

°
= °= = 1.389
𝑛𝑡𝑜𝑡𝑎𝑙 𝑃 1.8 𝑎𝑡𝑚
𝑛𝐴
The expansion factor is unchanged. Solving for :
𝑛𝐴 °

𝑛𝐴
1.389 = 1 + 2 ∗ (1 − )
𝑛𝐴 °

𝑛𝐴
= 0.8055
𝑛𝐴 °

Now, plug this into the batch reactor design equation we derived before to solve for time:

0.8055 = 𝑒𝑥𝑝[(−0.0359𝑚𝑖𝑛−1 )𝑡]

𝑡 ≈ 𝟔 𝒎𝒊𝒏𝒖𝒕𝒆𝒔
 Errors? Please direct to Jay Joshi
<jjoshi7@gatech.edu>
4. At room temperature, sucrose is hydrolyzed by the catalytic action of the enzyme sucrase
as follows:

sucrose → products

Starting with a sucrose concentration CA0 = 1.0 millimol/liter and an enzyme concentration
CE0 = 0.01 millimol/liter, the following kinetic data are obtained in a batch reactor
(concentrations calculated from optical rotation measurements):

CA, millimol/liter 0.84 0.68 0.53 0.38 0.27 0.16 0.09 0.04 0.018 0.006 0.0025
t, hr 1 2 3 4 5 6 7 8 9 10 11

Determine whether these data can be reasonably fitted by a kinetic equation of the Michaelis-
Menten type, or

where CM = Michaelis constant. If the fit is reasonable, evaluate the constants k3 and CM. Solve
by the integral method.

Solution

This problem is an example of using linear regression to fit data. The Michaelis-Menten equation
can be put into a linear form, where it can then be compared to the collected data to see if the
data fits the model.

With this in mind, we can attempt to linearize the given rate equation. To simplify this, we make
some substitutions:

𝑘3 𝐶𝐸
𝑘4 =
𝐶𝑀

1
𝑘5 =
𝐶𝑀

Substituting:

𝑑𝐶𝐴 𝑘3 𝐶𝐴 𝐶𝐸 𝑘4 𝐶𝐴
−𝑟𝐴 = − = =
𝑑𝑡 𝐶𝐴 + 𝐶𝑀 1 + 𝑘5 𝐶𝐴
 Errors? Please direct to Jay Joshi
<jjoshi7@gatech.edu>
Now, we have an ODE, which we can separate and integrate. This is the integral method of
fitting rate equations:

1 + 𝑘5 𝐶𝐴
HINT: This integral 𝑑𝐶𝐴 = −𝑑𝑡
𝑘4 𝐶𝐴
appears difficult, but try
separating the fraction,
𝐶
and then integrating it in 𝑘5 (𝐶𝐴 − 𝐶𝐴0 ) + 𝑙𝑛 |𝐶 𝐴 |
𝐴0
two, simpler parts = −𝑡
𝑘4

𝐶𝐴
𝑘5 (𝐶𝐴 − 𝐶𝐴0 ) 𝑙𝑛 |𝐶𝐴0 |
+ = −𝑡
𝑘4 𝑘4

Transforming to put into a more useful form (linear equation):

𝐶
𝑙𝑛 |𝐶 𝐴 | 𝑘4 𝑡
𝐴0
𝑘5 + =
(𝐶𝐴0 − 𝐶𝐴 ) (𝐶𝐴0 − 𝐶𝐴 )

𝐶
𝑙𝑛 |𝐶 𝐴 | 𝑘4
𝐴0
= 𝑡 − 𝑘5 “y-intercept
(𝐶𝐴0 − 𝐶𝐴 ) (𝐶𝐴0 − 𝐶𝐴 )
“Dependent variable”
“Slope” “Independent
Variable”

We can now plot our data, and see if it fits our derived model. A sketch of the graph is shown
below:
 Errors? Please direct to Jay Joshi
<jjoshi7@gatech.edu>
As written on the figure, fitting the data to our model reveals our unknown parameters:

𝑘3 = 𝟏𝟗. 𝟕 𝒉𝒓−𝟏
𝐶𝑀 = 𝟎. 𝟏𝟗𝟕 𝒎𝑴
So our final rate equation becomes:

𝟏𝟗. 𝟕𝑪𝑨 𝑪𝑬
−𝒓𝑨 =
𝑪𝑨 + 𝟎. 𝟏𝟗𝟕
To verify if our fit is appropriate, we can compare the given data to that generated from our
linearized Michaelis-Menten equation. The data that was used to generate the plot above is
shown. Because we successfully fit our data to the Michaelis-Menten model, we have shown
that it can be reasonably fitted:
 Errors? Please direct to Jay Joshi
<jjoshi7@gatech.edu>
5. An ampoule of radioactive Kr-89 (half life = 76 minutes) is set aside for a day. What does
this do to the activity of the ampoule? Note that radioactive decay is a first-order process

Solution

To begin, “activity” is a thermodynamic quantity, which is defined from the chemical

potential of a species relative to a selected standard state. Iin this context, it can be assumed
to be the effective concentration of Kr-89.

We are given that this is a first order process. From the design equation, we know that the
general equation for this reaction becomes:

𝐶𝐴0
𝑙𝑛 | | = 𝑘𝑡
𝐶𝐴
We are also given information about the half-life of the ampoule. At t = 76 min, we know that
CA = 0.5CA0. This allows us to solve the reaction rate constant:

𝐶𝐴0
𝑙𝑛 | | = 𝑙𝑛|2| = 𝑘(76𝑚𝑖𝑛)
0.5𝐶𝐴0
𝑘 = 0.00912 𝑚𝑖𝑛−1
So to gauge the relative change in activity, we can pick another time, and see how the
𝐶
concentration changes. For the half-life, we found 𝐶 𝐴 = 0.5. Let’s find what this ratio
𝐴0
becomes after one day has elapsed:

𝐶𝐴 24 ℎ𝑜𝑢𝑟𝑠 60 𝑚𝑖𝑛
= 𝑒𝑥𝑝 [−(0.00912 𝑚𝑖𝑛−1 ) (1 𝑑𝑎𝑦 × × )]
𝐶𝐴0 𝑑𝑎𝑦 ℎ𝑜𝑢𝑟
𝐶𝐴
= 1.98 × 10−6
𝐶𝐴0
So, the activity has dropped to about 2 × 10−6 of its original value
 Errors? Please direct to Jay Joshi
<jjoshi7@gatech.edu>
6. Find the first-order rate constant for the disappearance of A in the gas reaction 2A → R if,
on holding the pressure constant, the volume of the reaction mixture, starting with 80% A,
decreases by 20% in 3 min.

Solution

Assume: Ideal gas

This problem is very similar to #3 on this assignment. To begin, we write the batch reactor
design equation. We are told implicitly through the information regarding the reaction rate
constant that the reaction must be first order:

𝑑𝑛𝐴
= −𝑘𝐶𝐴 𝑉 = −𝑘𝑛𝐴
𝑑𝑡

Which yields the solution:

𝑛𝐴
= 𝑒𝑥𝑝[−𝑘𝑡]
𝑛𝐴 °
𝑛𝐴
To find k, we must first find . We can do this by first evaluating what the change in the
𝑛𝐴 °
total number of moles are. This can be done by through the ideal gas assumption:

𝑅𝑇𝑛𝑡𝑜𝑡𝑎𝑙 𝑃𝑉
° =
𝑅𝑇𝑛𝑡𝑜𝑡𝑎𝑙 𝑃𝑉 °

Pressure and temperature are held constant. We are also told that the volume decreases by
20% at a given time, so:

𝑛𝑡𝑜𝑡𝑎𝑙 𝑉 𝑉 ° − 0.2𝑉 °
= = = 0.8
𝑛𝑡𝑜𝑡𝑎𝑙 ° 𝑉 ° 𝑉°

Additionally, we write the relationship relating the change in total moles to the conversion of
our reactant and the molar expansion factor:

𝑛𝑡𝑜𝑡𝑎𝑙
= 1 + 𝜀𝐴 𝑓𝐴
𝑛𝑡𝑜𝑡𝑎𝑙 °

Conversion of A can be written in terms of moles of A:

𝑛𝐴
𝑓𝐴 = 1 −
𝑛𝐴 °

Plugging in:
 Errors? Please direct to Jay Joshi
<jjoshi7@gatech.edu>
𝑛𝑡𝑜𝑡𝑎𝑙 𝑛𝐴
= 1 + 𝜀𝐴 (1 − )
𝑛𝑡𝑜𝑡𝑎𝑙 ° 𝑛𝐴 °
𝑛
Now, rearrange this equation so that it can be used to plug in for 𝑛 𝐴° :
𝐴

𝑛𝑡𝑜𝑡𝑎𝑙
𝑛𝐴 𝜀𝐴 + 1 − 𝑛𝑡𝑜𝑡𝑎𝑙 °
=
𝑛𝐴 ° 𝜀𝐴

Plug this into our derived solution to the design equation:

𝑛𝑡𝑜𝑡𝑎𝑙
𝜀𝐴 + 1 −
𝑛𝑡𝑜𝑡𝑎𝑙 °
= 𝑒𝑥𝑝[−𝑘𝑡]
𝜀𝐴

𝑛
1 𝜀𝐴 + 1 − 𝑡𝑜𝑡𝑎𝑙°
𝑛𝑡𝑜𝑡𝑎𝑙
𝑘 = − 𝑙𝑛 | |
𝑡 𝜀𝐴

We can almost solve for the reaction rate constant through the design equation, but we still
need to solve for the molar expansion factor. Refer to the equation from Fogler:

𝜀𝐴 = 𝑦𝐴0 𝛿

The problem statement gives us that the initial mole fraction of A is 80%. So, we can
evaluate εA:

𝑟
𝜀𝐴 = (0.8) ( − 1)
𝑎

--Where "r" and "a" are the stoichiometric coefficients of species R and A, respectively

1
𝜀𝐴 = (0.8) ( − 1) = −0.4
2

Now, we solve for the reaction rate constant directly through our modified design equation:

1 (−0.4) + 1 − 0.8
𝑘=− 𝑙𝑛 | |
3 𝑚𝑖𝑛 (−0.4)

𝑘 = 𝟎. 𝟐𝟑𝟏 𝒎𝒊𝒏−𝟏