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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 K:
1 = 1 1 = (

2 = 2 2 = (

) (1 )

) (1 )

You can then substitute in 1 and 2 for the vapor mole fractions in both equations. Plugging
in the given equilibrium constants at reaction conditions as well transforms the equations:
(1 2 )(1 1 2 )
1

5 (0.5 1 )(0.5 1 2 )
1
2 (1 1 2 )
0.88 =
5 (1 2 )(0.5 1 2 )

6.6 103 =

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Now, we can construct our ICE table to relate the equilibrium constants to composition:
Initial
Change
Final
Toluene
1 -21-22-23 1-21-22-23

Para

0 1

Ortho

0 2

Meta

0 3

1+2+3
0 1+2+3
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:
Benzene

( )( )
1 (1 + 2 + 3 )
=
= 0.075
2
(1 21 22 23 )2

( )( )
2 (1 + 2 + 3 )
2 =
=
= 0.078
(1 21 22 23 )2
2
( )( )
3 (1 + 2 + 3 )
1 =
=
= 0.167
(1 21 22 23 )2
2
This is a system of three equations and three unknowns. The s can be solved to find:
1 =

1 = 0.062
2 = 0.065
3 = 0.138
Now, the composition can be evaluated:
Toluene:
Benzene:
Ortho-xylene:
Meta-xylene:
Para-xylene:

= 1 21 22 23 = 1 2 0.062 2 0.065 2 0.138 = .

= 1 + 2 + 3 = 0.062 + 0.065 + 0.138 = .
= 2 = .
= 3 = .
= 1 = .

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

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Solving the system of equations gives 1 and 2, 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:

= 1

0.012
=1
= .

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 (1 2 )(10 1 2 )

5 (0.5 1 )(0.5 1 2 )
1
2 (10 1 2 )
0.88 =
5 (1 2 )(0.5 1 2 )

6.6 103 =

Solving for 1 and 2, we can evaluate the compositions of the final mixture:

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Analogously to part (a), the equilibrium conversion is found using the new final acetylene
amount:
, = 1

0.0014
= .
0.5

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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:

= =

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

= []

We do not know . However, we can find it through the molar expansion factor. To do this,

start by using the ideal gas law to define the ratio of initial and final total moles:

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:

0.7 +
=
=
= 1.7

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

= 1 +

The expansion factor can be found using the given information
31
= (1) (
)=2
|1|

Write conversion in terms of . Then, plug in the appropriate numbers and solve:

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1.7 = 1 + 2 (1

= 0.65

Now, we can plug this into our solution of the batch reactor balance to solve for the reaction
rate constant:
0.65 = [ 12]
= 0.0359 1
Now, we can start to consider the actual variable pressure case in the problem statement.

However, from the design equation will not be the same as before. We can still find it

using the same method though. So, we write out the ideal gas law again:

2.5
= =
= 1.389

1.8
The expansion factor is unchanged. Solving for

1.389 = 1 + 2 (1

= 0.8055

Now, plug this into the batch reactor design equation we derived before to solve for time:
0.8055 = [(0.03591 )]

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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
t, hr

0.84 0.68 0.53

1

0.38 0.27
4

0.16

0.09 0.04
7

0.018 0.006 0.0025

9

10

Determine whether these data can be reasonably fitted by a kinetic equation of the MichaelisMenten 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:
4 =

5 =

Substituting:
=

3
4
=
=

+ 1 + 5

11

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Now, we have an ODE, which we can separate and integrate. This is the integral method of
fitting rate equations:
HINT: This integral
appears difficult, but try
separating the fraction,
and then integrating it in
two, simpler parts

1 + 5
=
4

5 ( 0 ) + | |
0

5 ( 0 ) |0 |
+
=
4
4
Transforming to put into a more useful form (linear equation):

5 +

| |
0

(0 )

| |
0

(0 )
Dependent variable

4
(0 )

4
5
(0 )

Slope

y-intercept

Independent
Variable

We can now plot our data, and see if it fits our derived model. A sketch of the graph is shown
below:

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As written on the figure, fitting the data to our model reveals our unknown parameters:

So our final rate equation becomes:

3 = .
= .

.
+ .
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:
=

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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:
0
| =

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:
|

0
|
| = |2| = (76)
0.50
= 0.00912 1
So to gauge the relative change in activity, we can pick another time, and see how the

concentration changes. For the half-life, we found = 0.5. Lets find what this ratio
becomes after one day has elapsed:

24 60
= [(0.00912 1 ) (1

)]
0

= 1.98 106
0
So, the activity has dropped to about 2 106 of its original value

Errors? Please direct to Jay Joshi

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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:

= =

Which yields the solution:

= []

To find k, we must first find

. We can do this by first evaluating what the change in the

total number of moles are. This can be done by through the ideal gas assumption:

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

0.2
=
=
= 0.8

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

= 1 +

Conversion of A can be written in terms of moles of A:
= 1
Plugging in:

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=
1
+

(1

Now, rearrange this equation so that it can be used to plug in for :

+ 1
=

Plug this into our derived solution to the design equation:

+ 1

= []

+ 1
1

= |
|

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:
= 0
The problem statement gives us that the initial mole fraction of A is 80%. So, we can
evaluate A:

= (0.8) ( 1)

--Where "r" and "a" are the stoichiometric coefficients of species R and A, respectively
1
= (0.8) ( 1) = 0.4
2
Now, we solve for the reaction rate constant directly through our modified design equation:
=

(0.4) + 1 0.8
1
|
|
(0.4)
3
= .