1

Taller
Segundo parcial – Ingeniería de las reacciones químicas

1 What two things are wrong with this solution?

The reaction A → B is carried out in a constant volume batch reactor. Determine the
reaction order and specific reaction rate from the following data.

t (min) 0 10 20 30

CA(mol/dm3) 1 0.6 0.4 0.3

Solution

t CA

0 1

0.4 -(0.6-1.0)/(10-0)=0.04

10 0.6

0.2 -(0.4-0.6)/(20-10)=0.02

20 0.4

0.1 -(0.2-0.4)/(30-20)=0.01

30 0.3

First find
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t CA

0 1 0.05

0.04

10 0.6 0.03

0.02

20 0.4 0.015

0.01

30 0.3 0.005

Now plot versus t and it should be a straight line.

The plot is essentially linear, therefore the reaction is zero order. From the slope of the
line we find k=0.00167 mol/dm3 min.
What two things are wrong with this solution?
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Answer

 1) The graphical differentiation of the data is incorrect as is plotted as function of

. First, even the data of versus is not plotted correctly. According to

this incorrect analysis, it should rise linearly. However, this fact is irrelevant because the
x-axis should be time, not . The correct plot is as follows.

t CA

0 1 0.053

10 0.6 0.028

20 0.4 0.017

30 0.3 0.014

2) The plot to determine the reaction order and rate constant is incorrect. Combined
mole balance and postulated rate law is

taking the natural log of both sides

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Plot versus ln CA or plot versus CA on log-log paper to determine the

reaction order. The correct plot on log-log is as follows.

The reaction order is

therefore,

When CA=1.0 mol/dm3 then

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2. Analysis of Pressure–Time Data

Determine the reaction order for the gas-phase decomposition of ditert-butyl peroxide,

(CH3)3COOC(CH3)3 →C2H6 + 2CH3COCH3

This reaction was carried out in the laboratory in an isothermal batch system of
constant volume in which the total pressure was recorded at various times during the
reaction. The data given in Table 1 apply to this reaction. Only pure ditert-butyl
peroxide was initially present in the reaction vessel.

Table 1. Pressure – time data

Time (min) Total Pressure (mmHg)

0.0 7.5
2.5 10.5
5.0 12.5
10.0 15.8
15.0 17.9
20.0 19.4

While the proper SI units of pressure are pascal (Pa) or kilopascal (kPa), a significant
amount of kinetic data in past literature are reported in units of mmHg (torr),
atmospheres, or psi. Consequently, we must be able to analyze pressure–time rate data
in any one of these units.

1 atm ≡ 14.7 psi ≡ 1.103 bar ≡ 101.3 kPa ≡ 760 mmHg

3 Use the integral method to determine the reaction order for the di-tert-butyl peroxide
decomposition described in Example 5-2.
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Solution
Recalling Example 5-1, the combined mole balance and rate law for a constant-volume
batch reactor can be expressed in the form          

(E5-1.5)         As a first guess we might try zero order, = 0, for which equation (ES-1.5)
becomes          

(CDE5-1.1)         Integrating gives us          

    
Assuming a zero-order reaction
If this is the correct order, a plot of P Tversus t should be linear. After using the data in
Table CDE5-1.1 to obtain Figure CDE5-1.1, we see that PT is not a linear function of t.
Consequently, we conclude that the reaction is not zero-order.          

Figure CDE5-1-1
          Next we try second order, = 2:          

          Integrating yields          

Assuming a second-order reaction If the reaction is second order, a plot of

versus t should be linear:           After forming Table CDE5-1.1, a
plot of versus t was constructed and is shown in Figure CDE5-1.2. From
the curvature of the plot, we conclude that the reaction is not second order.    
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Figure CDE5-1-2

        Finally, we try first order (i.e. = 1). If zero, first, or second order do not seems to
describe the reaction rate equation, it is usually best to try some other method of
determining the reaction order. for = 1,          

          Integrating with limits, when t = 0 yields          

          If the reaction is first order, a plot of versus t should be

linear. After completing Table CDE5-1.2 using the raw data, a plot of
as a function of time is made using semilog paper as shown in
Figure CDE5-1.3. From the plot we see that is indeed linear with
time, and we therefore conclude that the decomposition of di-tert-butyl peroxide follows
first-order kinetics. From the slope of the plot in Figure CDE5-1.3, we can determine
the specific reaction rate, k = 0.08 min -1          
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Figure CDE5-1.3
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4. The irreversible isomerization

A B
was carried out in a batch reactor and the following concentration-time data were
obtained:

Determine the reaction order, , and the specific reaction rate, kA.

5 What Type of Reaction is Taking Place?

Three species were found in a CSTR. The following concentration data were obtained
as a function of temperature. The initial concentration of the single reactant, A, was the
same at all temperatures. Both B and C are products. CA0 = 2 mol/dm3

Run T (oC) CA (mol/dm3) CB (mol/dm3) CC (mol/dm3)

1 30 1.7 0.01 0.29

2 50 1.4 0.03 0.57

3 70 1.0 0.1 0.90

4 100 0.5 1.25 1.25

5 120 0.1 1.80 0.1

6 130 0.01 1.98 0.01

Explain the above data, what type of reaction is taking place, independent, complex,
series or parallel?
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1.5

1
Ci

0.5

0
30 50 70 90 110 130 150
Temperature, ºC

CA CB CC

Hint 1

Observations

At low temperatures

1)   Little conversion of A

2)   Little B formed

3)   Mostly C formed (but not too much because of the low conversion - 15 to 30% - of
A)

At high temperatures

1)   Virtually complete conversion of A

2)   Mostly B formed

     
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Data suggest 2 reactions

  

Reaction (1) is dominant at high temperatures

k2 = A2e-E2/RT

Reaction (2) is dominant at low temperatures

E1 > E2

6 Maximizing the Selectivity - Parallel Reactions

Determine the instantaneous selectivity, SD/U, for the liquid phase reactions:
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Sketch the selectivity as a function of the concentration of A. Is there an optimum and if

so what is it?

Solution

Finding the optimum concentration:

Use CSTR with exit concentration C*A

7. Finding the selectivity

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For the elementary reactions: , with k1=.1 s-1 and k2=.2 s-1 with
3
CAO= 2 mol/dm . Plot the concentration of B and overall selectivity of B to C as a
function of space time in a CSTR.

Solution

CSTR

A. Balance on Species A

B.Balance on Species B

C.Balance on Species C
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The space time, , is the minimum value of V (i.e. ) at which there is an acceptable
molar flow rate of the desired product B from the CSTR.

8 Writing net rates of formation

The reactions:
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are elementary. Write the net rates of formation for A, B, C and D.

9 The complex liquid phase reactions follow elementary rate laws

(1) A + 2B → C -r1A = k1ACAC2B

(2) 2A + 3C → D -r2C = k2CC2AC3C

and take place in a flow reactor. The feed is equal molar in A and B with FA0 = 200
mol/min and the volumetric flow rate is 100 dm3/min. The reaction volume is 50 dm3
and the rate constants are

Plot FA, FB, FC, FD, FCsg and SC/D as a function of V

Gas Phase PBR with ΔP

Liquid Phase PFR

Liquid Phase CSTR

Gas Phase Membrane Reactor with ΔP

Liquid Phase Semibatch Reactor

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10 Multiple Reactions

Before carrying out any calculations, make a sketch as to what you expect the molar
flow rate profiles to look like

Solution

A is consumed in reactions 1 and 2, so Fa will steadily decrease B is consumed in

reaction 1, and once A is consumed, it will no longer be able to react and the flow rate
will remain constant C is produced in reaction 1, consumed in reaction 2, and therefore
the molar flow rate will go through a maximum will also no longer be consumed once A
is used up D will be produced once C is formed and will continue to increase until A is
consumed

You may want to solve for these profiles quantatatively by using Polymath
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11 What is wrong with this solution?

Problem

Consider the elementary gas phase reactions

Set up the equations to calculate the concentration of each species as a function of time
in a constant volume batch reactor. The reaction is carried out isothermally.

Solution

A combined mole balance (1) and rate laws(2)

(3)  Stoichiometry
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at t = 0  then  NA = NA0 and  

These equations will be typed into Polymath.

What five things are wrong with each of the first three steps of the multiple reaction
algorithm?

Answer

(1)Mole Balance:  V missing on right hand side of each of the combined mole balance
and rate law equations (1) through (4).

(2)Stoiciometry:  The gas reaction occurs in a constant volume rigid container, V = V0.
Therefore the equations [(5) and (6)] for the concentration of the reacting species are not
correct

(3)Rate laws, relative rates, and net rates:  The net rate of reaction is not correct for B,C,
and D, i.e., equations (2), (3), and (4).

Correct Solutions

Since V = V0
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Mole Balance

(1)                                                     

(2)                                                     

(3)                                                    

(4)                                                    

Net Rates and Rate Laws

Net Rates

Species A

Species B
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Species C

Species D

Summary
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Stoichiometry

The pressure inside the vessel is

12. An example of a gas phase chain reaction involving free radicals is

hydrodealkylation, in which alkyl aromatics are converted to unsubstituted aromatics.
A process for the hydrodealkylation of toluene from petroleum stocks to produce
benzene and methane has been developed. The hydrodealkylation occurs in the gas
phase at high temperature and involves free radical. The free radical mechanism is
believed to proceed by the sequence

The specific reaction rates k1 and k4 are defined w.r.t. H2.

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Derive the reaction rate law for the rate of formation of benzene based on this
mechanism.
Hint: the reaction is 1/2 order in H2 and 1st order in toluene.

13 Find the reaction rate of formation of NO2 according to the following mechanism.

Mechanism:

(1)

(2)

(3)

14 Derive the Rate Law for Competitive Inhibition

Competitive Inhibition

Developing the rate laws

We obtain
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Total enzyme

15 Derive the Rate Law for Uncompetitive Inhibition

Uncompetitive Inhibition

Inhibition only has affinity for enzyme-substrate complex

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Developing the rate law

Adding (1) and (2)

From (2)

Total enzyme
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16 Sketch Non-Competitive Inhibition on a Lineweaver-Burk Plot

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17 Finding the rate law and mechanism for A + B  C + D

The following data were reported for the reaction A + B goes to C + D

Which of the following mechanisms is consistent with the above data?

Answer:(d)

Recall
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-r'A=-r'B=r'C=r'D

Figure (a) suggests

Figure (b) suggests

Figure (c) suggests

-rA is not a function of PD, therefore the reaction is irreversible and D is not on the
surface.Figure (d) suggests
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Combining all the above

Therefore, (d)is consistent

19 Analysis of a Heterogeneous Reaction

  Experimental data for the gas-phase catalytic reaction

   

  

   

are shown below. The limiting step in the reaction is known to be irreversible, so
  that the overall reaction is irreversible. The reaction was carried out in a differential
reactor to which A, B, and C were all fed.

   
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(a) Sketch as a function of PA, as a function of PB, and as a function of P C.

(b) From your observations in part (a), which species would appear in the numerator
of the rate expression? Which species would appear in the denominator of the rate
expression? To what power is the denominator raised?

  

(c) From your conclusions from part (b), suggest a rate law consistent with the
experimental data.
(d) Evaluate the rate law parameters.

(e) From your rate expression, which species can you conclude are adsorbed on the
surface?

(f) From your conclusions in part (e), suggest a mechanism and rate-limiting step for
  this reaction.

(g) For an entering partial pressure of A of 2 atm in a PBR, what is the ratio of sites
of A to C sites at 80% conversion of A?

(h) At what conversion are the number of A and C sites equal?

   

  
Solution

(a) Compare runs 1, 3, 6, and 7. P B and P C are fixed. As P A increases the rate first
increases then levels off. Therefore, P A must be in both the numerator and
denominator.
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Compare runs 4 and 5. PA and PB are fixed. Because the reaction is irreversible, PC

  

must be in the denominator.

   
Compare runs 2 and 7. PA and PC are fixed. increases by a factor of 10 when
PB increases by a factor of 10. PB is only in the numerator.

  
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(b) A and B are in the numerator, C and A are in the denominator.

  (c)

(d) For fixed P C and P B ,

  

   

  

  For fixed P A and P B

   
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We note that the non-linear regression techniques described in Chapter 5 could have
easily been used.

Find the Mechanism and Rate Limiting Step

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 (f) A and C are on the surface

20 Finding the Mechanism

      

The following data were obtained for the oxidation of CO over a catalyst. All rates are
initial rates
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.020 0.01 1

.035 0.01 3

.049 .001 6

.060 .001 9

.196 .1 1

.384 .2 1

.902 .5 1

1.653 1 1

4.44 5 1

5.00 10 1

4.44 20 1

2.77 50 1

The initial rate was found to be independent of CO2.  

a)   Suggest a rate law consistent with the data

b)   Suggest mechanisms consistent with the rate law

Hint 1  Sketch  versus CO2.

Use only the data points for which the concentration of CO is the same.
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Hint 2: Low concentration

For constant CO2

We see at low concentration the rate is linear in CO and

Hint 3: High concentration

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At high concentrations the rate decreases with increasing concentration

Full Solution: Part A

Combining

For fixed concentration of O2 and low concentration of CO and

                       

High concentration

             

Consequently the rate law

Satisfies the data

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b Hint 1 What do the trends suggest?

From the denominator of the rate law, we see that CO is adsorbed and that O2 is either
weakly adsorbed (KO2PO21/2 << 1) or not adsorbed at all.  

The 1/2 order with respect to oxygen suggests dissociative adsorption.  

Because the initial rate is independent of CO2, it is either not adsorbed on the surface or
weakly adsorbed.  

Hint 2 What is the mechanism?

The following mechanism is consistent with the rate law

Molecular Adsorption                             

   

Dissociative Adsorption                          

       

Surface Reaction                             
                        

Full Solution: Part B

The following mechanism is consistent with the rate law

Molecular Adsorption                             

   
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Dissociative Adsorption                          

       

Surface Reaction                             
                        

Assume surface reaction limits

                                                        

            1)                                     

                                                            

            2)                                       

                                                           

            3)                    

            4)                                          

                                                  

            5)                           

We see that oxygen is weakly adsorbed (very small ) such that

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21 Finding the rate law and mechanism for A+B<=>C+D

The following data were reported for the reaction A + B goes to C + D

Which of the following mechanisms is consistent with the above data?

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Solution

Answer:(d)

Recall

-r'A=-r'B=r'C=r'D

Figure (a) suggests

Figure (b) suggests

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Figure (c) suggests

-rA is not a function of PD, therefore the reaction is irreversible and D is not on the
surface.Figure (d) suggests

Combining all the above

Therefore, (d)is consistent

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