UNIVERSIDAD DE ANTIOQUIA

FACULTAD DE INGENIERÍA
DEPARTAMENTO DE INGENIERÍA QUÍMICA
CURSO: IQU-458 INGENIERÍA DE LAS REACCIONES QUÍMICAS
Homework 5
20/09/2018
Carolina Arias Gallego [1], Marcela Jaramillo Baquero [2], Manuela Ospina Arboleda [3]
[1]
[email protected] [2] [email protected] [3]

[email protected]

1. Brittan, Bliss, and Walker [1] studied the catalytic oxidation of carbon monoxide, Equation
(1.1).
1
𝐶𝑂 + 2𝑂2 ↔ 𝐶𝑂2 (1.1)

Using a hopcalite catalyst (a mixture of oxides of manganese and copper and small quantities of
other oxides). They used a batch circulation reactor (constant volume) and obtained the data
shown in Table 1.1, for one of their runs.

Table 1.1 Laboratory study of catalytic oxidation of CO at 40°C.

System temperature 40°C
Time, t (ksec) Partial Pressures (kPa)
CO O2 CO2
0.0 13.6 14.5 1.2
0.12 12.1 13.7 2.8
0.30 10.3 13.1 4.3
0.60 8 12.3 6.3
1.20 5.7 10.8 8.4
1.86 3.9 10.3 10.3
2.58 2.7 9.5 12
3.48 1.3 8.5 13.1
4.98 0.3 8.3 13.9

a. In many previous studies of the catalytic oxidation reaction it has been found that the
reaction is first-order with respect to carbon monoxide, Equation (1.2).

𝑟 = 𝑘𝑃𝐶𝑂 (1.2)

Determine if the data obtained by Brittan, Bliss, and Walker are consistent with this type of rate
expression.

First, it must be established that CO will be called substance A, substance B is O2 and substance
C is CO2. Define Equation (1.3) as the design equation of a batch of reactors for the case of A.
 𝑑𝐶𝐴
= 𝑟𝐴 (1.3)
𝑑𝑡

Equation (1.3) must be converted into pressure terms as shown in Equation (1.4) by means of the
ideal gas state equation (Pj = CjRTj), where "j" corresponds to each reagent or product.
𝑑𝑃𝐴
= 𝑅𝑇𝑟𝐴 (1.4)
𝑑𝑡

Once this is defined, we use the expression of reaction speed proposed by the author to
determine if the data obtained by the author are consistent with this expression, which is
presented in Equation (1.2). The first thing that is done is to express this in specific terms of
reactant A as shown in Equation (1.5).

𝑟𝐴 = (−1)𝑘𝑃𝐴 = −𝑘𝑃𝐴 (1.5)

Equation (1.5) is replaced in Equation (1.4) corresponding to the design equation, in order to
obtain an expression corresponding to the pressure of the CO as shown in Equations 1.6, 1.7 and
1.8.
𝑃 𝑑𝑃𝐴 𝑡
∫𝑃 = −𝑅𝑇𝑘 ∫0 𝑑𝑡 (1.6)
𝑜 𝑃𝐴

𝑃
𝐿𝑛 ( 𝑃𝐴) = −𝑅𝑇𝑘𝑡 (1.7)
𝑜

𝑃𝐴 = 𝑃𝐴𝑜 𝑒 −𝑅𝑇𝑘𝑡 (1.8)

Using Equation (1.7) and the experimental data provided in Table 1.1 it is possible to plot Ln
𝑃
𝐿𝑛 ( 𝑃𝐴) vs t and the slope of this graph will correspond to the RTK factor where T corresponds
𝑜
to the Kelvin temperature of 313.15K, R corresponds to the universal constant of the gases, with
a value of 0.008314472 kPa * m3 / mol * K and the K parameter corresponds to the reaction rate
constant which will be determined. In Figure 1.1 we can see this straight line with its respective
slope.
 Ln(Po/PA) vs Time
4,5
4
3,5
3
Ln(Po/PA)

2,5
2
Ln(P0/P)
1,5
1
0,5
0
0 1 2 3 4 5 6
Time (ksec)

Figure 1.1. Linearization of the design equation for the CO.

The slope obtained from this graph is 0.71976783, value that is divided by R * T to obtain the
value of the reaction rate constant which is 0.27644284ksec-1. Once the constant value has been
obtained, it is possible to propose the reactor design equation for CO2 and O2, starting with the
approach of the reaction rates as shown in Equations (1.9) and (1.10) respectively.
1
𝑟𝐵 = − 2 𝑘𝑃𝐴 (1.9)
𝑟𝐶 = 𝑘𝑃𝐴 (1.10)
Now, these equations are reproduced in the design equation of a batch reactor for each reagent,
Equations (1.11) and (1.12) are obtained.
𝑃𝐵 𝑡 1
∫𝑃 𝑑𝑃𝐵 = ∫0 − 2 𝑅𝑇𝑘𝑃𝐴 𝑑𝑡 (1.11)
𝐵𝑜
𝑃𝐶 𝑡
∫𝑃 𝑑𝑃𝐶 = ∫0 𝑅𝑇𝑘𝑃𝐴 𝑑𝑡 (1.12)
𝐶𝑜
Substituting Equation (1.8) in Equations (1.11) and (1.12) and performing the respective
integrals, we then obtain Equations (1.13) and (1.14) for O2 and Equations (1.15) and (1.16) for
CO2 also Equation (1.17) shows the result of the integral needed to obtain a synthesized
expression for the pressures of products and reagents.

1
𝑃𝐵 = − 𝑅𝑇𝑘𝑃𝐴𝑜 ∫ 𝑒 −𝑅𝑇𝑘𝑡 𝑑𝑡 + 𝑃𝐵𝑜 (1.13)
2

1
𝑃𝐵 = − 2 𝑃𝐴𝑜 [1 − 𝑒 −𝑘𝑅𝑇𝑡 ] + 𝑃𝐵𝑜 (1.14)

𝑃𝐶 = 𝑅𝑇𝑘𝑃𝐴𝑜 ∫ 𝑒 −𝑅𝑇𝑘𝑡 𝑑𝑡 + 𝑃𝐶𝑜 (1.15)

1−𝑒 −𝑘𝑅𝑇𝑡
𝑃𝐶 = 𝑅𝑇𝑘𝑃𝐴𝑜 [ ] + 𝑃𝐶𝑜 (1.16)
𝑘𝑅𝑇
1−𝑒 −𝑅𝑘𝑇𝑡
∫ 𝑒 −𝑅𝑇𝑘𝑡 𝑑𝑡 = 𝑘𝑅𝑇
(1.17)
Now using Equations (1.8), (1.14) and (1.16) together with the value of the constant K
previously determined and the values of time and initial pressures that are reported in Table 1.1 it
is possible to evaluate the pressures with the model of proposed reaction rate, obtaining the
results shown in Table 1.2.

Table 1.2. Partial pressures calculated by means of the reaction velocity model.
Partial pressure [=] kPa
PCO PO2 PCO2
13.6000 14.5000 1.2000
12.4746 13.9373 2.3254
10.9588 13.1794 3.8412
8.8305 12.1152 5.9695
5.7336 10.5668 9.0664
3.5655 9.4827 11.2345
2.1235 8.7618 12.6765
1.1110 8.2555 13.6890
0.3774 7.8887 14.4226
By performing an analysis using the standard deviations of the results obtained in Table 1.2 with
those reported in Table 1.1, the results presented in Table 1.3 are obtained.

Table 1.3. Standard deviation between experimental and calculated data for pressures.
Standard deviation
CO ± 4.802
O2 ± 2.344
CO2 ± 4.720

The results obtained in Table 1.3 indicate that the data obtained by the authors in Table 1.1 can
be considered consistent with the reaction velocity expression proposed in Equation 1.2 given
that the standard deviations obtained indicate that the calculated values can be found in a range
above or below 4kPa, 2kPa and 4kPa for CO, O2 and CO2 respectively, which converted into
percentages of error, can still be considered low considering that it is a modeling and this
involves an error associated with the mathematical representation. These error percentages are
reported in Table 1.4.

Table 1.4. Percentages of error between the data of calculated pressures and those reported in the
literature.
%ERROR
CO O2 CO2
0.00 0.00 0.00
3.10 1.73 16.95
6.40 0.61 10.67
10.38 1.50 5.25
0.59 2.16 7.93
 8.58 7.93 9.07
21.35 7.77 5.64
14.54 2.88 4.50
25.81 4.96 3.76

Based on these results, it is concluded that the data obtained by the authors are consistent with
the type of reaction velocity excretion given. In Annexes A you can find the comparative graphs
of the pressures of each of the species present in the reaction.

b. On the basis of their experimental data, Walker, Bliss, and Brittan proposed the following
mechanism for this reaction:
𝐾1
𝐶𝑂 + 𝑂𝜎 → 𝑂𝜎 (𝐶𝑂) slow Reaction 1
𝐾2
𝐶𝑂 + 𝑂𝜎 → 𝐶𝑂2𝜎 fast Reaction 2
𝐾3
𝑂𝜎 (𝐶𝑂) → 𝐶𝑂2 +𝜎 fast Reaction 3

1 𝐾4
𝑂𝜎 (𝐶𝑂) + 2 𝑂2 → 𝐶𝑂2 + 𝑂𝜎 Reaction 4

1 𝐾5
𝜎 + 2 𝑂2 → 𝑂𝜎 Reaction 5

Where:
𝑂𝜎 = atomically adsorbed oxygen.
𝜎 = Vacant catalyst site.
𝑂𝜎 (𝐶𝑂) = complex formed on surface of catalyst.

If the adsorption of CO is rate controlling, derive the kinetic expression for the rates of change of
the concentrations (partial pressures) of CO, O2, and CO2.
Note that the reaction does not proceed stoichiometrically and the hopcalite may act as a source
or sink for the oxygen. Hence separate rate expressions are required for each component.
From the information provided we have Equations (1.18) and (1.19), which correspond to the
adsorbed oxygen pressure and the empty sites respectively.
𝑃𝑂𝜎 = 𝑃𝑂𝑜𝜎 + (𝑃𝐶𝑂 − 𝑃𝐶𝑂
𝑜 )
− 2(𝑃𝑂2 − 𝑃𝑂𝑜2 ) (1.18)
𝑜
𝑃𝜎 = 𝑃𝜎𝑜 + (𝑃𝐶𝑂2 − 𝑃𝐶𝑂2
) + 2(𝑃𝑂2 − 𝑃𝑂𝑜2 ) (1.19)

Subsequently, the reaction speed expression of CO, CO2 and O2 is presented, as shown in
Equations (1.20), (1.21) and (1.22) respectively.
𝑟𝐶𝑂 = −𝑘1 𝑃𝐶𝑂 𝑃𝑂𝜎 − 𝑘2 𝑃𝐶𝑂 𝑃𝑂𝜎 (1.20)
 1
𝑟𝐶𝑂2 = 𝑘3 𝑃𝑂𝜎 (𝐶𝑂) + 𝑘4 𝑃𝑂𝜎 (𝐶𝑂) 𝑃𝑂22 (1.21)
1 1
1 1
𝑟𝑂2 = − 2 𝑘4 𝑃𝑂22 𝑃𝑂𝜎 (𝐶𝑂) − 2 𝑘5 𝑃𝜎 𝑃𝑂22 (1.22)

Given that the production ratio of the carbon oxide-monoxide complex to participate in several
reactions will be considered net equal to zero, we can then pose Equation (1.23) and from there
obtain the concentration of said complex (Equations (1.24) and (1.25)) required to simplify the
reaction rate equations of the reaction species.
1
2
𝑟𝑂𝜎(𝐶𝑂) = 𝑘1 𝑃𝐶𝑂 𝑃𝑂𝜎 − 𝑘3 𝑃𝑂𝜎 (𝐶𝑂) − 𝑘4 𝑃𝑂𝜎 𝐶𝑂 𝑃 = 0 𝑂2 (1.23)
1
2
𝑘1 𝑃𝐶𝑂 𝑃𝑂𝜎 = 𝑃𝑂𝜎 (𝐶𝑂) [𝑘3 + 𝑘4 𝑃 ] 𝑂2 (1.24)

𝑘1 𝑃𝐶𝑂 𝑃𝑂𝜎
𝑃𝑂𝜎 (𝐶𝑂) = 1 (1.25)
2
𝑘3 +𝑘4 𝐶𝑂
2

On this basis the equations for the reaction rate of each species in the reaction are again restated
as shown in Equations (1.26), (1.27) and (1.28)
𝑟𝐶𝑂 = −𝑃𝐶𝑂 [𝑃𝑂𝑜𝜎 + (𝑃𝐶𝑂 − 𝑃𝐶𝑂
𝑜 )
− 2(𝑃𝑂2 − 𝑃𝑂𝑜2 )](𝑘1 + 𝑘2 ) (1.26)

𝑟𝐶𝑂2 = 𝑘1 𝑃𝐶𝑂 [𝑃𝑂𝑜𝜎 + (𝑃𝐶𝑂 − 𝑃𝐶𝑂

𝑜 )
− 2(𝑃𝑂2 − 𝑃𝑂𝑜2 )] (1.27)

1
1 𝑘1 𝑃𝐶𝑂 𝑃𝑂𝜎
𝑟𝑂2 = − 2 𝑃𝑂22 [ 1 + 𝑘5 𝑃𝜎 ] (1.28)
𝑘3
+𝑃𝑂2
𝑘4 2

c. Determine whether the expression obtained from this mechanism for the disappearance of
carbon monoxide agrees with the experimental results:

𝐾1 + 𝐾2 = 0.00737 (𝑚𝑖𝑛−1 )(𝑚𝑚𝐻𝑔−1 )

𝑃𝑂0𝜎 = 11.81 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑚𝑚𝐻𝑔 (𝑖𝑛𝑖𝑐𝑖𝑎𝑙 𝑙𝑒𝑣𝑒𝑙)

𝑃𝜎0 = 0.95 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑚𝑚𝐻𝑔 (𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑙𝑒𝑣𝑒𝑙 )

𝐾1 = 0.00732(𝑚𝑖𝑛−1 )(𝑚𝑚𝐻𝑔−1 )

𝐾3
= 3.13 (𝑚𝑚𝐻𝑔)1/2
𝐾4

𝐾5 = 0.0085 (𝑚𝑖𝑛−1 )(𝑚𝑚𝐻𝑔−1 )

Using Equations (1.26), (1.27) and (1.28) and replacing the values of the constants given in the
statement it is possible to develop an algorithm in the MatLab software that is capable of solving
the system of differential equations that is obtained by replacing the expressions of reaction
velocity obtained in the design equations presented in Equations (1.29), (1.30) and (1.31)
𝑑𝑃𝐴
= 𝑟𝐴 (1.29)
𝑑𝑡

𝑑𝑃𝐵
= 𝑟𝐵 (1.30)
𝑑𝑡

𝑑𝑃𝐶
= 𝑟𝐶 (1.31)
𝑑𝑡

Annex B presents the algorithm used to solve this system of equations. Table 1.5 shows the
partial pressures obtained from the System solution.

Table 1.5. Partial pressures obtained using the initial velocities of the previous literal.
Partial pressures [=] kPa
PCO PO2 PCO2
13.6000 14.5000 1.2000
11.6770 13.7135 2.9447
9.7468 12.8665 4.6928
7.6083 11.8775 6.6255
5.0291 10.6584 8.9499
3.4109 9.8943 10.4042
2.3490 9.3958 11.3568
1.5476 9.0219 12.0747
0.8314 8.6897 12.7156

Next in Figures 1.2, 1.3 and 1.4 it is possible to verify the similarity between the results obtained
from the derived expressions and those reported in the literature.
Figure 1.2. Difference between the experimental results and those calculated for the CO.

Figure 1.3. Difference between the experimental results and those calculated for the O2.
Figure 1.4. Difference between the experimental results and those calculated for the CO2.

2. An anionic polymerization is to be carried out in a CSTR. The reaction steps are given by
Equation (2.1) and (2.2).
𝑘𝑖
𝐼 + 𝑀 → 𝑅1 (2.1)
𝑘𝑝
𝑅𝑗 + 𝑀 → 𝑅𝑗+1 (2.2)

The entering concentration of monomer (M) and initiator (I) are M0 and I0, respectively.
a. Derive an equation involving the monomer concentration and only the variables kp, k1, I0,
τ and M0.
First, it is necessary to define the assumptions for this system: the CSTR reactor operates at
isothermal and constant volume conditions. Also, the reactor is in steady state and it is well
stirred. All the reactions developed in the system are elemental and all compounds are liquid.
Those reactions represent a chain polymerization. Reaction (2.1) defines the initiation step and
Reaction (2.2) is one of the reactions of the propagation step where all the constants of the
velocity of reaction are equal to kp. [2]
Then, it is applied the mole balance to I according to the assumptions made so it can be obtained
the Equation (2.3).
 𝑉
𝑑𝑁𝐼
𝐹𝐼0 − 𝐹𝐼 + ∫ 𝑟𝐼 𝑑𝑉 = =0
𝑑𝑡
𝐹𝐼0 − 𝐹𝐼 + 𝑟𝐼 𝑉 = 0
𝑟𝐼 𝑉 = −(𝐹𝐼0 − 𝐹𝐼 )
𝐹𝐼0 − 𝐹𝐼
𝑉=
−𝑟𝐼
𝐹𝑗 𝑉
As 𝐶𝑗 = and 𝜏 = 𝑣 , it is possible to divide by 𝑣.
𝑣

𝐼0 − 𝐼
𝜏= (2.3)
−𝑟𝐼
As I is only in the initiation step (Reaction (2.1)), its velocity of disappearance can be written as
it is in Equation (2.4).
−𝑟𝐼 = 𝑘𝑖 𝑀𝐼 (2.4)
Replacing (2.3) into (2.4), it is obtained Equation (2.5).
𝐼0 − 𝐼
𝜏=
𝑘𝑖 𝑀𝐼
𝐼0 1
𝜏= −
𝑘𝑖 𝑀𝐼 𝑘𝑖 𝑀
1 𝐼0
𝜏+ =
𝑘𝑖 𝑀 𝑘𝑖 𝑀𝐼
𝜏𝑘𝑖 𝑀 + 1 𝐼0
=
𝑘𝑖 𝑀 𝑘𝑖 𝑀𝐼
1 𝐼
=
𝜏𝑘𝑖 𝑀 + 1 𝐼0
𝐼0
𝐼= (2.5)
𝜏𝑘𝑖 𝑀 + 1
Mole balance is applied to M establish the Equation (2.6). It is found that the procedure is
analogous to the one realized for I.
𝑀0 − 𝑀
𝜏= (2.6)
−𝑟𝑀
Now, the velocity of disappearance must be expressed. It is divided in two parts:
 • The disappearance velocity in the propagation step. Assuming Reactions (2.7), (2.8) and
(2.2), Equations (2.9), (2.10) and (2.11) are gotten for the disappearance velocity in each
reaction.
𝑘𝑝
𝑅1 + 𝑀 → 𝑅2 (2.7)
𝑘𝑝
𝑅2 + 𝑀 → 𝑅𝑗 (2.8)
𝑘𝑝
𝑅𝑗 + 𝑀 → 𝑅𝑗+1 (2.2)

−𝑟𝑀,7 = 𝑘𝑃 𝑀𝑅1 (2.9)

−𝑟𝑀,8 = 𝑘𝑃 𝑀𝑅2 (2.10)

−𝑟𝑀,2 = 𝑘𝑃 𝑀𝑅𝑗 (2.11)

The reaction velocity of the propagation is calculated by the summation of (2.9), (2.10) and
(2.11). Equation (2.12) is obtained when the concentration of radicals (𝑅𝑗 ) tends to infinite.

−𝑟𝑀,𝑃 = 𝑘𝑃 𝑀𝑅1 + 𝑘𝑃 𝑀𝑅2 + 𝑘𝑃 𝑀𝑅𝑗

−𝑟𝑀,𝑃 = 𝑘𝑃 𝑀(𝑅1 + 𝑅2 + 𝑅𝑗 )
∞

−𝑟𝑀,𝑃 = 𝑘𝑃 𝑀 ∑ 𝑅𝑗 (2.12)
𝑗=1

• The disappearance velocity in the initiation step by Equation (2.13).

−𝑟𝑀,𝐼 = 𝑘𝑖 𝑀𝐼 (2.13)
Then, Equations (2.12) and (2.13) are added to obtain the reaction velocity of M (Equation
(2.14)).
∞

−𝑟𝑀 = 𝑘𝑃 𝑀 ∑ 𝑅𝑗 + 𝑘𝑖 𝑀𝐼
𝑗=1

−𝑟𝑀 = 𝑀 (𝑘𝑃 ∑ 𝑅𝑗 + 𝑘𝑖 𝐼) (2.14)

𝑗=1

Equations (2.5) and (2.14) are put into (2.6) to reach Equation (2.16).
𝑀0 − 𝑀
𝜏= (2.15)
𝑀(𝑘𝑃 ∑∞
𝑗=1 𝑅𝑗 + 𝑘𝑖 𝐼)
 ∞
𝑀0
𝜏 (𝑘𝑃 ∑ 𝑅𝑗 + 𝑘𝑖 𝐼) = −1
𝑀
𝑗=1

∞
𝐼0 𝑀0
𝜏𝑘𝑃 ∑ 𝑅𝑗 + 𝜏𝑘𝑖 +1=
𝜏𝑘𝑖 𝑀 + 1 𝑀
𝑗=1
∞
𝑀0 𝜏𝑘𝑖 𝐼0
𝜏𝑘𝑃 ∑ 𝑅𝑗 + 1 = −
𝑀 𝜏𝑘𝑖 𝑀 + 1
𝑗=1

𝑀
∞
𝑀0 𝐼0 𝑀𝑀0 + 0 − 𝐼0 𝑀
𝜏𝑘𝑖
𝜏𝑘𝑃 ∑ 𝑅𝑗 + 1 = − =
𝑀 𝑀+ 1 𝑀
𝑗=1 𝑀2 +
𝜏𝑘𝑖 𝜏𝑘𝑖

∞ 𝑀0 𝑀0
𝑀(𝑀0 − 𝐼0 ) + 𝑀0 − 𝐼0 +
𝜏𝑘𝑖 𝑀𝜏𝑘𝑖
𝜏𝑘𝑃 ∑ 𝑅𝑗 + 1 = =
𝑀 1
𝑗=1 𝑀2 + 𝑀+
𝜏𝑘𝑖 𝜏𝑘𝑖

∞ 𝑀(𝑀0 − 𝐼0 )𝜏𝑘𝑖 + 𝑀0
𝑀𝜏𝑘𝑖 𝑀(𝑀0 − 𝐼0 )𝜏𝑘𝑖 + 𝑀0
𝜏𝑘𝑃 ∑ 𝑅𝑗 + 1 = =
𝜏𝑘𝑖 𝑀 + 1 𝜏𝑘𝑖 𝑀2 + 𝑀
𝑗=1
𝜏𝑘𝑖
∞ ∞
2 2 )𝑀2
(𝜏 𝑘𝑃 𝑘𝑖 ∑ 𝑅𝑗 ) 𝑀 + (𝜏𝑘𝑖 + (𝜏𝑘𝑃 ∑ 𝑅𝑗 ) 𝑀 + 𝑀 = 𝑀(𝑀0 − 𝐼0 )𝜏𝑘𝑖 + 𝑀0
𝑗=1 𝑗=1

∞ ∞
2 2
(𝜏 𝑘𝑃 𝑘𝑖 ∑ 𝑅𝑗 + 𝜏𝑘𝑖 ) 𝑀 + (𝜏𝑘𝑃 ∑ 𝑅𝑗 + 1 − (𝑀0 − 𝐼0 )𝜏𝑘𝑖 ) 𝑀 − 𝑀0 = 0
𝑗=1 𝑗=1

−(𝜏𝑘𝑃 ∑∞ ∞ 2 2 ∞
𝑗=1 𝑅𝑗 + 1 − (𝑀0 − 𝐼0 )𝜏𝑘𝑖 ) + √(𝜏𝑘𝑃 ∑𝑗=1 𝑅𝑗 + 1 − (𝑀0 − 𝐼0 )𝜏𝑘𝑖 ) + 4𝑀0 (𝜏 𝑘𝑃 𝑘𝑖 ∑𝑗=1 𝑅𝑗 + 𝜏𝑘𝑖 )
𝑀=
2(𝜏 2 𝑘𝑃 𝑘𝑖 ∑∞
𝑗=1 𝑅𝑗 + 𝜏𝑘𝑖 )

−𝜏𝑘𝑃 ∑∞ ∞ 2 ∞
𝑗=1 𝑅𝑗 − 1 + (𝑀0 − 𝐼0 )𝜏𝑘𝑖 + √(𝜏𝑘𝑃 ∑𝑗=1 𝑅𝑗 + 1 − (𝑀0 − 𝐼0 )𝜏𝑘𝑖 ) + 4𝑀0 𝜏𝑘𝑖 (𝜏𝑘𝑃 ∑𝑗=1 𝑅𝑗 + 1)
𝑀= (2.16)
2𝜏𝑘𝑖 (𝜏𝑘𝑃 ∑∞
𝑗=1 𝑅𝑗 + 1)

Finally, taking Equation (2.16) to a valid expression, concentrations of the radicals must be
stated also in terms of the know constants.
From Equation (2.5), the explicit Equation (2.17) is obtained.
𝐼0 − 𝐼 = 𝜏𝑘𝑖 𝑀𝐼 (2.17)
Then, it is proposed Reaction (2.18) as an extension of Reaction (2.8) which is now redefined
with R3 as the product.
𝑘𝑝
𝑅2 + 𝑀 → 𝑅3 (2.8)
𝑘𝑝
𝑅3 + 𝑀 → 𝑅4 (2.18)
Then, mole balances are mare for R1, R2 and R3 (Equations (2.19), (2.20) and (2.21),
respectively) according to Reactions (2.7), (2.8) and (2.18). If R4 and R3 are Rj+1 radicals, it is
feasible to say that those kinds of species with high molecular weight are less probable to be
generated in a chain reaction. This way, its concentration tends to be so small, that it can be
despised.
For R1:
−𝐹𝑅1 + 𝑟𝑅1 𝑉 = 0
−𝑅1 + (𝑘𝑖 𝑀𝐼 − 𝑘𝑃 𝑅1 𝑀)𝜏 = 0
−𝑅1 + 𝑘𝑖 𝑀𝐼𝜏 − 𝑘𝑃 𝑅1 𝑀𝜏 = 0 (2.19)
For R2:
−𝐹𝑅2 + 𝑟𝑅2 𝑉 = 0
−𝑅2 + (𝑘𝑃 𝑅1 𝑀 − 𝑘𝑃 𝑅2 𝑀)𝜏 = 0
−𝑅2 + 𝑘𝑃 𝑅1 𝑀𝜏 − 𝑘𝑃 𝑅2 𝑀𝜏 = 0 (2.20)
For R3:
−𝐹𝑅3 + 𝑟𝑅3 𝑉 = 0
−𝑅3 + (𝑘𝑃 𝑅2 𝑀 − 𝑘𝑃 𝑅3 𝑀)𝜏 = 0
−𝑅3 + 𝑘𝑃 𝑅2 𝑀𝜏 − 𝑘𝑃 𝑅3 𝑀𝜏 = 0
𝑘𝑃 𝑅2 𝑀𝜏 = 𝑘𝑃 𝑅3 𝑀𝜏 + 𝑅3 (2.21)
Equation (2.22) is obtained by putting (2.21) into (2.20).
−𝑅2 + 𝑘𝑃 𝑅1 𝑀𝜏 − 𝑘𝑃 𝑅3 𝑀𝜏 − 𝑅3 = 0
𝑘𝑃 𝑅1 𝑀𝜏 = 𝑘𝑃 𝑅3 𝑀𝜏 + (𝑅3 + 𝑅2 ) (2.22)
Then, Equation (2.23) is a result of (2.22) into (2.19).
−𝑅1 + 𝑘𝑖 𝑀𝐼𝜏 − 𝑘𝑃 𝑅3 𝑀𝜏 − (𝑅3 + 𝑅2 ) = 0
𝑘𝑖 𝑀𝐼𝜏 = 𝑘𝑃 𝑅3 𝑀𝜏 + (𝑅3 + 𝑅2 + 𝑅1 ) (2.23)
Finally, Equation (2.24) has been gotten by taking (2.23) into (2.17) and assuming and infinite
summation of Rj species which represents infinite propagation reactions. And considering the
assumption made before for the concentration of radicals with high molecular weight (Rj+1≈0),
Equation (2.25) is gotten. And by definition of I from Equation (2.5), (2.26) is obtained.
∞

𝐼0 − 𝐼 = 𝑘𝑃 𝑅𝑗+1 𝑀𝜏 + ∑ 𝑅𝑗 (2.24)
𝑗=1
∞

𝐼0 − 𝐼 = ∑ 𝑅𝑗 (2.25)
𝑗=1

𝑀𝜏𝑘𝑖
𝐼0 − 𝐼 = 𝐼0 ( ) (2.26)
𝑀𝜏𝑘𝑖 + 1
Then, (2.25) and (2.26) are replaced into (2.15) to get the final expression in Equation (2.17). It
is possible to get the same result of (2.27) if replacing the mentioned equations into (2.16), but
the procedure is easier if starting over from (2.15).
𝑀0 − 𝑀
𝜏=
𝑀(𝑘𝑃 (𝐼0 − 𝐼) + 𝑘𝑖 𝐼)
𝜏𝑀𝑘𝑃 (𝐼0 − 𝐼) + 𝜏𝑘𝑖 𝐼𝑀 = 𝑀0 − 𝑀
𝑀𝜏𝑘𝑖 𝐼0
𝜏𝑀𝑘𝑃 𝐼0 ( ) + 𝜏𝑘𝑖 𝑀 ( ) = 𝑀0 − 𝑀
𝑀𝜏𝑘𝑖 + 1 𝜏𝑘𝑖 𝑀 + 1
𝜏 2 𝑀2 𝑘𝑃 𝐼0 𝑘𝑖 + 𝜏𝑘𝑖 𝑀𝐼0 = (𝑀0 − 𝑀)(𝑀𝜏𝑘𝑖 + 1)
𝜏 2 𝑀2 𝑘𝑃 𝐼0 𝑘𝑖 + 𝜏𝑘𝑖 𝑀𝐼0 = 𝑀0 𝑀𝜏𝑘𝑖 + 𝑀0 − 𝑀2 𝜏𝑘𝑖 − 𝑀
𝜏 2 𝑀2 𝑘𝑃 𝐼0 𝑘𝑖 + 𝜏𝑘𝑖 𝑀𝐼0 − 𝑀0 𝑀𝜏𝑘𝑖 − 𝑀0 + 𝑀2 𝜏𝑘𝑖 + 𝑀 = 0
(𝜏 2 𝑘𝑃 𝐼0 𝑘𝑖 + 𝜏𝑘𝑖 )𝑀2 + (𝜏𝑘𝑖 𝐼0 − 𝑀0 𝜏𝑘𝑖 + 1)𝑀 − 𝑀0 = 0
(𝜏𝑘𝑖 (𝜏𝑘𝑃 𝐼0 + 1))𝑀2 + (𝜏𝑘𝑖 (𝐼0 − 𝑀0 ) + 1)𝑀 − 𝑀0 = 0

−(𝜏𝑘𝑖 (𝐼0 − 𝑀0 ) + 1) + √(𝜏𝑘𝑖 (𝐼0 − 𝑀0 ) + 1)2 + 4𝑀0 𝜏𝑘𝑖 (𝜏𝑘𝑃 𝐼0 + 1)

𝑀=
2𝜏𝑘𝑖 (𝜏𝑘𝑃 𝐼0 + 1)

−𝜏𝑘𝑖 (𝐼0 − 𝑀0 ) − 1 + √(𝜏𝑘𝑖 (𝐼0 − 𝑀0 ) + 1)2 + 4𝑀0 𝜏𝑘𝑖 (𝜏𝑘𝑃 𝐼0 + 1)

𝑀= (2.27)
2𝜏𝑘𝑖 (𝜏𝑘𝑃 𝐼0 + 1)
b. Derive an equation of the radical concentration as a function of space time (𝜏).
From Equation (2.19) it can be obtained Equation (2.28).
𝑅1 (1 + 𝑘𝑃 𝑀𝜏) = 𝑘𝑖 𝑀𝐼𝜏
𝑘𝑖 𝑀𝐼𝜏
𝑅1 = (2.28)
1 + 𝑘𝑃 𝑀𝜏
Analogous, (2.29) comes from (2.20) and (2.28).
𝑅2 (1 + 𝑘𝑃 𝑀𝜏) = 𝑘𝑃 𝑅1 𝑀𝜏
𝑘𝑃 𝑀𝜏 𝑘𝑖 𝑀𝐼𝜏 𝑘𝑃 𝑀𝜏
𝑅2 = 𝑅1 =( )( ) (2.29)
1 + 𝑘𝑃 𝑀𝜏 1 + 𝑘𝑃 𝑀𝜏 1 + 𝑘𝑃 𝑀𝜏
By the same procedures, for R3 was gotten Equation (2.30) from (2.21) and (2.29).

𝑘𝑃 𝑀𝜏 𝑘𝑖 𝑀𝐼𝜏 𝑘𝑃 𝑀𝜏 2
𝑅3 = 𝑅2 =( )( ) (2.30)
1 + 𝑘𝑃 𝑀𝜏 1 + 𝑘𝑃 𝑀𝜏 1 + 𝑘𝑃 𝑀𝜏
Equation (2.30) allows to get a general expression for any Rj which is observed in Equation
(2.31). (For this result it was also used Equation (2.5)).

𝑘𝑖 𝑀𝐼𝜏 𝑘𝑃 𝑀𝜏 𝑗−1
𝑅𝑗 = ( )( )
1 + 𝑘𝑃 𝑀𝜏 1 + 𝑘𝑃 𝑀𝜏

𝑘𝑖 𝑀𝜏 𝑘𝑃 𝑀𝜏 𝑗 1 + 𝑘𝑃 𝑀𝜏
𝑅𝑗 = 𝐼 ( )( ) ( )
1 + 𝑘𝑃 𝑀𝜏 1 + 𝑘𝑃 𝑀𝜏 𝑘𝑃 𝑀𝜏

𝑘𝑖 𝑘𝑃 𝑀𝜏 𝑗
𝑅𝑗 = 𝐼 ( ) ( )
𝑘𝑃 1 + 𝑘𝑃 𝑀𝜏

𝐼0 𝑘𝑖 𝑘𝑃 𝑀𝜏 𝑗
𝑅𝑗 = ( )( )( ) (2.31)
𝜏𝑘𝑖 𝑀 + 1 𝑘𝑃 1 + 𝑘𝑃 𝑀𝜏
3. An understanding of bacteria transport in porous media is vital to the efficient operation of the
water flooding of petroleum reservoirs. Bacteria can have both beneficial and harmful effects on
the reservoir. In enhanced microbial oil recovery, EMOR, bacteria are injected to secrete
surfactants to reduce the interfacial tension at the oil-water interface so that oil will flow out
more easily. However, under some circumstances the bacteria can be harmful, by plugging the
pore space and thereby block the flow of water and oil. One bacteria that has been studied,
Leuconostocmesenteroides, has the unusual behavior that when it is injected into a porous
medium and fed sucrose, it greatly reduces the flow (i.e., damages the formation and reduces
permeability). When the bacteria are fed fructose or glucose, there is no damage to the porous
medium. [R. Lappan and H.S. Fogler, SPEProd. Eng., 7(2), 167-171 (1992)]. The cell
concentration, CC, is given below as afunction of time for different initial sucrose
concentrations.

a. From the data of Table 3.1, determine the lag time, the time to reach the stationary phase,
the Michaelis constant, KS, and the reaction velocity, 𝜇, as a function of sucrose
concentration.

Table 3.1. Cell concentration data

Sucrose Conc. (g/cm3) 1 5 10 15
Cc *10^-7 Cc *10^-7 Cc *10^-7 Cc *10^-7
Time (h)
(no/cm3) (no/cm3) (no/cm3) (no/cm3)
 0 3 2 2 1.33
1 4.16 3.78 6.71 5.27
2 5.34 5.79 1.11 0.3
3 7.35 - 5.72 3.78
4 6.01 9.36 3.71 7.65
5 8.61 6.68 8.32 10.3
6 10.1 17.6 21.1 17
7 18.8 35.5 37.6 38.4
8 28.9 66.1 74.2 70.8
9 36.2 143 180 194
10 42.4 160 269 283
11 44.4 170 237 279
12 46.9 165 256 306
13 46.9 163 149 289

Table 3.2 shows the nomenclature used along the mathematic process.
Table 3.2. Nomenclature used in the mathematic process.
Symbol Description Units
Cc Cell concentration n°/cm3
Cc0 Initial cell concentration n°/cm3
Cs Sucrose concentration g/cm3
T Time h
rg Growth rate of cells n°/cm3 h
Ks Monod constant g/cm3
Μ Specific growth rate 1/h
μmax Maximum specific growth rate 1/h

To determine the cell growth phases at different initial sucrose concentration, a graphic of
natural logarithm of cell concentration respect time is made (Figures 3.1, 3.2, 3.3 and 3.4).
 20,5

20

19,5

19
Ln(Cc)

18,5

18

17,5

17
0 2 4 6 8 10 12 14
Time (h)

Figure 3.1. Cell growth phases at 1 g/cm3 of sucrose.

22

21

20
Ln(Cc)

19

18

17

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

Figure 3.2. Cell growth phases at 5 g/cm3 of sucrose.

 22

21

20
Ln(Cc)

19

18

17

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

Figure 3.3. Cell growth phases at 10 g/cm3 of sucrose.

24

22

20
Ln(Cc)

18

16

14

12
0 2 4 6 8 10 12 14
Time (h)

Figure 3.4. Cell growth phases at 15 g/cm3 of sucrose.

The cell growth as function of time in a batch reactor is given by four phases:
 1. Lag phase: in this phase cell concentration doesn’t increase significantly, cells are
adjusting to the new environment. In Figures 3.1 to 3.4, lag time is appreciable, cell
concentration doesn’t grow significantly, for Figures 3.1 and 3.3, this phase is between
initial time and four hours of reaction, for Figure 3.2 until five hours of reaction and for
Figure 3.4 until six hours of reaction.
2. Exponential growth phase: in this phase the rate of cell growth is proportional to cell
concentration. In Figures 3.1 the exponential growth is significantly since four hours of
reaction until ten hours, for Figure 3.2 since five hours until nine hours of reactions, for
Figures 3.3 and 3.4 the cell concentration increase exponentially in a period of time
between four and ten hours.
3. Stationary phase: in this phase rate of cell growth is zero due to nutrients in the
environment began to decrease, cell concentration is constant and there is accumulation
of toxins and organic acids in the environment. In Figures 3.1 to 3.4 after maximum
concentration of cell is achieved it begins to behave constant in time.
4. Death phase: Cell concentration decrease due to nutrients exhaustion and accumulation of
toxins substances. In Figures 3.1 to 3.4 the reaction time wasn’t enough to reach this
phase.

In the exponential phase, the growth rate of cell is given by the equation of Monod:
𝑟𝑔 = 𝜇𝐶𝑐 (3.1)
𝜇𝑀𝑎𝑥 𝐶𝑠
𝜇= (3.2)
𝐾𝑠 + 𝐶𝑠
Parameters of Monod equation are defined in Table 3.2. To obtain those parameters, the design
equation of a batch reactor at constant volume is used.
𝑑𝐶𝑐
= 𝑟𝑔 (3.3)
𝑑𝑡
To solve the differential Equation (3.3) the method of separable variables is convenient,
integrating in both sides of equation and organizing to obtain a form similar to a straight line.
𝐶𝑐 𝑡
𝑑𝐶𝑐
∫ = ∫ 𝜇𝑑𝑡 (3.4)
𝐶𝑐0 𝐶𝑐 𝑡0

𝐶𝑐
𝑙𝑛 ( ) = 𝜇(𝑡 − 𝑡0 ) (3.5)
𝐶𝑐0
𝑙𝑛(𝐶𝑐 ) = 𝑙𝑛(𝐶𝑐0 ) + 𝜇(𝑡 − 𝑡0 ) (3.6)
Using the Equation (3.6) it is possible to obtain the specific growth rate for each concentration of
sucrose; the natural logarithm of the cell concentration is “y” and de time difference is “x” then
the slope of the line is the specific growth rate and the intercept is the natural logarithm of initial
cell concentration. Ranges of data from Table 3.1 are used for each sucrose concentration, these
ranges belong to a linear stretch of the exponential phase.
Table 3.3. Specific growth rate and the predicted initial cell concentration.
Time range (h) Cs (g/cm3) μ (1/h) Ln(Cc0) Cc0 (n°/cm3)
4-8 1.0 0.39218 17.84506 56235511.53770
5-9 5.0 0.74507 18.12606 74481670.35311
4-8 10.0 0.74998 17.50068 39851932.52178
6-9 15.0 0.79157 18.93298 166912827.63589

To obtain the Monod constant and the maximum specific growth rate, the Equation (3.2) is
linearized as follows:
1 𝐾𝑠 1 1
=𝜇 +𝜇 (3.7)
𝜇 𝑀𝑎𝑥 𝐶𝑠 𝑀𝑎𝑥

With data obtained in Table 3.3 and Equation (3.7) the parameters of Monod equation are
obtained; the inverse of specific growth rate is “y” and the inverse of sucrose concentration is
“x” then the slope is the inverse of the maximum specific growth rate and the intercept gives the
Monod constant.
Table 3.4. Monod Parameters.
1/μmax Ks/μmax μmax (1/h) Ks (g/cm3)
1.14594 1.39385 0.87264 1.21634

b. Will an inhibition model of the form in Equation (3.8).

𝑛
𝐶𝑐 − 𝐶𝑐0
𝑟𝑔 = 𝜇𝐶𝑐 (1 − ) (3.8)
𝐶𝑝∗
where n and Cp* are parameters, fit your data?

The parameter Cp* is obtained from the Equation (3.8), the growth rate of cell is equal to zero
when the stationary phase is reached and assuming that n is equal to 1.

𝐶𝑝∗ = 𝐶𝑐 𝑆𝑡𝑎𝑡𝑖𝑜𝑛𝑎𝑟𝑦 𝑝ℎ𝑎𝑠𝑒 − 𝐶𝑐0 𝑝𝑟𝑒𝑑𝑖𝑐𝑡𝑒𝑑 (3.9)

Table 3.5. Parameter of the inhibition model for each sucrose concentration.
Cs (g/cm3) Cc stationary (n°/cm3) Cp* (n°/cm3)

1 469000000.0 412764488.5
5 1700000000.0 1625518329.6
10 2560000000.0 2520148067.5
15 3060000000.0 2893087172.4
Equaling Equation (3.3) with (3.8) the following expression is obtained:
𝑛
𝑑𝐶𝑐 𝐶𝑐 − 𝐶𝑐0
= 𝜇𝐶𝑐 (1 − ) (3.10)
𝑑𝑡 𝐶𝑝∗
A code in MatLab R2013b is used to obtain the cell concentration given by the inhibition model,
assuming n is equal to 1 and using the experimental data and the specific growth rate for each
sucrose concentration.

clc
clear all
format long

%1= 1g/cm3, 2=5g/cm3, 3=10g/cm3, 4=15g/cm3

miu1= 0.392176624;
miu2=0.745072313;
miu3=0.749980634;
miu4=0.791573599;

Cp1=412764488.5;
Cp2=1625518330;
Cp3=2520148067;
Cp4=2893087172;

n=1;

C0(1)=30000000;
C0(2)=20000000;
C0(3)=20000000;
C0(4)=13000000;

t=0:1:13; %tiempo en horas

dCj_dt= @(t,C)[miu1*C(1)*(1-((C(1)-C0(1))/Cp1))^n;
miu2*C(2)*(1-((C(2)-C0(2))/Cp2))^n;
miu3*C(3)*(1-((C(3)-C0(3))/Cp3))^n;
miu4*C(4)*(1-((C(4)-C0(4))/Cp4))^n];

[t,C]= ode45(dCj_dt,t,C0)

plot(t,C(:,1),'m')
hold on
plot(t,C(:,2),'g')
hold on
plot(t,C(:,3),'r')
hold on
plot(t,C(:,4),'b')
 legend('1 g/cm^3','5 g/cm^3','10 g/cm^3','15 g/cm^3')

xlabel('Time (h)')
ylabel('Cell concentration (n°/cm^3)')

Figure 3.5. Predicted cell concentration by the inhibition model respect time.

310
Cell Concentration x 10^-7 (n°/cm^3)

260

210

160

110

60

10
-1 1 3 5 7 9 11 13
-40
Time (h)

1 g/cm^3 5 g/cm^3 10 g/cm^3 15 g/cm^3

Figure 3.6. Experimental cell concentration respect time.

Comparing Figure 3.5 with 3.6, it is concluded that the inhibition model does fit the experimental
data due to similar behavior in the graphics as function of time, nevertheless as in any group of
experimental data, there are some points that don’t fit in the behavior of the predictive model.

4. The thermal decomposition of ethane studied by K. J. Laidler and B. W. Wojciechowski,

Deparment of Chemistry, University of Ottawa, Canada.

The uninhibited ethane decomposition was studied from 550 to 640 °C with the object of
determining the overall mechanism that can be described with the following equations and which
kinetic parameters are given in Table 4.1
𝐾1
𝐶2 𝐻6 → 2𝐶𝐻3 (4.1)
𝐾2
𝐶𝐻3 + 𝐶2 𝐻6 → 𝐶𝐻4 + 𝐶2 𝐻5 (4.2)
𝐾3
𝐶2 𝐻5 → 𝐻 + 𝐶2 𝐻4 (4.3)
𝐾4
𝐻 + 𝐶2 𝐻6 → 𝐻2 + 𝐶2 𝐻5 (4.4)
𝐾5
𝐻 + 𝐶2 𝐻5 → 𝐻2 + 𝐶2 𝐻4 (4.5)

Table 4.1. Kinetic parameters of decomposition of ethane.

Reaction A0 E(Kj/mol)
1 1.0E+17 356
2 2.0E+11 44
3 3.0E+14 165
4 3.4E+12 28
5 1.6E+13 0

The preexponential factor A0 has units of s−1 or cm3/mol.s for first- and second-order reactions,
respectively.
Show the change of reagents and products molar flow in function of the reactor volume with the
following operation conditions:
• The reaction is performed in a 100 cm3 isothermal PFR, operating at a constant pressure
of 1.0 atm and at 925 K.
• The feed consists of Ethane in a steam diluent.
• The inlet partial pressure of Ethane is 50 Torr and the partial pressure of steam is 710
Torr.
• The feed flowrate is 35 cm3/s.

Table 4.2 shows the nomenclature employed along the mathematic process.
 Table 4.2. Nomenclature used in the mathematic process.
Symbol Description
Cj Concentration of specie j
CT0 Initial total concentration
Ki Kinetic constant of reaction i
rij Rate of appearance of specie j in reaction i
rj Net rate of appearance of specie j in reaction i
A0i Preexponential factor of reaction i
Ei Activation energy of reaction i
R Ideal gas constant
Fj Molar flow of specie j
Fj0 Initial molar flow of specie j
FT Total molar flow
v0 Initial volumetric flow
V Reactor volume
P Pressure
T Temperature
yjo Initial molar fraction of specie j
Pj0 Initial partial pressure of specie j

The intermediate species in the mechanism of reaction given by the previous equations are CH3,
C2H5 and H, through this mechanism decomposition of ethane produce Methane, Hydrogen and
Ethylene. Using the pseudo-steady state principle (PSSH) the rate of appearance of intermediate
species is equal to zero. To obtain the rates of appearance of all species present in the mechanism
it is made the Table 4.3.

Table 4.3. Rate of appearance of each specie in each reaction.

Reaction riH2 riC2H6 riCH3 riCH4 riC2H5 riH riC2H4
0
4.1 -K1CC2H6 2K1CC2H6 0 0 0 0

4.2 0 -K2CC2H6CCH3 -K2CC2H6CCH3 K2CC2H6CCH3 K2CC2H6CCH3 0 0

0
4.3 0 0 0 -K3CC2H5 K3CC2H5 K3CC2H5
0
4.4 K4CC2H6CH -K4CC2H6CH 0 K4CC2H6CH -K4CC2H6CH 0
4.5 K5CHCC2H5 0 0 0 - K5CHCC2H5 - K5CHCC2H5 K5CHCC2H5

The net rate of appearance of each specie is given by the summation of each rate of appearance
in each reaction, the following equations are result of the summation of the rates of the Table 4.3
for each specie.
𝑟𝐻2 = 𝐾4 𝐶𝐶2𝐻6 𝐶𝐻 + 𝐾5 𝐶𝐻 𝐶𝐶2𝐻5 (4.6)
𝑟𝐶2𝐻6 = −𝐾1 𝐶𝐶2𝐻6 − 𝐾2 𝐶𝐶𝐻3 𝐶𝐶2𝐻6 − 𝐾4 𝐶𝐶2𝐻6 𝐶𝐻 (4.7)
𝑟𝐶𝐻3 = 2𝐾1 𝐶𝐶2𝐻6 − 𝐾2 𝐶𝐶𝐻3 𝐶𝐶2𝐻6 (4.8)
 𝑟𝐶𝐻4 = 𝐾2 𝐶𝐶𝐻3 𝐶𝐶2𝐻6 (4.9)
𝑟𝐶2𝐻5 = 𝐾2 𝐶𝐶𝐻3 𝐶𝐶2𝐻6 − 𝐾3 𝐶𝐶2𝐻5 + 𝐾4 𝐶𝐶2𝐻6 𝐶𝐻 − 𝐾5 𝐶𝐻 𝐶𝐶2𝐻5 (4.10)
𝑟𝐻 = 𝐾3 𝐶𝐶2𝐻5 − 𝐾4 𝐶𝐶2𝐻6 𝐶𝐻 − 𝐾5 𝐶𝐻 𝐶𝐶2𝐻5 (4.11)
𝑟𝐶2𝐻4 = 𝐾3 𝐶𝐶2𝐻5 + 𝐾5 𝐶𝐻 𝐶𝐶2𝐻5 (4.12)
Using the PSSH for the intermediate species, Equations (4.8), (4.10) and (4.11) are equal to zero
and is possible to obtain expressions for the concentration of these species in terms of known
data.
2𝐾1
𝐶𝐶𝐻3 = (4.13)
𝐾2
−2𝐾1 𝐶𝐶2𝐻6 − 𝐾4 𝐶𝐶2𝐻6 𝐶𝐻
𝐶𝐶2𝐻5 = (4.14)
−𝐾3 − 𝐾5 𝐶𝐻
1
(𝐾1 𝐾5 (𝐾1 𝐾5 + 4𝐾3 𝐾4 ))2 + 𝐾1 𝐾5
𝐶𝐻 = − (4.15)
2𝐾4 𝐾5
The following code in MatLab R2013b was used to obtain the equations (4.13), (4.14) and
(4.15).
clc
clear all
syms C_C2H6 C_C2H5 C_CH3 C_H T K1 K2 K3 K4 K5

C_CH3= 2*(K1/K2)
C_C2H5=((-2*K1*C_C2H6)-(K4*C_C2H6*C_H))/(-K3-K5*C_H);
FUN=(K3*C_C2H5)-(K4*C_C2H6*C_H)-(K5*C_H*C_C2H5);
SOL=solve(FUN, C_H);
C_H=SOL(1)
C_C2H5=((-2*K1*C_C2H6)-(K4*C_C2H6*C_H))/(-K3-K5*C_H)

To obtain the molar flows of Ethane, Methane, Hydrogen, Ethylene and the steam as an inert, the
design equation of a PFR is used.
𝑑𝐹𝐽
= 𝑟𝑗 (4.16)
𝑑𝑉
Where j: Ethane, Methane, Hydrogen, Ethylene and steam.
The expression for the molar flow of the inert compound is equal to zero because its flow is
constant in the reaction.
𝑑𝐹𝑆𝑡𝑒𝑎𝑚
=0 (4.17)
𝑑𝑉
Considering ideal gas due to constant low pressure and high temperature, it is possible to obtain
the following expression of the concentration of each specie in terms of molar flows.
 𝐹𝑗
𝐶𝑗 = 𝐶𝑇0 (4.18)
𝐹𝑇
𝑃𝑅
𝐶𝑇0 = (4.19)
𝑇

𝐹𝑇 = ∑ 𝐹𝑗 (4.20)

To obtain the initial molar flow of the feed entering to the reactor, concentration definition is
used with an initial volumetric flow of 0.035 L/s.
𝐹𝑇0 = 𝐶𝑇0 𝑣0 (4.21)
Considering again ideal gas condition, Raoult’s law is applicable to find the molar fraction of the
species present in the feed of the reactor.
𝑃𝑖0
𝑦𝑗0 = (4.22)
𝑃
𝐹𝑗0 = 𝑦𝑖0 𝐹𝑇0 (4.23)

To find the kinetic constant of the reactions Arrhenius equation is used.

−𝐸𝑖
𝐾𝑖 = 𝐴0𝑖 𝑒 𝑅𝑇 (4.24)
To solve the mathematic process a code in MatLab R2013b is used with a variation of reactor
volume since 0 until 0.1 L with a step of 0.001L.
clc
clear all
syms C_C2H6 C_C2H5 C_CH3 C_H
format long

R=8.314472*10^(-3); %Kj/mol K
T=925; %K
K1=(1*10^17*exp(-356/(R*T)));
K2=(2*10^11*0.001*exp(-44/(R*T)));
K3=(3*10^14*exp(-165/(R*T)));
K4=(3.4*10^12*0.001*exp(-28/(R*T)));
K5=(1.6*10^13*0.001*exp(-0/(R*T)));

C_CH3= 2*(K1/K2);
C_C2H5=((-2*K1*C_C2H6)-(K4*C_C2H6*C_H))/(-K3-K5*C_H);
FUN=(K3*C_C2H5)-(K4*C_C2H6*C_H)-(K5*C_H*C_C2H5);
SOL=double(solve(FUN, C_H));
C_H=SOL(1);

v0=0.035; %L/s
R_gas=0.08205746; %atm.L/mol*k
P=1; %atm
CT0=P/(R_gas*T); %mol/L
FT0=CT0*v0; %mol/s
%1:C2H6 2:INERTE 3:CH4 4:H2 5:C2H4

F0(1)= (50/760)*FT0;%mol/s
F0(2)=(710/760)*FT0; %mol/s
F0(3)=0; %mol/s
F0(4)=0; %mol/s
F0(5)=0; %mol/s

V=0:0.001:0.1; %L

dFj_dV= @(V,F)[-K1*(CT0*F(1)/(F(1)+F(2)+F(3)+F(4)+F(5)))-
K2*(CT0*F(1)/(F(1)+F(2)+F(3)+F(4)+F(5)))*C_CH3-
K4*(CT0*F(1)/(F(1)+F(2)+F(3)+F(4)+F(5)))*C_H;
0;
K2*(CT0*F(1)/(F(1)+F(2)+F(3)+F(4)+F(5)))*C_CH3;
K4*(CT0*F(1)/(F(1)+F(2)+F(3)+F(4)+F(5)))*C_H+K5*C_H*(((-
2*K1*(CT0*F(1)/(F(1)+F(2)+F(3)+F(4)+F(5))))-
(K4*(CT0*F(1)/(F(1)+F(2)+F(3)+F(4)+F(5)))*C_H))/(-K3-K5*C_H));
K3*(((-2*K1*(CT0*F(1)/(F(1)+F(2)+F(3)+F(4)+F(5))))-
(K4*(CT0*F(1)/(F(1)+F(2)+F(3)+F(4)+F(5)))*C_H))/(-K3-K5*C_H))+K5*C_H*(((-
2*K1*(CT0*F(1)/(F(1)+F(2)+F(3)+F(4)+F(5))))-
(K4*(CT0*F(1)/(F(1)+F(2)+F(3)+F(4)+F(5)))*C_H))/(-K3-K5*C_H))];

[V,F]= ode45(dFj_dV,V,F0) %F en mol/s

plot(V,F(:,1),'hm')
hold on
plot(V,F(:,3),'og')
hold on
plot(V,F(:,4),'sc')
hold on
plot(V,F(:,5),'.k')
legend('F C2H6','F CH4','F H2','F C2H4')
xlabel('Volume (L)')
ylabel('Molar Flow (mol/s)')
Figure 4.1. Behavior of molar flow of each specie respect to the reactor volume.

Figure 4.1 illustrate the behavior of molar flow of each specie respect to the reactor volume. As
expected from the reaction mechanism given by Equations (4.1)-(4.5) the molar flow of ethane
decreases with the reactor volume because in the mechanism behaves only as a reactive in
Equations (4.1), (4.2) and (4.4), the molar flow of Methane is almost zero, this is due to the fact
that the limit reactive in Equation (4.2) that generates methane is an intermediate specie that is in
low concentration, another factor is that the activation energy of this reaction is low, this means
that reaction is not sensitive to the temperature and also the kinetic constant is the lowest in the
mechanism. The Hydrogen and Ethylene molar flows increase in same proportion respect to the
reactor volume and the steam flow remains constant.

Referencias

[1] M. Brittain, H. Bliss y C. Walker, «Kinetics os the Hopcalite-Catalyzed Oxidation of Carbon

Monoxide,» AIChE Journal, vol. 16, nº 2, pp. 305-314, 1970.

[2] S. Fogler, Elementos de Ingeniería de las Reacciones Químicas, Tercera ed., México:
Prentice Hall, 1999.
ANNEXED A - Comparative figures of calculated and experimental results.

O2 Calculate vs O2 Experimental
16,00
14,00
Pressure (kPa)

12,00
10,00
8,00 O2-CALCULATE
6,00
4,00 O2-
EXPERIMENTAL
2,00
0,00
0 2 4 6
Time (ksec)

Figure A1. Difference between the calculated and experimental pressures for O2.

CO Calculate vs CO Experimental
16
14
Pressure (kPa)

12
10
8
CO Calculate
6
4 CO Experimental
2
0
0 2 4 6
Time (ksec)

Figure A2. Difference between the calculated and experimental pressures for CO.
 CO2 Calculate vs CO2 Experimental
16
14
Pressure (kPa) 12
10
8
CO2-Calculate
6
CO2-Experimental
4
2
0
0 2 4 6
Time (ksec)

Figure A3. Difference between the calculated and experimental pressures for CO2.
ANNEXED B - Algorithm to determine the pressures of each species.

• Function

function dudt = ECUACIONES(t,u)

P_CO= u(1);
P_CO2= u(2);
P_O2= u(3);

%Equations
P_CO_0=13.6; %KPA
P_O2_0=14.5; %KPA
P_CO2_0=1.2; %KPA
R=0.008314472; %kPa*m3/mol*K
T=313.15; %K
K=0.27644284; %mol/kPa*m3
Os0=11.81*0.133322387415; %kPa
K1K2=0.00737/(0.06*0.133322387415); %(ksec^-1)(kPa^(-1))
K1= 0.00732/(0.06*0.133322387415); %(ksec^-1)(kPa^(-1))
K3K4= 3.13*(0.133322387415^(1/2)); %(kPa^(1/2))
K4K3= (1/K3K4)/(0.133322387415^(1/2));%(kPa^(-1/2));
K5=0.0085/(0.06*0.133322387415);%(ksec^-1)(kPa^(-1))
SIGMA0= 0.95*0.133322387415; %kPa

Cos = Os0 + (P_CO-P_CO_0) - 2*(P_O2-P_O2_0);

Csigma = SIGMA0 + (P_CO2-P_CO2_0) + 2*(P_O2-P_O2_0);

rCO = -(P_CO)*(Cos)*(K1K2);
rCO2=
K1*(P_CO)*(Cos)*((1/(1+(K4K3*(P_O2))^(1/2)))+(((P_O2)^(1/2))/(K3K4+((P_O2)^(1
/2)))));
rO2 = -
(1/2)*((P_O2)^(1/2))*(((K1*(P_CO)*Cos)/(K3K4+((P_O2)^(1/2))))+(K5*Csigma));

%Differential Equations
dudt(1,1)= rCO;
dudt(2,1)= rCO2;
dudt(3,1)= rO2;

end

• Script

clear all
clc
format long

%Equations
t =[0 0.12 0.3 0.6 1.2 1.86 2.58 3.48 4.98];%ksec
Xi=[13.6 1.2 14.5];
[t,u] = ode45(@ECUACIONES,t,Xi);
P_CO = u(:,1)
P_CO2 = u(:,2)
P_O2 = u(:,3)

PCO=[13.6 12.1 10.3 8 5.7 3.9 2.7 1.3 0.3]; %kPa

PO2=[14.5 13.7 13.1 12.3 10.8 10.3 9.5 8.5 8.3]; %kPa
PCO2=[1.2 2.8 4.3 6.3 8.4 10.3 12 13.1 13.9]; %kPa

figure
plot(t,P_CO)
hold on
plot (t,PCO)
ylabel ('Partial Pressure of CO [=] kPa')
xlabel('Time [ksec]')
legend('Calculate','Experimental')

figure
plot(t,P_CO2)
hold on
plot (t,PCO2)
ylabel ('Partial Pressure of CO2 [=] kPa')
xlabel('Time [ksec]')
legend('Calculate','Experimental')

figure
plot(t,P_O2)
hold on
plot (t,PO2)
ylabel ('Partial Pressure of O2 [=] kPa')
xlabel('Time [ksec]')
legend('Calculate','Experimental')