UNIVERSITY OF ANTIOQUIA

ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING
CLASS: IQU-458 ENGINEERING OF CHEMICAL REACTIONS
Homework 4
04/09/2018

Carolina Arias Gallego [1], Marcela Jaramillo Baquero [2], Manuela Ospina Arboleda [3]
[1]
carolina.ariasg@udea.edu.co [2] marcela.jaramillob@udea.edu.co
[3]
manuela.ospinaa@udea.edu.co

1. L. C. Abella, P. A. D. Gaspillo, M. Maeda, and S. Gato [Int. J. Chem. Kinet., 31, 855–
859 (1999)] studied the dehydration of tert-butyl alcohol (TBA) in the presence of
ionexchange resins for producing water and isobutylene (IB), Equation (1).

The reaction can be regarded as irreversible because the product isobutylene is rapidly
vaporized at the temperature of interest.

a.) Taking in account the data shown in Table 1, estimate the order of the reaction and
the rate constant with its corresponding units?

Table 1. Concentration of Tert-butanol during dehydration reaction at 338 k.

t (h) CTBA(M)
0 1
0.25 0.94
0.5 0.9
0.7 0.86
1.1 0.8
1.5 0.72
1.9 0.66
2.5 0.59
3 0.55
4 0.43
5.1 0.35
6 0.28

Considering that the reaction is carried out isothermally at 338k and with a volume reactor
constant, also that the reaction is irreversible due to instant vaporization of the product and
that the rate of appearance of specie TBA can be expressed as a power function in terms
only of its concentration. The differential method of velocity analysis is employed.

1
Where α is the order of the reaction and k is the rate constant.

Using the design equation of a batch reactor it is possible to obtain a linear form applying
natural logarithm in both sides of equation (4)

Replacing equation (2) into (3)

Using the logarithm properties a, the linear form of the design equation of a batch reactor is
given by equation (5), where α is the slope and ln(k) is the intercept with the axis.

To determinate the units of the rate constant a dimensional analysis of equation (4) is
employed. The derivative of the concentration of TBA respect to time gives units of mol/Lh
so the other side of the equation should give the same units as it’s showed in equation (6).

To obtain the derivative of the concentration of TBA respect to time, a fitting curve of data
is used. Is chosen a fourth order polynomial, if a polynomial of lower order is used, the
fitting curve won't capture the tendency of the data, otherwise if a higher order is chosen,
the fitting curve could have crests and valleys passing through the points and it will
produce important mistakes in the derivative of the polynomial.

2
 1.2

Concentration of TBA (M)

y = 5E-05x4 - 0.0019x3 + 0.0261x2 - 0.2164x + 0.9987
0.8 R² = 0.9991

0.6

0.4

0.2

0
0 1 2 3 4 5 6 7
Time (h)

Figure 1. Concentration of TBA respect time and curve fitting of data.

As explained before the fitting curve may not capture the tendency of the data, nevertheless
in figure 1 the determination coefficient with a value of 0.9991 shows that the fitting curve
is suitable to model the behavior of concentration of TBA respect to time.

0
-1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0

-0.5

-1
ln(-dCTBA/dt)

y = 1.0301x - 1.5584
R² = 0.9909
-1.5

-2

-2.5

-3
ln(CTBA)

Figure 2. Linear form of design equation of a batch reactor.

3
In figure 2 it can be seen that the linear adjustment goes through the majority of data with a
coefficient of determination of 0.9909, indicating an adequate modeling of the data. The
slope corresponds to the order of the reaction with a value of 1.0301 and the intercept with
the y-axis corresponds to the natural logarithm of the reaction constant, then the value of
the reaction constant is 0.21048 (mol/L)-0.0301 h-1.

Table 2. Order of reaction α and rate constant k.

α k ( [mol/L]-0.0301 h-1 )
1.03010 0.21048

b. Table 3 shows data of temperature effect on the rate constant corrected because the
inhibitory effect of water, the effect can be explained as a step of “adsorption” in the ion
exchange resin.

Determine the activation energy and the pre-exponential factor for this reaction. Take in
account that the value of the rate constant determined in part a will not be consistent with
the
data for part b because the rate constant in Table 2 correspond to values corrected for the
inhibitory effect of water.

Table 3. Rate constants corrected by the inhibitory effect of water at different temperatures.

T(°C) k ( [mol/L]-0.0301 h-1 )

51 0.0088
56 0.0167
66 0.0900
71 0.2153
78 0.4356

To determine the activation energy and the pre-exponential factor, the Arrhenius equation
is used to check the dependence of the rate constant respect to the temperature at which it
takes place the reaction.

Where:

 Rate constant of reaction, where α is the order of reaction.

 Pre-exponential factor.

4
  E Activation Energy
 T Absolute temperature.
 Idea gas constant.

Through a dimensional analysis, the dimensions of the parameters of equation (9) are
determined. Due to the exponential term of the equation is dimensionless, it implies that the
units of the pre-exponential factor A are the same as those of the reaction constant k, in
addition it has that the exponent must also be dimensionless, therefore the dimensions of E
and T are such that they cancel out with those of R.

Applying natural logarithm to both sides of equation (9) the linear form of Arrhenius
equation is obtained.

With the information provided in table 3 and the linearized form of the Arrhenius equation
(10), the natural logarithm of the velocity constant can be plotted against the inverse of the
temperature and, through a fitting curve of the data, it is obtained the slope which
represents the relation between the activation energy and the ideal gas constant and the
intercept with y-axis is the natural logarithm of the pre-exponential factor.

0
0.0028 0.00285 0.0029 0.00295 0.003 0.00305 0.0031

-1

-2
ln(k)

-3

y = -17136x + 48.088
-4
R² = 0.9946

-5

-6
1/T (K-1)

Figure 3. Linear form of Arrhenius equation.

5
 Table 4. Activation Energy and pre-exponential factor.

A ( [mol/L]1-α h-1 ) E (J/mol)

7.66261E+20 -142475.210716

The activation energy is the minimum energy necessary for the reaction to be carried out,
determines the sensitivity of the reaction with temperature, the higher the slope the reaction
is much more sensitive to temperature. In Figure 3 a steep slope can be seen and in Table 4
the value obtained from the activation energy is high, this indicates that the reaction given
by equations (1) is sensitive to temperature. It can also be deduced from the Arrhenius plot
and equation (9), regardless of whether the reaction is exothermic or endothermic, if the
temperature of the system rises, the reaction rate constant or kinetics will also increase.

Both the Arrhenius activation energy and the kinetic speed constant represent macroscopic
reaction parameters, the result of many individual collisions with different collision
parameters such as collision angle, vibrational energy among others; while the pre-
exponential factor indicates the frequency of the collisions between the reagent molecules,
according to the theory of collision a fraction of those shocks leads to the occurrence of the
reaction.

2. Consider the following network of competitive first-order reactions, Equation (2), that
take place in a PFR operating at steady state, in which species V is the desired product.

a. If the reactor is operated at the flow rate corresponding to the optimum (maximum
concentration of desired product), determine the effluent concentrations of species A, V,
and W when the temperature of the effluent is 60°C. At this temperature, kf = 0.50 min-1, kr
= 0.125 min-1, and k2 = 0.08 min−1. The concentration of A in the feed stream is 2.0 M.
Plot the concentrations of each specie as a function of space time.

Reactions given by (12) and (13) equations are first order series-parallel reactions in steady
sate, to determinate the concentrations of each species as function of space time it is
necessary to begin with a mole balance of a differential control volume as it is illustrated in
figure 4. It will be consider that the reaction takes place in liquid phase, therefore
volumetric flow is constant.

6
 Figure 4. Differential control volume in a PFR.

Solving the integral, divided between Δy and extracting the limit when Δy tends to zero, we
obtain the following form.

Dividing and multiplying in the left side of equation (15) between initial volumetric flow
v0, and considering that volumetric flow is constant, the following form is achieved.

Considering definition of special time and concentration, the concentration as function of

space time is given by equation (18).

7
Due to series-parallel reactions are first order reaction, the following table gives the
corresponding rate appearance of each species.

Table 5. Rate of appearance of each species.

Reaction k (min-1) riA riV riW
1 A---> V kf = 0.5 -kfCA kfCA 0
2 V---> A kr = 0.125 krCV -krCV 0
3 A---> W k2 = 0.08 -k2CA 0 k2CA
rj =∑ rij -kfCA +krCV-k2CA kfCA-krCV k2CA

The following code in MatLab R2013b is used to solve the system of differential equations,
varying space time in a range of [0-15] min.

clc
clear all
format long

CA0=2; %M
Kf=0.5; %1/min
Kr=0.125; %1/min
K2=0.08; %1/min

%CA=1 CV=2 CW=3

C0(1)=CA0; %mol/s
C0(2)=0; %mol/s
C0(3)=0; %mol/s

%dCj_dTao=rj
Tao=0:0.01:15; %Tiempo espacial en min

dCj_dTao= @(Tao,C)[-C(1)*(Kf+K2)+Kr*C(2); Kf*C(1)-Kr*C(2);

K2*C(1)];

[Tao,C]= ode45(dCj_dTao,Tao,C0)

plot(Tao,C)
legend('FA','FV','FW')
xlabel('Spacial time (min)')
ylabel('Concentration (M)')

8
 Figure 5. Concentration of each species as function of space time at 60°C.

In figure 5 it is seen that concentrations of species A and V tends to a constant value after
an optimum space time is achieved, this occurs due to reaction between these species is an
reversible reaction and when concentration begins to behavior as constant in space time it
indicates that equilibrium conditions are reached. This optimum space time correspond to
major value of concentration of the product of interest V, in table 6 these values are
reported. Otherwise for specie W it only tends to increase with space time, due to reaction
between A and W is irreversible.

Table 6. Maximum concentration of specie V and optimum space time at 60°C.

Cv max (M) (min)
1.33 5.72

b. If the activation energies associated with kf, kr, and k2 are 20, 30, and 40 kcal/mol, does
the maximum effluent concentration of species V increase, decrease, or stay the same when
the operating temperature is increased by 10 K? First present a qualitative argument and
then be as quantitative as possible.

9
It is to be expected that if the temperature increases, the rate constants will also increase,
regardless of whether the reaction is exothermic or endothermal. It is also known that if the
activation energy is greater, it indicates that the reaction is more sensitive to temperature,
therefore as the activation energy in the reversible reaction between A and V is greater in
the left direction of equation (12) the equilibrium tends to move to the left, therefore the
concentration of V will decrease with the increase of the temperature.

To determinate the rate constants at the new temperature equation of Arrhenius is used. Sub
index 1 indicates conditions at 60°C and sub index 2 indicates conditions at 70°C.

Dividing equation (20) between (19) and reorganizing the expression to obtain the new rate
constant at the new temperature condition.

To obtain the concentrations as function of space time, the same procedure followed in 2.a
is employed.

clc
clear all
format long
CA0=2; %M
%K=K1Exp(E/R(1/T1-1/T))
Ef=20000; %Cal/mol
Er=30000;%Cal/mol
E2=40000; %Cal/mol
R=1.987207; %Cal/mol K
T1=60+273.15; %K
T2=70+273.15; %K
Kf1=0.5; %1/min
Kr1=0.125; %1/min
K21=0.08; %1/min
Kf2=Kf1*exp((Ef/R)*((1/T1)-(1/T2))) %1/min
Kr2=Kr1*exp((Er/R)*((1/T1)-(1/T2))) %1/min
K22=K21*exp((E2/R)*((1/T1)-(1/T2))) %1/min
%CA=1 CV=2 CW=3
C0(1)=CA0; %mol/s
C0(2)=0; %mol/s
C0(3)=0; %mol/s
%dCj_dTao=rj
Tao=0:0.01:15; %Tiempo espacial en min

10
dCj_dTao= @(Tao,C)[-C(1)*(Kf2+K22)+Kr2*C(2); Kf2*C(1)-Kr2*C(2);
K22*C(1)];
[Tao,C]= ode45(dCj_dTao,Tao,C0)
plot(Tao,C)
legend('FA','FV','FW')
xlabel('Space time (min)')
ylabel('Concentration (M)')

Figure 6. Concentration of each species as function of space time at 70°C.

Comparing figure 5 with figure 6, it is seen that concentration of specie V decreased

significantly with the temperature, also that the optimum space time is reached sooner than
at 60°C., in the table 7 is reported the maximum concentration of V and the optimum space
time. Another aspect that can be seen is that for specie W, the concentration increases
higher at 70°C than at 60°C, this occurs due to activation energy of this reaction between A
and W is greater than the reversible reaction between A and V, therefore its concentration
will increase significantly with increase of temperature. Due to V is the product of interest
and W is undesired it is better to carried out the reactions at 60°C.

Table 7. Maximum concentration of specie V and optimum space time at 70°C.

Cv max (M) (min)
1.01 1.53

11
3. A. M. Davis and W. H. Corcoran [Ind. Eng Chem., 11, 431 (1972)] studied the reaction
between nitrogen dioxide and acetaldehyde in gas phase. The initial rate data in Table 8
were obtained at ambient temperature (22°C) and atmospheric pressure in a constant
volume batch reactor.

Table 8. Laboratory data of nitrogen dioxide and acetaldehyde reactions taken at 22°C.

What is the order of the reaction with respect to each reactant? What is the constant?

12
Based on the experimental results presented in Table 8 of initial concentrations and reaction
rates, it was decided to use the initial velocity method to determine the required kinetic
parameters, such as the reaction orders of each reagent and the velocity constant. of
reaction; given that a series of experiments at different concentrations are carried out to
determine the initial reaction rate for each experiment.

In Equation (22) the balance of moles in a batch reactor of constant volume is presented
when you have two reagents.

(22)

Where:

= Order of reaction with respect to nitrogen dioxide.

= Order of reaction with respect to acetaldehyde.

= Concentration of nitrogen dioxide..

= Concentration of acetaldehyde.

= Reaction rate constant.

Once this is established, the linearized form of Equation (22) is defined by the initial
velocities method.

(23)

It is said then that Equation (23) can be modeled as shown in Equation (24).

(24)

Where:

= ; where is the initial concentration of A in the j-th test.

= ; where is the initial concentration of B in the j-th test..

13
In order to determine the unknowns they are simultaneously solving the system
that is presented in the Equations (25, 26, 27).

(25)

(26)

(27)

As we can see, three linear equations are obtained with each one with three unknowns that
will be solved using the least squares method for systems resolutions of linear equations;
for this the system of equations previously raised to the form of an equation is taken
.

Where the matrix A, X and b are expressed in Equations (28, 29 and 30).

(28)

(29)

(30)

As we see the vector that contains the response parameters is "X" which is determined as
. Initially using MatLab and the logarithm of the experimental data proposed in
Table 8, the following results are obtained for the summations that must be calculated
before solving the system of equations.

14
Once these values are obtained, the matrix system proposed in equations (28-30) can be
developed as shown in the following lines of code, obtaining the results shown in Table 9.
clc
clear all
%Calculation of the kinetic parameters for the reaction between dioxide
nitrogen and acetaldehyde.
%A=Nitrogen dioxide.
%B= Acetaldehyde.
N=24;
X1j=log([0.000849 0.000821 0.001247 0.000978 0.001071 0.000801 0.001008
0.000677 0.000662 0.000698 0.000844 0.000633 0.000751 0.000941 0.00078
0.000691 0.001281 0.000919 0.000782 0.000837 0.000971 0.00072 0.000661
0.001144]);
X2j=log([4.04 2.65 6.88 6.7 1.93 7.98 1.24 2.8 7.06 7.97 4.19 4.36 4.7
3.09 5.68 5.92 6.56 5.18 5.5 6.2 4.27 4.64 2.22 5.58]);
Yj=log([2.895E-08 1.919E-08 7.198E-08 5.65E-08 1.798E-08 5.451E-08
1.099E-08 1.662E-08 4.01E-08 4.739E-08 3.089E-08 2.439E-08 3.101E-08
2.444E-08 3.862E-08 3.418E-08 7.274E-08 4.068E-08 3.66E-08 4.479E-08
3.471E-08 2.87E-08 1.265E-08 5.586E-08]);
X1j_cuadrado=X1j.^2;
X2j_cuadrado=X2j.^2;
X1jX2j=X1j*X2j';
X1jYj=X1j*Yj';
X2jYj=X2j*Yj';

15
X1j_Suma=sum(X1j);
X2j_Suma=sum(X2j);
Yj_Suma=sum(Yj);
X1j_cuadrado_Suma=sum(X1j_cuadrado);
X2j_cuadrado_Suma=sum(X2j_cuadrado);
X1jX2j_Suma=sum(X1jX2j);
X1jYj_Suma=sum(X1jYj);
X2jYj_Suma=sum(X2jYj);

A=[N X1j_Suma X2j_Suma; X1j_Suma X1j_cuadrado_Suma X1jX2j_Suma; X2j_Suma

X1jX2j_Suma X2j_cuadrado_Suma ];
b=[Yj_Suma; X1jYj_Suma; X2jYj_Suma];

x=inv(A)*b

From this vector X it is possible to directly obtain the reaction orders and for the reaction
rate constant it is necessary to apply the exponent to the value obtained since this is Ln(K).

Table 9. Results of reaction kinetic parameters obtained.

Reaction rate constant Reaction order for nitrogen Reaction order for
[=]m0.9754/mol0.9754*s dioxide. acetaldehyde.
8.1586e-06 0.9894288 0.9860001

Another alternative solution that can be used to solve the unknowns is posed using the tool
<< Curve Fitting Tool >> where the X axis corresponds to the log of the concentration of
the nitrogen dioxide of experiment j-th, the Y axis corresponds to the log of the
acetaldehyde concentration of experiment j-th and finally the Y axis corresponds to the log
of the initial reaction speed where the results obtained by this tool are shown in Table 10 as
well as the response surface thrown by the tool, which It is shown in Figure 7.

Table 10. Results of reaction kinetic parameters obtained by the Curve Fitting Tool
program.
Reaction rate constant [=] Reaction order for nitrogen Reaction order for
m0.9754/mol0.9754*s dioxide. acetaldehyde.
8.1296e-06 0.9894 0.986

16
Figure 7. Response surface for the kinetic parameters in the reaction of interest.

As we can see between Tables 9 and 10, the results are the same. This is because the
MatLab tool performs its solution also in a least squares development.

4. In an industrial process design an important criterion to choose a chemical route is how

much earnings, generated for our investment, can be reflected in the added value, Equation
(31), obtained from the route.

(31)

Where:

= mass of the product i.

= mass of the reagent i.

One route to produce the terephthalic acid is described with the following chemical
balanced equations and Table 11 shows the prices of each of the components involved in
the route showed in the Equations (32, 33 and 34).

(32)

(33)

(34)

17
Table 11. Prices of substances involved in route per kilogram and their quality.
Substance Prize ($US/Kg) Quality
p-xylene ( 1.38 100%
p-toluic acid ( ) 1.01 99.5%
4-formylbenzoic acid ( ) 54.18 98%
Oxygen 0 ---
Terephthalic acid ( ) 1.135 99%
Water 0 ---

The operating conditions of the process are:

Temperature: 175-225 °C
Pressure: 1500-3000 kPa
Catalyst (Oxidation catalyst Amoco): Co / Mn / Br
Solvent: Acetic acid,
Proportion of each reagent: 5 mol / 1 mol p-xylene.
5000 ppm of 4-formylbenzoic acid (5000 mg de Kg total of products)

Conversion: 100% for the p-xylene.

Selectivity type S (moles of product at outlet af reactor respect moles of reagent that react
in the reactor): 95.4% mol terephthalic acid/mol p-xylene consumed.
If it is needed to produce 1 Kg of terephthalic acid starting from this route, does it generate
profits or losses?

In order to determine if there are losses or gains, it is necessary to determine the mass of the
products and reagents; for this, it starts by consulting the molecular weights of all the
reactants and products involved in the reaction; these are presented in Table 12.

Table 12. Molecular weight of all the compounds involved in the reaction.
COMPOUND MOLECULAR WEIGHT
p-xylene ( ) 106.12 g/mol
Oxygen 31.9988 g/mol
p-toluic acid ( ) 136.15 g/mol
Water 18.01528 g/mol
4-formylbenzoic acid ( ) 150.13 g/mol
Terephthalic acid ( ) 166.13 g/mol

Now it is necessary to state the mass balance for each compound in terms of the extent of
reaction as shown below.

18
  Mass balance for p-xylene (Equation 35).

(35)

 Mass balance for oxygen (Equation 36).

(36)

 Mass balance for p-toluic acid (Equation 37).

(37)

 Mass balance for water (Equation 38).

(38)

 Mass balance for 4-formylbenzoic acid (Equation 39).

(39)

 Mass balance for Terephthalic acid (Equation 40).

(40)

Where:

= extent of reaction 1.

= extent of reaction 2.

= extent of reaction 3.

And the N refers to the moles of the respective compound that is specified.

It should be noted that as not all reagents are added initially, then you have to:

=0,

=0,

=0,

=0.

19
And knowing from the statement that the conversion of p-xylene is 100% then we obtain
that:

= 0.

Using the 1 Kg terephthalic acid production, we can calculate the final moles of this
compound as shown in Equation (41).

(41)

By replacing the result obtained in Equation (41) in the mass balance of Equation (40) it is
possible to obtain the value of the extent of reaction proposed in Equation 34; getting:

Now using the selectivity given in the statement it is also possible to obtain the initial
moles of p-xylene as shown in Equation (42).

 (42)

Using the initial moles of p-xylene found and replacing in Equation (35) it is possible to
obtain the degree of advancement of reaction 1 showed in Equation (32) as shown below.

To know the initial moles of oxygen, use is made of the relationship given in the statement
as shown in Equation (43) below.

(43)

Finally we can make use of the mass ratio of 4-formylbenzoic acid and the total kg of
products as shown in Equation (44).

(44)

Where each of the masses is expressed in terms of moles by their respective molecular
weight, using Equations (35-40) and Table 12.

Thus, the entire equation remains in a single unknown, which would be the extent of
reaction 2 ( ), which was determined by applying the Excel Solver tool to Equation (44).

20
Obtaining as a result = 0.0060752, result that finally allows to solve all mass balances of
each compound and find the moles that will then be multiplied by their respective
molecular weight obtaining the following results.

Where the notation << M >> refers to the masses of each compound respectively.

Finally, these values of the masses obtained in Equation 31 can be replaced to determine if
the process generates losses or gains taking into account that the masses must be divided
between the purity with which each product is obtained which is specified in Table 11; and
making this replacement you get:

This tells us that the process is generating profits since the cost of the products is much
higher than that of the reagents, for this reason the route is profitable.

REFERENCES

 Fogler, H.S. (2008). Elementos de ingeniería de las reacciones químicas. Edición 4,

Pearson Prentice Hall, USA

 Davis, A.M. (1972). Rate and Mechanism of the Partial Oxidation of Acetaldehyde
by Parts-per-Million Concentrations of Nitrogen Dioxide. Ind. Eng. Chem. Fundam,
Vol (11), N°4.

21