UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA

DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

HOMEWORK2

PRESENTED BY

ANDRES FELIPE SOTO CUELLAR

DAYANA BARRETO ARENAS
LAURA MUÑOZ MUÑOZ

ENGINEERING OF CHEMICAL REACTIONS

MEDELLIN-ANTIOQUIA
JUNE 18TH OF 2019
 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

1. Design a batch reactor to perform the thermal decomposition of A, which is given by equation (1), and
obeys a second order rate law.

2�(�) → 2�(�) + �(�) (1)

The reactive is fed to the reactor with an inert gas at a pressure of 5 kPa. Experimental data of the
kinetics of the given reaction is shown in table 1.

Tabla 1 Reaction rate constant at different temperatures.

a) Set a stoichiometric table for the process and reaction given.

b) Determine the Arrhenius equation parameters for the reaction.
c) What kind of reactor would you choose: a constant volume reactor or constant pressure reactor?
Support your answer with a quantitative analysis of conversion as a function of time.
d) For the chosen reactor, make a plot of residence time as a function of temperature for a
conversion of 88%. What can you conclude from your results?

2. The reaction shown in equation (2) is normally carried out at 350°C and 213 atm.

��(�) + 2�2(�) ↔ ��3��(�) (2)

There is a new catalyst that allows to reduce the reaction temperature to 230°C.
 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

a) What is the total pressure that yields the same equilibrium

composition at 230°C that at 350°C and 213 atm?
b) What is that composition?
Please, carry out the analysis starting with a stoichiometric mixture of carbon monoxide and
hydrogen.

The equilibrium constant is given by equation (3).

5304
ln k p −12.89 (3)
T

With 𝐾� in atm-2 and T in K.

3. One important process in the microelectronics industry is to apply coatings to the integrated circuits in
order to improve the chemical and mechanical resistance. One coating particularly resistant to oxidation
is Si3N4, which is produced by means of the reaction given by equation (4).

3𝑆𝑖�4(�) + 4𝑁�3(�) → 𝑆𝑖3𝑁4(�) + 12�2(�) (4)

Set up a stoichiometric table for this reaction and plot the concentration of each species as a function of
conversion for an equimolar feed of NH3 and SiH4. Consider the process to be carried out in a PFR at
constant temperature of 700°C and constant pressure of 1 atm.

4. Make a comparison between the collision and the transition state theory.

5. List the reaction rate of three non-elementary reactions. Include also the Arrhenius parameters or the
reaction rate at a known temperature and the corresponding activation energy. Remember to include
the references.
 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

Solution

1.
a) As of equation and dividing both sides by 2, we obtain equation 5:

(�) → �(�) + (1/2)�(�) (5)

Tabla 2 Stoichiometric table

Specie initial moles change (moles) renmains

A N A0 N N
(¿¿ A 0 X ) (¿¿ A 0 X )
−¿ N A =N A 0−¿
B NB0 N N
1 1
(¿¿ A 0 X ) (¿¿ A 0 X )
1 1
+¿ N B =N B 0+ ¿
C NC0 N N
1 1
2 2
(¿ ¿ A 0 X) (¿ ¿ A 0 X)
1 1
+¿ N C =N C 0+ ¿
I NI0 N I =N I 0
TOTAL NT0 N T =N T 0 +δ ( N A 0 X )

1
Where b c 1 2 1
δ= + −1= + −1=
a a 1 1 2

N T =N T 0 + ( 12 )∗( N A0 X)

b) To determine the activation energy and the pre-exponential factor, we proceed to perform a linear
regression analysis of the arrhenius ecucaion, taking the data provided by Table 1

−E
k A ( T )= A∗e R∗T (6)

Where:
 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

 k A : Reaction rate constant.

 A : Pre-exponential factor.
 E : Activation energy.
J
 R : universal constant of gases: 8.314
mol . K
 T : Temperature, Kelvin
Equation 6 is transformed in logarithmic form to perform the regression analysis

E 1
ln k A =lnA− ∗( ) (7)
R T
The logarithms of the reaction rate constants are calculated using the data in Table 1 and are taken to
EXCEL where a data dispersion graph is made and the regression analysis is done:

Table 3 Base data to do the regression

the graphical follow-up shows the linear regression that is applied to the data in table 3
 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

Object 51

Graph 1 linear regression and equation of the line

from graph 1 the equation of the straight line is obtained:

Y = -13817x + 10,729 (8)

where:

 Y = ln k A
−E
 -13817=
R
 lnA = 10,729

finding the variables that need to be determined:

E= -13817*-R = 114874.538 J/mol = 114.874538 KJ/mol

A = e 10,729 = 45661.01 L/mol.s

c) To do the analysis in both cases, we start from the general design equation for a batch reactor:

dNj
=r j∗V (9)
dt

For a constant volume reactor:

Considerations:
 V constant.
 Design parameter is time.
 No stationary state.
 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

 Homogeneous temperature and concentration in the reactor

ν

because it assumes good agitation, ∫ r j dV = rj V.

0
 Reaction in gas phase.
 Second order reaction
 Feeding pressure P= 5kPa.
 Temperature constant.

From equation 9, the consideration of constant volume, and taking into account that A is the limit
reagent and that which is consumed:

1
∗d N A
V (10)
=−r A
dt

NA
d
V (11)
=−r A
dt
dCA
=−r A (12)
dt
The conversion is defined as:
N A 0−N A
X= (13)
NA0

X = Conversion of A in the reaction.

NA0 = Initial moles of A.
NA0 – NA = Moles converted.

From the above equation NA is cleared in terms of the conversion and the
initial moles, such that:

N A =N A 0−N A 0 X (14)

N A =N A 0 (1−X ) (15)

the definition of concentration is:

NA
CA= (16)
V
 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

From volume constant V=V0

N A 0 (1−X )
CA= (17)
V0

C A =C A 0 (1−X ) (18)

we replace equation 18 in equation 12:

C
(¿ ¿ A 0−C A 0 X ) (19)
d =−r A
dt
¿

Since the reaction is of second order, the speed law has the following form:

r A =k A∗C 2A (20)

2 2
r A =k A∗C A 0∗( 1−X ) (21)

we replace equation 21 in equation 19:

C
(¿ ¿ A 0−C A0 X ) 2 2
d =¿ −k A∗C A 0∗( 1− X ) (22)
dt
¿

solving the drift:

dX
−C A 0 =−k A∗C2A 0∗( 1−X )2 (23)
dt

applying separation of variables, reorganizing terms and applying integrals to both sides of the equation:

X t
1 1
∗∫ dX =∫ dt (24)
k A C A 0 0 ( 1−X )2 0

Using the equation (A-2) of the appendix of the book "Element of engineering of the chemical reactions"
we give solution to the integral
 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

t=
1
∗
X
[ ]
k A C A 0 1−X
(25)

As it is observed we arrive at an expression that relates the time with the conversion.
Now we find the input parameters for the solution of equation 25:

k A =¿ 4,072E-05 (L/mol.s) The KA is obtained from table 1

PA 0 5 kPa
C A 0=
R∗T A 0
= 8.314
kPa . L
∗663.15 K = 9,0688E-04
mol . K

With the equation 25 and the initial parameters found, we make a table with different conversions and
find the time that the reactor requires to reach that point of conversion:

Table 4 Time needed to reach a certain level of conversion

 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

For a variable volume reactor:

Considerations:
 P constant.
 Design parameter is time.
 No stationary state.
 Homogeneous temperature and concentration in the reactor because it assumes good
ν

agitation, ∫ r j dV = rj V.
0
 Reaction in gas phase.
 Second order reaction
 Feeding pressure P= 5kPa.
 Temperature constant.

From equation 9, the consideration of variable volume, and taking into account that A is the limit reagent
and that which is consumed:

−d N A
=−r A V (26)
dt

we replace equation 14 in equation 26:

N
(¿ ¿ A 0−N A 0 X ) (27)
d =−r A V
dt
−¿

where the derivative of equation 27 is:

dX
0−N A 0 (28)
dt

dX
N A0 =−r A V (29)
dt

In gas phase reactions that do not have the same number of moles of products and reagents, the
following procedure is considered:

For a time t P∗V =Z∗N T ∗R∗T (30)

 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

For a time t=0 P0∗V 0=Z 0∗N T 0∗R∗T (31)

We clear the variable volume and divide equations 30 and 31 between each other:

V =V 0∗ ( PP )∗( TT )∗( ZZ )∗( NN )

0

0 0 T0
T
(32)

We know that:

N T =N T 0 +δ ( N A 0 X ) (33)

dividing equation 33 by NT0 :

NT NA0
=1+δ ( X) (34)
NT 0 NT0

NT
=1+δ (Y A 0 X ) (35)
NT 0

We define a new term:

Total number of moles fed
Change∈the total number of moles for total conversion
ε= thereactor ¿
¿

b c
ε=
( a a )
+ −1 ∗N A0
=δ Y A 0
(36)
N T0

we replace equation 35 and 36 in equation 32, and considering that for an ideal gas Z = 1

V =V 0∗ ( PP )∗(1+ ε∗X)∗( TT )
0

0
(37)

From the considerations it is known that P = P 0 and T = T0

V =V 0∗(1+ ε∗X) (38)

As the reaction, only one reagent intervenes:

N A 0 =N T 0 (39)

ε =δ =1/2

we replace equation 15 and 38 in equation 16

 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

NA N (1− X)
CA= = A0 (40)
V V 0∗(1+ε∗X )

from the equation 29:

dX −r A . V
= (41)
dt N A0

we replace equation 38 in equation 41

dX −r A . V 0∗(1+ε∗X )
= (42)
dt N A0

we replace equation 20 in equation 42 and using the definition of concentration

2
dX −k A∗C A∗V 0 (1+ε∗X )
= (43)
dt C A 0∗V 0

we replace equation 40 in equation 43

2 2

dX
=
kA
( C A 0 (1−X )
(1+ ε∗ X)2 ) V 0∗(1+εX )
(44)
dt C A0 V 0

By performing simplification and separation of variables to equation (44) operations, we obtain:

1
∗(1+εX )
k A C A0
dX=dt ( 45)
( 1− X )2
Applying separation of variables, reorganizing terms and applying integrals to both sides of the equation:

x t
1 ( 1+ εX )
∗∫ dX =∫ dt (46)
k A C A 0 0 ( 1−X )2 0

Using the equation (A-5) of the appendix of the book "Element of engineering of the chemical reactions"
we give solution to the integral:
 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

t=
1
[
( 1−ε ) X
k A C A 0 1−X
−ε ln
1
(
1− X )] (47)

As it is observed we arrive at an expression that relates the time with the conversion.
Now we find the input parameters for the solution of equation 47

k A =¿ 4,072E-05 (L/mol.s) The Ka is obtained from table 1

PA 0 5 kPa
C A 0=
R∗T A 0
= 8.314
kPa . L
∗663.15 K = 9,0688E-04
mol . K
With the equation 47 and the initial parameters found, we make a table with different conversions and
find the time that the reactor requires to reach that point of conversion:

Table 5 Time needed to reach a certain level of conversion

 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

From the quantitative analysis that is carried out both for a constant volume
reactor and for a variable volume, it is concluded that the recommended reactor is the
variable volume, since when observing tables 4 and 5, the constant pressure reactor obtains a conversion
specific in a shorter time with respect to the constant volume reactor.

d) To make a graph that relates the residence time based on the temperature, we use equation 47 and
the data of table 1 and we make the following table:
Table 6 Data to plot residence time vs temperature

where :
 The squares of CA0 are obtained with the ideal gas equation.
PA 0
C A 0=
R∗T A 0
P A 0=5 kPa
T A 0=T ( K )

 The squares of t(s) are obtained with 47 equation

X= 0.88
ε= 1/2

 The squares of t(h) are obtained with t(S)/3600

 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

time vs Temperature
700000000
600000000
500000000
400000000
Time (t)

300000000
200000000
100000000
0
590 600 610 620 630 640 650 660 670
Temperature (T)

Graph 2 time vs Temperature

As it is well known, the activation energy E has been considered as the minimum energy that the reagent
molecules must possess for the reaction to occur. It has been shown over time that the higher the activation
energy, the more sensitive to temperature is the reaction rate, and this is observed with the gas phase reaction
of reagent A since it has an E = 114 KJ / mol which is high, therefore analyzing graph 2, it thinks about that at
higher temperatures the reaction inside the reactor will reach a conversion of 88% in a shorter time.

4. A brief description of the two theories is given:

Collision theory: first it is assumed that the molecules behave like rigid spheres, then it is considered that the
reaction rate is calculated by the product of the frequency of collisions by the fraction of the collisions that have
enough energy to react, that is, not all collisions are reactive; only collisions that have an E or greater energy will
produce a reaction.

Transitory state theory: According to this theory, the reactants combine to form unstable intermediates called
activated complexes, which will then decompose spontaneously giving the products. It also assumes that, at all
 UNIVERSIDAD DE ANTIOQUIA FACULTAD DE INGENIERÍA
DEPARTMET OF ENGINEERING
ENGINEERING OF CHEMICAL REACTIONS 2019-1
TEACHER: Aida Luz Villa D.

times, the concentrations of the reactants are in equilibrium with those of the
activated complex and that the rate of decomposition of the complex is the same for all
reactions.

Comparison between both theories: It is interesting to note the differences between theories of collision and the
state of transition. Consider that A and B collide and form an unstable intermediate product that later
decomposes giving the product, that is:

A + B →AB*→AB (4.1)

The theory of collision considers that the speed is governed by the number of energy collisions between the
reactants and dispenses with what happens with the unstable intermediate product. It is simply assumed that
this intermediate product decomposes fairly quickly in the products, so it does not influence the overall speed of
the process. On the contrary, the theory of the state of transition considers that the reaction rate is governed by
the rate of decomposition of the intermediate product; it is assumed that the speed of formation of the
intermediate product is so rapid that at all times its concentration is that of equilibrium, regardless of the way in
which it can be formed. Consequently, the theory of collision considers that the first stage of Eq. (4.1) is slow, and
is the one that controls the speed, while the transition state theory considers that the second stage of Eq. (4.1)
and the concentration of the complex are the controlling factors of the speed. In a way, these two theories
complement each other.

5.