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FACULTAD DE INGENIERIA
PROGRAMA DE INGENIERIA QUIMICA
PRESENTADO POR:
NESTOR DAVID ARTEAGA OSPINO
JESUS DAVID JULIO RACINE
PRESENTADO A:
MARIA TERESA ACEVEDO MORANTES
CARTAGENA DE INDIAS D. T. Y C.
JUNIO DE 2015
EJERCICIO 1.
Consider the following gas-phase reaction that occurs at 350 K and a constant pressure of 200 kPa
(Lynch, 1986): A B + C, for which the rate law is () = 0.253 /(1 + 0.429 )2 where (-rA)
has units of mol m-3 s-1; CA has units of mol m-3. Pure A is fed to a reactor at a rate of 8 mol s-1.
The desired fractional conversion, fA, is 0.99. A recycle PFR is proposed for the reaction. When the
recycle ratio, R, is zero, the recycle reactor is equivalent to a PFR. As R approaches infinity, the
system is equivalent to a CSTR. However, it is generally stated that the recycle reactor behavior is
close to that of a CSTR once R reaches approximately 10 to 20. Furthermore, it is often stated that,
for an equivalent fractional conversion, the volume of a PFR is less than that of a CSTR. Check the
generality of these statements by
(a) Determining the volume of a PFR needed for 99% conversion;
(b) Determining the volume of a CSTR needed for 99% conversion;
(c) Determining the volume of a recycle PFR required for 99% conversion, if R = 0, 1, 10, 20, and 500.
(d) Comment on your findings.
Note: The equations used may be integrated numerically (using E-Z Solve) or analytically.
For an analytical solution, use the substitution = (1 )/(1 + ).
Solucin
a. Para un PFR
La ecuacin de diseo de un reactor PFR es:
0
=
0.253
(1 + 0.427 )2
0
(1 + 0.429 )2
0.253
0.99 (1 +
0.2530 0
) (1 + 0.429 0
(1 )
8
(402.41)
0.253(68.73)
(1 ) 2
)
(1 + )
= 185.14
Obtenemos entonces que el volumen del reactor PFR ser 185.14 L
b. Para un CSTR
De la ecuacin de diseo de un CSTR
=
(1 + 0.429 )2
= 0 1+
= 0
=1
1
1+
0
=
200 (1)
(350 )(8.314 103
0 = 68.73
= 68.73
=
1 0.99
= 0.34
1 + 0.99
3
0.253 0.345
3
= 0.066
1 + 0.429 (0.345)
8 0.99
=
= 119.58 3
3
0.066
(1 + )0
0.253
(1
+ 0.429 )2
Donde
0 = 8
= 0.99
0 = 68.78
0 =
1
1+
R=0
0 =
0
(0.99) = 0
1+0
0.99 (1 +
(1)0
0.253 0
1 2
) (1 + 0.429 0 1 + )
1
=0 = 185.14 3
R=1
0 =
0.99
(1.495)0
0.253 0
=1 =
1
(0.99) = 0.495
1+1
(1 + ) (1 + 0.429 0
1 2
1 + )
0.495
1.495 8
(103.495) = 71.18 3
0.253 0
R=10
0 =
(1 + 10)0
0.253 0
=10 =
10
(0.99) = 0.9
1 + 10
0.99 (1 +
0.9
1 2
) (1 + 0.429 0 1 + )
1
11 8
(12.0494) = 60.98 3
0.253 68.73
R=20
0 =
(1 + 20)0
0.253 0
=20 =
20
(0.99) = 0.9428
1 + 20
0.99
0.9428
(1 + ) (1 + 0.429 0
1 2
1 + )
21 8
(7.25868) = 70.13 3
0.253 68.73
R=500
0 =
(1 + 500)0
0.253 0
=1 =
500
(0.99) = 0.986
1 + 500
0.99
0.986
(1 + ) (1 + 0.429 0
1 2
)
1+
501 8
(0.49) = 112.99 3
0.253 68.78
d. A partir de los resultados obtenidos podemos observer varias cosas, que el recirculado
disminuye el volume del reactor PFR, aunque hay un rango optimo de reciclo, tanto reciclos
muy bajos o muy altos dan volumenes grandes, ademas para reciclo 0 se comporta como
un PFR y un alto reciclo como un CSTR.
EJERCICIO 2.
(a) The rate of the liquid-phase reaction A B + . . . is given by (rA) = k A CA CB. Data obtained
from the steady-state operation of a small-scale (50-liter) CSTR are to be used to determine the size
of a commercial-scale recycle PFR operating isothermally at the same T as in the CSTR. The feed
composition is the same for both reactors and CA0>>CB0. The throughput (v0) for the recycle PFR
is 100 times that for the CSTR. If the fractional conversion (fA) obtained in the CSTR is 0.75, what
size (m3) of recycle PFR is required to obtain the same conversion with a recycle ratio (R) of 2?
(b) What is the optimal value of R to minimize the volume in (a), and what is the minimum volume?
Solucin
a. CSTR
= = 0 (1 )(0 ) = 20 (1 )
=
0 (1 ) = 0
0 = 100 0
0
= 0
100
0 (1 ) =
0
100
0 = 100 0 (1 )
0 = 100 50 0 (1 0.75) = (1250 )( 0 )
Para un reactor PFR con recirculado y velocidad de reaccin =
=
+ 1
1+
ln ( 0
)
0
1
1+
ln ( 0 + 1)
0
1
0
1+
ln (
+ 1)
0
0 (1 )
= 0
1+
1
ln (
+ 1)
0
(1 )
= (1250 )( 0 )
1+
1
ln (
+ 1)
0
(1 )
= (1250 )(1 + ) ln (
= 1250 3 ln (
1
+ 1)
(1 )
1
+ 1) = 4119.8
2(0.25)
= 4.1198 3
b.
+ 0
0 +
ln ( 0
)=
(0 + )
4
1 +
ln (
+ 1) =
2
+ 0.25
= 0.97
=
= (1 + )2 /( (0 + )
0
=
1250 0 (1 + )2
2
0 +
0 (1 )
1250 (1 + 0.97)2
0.97 + (0.97)2 (0.25)
= 4025.08 = 4.025 3
EJERCICIO 3.
The hydrolysis of ethylnitrobenzoate by hydroxyl ions
2 6 4 2 5 + 2 6 4 + 2 5
Procedes as follows at 15C when the initial concentrations of both reactants are 0.05 mol L-1
(constant-volume batch reactor):
Use (a) the differential method and (b) the integral method to determine the reactor order, and the
value of the rate constant. Comment on the results obtained by the two methods.
t (s)
% hydrolyzed
120
32.95
180
41.75
240
48.8
330
58.05
530
69.0
600
70.4
Solucin
Tenemos una reaccin irreversible a volumen constante, podemos escribir la concentracin del
reactivo A con la ecuacin:
= 0 (1 ) = 0.05
(1 )
(/)
0.05
0.034
0.029
0.026
0.021
0.016
0.015
+
=
) = ln + ln
CA vs tiempo
0.06
0.05
CA (mol/L)
0.04
y = -4E-05x3 + 0.001x2 - 0.0096x + 0.0498
R = 0.9984
0.03
0.02
0.01
0
0
10
12
Tiempo (min)
ln
ln( /)
-0.00960
-0.00608
-0.00468
-0.00352
-0.00223
-0.00130
-0.00132
0.00960
0.00608
0.00468
0.00352
0.00223
0.00130
0.00132
-2.99573
-3.39546
-3.53616
-3.66516
-3.86442
-4.16692
-4.21313
-4.64599
-5.10275
-5.36446
-5.64929
-6.10575
-6.64796
-6.63012
Ahora graficamos
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
-1
ln(/)
-2
-3
y = 1.7516x + 0.7298
R = 0.983
-4
-5
-6
ln
-7
Observamos que la pendiente tiene un valor aproximado de 1.8, lo que quiere decir que la reaccin
se acerca a un orden de grado 2.
) ,
luego
usamos la ecuacin:
( )
( )
Para = 0.03 /
ln(0.03) = 3.507
ln( /) = 1.7516(3.508) + 0.7298 = 5.412
(
) = 5.412 = 0.00446
0.00446
0.032
= 4.957
b) Mtodo Integral
Teniendo la ecuacin de velocidad
Suponemos un valor para n y si es el correcto la grfica del tiempo vs el resultado de la integral debe
dar una lnea recta, como para el mtodo diferencial el orden era cercano a 2 usaremos este valor
y asi corroboramos lo hecho en el inciso a
= 2
=
2
Reordenamos
=
0
]
= []0
1
0
1
=
]
0
1
1
=
0
1
1
= +
0
Graficamos vs 1/
70
60
1/CA
50
40
30
20
10
0
0
10
12
Tiempo
Podemos observar que los datos graficados cumplen con la forma de una lnea recta y efectivamente
la ley de velocidad de reaccin es de orden 2, para la constante de velocidad de reaccin:
=
= 4.8878
Comentarios: A partir del uso de los dos mtodos podemos decir que en el mtodo diferencial al no
tener valores equidistantes para el tiempo, realizar los clculos a partir de un ajuste polinmico va
a generar errores que conducen a que la determinacin del orden de reaccin no sea
completamente precisa dando un valor de 1.8, cercano al orden 2 sin embargo no es
completamente seguro, el mtodo integral nos soluciona esa duda ya que es de aplicacin ms
simple y verificamos que la ley de velocidad de reaccin si es de orden 2.
EJERCICIO 4.
The reaction 2 + 22 2 + 22 was studied in a constant-volume BR with equimolar
quantities of and 2 at various initial pressures:
P0 (kPa)
47.2
45.5
50.0
38.4
T1/2 (s)
81
102
95
140
Calculate the overall order of the reaction (Moore, p. 416).
33.5
180
32.4
176
26.9
224
Solucin
Ley de velocidad de reaccin
=
+
=
0
0
1
1
( 0 ) =
( 0 )
0
0 0
Como
0 = 0 0
Entonces
=
1
( 0 )
0
Adems
0 =
0 0 0
=
0 0
1
( 0 ))
(
0
Para la reaccin
= 1 + 2 2 2 = 1
0 = 0.5
0 = 0.50
Entonces la ecuacin de queda
=
0.50
Derivando la ecuacin de
=
= (
)
= ()() ( 0.50 )
= ()1 ( 0.50 )
= ()1
= ( 0.50 )
Reordenando
=
( 0.50 )
= 0.50
=
=
+ 1
1
1
( 1 ) =
1
1
1
(
)
=
1 ( 0.50 )1
0
1
1
1
(
)=
1
(0.50 )1
( 1) ( 0.50 )
1
0.50 1
)
1) =
((
(0.50 )1 ( 1) 0.50
La vida media se define como el tiempo necesario para que la concentracion disminuya a la mitad
de su valor inicial, esto es:
= 1/2
1
= 0
2
2
2
0.50 = 0.250
= 0.750
Entonces
1/2
1/2
1
0.50 1
=
)
1)
((
(0.50 )1 ( 1) 0.250
(2)1 1
(2/0.5)1 1
1
1
=
=
(
)
(
)
1
1
(0.5)1 ( 1) 0
( 1)
0
1/2 =
(4)1 1 1
( )
( 1) 0
(4)1 1
+ (1 ) ln 0
( 1)
Calculamos el logaritmo natural de 0 y de 1/2 a los valores de la grfica que nos dan y los
graficamos, hallamos la ecuacin de la recta con Excel y determinamos la pendiente
y = -1.6196x + 10.802
R = 0.9464
ln t(1/2)
0
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
ln P0
Tenemos que:
= (1 )
= 1
= 1 (1.6196) = 2.6296
El orden global de reaccin es de 2.6, aproximndolo al siguiente orden ms cercano sera un orden
de grado 3 para esta reaccin en fase gaseosa.