CINÉTICA DE LAS REACCIONES
Fundamentos de Procesos Ambientales 2017 Profesor: Juan Pablo Silva V.
[email protected] Juan Pablo Silva V. Permitido para uso
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Tipos de Reacciones !
!
!
Reacciones Homogéneas: Implican una sola fase. Los
reactivos se distribuyen uniformemente a través de dicha fase. Reacciones Heterogéneas: Implican más de una fase, con la reacción ocurriendo en la superficie de las fases (interfase). Reacciones Irreversibles: Ocurren en una sola dirección A
!
B
aA + bB ! P
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Velocidad de Reacción Es la velocidad o rapidez con que se consumen los reactivos o con que se forman los productos. La velocidad de reacción se expresa como el cambio de concentración en el tiempo. Sus unidades son [mol/L !s] o [g/L!s] Considerando la reacción sencilla: A
!
B dC
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Velocidad V elocidad de Reacción y Estequiometría En general, con respecto a la reacción: aA
bB B + b
!
cC
+
dD
La velocidad de la reacción esta dada por:
r
1 dC A =
!
1 dC B =
!
1 dCC =
1 dC D =
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Velocidad V elocidad de Reacción y Estequiometría 2HI( g ) r HI "
!
dC HI
!
r H
dt
2
r
H2(g)
!
2
dt
I 2 (g )
dC H !
=
r I
2
dt
dC H
1 dCHI =
+
dt
2
2
dCI =
dt
2
dC I !
2
dt
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Ley de Velocidades aA
bB B + b
r
!
cC
+
n
=
kC A C B
k = Constante de velocidad
dD m
m + n = órden de la reacción.
Para una reacción de eliminación (degradación): A
!
B
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CINETICA DE LAS REACCIONES aA + bB ! cC + dD r A 2 A
r
!
a
2 R
kC
2
r
=
r B b
=
r c c
=
r D d
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CINÉTICA DE
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TIPOS DE REACTORES BATCH
No hay flujo de entrada ni de salida. Todos los elementos están expuestos por un tiempo igual. Las partículas del fluido
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REACTOR BATCH No hay entrada ni salida. En el tiempo t=0, el reactor se llena, hay mezcla, todos los elementos son sometidos al mismo tratamiento, por un tiempo igual, finalizado el proceso, se descarga. Para una sustancia A
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REACTOR BATCH V
dC A dt
0
+
CA
dV dt
=
rV
V
dC A dt
=
rV
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Reactor Batch, Cinética Orden Cero
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RCM en Serie – Cinética de Orden Uno C1
Cn
=
=
C0
C2
1 + k 1t 1
=
C1 1 + k 1t 2
=
C0 (1 + k 1t1 )(1 + k 1t 2 )
C0 (1 + k 1t1 )(1 + k 1t 2 )(1 + k 1t 3 )…(1 + k 1t n ) t1
=
t2
=
…t
n
=
tT n
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RCMS, Cinética de Orden Uno
Compare el volumen total del reactor requerido para la remoción del 90% de una sustancia que se descompone con cinética de primer orden y constante de reacción de 0.05 d-1 en un sistema de mezcla completa; contra el volumen de tres reactores iguales de mezcla completa en serie.
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REACTOR FLUJO PISTÓN x
x+!x
V #C #t #C #t
dC dt
" QC
=
Q e C e ! Q s Cs
!V
=
QC x
!V
=
QC " Q(C + !C) + r !V
( x + !x )
+
r !V
+
rV
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REACTOR FLUJO PISTÓN 0 = QC " Q(C + !C) + r !V V
=
A!x
0 = QC " Q(C + !C) + rA!x
0 = QC " QC " Q!C) + rA!x Q!C
rA!x
!C
A =
r !x
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RFP - Cinética de Orden Cero dC
A =
Q
rdx
dC
" kA
C
! dC C0
C ! C0
=
!k 0
AL
=
Q
=
! k 0 A Q
dx
L
! dx 0
C ! C0
=
!k 0
V
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RFP - Cinética de Orden Uno dC
A =
Q
rdx
dC
dC
k A
=
! k 1CA Q
dx
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RFP - Cinética de Orden Dos dC
A =
Q
2
rdx
dC
dC
k A
=
! k 2C A Q
dx
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Expresiones Cinéticas Orden Cero Batch C
=
C0 ! k 0 t
Orden Uno C
=
C0e
! k 1t
Orden Dos 1 C
1 =
C0
+
k 2 t
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Dependencia de k con la Temperatura Ecuación de Arrhenius
dLnk
Ea
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A + B Reacción Exotérmica
+ AB+
C+D Reacción Endotérmica
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Ecuación de Arrhenius
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Coeficiente de Temperatura
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Tabla 2 valores de ! reportados reportados
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Reflexiones Finales