This document discusses heterogeneous reactions and catalysis. It defines heterogeneous reactions as those involving two or more simultaneous phases. There are six basic steps that occur in heterogeneous catalysis: 1) arrival of reactants at the pore entrance, 2) diffusion of reactants to the catalyst surface and active site, 3) adsorption of the reactant onto the catalyst surface, 4) surface reaction to produce products, 5) desorption of products, and 6) diffusion of products away from the active site. Adsorption of reactants onto the catalyst surface is a key part of the heterogeneous reaction process. The rate of transformation can be controlled by any step that is slower than the others, like resistance in series.
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Estudio de los conceptos:
Regla de las Fases de Gibbs
Grados de Libertad
Presión de Vapor
Fluido Supercrítico
Equilibrio Líquido Vapor
Ley de Raoult
Ecuación de Antoine
Punto de Rocío
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Se comparte una presentación referente al uso y aplicación del triángulo de Gibbs para la representación gráfica de sistemas ternarios de líquidos inmiscibles. Se abordan temáticas como miscibilidad, regla de las fases, lagunas de inmiscibilidad, equilibrio liquido-liquido y trángulo de Gibbs.
Definición. Modelos cinéticos para reacciones no elementales. Ecuaciones de velocidad a partir de mecanismos propuestos. Los Tipos de reacciones no elementales (Polimerización, Biológicas, Catalíticas).
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2. REACCIONES
HETEROGÉNEAS.
• Las reacciones heterogéneas son las transformaciones
químicas que ocurren cuando existen dos o mas fases
simultaneas.
• En toda reacción heterogénea hay una fase dispersa y una
fase dispersante. La dispersa es la no continua y la
dispersante es la continua (siempre en exceso.
3. CLASIFICACIÓN DE LAS
REACCIONES QUÍMICAS
EN FUNCIÓN DEL NÚMERO DE
FASES:
Homogéneas o monofásicas:
Homogeneidad, isotropía.
Líquidos miscibles, gases, sólidos
disueltos en un mismo disolvente
Ej. Formación y descomposición del
ozono en la estratosfera
4. HETEROGÉNEAS O POLIFÁSICAS:
HETEROGENEIDAD, ANISOTROPÍA
• G-L, L-L, G-S, L-S, S-S, G-L-S, L-L-S
G-L: Alquilación de fenol
L-L: Obtención de biodiesel por transesterificación de aceite y metanol
G-S: Oxidación de SO2, Coquización, reformado para mejora de gasolinas.
L-S: Tratamiento ácido de minerales, Isomerización de glucosa a fructosa.
S-S: Reacciones de reducción de menas metálicas con coque (alto horno)
G-L-S: Tratamiento de aguas por oxidación catalítica avanzada.
L-L-S: Reacciones L-L con catalizador sólido, Esterificaciones, acilaciones, etc.
6. 6 etapas básicas que ocurren en la catálisis
heterogénea cuando una mezcla gaseosa es
pasada a través de un reactor catalítico se
pueden describir de la siguiente manera:
1) Llegada a la
entrada del poro
2) difusión de los
reactivos hacia la
superficie del
catalizador y al sitio
activo.
3) adsorción del
reactivo sobre la
superficie del
catalizador.
4) reacción
superficial para
producir los
productos.
5) desorción de los
productos
6) difusión de los
productos fuera del
sitio activo
7. TRANSFORMACIONES
HETEROGÉNEAS
1) Llegada a la entrada del poro
2) difusión de los reactivos hacia la superficie del catalizador y al sitio activo.
Mbulk Mfilm
3) adsorción del reactivo sobre la superficie del catalizador.
Mfilm+ S [M-S]FIJACIÓN
4) reacción superficial para producir los productos.
[M-S] [M-S]* COMPUESTO ACTIVADO [P-S]
5) desorción de los productos.
[P-S] S + Pfilm
6) difusión de los productos fuera del sitio active
Pfilm Pbulk
8. Adsorción.
Hemos visto que el fenómeno catalítico heterogéneo requiere de la adsorción química en la
superficie del catalizador de al menos uno de los reactivos. Dado que la reacción se lleva a cabo en
la superficie del catalizador, el conocimiento de la cantidad de moléculas adsorbidas en esta
superficie reviste gran importancia.
La adsorción de un reactivo A sobre un sitio S puede representarse:
A + S A S
Donde AS representa una nueva especie “A adsorbida”
A
9. IOsoterma de adsorción del Adenosin 5’-
monofosfato sobre el semiconductor óxido
de tungsteno en un medio alcalino,
La concentración de reactivo adsorbido
se relaciona por lo tanto con la
concentración (presión) del reactivo en
la fase gas (fluido). Para encontrar esta
relación supongamos un sólido al cual
se le suministra una cierta cantidad de
gas (por ejemplo hidrógeno). Parte del
gas se adsorberá en la superficie del
sólido y parte quedará en la fase gas.
Cuando la adsorción se ha completado y
se alcanza el equilibrio, la relación entre
la concentración de gas adsorbido y la
presión del gas con la que está en
equilibrio a temperatura constante se
denomina isoterma de adsorción.
10. • Cualquiera de estas etapas puede controlar la
velocidad de transformación, si es mas lenta de
todas ellas (como resistencia en serie
1
𝐾𝑖
).
• La isoterma de Langmuir es uno de los modelos
fenomenológicos más poderosos y descriptivos
del proceso de adsorción. En el caso de
superficies fluidas, aunado a la ecuación de
adsorción de Gibbs, proporciona una clara
descripción física del comportamiento de la
tensión superficial en términos moleculares. La
ecuación de estado resultante puede expresarse
en composición tanto de la fase volumétrica
como de la fase superficial, evaluar la
concentración micelar crítica en tensoactivos y
calcular de forma directa e inmediata las
energías de adsorción y micelización, sin
necesidad de constantes empíricas.
11. Transferencia de masa
El flux de masa Qs del compuesto A a través de un fluido esta dado por la
Ley de Fick
𝑄𝑠 = − 𝒟
𝜕𝐶𝐴
𝜕𝑥
Donde 𝒟 = Difusividad (cm2/seg)
CA = Concentración (gr/cm3)
X = dirección del flujo (cm)