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This lecture covers: Inorganic and enzyme catalysis and their properties; kinetics of
heterogeneous catalytic reactions; adsorption isotherms, derivation of rate laws; and
Langumuir-Hinshelwood kinetics
B
A
Product
Hot
Fire
Figure 2. Schematic of tube reactor.
A catalyst
Cite as: William Green, Jr., course materials for 10.37 Chemical and Biological Reaction Engineering,
Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
Downloaded on [DD Month YYYY].
transition state
E
products
~Ea
reactants
rxn coordinate
rate constant:
k BT (G Greactants )
k= exp ts
h RT
G = H TS
e G / RT = e H / RT e S / R
no catalyst
E
The reaction forms many intermediates. A catalyst lowers the energy of these
intermediates.
Acid/Base catalysis
ROR + H 2O 2ROH
k1 H
ROR + H ROR
k1
H k2
ROR ROH + R
k3
R + H 2O ROH + H
Cite as: William Green, Jr., course materials for 10.37 Chemical and Biological Reaction Engineering,
Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
Downloaded on [DD Month YYYY].
H
QSSA ROR , R
H
d ROR
= k H + ROR (k + k ) ROR
H
O 1 [ ] 1 2
dt
H k1
ROR = H + [ ROR ]
QSSA k 1 + k 2
d [ ROH ] H
= 2k2 ROR
dt QSSA
d [ ROH ] 2k1k2
H + [ ROR ] = r
dt k1 + k2
rA [ A]
rA [ catalyst ] (where denotes proportional to)
H N +
H + + R O R + R + = H added = H +
V added
k [ ROR ] k1k2 [ ROR ]
H + 1 + 1 + = H +
k1 + k2
k3 (k1 + k2 ) [ H 2O ] added
keff [ ROR ] H +
r= added
1+ k [ ROR ]
k [ catalyst ] [ A]
r=
1+ k A [ A] + k B [ B ] + ...
Eley-Rideal: one reagent binds, 2nd reagent reacts with bound form
dN A
= VrA
f ([ A] , H )
+
dt
10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 16
Prof. William H. Green Page 3 of 4
Cite as: William Green, Jr., course materials for 10.37 Chemical and Biological Reaction Engineering,
Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
Downloaded on [DD Month YYYY].
moles
dN A
= ( area of metal ) rA area s
dt
f ( A )
N A bound
where A =
N total sites
on surface
Cite as: William Green, Jr., course materials for 10.37 Chemical and Biological Reaction Engineering,
Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
Downloaded on [DD Month YYYY].