10.

37 Chemical and Biological Reaction Engineering, Spring 2007

Prof. William H. Green
Lecture 16: Catalysis

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

What initiates the reaction?

A + B starts upon mixing

B
A

Product

Figure 1. Bi-molecular reaction in a CSTR.

Temperature drastically increases reaction rate.

Hot

C2H6 Rxn occurs

Fire
Figure 2. Schematic of tube reactor.

Catalyst dramatically increases reaction rate.

A catalyst

Figure 3. Schematic of packed bed reactor.

Catalyst: Accelerates rate of reaction but is not consumed

Cite as: William Green, Jr., course materials for 10.37 Chemical and Biological Reaction Engineering,
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 transition state
E

products
~Ea
reactants
rxn coordinate

Figure 4. Reaction diagram.

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

with catalyst rxn coordinate

Figure 5. Reaction diagram with and without catalyst.

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

10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 16

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 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 ] + ...

All the things that the

catalyst binds to

Langmuir-Hinshelwood: all reagents bind to catalyst, bound forms react

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
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 moles
dN A
= ( area of metal ) rA area s
dt

f ( A )
N A bound
where A =
N total sites
on surface

10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 16

Prof. William H. Green Page 4 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.
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