Charles N. Satterfield Heterogeneous Catalysis in Industrial Practice Krieger Pub Co 1996
Industrial Catalysis (Second Edition)
260
Jens Hagen Industrial Catalysis Related Titles I. Chorkendorff, J. W. Niemantsverdriet Concepts of Modern Catalysis and Kinetics 2003 ISBN 3-527-30574-2 J. M. Thomas,W. J. Thomas Principles and Practice of Heterogeneous Catalysis 1996 ISBN 3-527-29288-8 J. G. Sanchez Marcano,T.T. Tsotsis Catalytic Membranes and Membrane Reactors 2002 ISBN 3-527-30277-8 J. W. Niemantsverdriet Spectroscopy in Catalysis An Introdution 2000 ISBN 3-527-30200-X B. Cornils,W. A. Herrmann, R. Schlögl, C.-H. Wong Catalysis from A to Z A Concise Encyclopedia 2nd Edition 2003 ISBN 3-527-30373-1 R. I. Wijngaarden, K. R. Westerterp, A. Kronberg Industrial Catalysis Optimizing Catalysts and Processes 1998 ISBN 3-527-28581-4
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Transcript of Industrial Catalysis (Second Edition)
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Jen
sH
agen
Ind
ust
rial
Cat
alys
is
Rela
ted
Tit
les
I.C
ho
rken
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1.1
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Cat
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Exer
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2H
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Cat
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.1C
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Exer
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51
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58
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om
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Ind
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Pro
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3.1
Over
vie
w59
3.2
Exam
ple
sof
Indust
rial
Pro
cess
es62
3.2
.1O
xo
Synth
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62
3.2
.2P
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of
Ace
tic
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of
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65
3.2
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ne
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the
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67
3.2
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xid
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nof
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69
3.2
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70
3.2
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ligom
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(SH
OP
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3.2
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etal
loce
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bas
edO
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oly
mer
izat
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73
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mm
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troduct
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75
3.3
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76
3.3
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3.3
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Enan
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78
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Exer
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83
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83
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cata
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87
4.3
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ith
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ter
497
5H
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Cat
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Fu
nd
amen
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99
5.1
Indiv
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ps
inH
eter
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Cat
alysi
s99
5.2
Kin
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san
dM
echan
ism
sof
Het
erogen
eousl
yC
atal
yze
dR
eact
ions
102
5.2
.1T
he
Import
ance
of
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rpti
on
inH
eter
ogen
eous
Cat
alysi
s102
5.2
.2K
inet
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reat
men
t107
5.2
.3M
echan
ism
sof
Het
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yC
atal
yze
dG
as-P
has
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eact
ions
109
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.3.1
Lan
gm
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H
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elw
ood
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han
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(1921)
109
5.2
.3.2
Ele
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idea
lM
echan
ism
(1943)
111
Exer
cise
sfo
rS
ecti
on
5.2
114
5.3
Cat
alyst
Conce
pts
inH
eter
ogen
eous
Cat
alysi
s116
5.3
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ner
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icA
spec
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Cat
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cA
ctiv
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116
Exer
cise
sfo
rS
ecti
on
5.3
.1130
VI
Con
ten
ts
-
5.3
.2S
teri
cE
ffec
ts131
Exer
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sfo
rS
ecti
on
5.3
.2142
5.3
.3E
lect
ronic
Fac
tors
143
5.3
.3.1
Met
als
145
5.3
.3.2
Bim
etal
lic
Cat
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5.3
.3.3
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155
5.3
.3.4
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tors
:A
cidic
and
Bas
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atal
yst
s169
Exer
cise
sfo
rS
ecti
on
5.3
.3177
5.4
Cat
alyst
Per
form
ance
179
5.4
.1Fac
tors
whic
hA
ffec
tth
eC
atal
yst
Per
form
ance
179
5.4
.2S
upport
edC
atal
yst
s180
5.4
.3P
rom
ote
rs189
5.4
.4In
hib
itors
194
Exer
cise
sfo
rS
ecti
on
5.4
195
5.5
Cat
alyst
Dea
ctiv
atio
nan
dR
egen
erat
ion
195
5.5
.1C
atal
yst
Pois
onin
g197
5.5
.2P
ois
onin
gof
Met
als
199
5.5
.3P
ois
onin
gof
Sem
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or
Oxid
es200
5.5
.4P
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onin
gof
Soli
dA
cids
200
5.5
.5D
eposi
tson
the
Cat
alyst
Surf
ace
201
5.5
.6T
her
mal
Pro
cess
esan
dS
inte
ring
203
5.5
.7C
atal
yst
Loss
esvia
the
Gas
Phas
e204
Exer
cise
sfo
rS
ecti
on
5.5
207
5.6
Char
acte
riza
tion
of
Het
erogen
eous
Cat
alyst
s207
5.6
.1P
hysi
cal
Char
acte
riza
tion
208
5.6
.2C
hem
ical
Char
acte
riza
tion
and
Surf
ace
Anal
ysi
s214
Exer
cise
sfo
rS
ecti
on
5.6
221
6C
atal
yst
Sh
apes
and
Pro
du
ctio
no
fH
eter
og
eneo
us
Cat
alys
ts223
6.1
Cat
alyst
Pro
duct
ion
223
6.2
Imm
obil
izat
ion
of
Hom
ogen
eous
Cat
alyst
s231
6.2
.1H
ighly
Dis
per
sed
Support
edM
etal
Cat
alyst
s235
6.2
.2S
SP
Cat
alyst
s235
6.2
.3S
LP
Cat
alyst
s236
Exer
cise
sfo
rC
hap
ter
6237
7S
hap
e-S
elec
tive
Cat
alys
is:
Zeo
lites
239
7.1
Com
posi
tion
and
Str
uct
ure
of
Zeo
lite
s239
7.2
Pro
duct
ion
of
Zeo
lite
s242
7.3
Cat
alyti
cP
roper
ties
of
the
Zeo
lite
s243
7.3
.1S
hap
eS
elec
tivit
y243
7.3
.1.1
Rea
ctan
tS
elec
tivit
y245
7.3
.1.2
Pro
duct
Sel
ecti
vit
y247
7.3
.1.3
Res
tric
ted
Tra
nsi
tion
Sta
teS
elec
tivit
y247
7.3
.2A
cidit
yof
Zeo
lite
s248
VII
Con
ten
ts
7.4
Isom
orp
hic
Subst
ituti
on
of
Zeo
lite
s252
7.5
Met
al-D
oped
Zeo
lite
s253
7.6
Appli
cati
ons
of
Zeo
lite
s255
Exer
cise
sfo
rC
hap
ter
7258
8H
eter
og
eneo
usl
yC
atal
yzed
Pro
cess
esin
Ind
ust
ry261
8.1
Over
vie
w261
8.1
.1P
roduct
ion
of
Inorg
anic
Chem
ical
s261
8.1
.2P
roduct
ion
of
Org
anic
Chem
ical
s261
8.1
.3R
efin
ery
Pro
cess
es262
8.1
.4C
atal
yst
sin
Envir
onm
enta
lP
rote
ctio
n264
8.2
Exam
ple
sof
Indust
rial
Pro
cess
es
Bulk
Chem
ical
s266
8.2
.1A
mm
onia
Synth
esis
266
8.2
.2H
ydro
gen
atio
n267
8.2
.3M
ethan
ol
Synth
esis
270
8.2
.4S
elec
tive
Oxid
atio
nof
Pro
pen
e272
8.2
.5O
lefi
nP
oly
mer
izat
ion
276
Exer
cise
sfo
rS
ecti
on
8.1
and
8.2
278
8.3
Fin
eC
hem
ical
sM
anufa
cture
281
8.3
.1F
ine
Chem
ical
san
dth
eir
Synth
esis
281
8.3
.2S
elec
ted
Exam
ple
sof
Indust
rial
Pro
cess
es285
8.3
.2.1
Hydro
gen
atio
n285
8.3
.2.2
Oxid
atio
n288
8.3
.2.3
Cat
alyti
cC
C
-lin
kag
e289
8.3
.2.4
Aci
d/B
ase
Cat
alysi
s291
Exer
cise
sfo
rS
ecti
on
8.3
292
9E
lect
roca
taly
sis
295
9.1
Com
par
ison
Bet
wee
nE
lect
roca
taly
sis
and
Het
erogen
eous
Cat
alysi
s295
9.2
Ele
ctro
chem
ical
Rea
ctio
ns
and
Ele
ctro
de
Kin
etic
s296
9.2
.1H
ydro
gen
Ele
ctro
de
Rea
ctio
n296
9.2
.2O
xygen
Ele
ctro
de
Rea
ctio
n298
9.3
Ele
ctro
cata
lyti
cP
roce
sses
302
9.3
.1E
lect
roca
taly
tic
Hydro
gen
atio
n302
9.3
.2E
lect
roca
taly
tic
Oxid
atio
n304
9.3
.3E
lect
roch
emic
alA
ddit
ion
305
9.3
.4E
lect
roca
taly
tic
Oxid
atio
nof
Met
han
ol
306
9.4
Ele
ctro
cata
lysi
sin
Fuel
Cel
ls307
9.4
.1B
asic
Pri
nci
ple
s307
9.4
.2Types
of
Fuel
Cel
lan
dC
atal
yst
308
9.4
.3Im
port
ant
Rea
ctio
ns
inF
uel
Cel
lTec
hnolo
gy
311
9.4
.3.1
The
Anodic
Rea
ctio
n311
9.4
.3.2
The
Cat
hodic
Rea
ctio
n312
9.4
.3.3
Met
han
ol
Oxid
atio
n313
Exer
cise
sfo
rC
hap
ter
9315
VII
IC
onte
nts
-
10
En
viro
nm
enta
lC
atal
ysis
and
Gre
enC
hem
istr
y317
10.1
Auto
moti
ve
Exhau
stC
atal
ysi
s317
10.2
NO
xR
emoval
Syst
ems
318
10.2
.1S
elec
tive
Cat
alyti
cR
educt
ion
of
Nit
rogen
Oxid
es318
10.2
.2N
Ox
Sto
rage-
Red
uct
ion
Cat
alyst
for
Lea
n-B
urn
ing
Engin
es320
10.3
Cat
alyti
cA
fter
burn
ing
322
10.4
Gre
enC
hem
istr
yan
dC
atal
ysi
s324
10.4
.1E
xam
ple
sof
Cat
alyti
cal
Pro
cess
es325
10.4
.1.1
Ald
ol
Conden
sati
on
325
10.4
.1.2
Die
ls-A
lder
Rea
ctio
n326
10.4
.1.3
Hydro
gen
atio
n327
10.4
.1.4
Cycl
izat
ion
inW
ater
327
10.4
.1.5
Use
of
Ionic
Liq
uid
s327
Exer
cise
sfo
rC
hap
ter
10
328
11
Ph
oto
cata
lysi
s331
11.1
Bas
icP
rinci
ple
s331
11.2
Photo
reduct
ion
and
Oxid
atio
nof
Wat
er333
11.2
.1W
ater
Red
uct
ion
334
11.2
.2W
ater
Oxid
atio
n335
11.3
Photo
clea
vag
eof
Wat
er336
11.4
Oth
erR
eact
ions
337
Exer
cise
sfo
rC
hap
ter
11
338
12
Ph
ase-
Tra
nsf
erC
atal
ysis
339
12.1
Def
init
ion
339
12.2
Cat
alyst
sfo
rP
TC
339
12.3
Mec
han
ism
and
Ben
efit
sof
PT
C340
12.4
PT
CR
eact
ions
341
12.5
Sel
ecte
dIn
dust
rial
Pro
cess
esw
ith
PT
C342
Exer
cise
sfo
rC
hap
ter
12
345
13
Pla
nn
ing
,D
evel
op
men
t,an
dT
esti
ng
of
Cat
alys
ts347
13.1
Sta
ges
of
Cat
alyst
Dev
elopm
ent
347
13.2
An
Exam
ple
of
Cat
alyst
Pla
nnin
g:
Conver
sion
of
Ole
fins
toA
rom
atic
s350
13.3
Sel
ecti
on
and
Tes
ting
of
Cat
alyst
sin
Pra
ctic
e355
13.3
.1C
atal
yst
Scr
eenin
g356
13.3
.2C
atal
yst
Tes
tR
eact
ors
and
Kin
etic
Model
ing
358
13.3
.3S
tati
stic
alTes
tP
lannin
gan
dO
pti
miz
atio
n[6
,21]
369
13.3
.3.1
Fac
tori
alTes
tP
lans
370
13.3
.3.2
Pla
cket
tB
urm
anP
lan
375
13.3
.3.3
Exper
imen
tal
Opti
miz
atio
nby
the
Sim
ple
xM
ethod
376
13.3
.3.4
Sta
tist
ical
Tes
tP
lannin
gw
ith
aC
om
pute
rP
rog
ram
379
13.3
.4K
inet
icM
odel
ing
and
Sim
ula
tion
383
IXC
onte
nts
13.3
.5M
odel
ing
and
Sim
ula
tion
wit
hP
OLY
MA
TH
396
13.3
.6C
atal
yst
Dis
cover
yvia
Hig
h-T
hro
ughput
Exper
imen
tati
on
397
Exer
cise
sfo
rC
hap
ter
13
400
14
Cat
alys
isR
eact
ors
403
14.1
Tw
o-P
has
eR
eact
ors
410
14.2
Thre
e-P
has
eR
eact
ors
413
14.2
.1F
ixed
-Bed
Rea
ctors
414
14.2
.2S
usp
ensi
on
Rea
ctors
416
14.3
Rea
ctors
for
Hom
ogen
eousl
yC
atal
yze
dR
eact
ions
420
Exer
cise
sfo
rC
hap
ter
14
422
15
Eco
no
mic
Imp
ort
ance
of
Cat
alys
ts425
16
Fu
ture
Dev
elo
pm
ent
of
Cat
alys
is429
16.1
Hom
ogen
eous
Cat
alysi
s429
16.2
Het
erogen
eous
Cat
alysi
s431
16.2
.1U
seof
Oth
er,
Chea
per
Raw
Mat
eria
ls433
16.2
.2C
atal
yst
sfo
rE
ner
gy
Gen
erat
ion
434
16.2
.3B
ette
rS
tate
gie
sfo
rC
atal
yst
Dev
elopm
ent
435
So
luti
on
sto
the
Exe
rcis
es439
Ref
eren
ces
483
Su
bje
ctIn
dex
493
XC
onte
nts
-
Pre
face
toth
eS
eco
nd
Ed
itio
n
Duri
ng
the
last
yea
rsca
taly
sis
has
mad
ea
rapid
pro
gre
ss,
ther
eca
nbe
obse
rved
man
ynew
appli
cati
ons
of
cata
lyst
s.For
obvio
us
reas
ons
cata
lysi
sis
the
key
toth
e
succ
ess
indev
elopin
gnew
pro
cess
esfo
rvar
ious
fiel
ds
inin
dust
ry.
The
use
of
suit
-
able
cata
lyst
sfo
rnew
pro
cess
esre
quir
esa
bas
icknow
ledge
of
cata
lyti
cpri
nci
ple
s.
Inth
isbook,
my
mai
nobje
ctiv
eis
topre
sent
anover
vie
won
cata
lysi
s,so
that
both
the
studen
tan
dth
eex
per
ience
dpra
ctit
ioner
can
see
the
bro
adpic
ture
.It
was
the
in-
tenti
on
toco
mpil
ea
text
of
about
500
pag
essu
rvey
ing
the
whole
area
of
cata
lysi
s,
that
mea
ns
hom
ogen
eous
cata
lysi
s,het
erogen
eous
cata
lysi
s,bio
cata
lysi
san
dsp
ecia
l
topic
sof
appli
edca
taly
sis.
Itis
felt
that
suff
icie
nt
info
rmat
ion
isgiv
enher
efo
ra
ra-
tional
appro
ach
tobe
appli
edin
abas
icunder
stan
din
gof
the
phen
om
enon
cata
lysi
s.
Inth
epre
sent
edit
ion
som
esp
ace
isded
icat
edto
spec
ial
topic
ssu
chas
elec
tro-
cata
lysi
s,photo
cata
lysi
s,as
ym
met
ric
cata
lysi
s,phas
e-tr
ansf
erca
taly
sis,
envir
onm
en-
tal
cata
lysi
s,an
dfi
ne
chem
ical
sm
anufa
cture
.O
nth
ebas
isof
fundam
enta
lre
acti
on
engin
eeri
ng
equat
ions,
exam
ple
sfo
rca
lcula
tion
and
model
ing
of
cata
lysi
sre
acto
rs
are
giv
enw
ith
the
easy
-to-l
earn
PC
pro
gra
mP
OLY
MA
TH
.W
ell
over
170
exer
cise
s
hel
pth
ere
ader
tote
stan
dco
nso
lidat
eth
egai
ned
know
ledge.
The
book
isbas
edon
my
ow
nle
cture
cours
efo
rch
emic
alen
gin
eers
atth
eU
niv
er-
sity
of
Appli
edS
cien
ces
Man
nhei
man
dse
ver
alvoca
tional
trai
nin
gse
min
ars
for
chem
ists
and
engin
eers
inin
dust
ry.
Ihope
this
book
wil
lbe
use
ful
both
tost
uden
ts
who
hav
est
udie
dch
emis
try
or
chem
ical
engin
eeri
ng
and
tog
raduat
esan
dch
emis
ts
who
work
inor
are
inte
rest
edin
the
chem
ical
indust
ry.
Gra
tefu
lap
pre
ciat
ion
isgiv
ento
the
foll
ow
ing
com
pan
ies
whic
hpro
vid
edphoto
-
gra
phic
mat
eria
l:D
eguss
aA
G,
Han
auan
dM
arl,
HT
EA
G,
Hei
del
ber
g,
and
Sd-
Chem
ieA
G,
Heu
feld
.I
ampar
ticu
lar
gra
tefu
lto
Pro
f.V
.M
.S
chm
idt,
Man
nhei
m,
for
his
val
uab
lead
vic
ein
elec
troca
taly
sis
and
addit
ional
mat
eria
l.I
also
wan
tto
than
kth
enum
erous
studen
tsw
ho
foll
ow
edm
yco
urs
esin
Man
nhei
m.
Ith
ank
the
publi
sher
s,fo
rth
eir
kin
dan
dco
mpet
ent
support
.I
gra
tefu
lly
acknow
l-
edge
the
hel
pof
Dr.
Rom
yK
irst
en,w
ho
dir
ecte
dth
epro
ject
,C
laudia
Gr
ssl
for
pro
-
duct
ion,
and
Dr.
Mel
anie
Rohn
for
copy-e
dit
ing.
Spec
ial
than
ks
and
appre
ciat
ion
to
my
wif
eJu
lia
for
her
pat
ience
,under
stan
din
gan
dth
een
coura
gem
ent
tost
ayw
ith
this
pro
ject
toit
sco
mple
tion.
Man
nhei
m,
Oct
ober
2005
Jens
Hagen
XI
Ind
ust
ria
lC
ata
lysi
s:A
Pra
ctic
al
Ap
pro
ach
,S
eco
nd
Ed
itio
n.
Jen
sH
agen
Co
py
rig
ht"
20
06
WIL
EY
-VC
HV
erla
gG
mb
H&
Co
.K
GaA
,Wei
nh
eim
ISB
N:
3-5
27
-31
14
4-0
Pre
face
toth
eF
irst
Ed
itio
n
Cat
alyst
shav
ebee
nuse
din
the
chem
ical
indust
ryfo
rhundre
ds
of
yea
rs,
and
man
y
larg
e-sc
ale
indust
rial
pro
cess
esca
nonly
be
carr
ied
out
wit
hth
eai
dof
cata
lysi
s.
How
ever
,it
isonly
since
the
1970s
that
cata
lysi
shas
bec
om
efa
mil
iar
toth
egen
eral
publi
c,m
ainly
bec
ause
of
dev
elopm
ents
inen
vir
onm
enta
lpro
tect
ion,
anex
ample
bei
ng
the
wel
lknow
nan
dw
idel
yuse
dca
taly
tic
conver
ter
for
auto
mobil
es.
Cat
alysi
sis
am
ult
idis
cipli
nar
yar
eaof
chem
istr
y,in
par
ticu
lar,
indust
rial
chem
is-
try.
Anyone
who
isin
volv
edw
ith
chem
ical
reac
tions
wil
lev
entu
ally
hav
eso
met
hin
g
todo
wit
hca
taly
sts.
Insp
ite
of
yea
rsof
exper
ience
wit
hca
taly
sts
and
the
vas
tnum
ber
of
publi
cati
ons
conce
rnin
gca
taly
tic
pro
cess
es,
ther
eis
stil
lno
fundam
enta
lth
eory
of
cata
lysi
s.A
s
isoft
enth
eca
sein
chem
istr
y,em
pir
ical
conce
pts
are
use
dto
expla
inex
per
imen
tal
resu
lts
or
tom
ake
pre
dic
tions
about
new
reac
tions,
wit
hg
reat
eror
less
erdeg
rees
of
succ
ess.
To
dat
eth
ere
has
bee
nno
stan
dar
dbook
that
dea
lseq
ual
lyw
ith
both
het
ero-
gen
eous
and
hom
ogen
eous
cata
lysi
s,as
wel
las
indust
rial
aspec
tsth
ereo
f.T
he
books
publi
shed
up
tonow
gen
eral
lydes
crib
ea
par
ticu
lar
area
or
spec
ial
aspec
tsof
cata
ly-
sis
and
are
ther
efore
less
suit
able
for
teac
hin
gor
studyin
gon
one
sow
n.
For
this
reas
on,
itis
not
easy
for
those
com
men
cing
thei
rca
reer
sto
bec
om
efa
mil
iar
wit
h
the
com
ple
xfi
eld
of
cata
lysi
s.
This
book
isbas
edon
my
ow
nle
cture
cours
efo
rch
emic
alen
gin
eers
atth
eFac
h-
hoch
schule
Man
nhei
m(M
annhei
mU
niv
ersi
tyof
Appli
edS
cien
ces
M.U
.A.S
)an
dis
inte
nded
for
studen
tsof
chem
istr
y,in
dust
rial
chem
istr
y,an
dpro
cess
engin
eeri
ng,
as
wel
las
chem
ists
,en
gin
eers
,an
dte
chnic
ians
inin
dust
ryw
ho
are
involv
edw
ith
cata
-
lyst
s.L
argel
ydis
pen
sing
wit
hco
mple
xth
eore
tica
lan
dm
athem
atic
altr
eatm
ents
,th
e
book
des
crib
esth
efu
ndam
enta
lpri
nci
ple
sof
cata
lysi
sin
anea
syto
under
stan
dfa
sh-
ion.
Num
erous
exam
ple
san
dex
erci
ses
wit
hso
luti
ons
serv
eto
conso
lidat
eth
eunder
-
stan
din
gof
the
mat
eria
l.T
he
book
ispar
ticu
larl
yw
ell
suit
edto
studyin
gon
one
s
ow
n.
Itis
assu
med
that
the
read
erhas
abas
icknow
ledge
of
chem
istr
y,in
par
ticu
lar,
of
reac
tion
kin
etic
san
dorg
anom
etal
lic
chem
istr
y.H
om
ogen
eous
tran
siti
on
met
alca
ta-
lysi
san
dhet
erogen
eous
cata
lysi
sar
etr
eate
don
the
bas
isof
the
most
import
ant
cata
-
lyst
conce
pts
,an
dth
eap
pli
cati
ons
of
cata
lyst
sar
edis
cuss
edw
ith
man
yex
ample
s.
The
book
aids
pra
ctic
ally
ori
ente
dre
ader
sin
bec
om
ing
fam
ilia
rw
ith
the
pro
cess
es
XII
I
Ind
ust
ria
lC
ata
lysi
s:A
Pra
ctic
al
Ap
pro
ach
,S
eco
nd
Ed
itio
n.
Jen
sH
agen
Co
py
rig
ht"
20
06
WIL
EY
-VC
HV
erla
gG
mb
H&
Co
.K
GaA
,Wei
nh
eim
ISB
N:
3-5
27
-31
14
4-0
-
of
cata
lyst
dev
elopm
ent
and
test
ing
and
ther
efore
dea
lsw
ith
aspec
tsof
test
pla
nnin
g,
opti
miz
atio
n,
and
reac
tor
sim
ula
tion.
Res
tric
ting
the
cover
age
tofu
ndam
enta
las
-
pec
tsm
ade
itnec
essa
ryto
trea
tce
rtai
nar
eas
that
would
be
of
inte
rest
tosp
ecia
list
s
inco
nci
sefo
rmor
toom
itth
emco
mple
tely
.
Iw
ish
toth
ank
all
those
who
support
edm
ein
pro
duci
ng
this
book.
Spec
ial
than
ks
are
due
toD
r.R
.E
isfo
ral
lth
ehar
dw
ork
and
care
he
inves
ted
inpre
par
ing
the
fig-
ure
san
dfo
rhis
hel
pfu
lco
ntr
ibuti
ons
and
sugges
tions.
Iam
gra
tefu
lto
the
foll
ow
ing
com
pan
ies
for
pro
vid
ing
photo
gra
phic
mat
eria
l:B
AS
F,L
udw
igsh
afen
,G
erm
any
;
Deg
uss
a,H
anau
,G
erm
any
;H
off
man
n-L
aRoch
e,K
aise
raugst
,S
wit
zerl
and
;D
oduco
,
Sin
shei
m,
Ger
man
y;
and
VIN
CI
Tec
hnolo
gie
s,R
uei
l-M
alm
aiso
n,
Fra
nce
.In
tere
stin
g
exam
ple
sof
cata
lyst
dev
elopm
ent
wer
eta
ken
from
the
Dip
lom
ath
eses
of
Fac
h-
hoch
schule
gra
duat
es,
of
whom
K.
Kro
mm
and
T.
Zw
ick
are
espec
iall
yw
ort
hy
of
men
tion.
Iw
asple
ased
toac
cept
the
publi
sher
soff
erto
pro
duce
anE
ngli
shver
sion
of
the
book.
The
intr
oduct
ion
of
inte
rnat
ional
study
cours
esle
adin
gto
aB
achel
or
sor
Mas
ter
sdeg
ree
inG
erm
any
and
oth
erco
untr
ies
mak
esit
nec
essa
ryto
pro
vid
est
u-
den
tsw
ith
books
inE
ngli
sh.
Iam
par
ticu
larl
yg
rate
ful
toD
r.S
.H
awkin
sfo
rhis
com
pet
ent
tran
slat
ion
of
the
Ger
man
text
wit
hval
uab
lead
vic
ean
dad
dit
ional
mat
e-
rial
. Ith
ank
the
publi
sher
s,W
iley
-VC
HW
einhei
m,
for
thei
rkin
dsu
pport
.T
han
ks
are
due
toD
r.B
.B
ck
,w
ho
dir
ecte
dth
epro
ject
,C
.G
rss
lfo
rpro
duct
ion,
and
S.
Pau
ker
for
the
cover
gra
phic
s.
Man
nhei
m,
Januar
y1999
Jens
Hagen
XIV
Pre
face
toth
eF
irst
Edi
tion
Ab
bre
viat
ion
s
Aar
ea[m
2]
A*
adso
rbed
(act
ivat
ed)
mole
cule
sof
com
ponen
tA
aca
taly
stac
tivit
y
as
area
per
mas
s[m
2/k
g]
Ael
ectr
on
acce
pto
r
AD
Hal
cohol
deh
ydro
gen
ase
enzy
me
ads
adso
rbed
(subsc
ript)
AE
SA
uger
elec
tron
spec
trosc
opy
aqaq
ueo
us
solu
tion
(subsc
ript)
bcc
body-c
ente
red
cubic
bip
y2,2!-
bip
yri
din
e
Bu
buty
lC
4H
9-
c ico
nce
ntr
atio
nof
com
ponen
ti
[mol/
L]
CB
conduct
ion
ban
d
C.I
.co
nst
rain
tin
dex
Cp
cycl
open
tadie
nyl
C5H
5-
CS
TR
conti
nuous
stir
red
tank
reac
tor
Ddif
fusi
on
coef
fici
ent
[m2/s
]
ddea
ctiv
atio
n(s
ubsc
ript)
Del
ectr
on
donor
DM
FC
dir
ect
met
han
ol
fuel
cell
EE
fact
or,
rate
of
was
te[k
g]
per
pro
duct
unit
[kg]
Ea
acti
vat
ion
ener
gy
[J/m
ol]
Eb
gban
dgap
ener
gy
[eV
]
EF
Fer
mi
level
Een
zym
e
e.e.
enan
tiom
eric
exce
ss[%
]
eff
effe
ctiv
e(s
ubsc
ript)
Ei
ionis
atio
nen
ergy
Er
redox
pote
nti
al[V
]
Et
ethyl
C2H
5-
ES
CA
elec
tron
spec
trosc
opy
for
chem
ical
anal
ysi
s
ES
Rel
ectr
on
spin
reso
nan
cesp
ectr
osc
opy
XV
Ind
ust
ria
lC
ata
lysi
s:A
Pra
ctic
al
Ap
pro
ach
,S
eco
nd
Ed
itio
n.
Jen
sH
agen
Co
py
rig
ht"
20
06
WIL
EY
-VC
HV
erla
gG
mb
H&
Co
.K
GaA
,Wei
nh
eim
ISB
N:
3-5
27
-31
14
4-0
-
eel
ectr
ons
FFar
aday
const
ant
[96
485
C/m
ol]
fcc
face
-cen
tere
dcu
bic
"G
Gib
bs
free
ener
gy
[J/m
ol]
Ggas
(subsc
ript,
too)
GH
SV
gas
hourl
ysp
ace
vel
oci
ty[h
1]
HH
enry
sla
wco
nst
ant
Hex
exte
rnal
hold
up
"H
ad
sad
sorp
tion
enth
alpy
[J/m
ol]
"H
fen
thal
py
chan
ge
of
form
atio
n[J
/mol]
Hm
modif
ied
Hen
rys
law
const
ant
"H
Rre
acti
on
enth
alpy
[J/m
ol]
H0
Ham
met
tac
idit
yfu
nct
ion
HC
hydro
carb
on
HS
AB
har
dan
dso
ftac
ids
and
bas
es
hhar
d
hcp
hex
agonal
close
pac
kin
g
Iin
hib
itor
ILio
nic
liquid
ISS
ion
scat
teri
ng
spec
trosc
opy
jcu
rren
tden
sity
[A/m
2]
Keq
uil
ibri
um
const
ant
Ki
adso
rpti
on
equil
ibri
um
const
ant
of
com
ponen
ti
Ki
inhib
itio
nco
nst
ant
KM
Mic
hae
lis
const
ant
kre
acti
on
rate
const
ant
k 0pre
-exponen
tial
fact
or
k La
Lgas
-liq
uid
mas
str
ansf
erco
effi
cien
t
k Sa
Sli
quid
-soli
dm
ass
tran
sfer
coef
fici
ent
k to
tglo
bal
mas
str
ansf
erco
effi
cien
t
Lli
quid
(subsc
ript)
Lli
gan
d
LE
ED
low
-ener
gy
elec
tron
dif
frac
tion
LF
liquid
flow
[L/m
in]
Mm
etal
mm
ass
[kg]
mcat.
mas
sof
cata
lyst
[kg]
MA
Om
ethyla
lum
inoxan
e
Med
med
iato
r,re
dox
cata
lyst
nnum
ber
of
mole
s[m
ol]
nord
erof
reac
tion
! nfl
ow
rate
[mol/
s]
! nA
,0fe
edfl
ow
rate
of
star
ting
mat
eria
lA
[mol/
s]
NA
Dnic
oti
nam
ide
aden
ine
din
ucl
eoti
de
cofa
ctor
NH
Enorm
alhydro
gen
elec
trode
XV
IA
bbre
viat
ion
s
NS
RN
Ox
stora
ge-
reduct
ion
OD
Eord
inar
ydif
fere
nti
aleq
uat
ion
Oxad
oxid
ativ
ead
dit
ion
Pto
tal
pre
ssure
[bar
]
PE
Gpoly
ethyle
ne
gly
col
PE
MF
Cpro
ton
exch
ange
mem
bra
ne
fuel
cell
Ph
phen
yl
C6H
5-
PP
h3
trip
hen
ylp
hosp
hin
e
PT
Cphas
e-tr
ansf
erca
taly
sis
ppre
ssure
[bar
]
pi
par
tial
pre
ssure
of
com
ponen
ti
[bar
]
py
pyri
din
e
Rid
eal
gas
law
const
ant
[Jm
ol
1K
1]
Rre
cycl
era
tio
Ral
kyl
rre
acti
on
rate
[mol
L
1h
1]
r eff
effe
ctiv
ere
acti
on
rate
per
unit
mas
sof
cata
lyst
[mol
kg
1
h
1]
rel
rela
tive
(subsc
ript)
r ddea
ctiv
atio
nra
te
STaf
elsl
ope
(ele
ctro
cata
lysi
s)
Ssu
rfac
ear
ea[m
2/k
g]
"S
entr
opy
chan
ge
[Jm
ol
1K
1]
Sp
sele
ctiv
ity
[mol/
mol]
or
[%]
Sso
lid
(subsc
ript,
too)
SC
Rse
lect
ive
cata
lyti
cre
duct
ion
SIM
Sse
condar
y-i
on
mas
ssp
ectr
osc
opy
SL
PC
support
edli
quid
phas
eca
taly
sts
SM
SI
stro
ng
met
al-s
upport
inte
ract
ion
SS
PC
support
edso
lid
phas
eca
taly
sts
sso
ft
ssa
mple
stan
dar
ddev
iati
on
s2ex
per
imen
tal
erro
rvar
iance
S
1m
ass
index
,ra
tio
of
all
the
mat
eria
ls[k
g]
toth
epro
duct
[kg]
Ssu
bst
rate
scsu
per
crit
ical
ST
Ysp
ace
tim
eyie
ld[m
ol
L
1h
1,
kg
L
1h
1]
Tte
mper
ature
[K]
TE
Mtr
ansm
issi
on
elec
tron
mic
rosc
opy
TF
tim
e-fa
ctor
[mcat/n
A,0
]
TO
Ftu
rnover
freq
uen
cy[s
1]
TO
Ntu
rnover
num
ber
[mol
mol
1s
1]
tti
me
[s,
h]
TP
Dte
mper
ature
-pro
gra
mm
eddes
orp
tion
TP
Rte
mper
ature
-pro
gra
mm
edre
duct
ion
TS
1ti
taniu
m(i
v)
sili
cali
teze
oli
teca
taly
st
XV
IIA
bbre
viat
ion
s
-
Uce
llvolt
age
[V]
Vvolu
me
[m3]
! Vvolu
met
ric
flow
-rat
e
VR
reac
tion
volu
me
[m3]
VB
val
ence
ban
d
VO
Cvola
tile
org
anic
com
pound
Xco
nver
sion
[mol/
mol]
or
[%]
" xm
ean
val
ue
of
mea
sure
men
ts
! xposi
tional
vec
tor
(sim
ple
xm
ethod)
ztu
be
length
[m]
!per
centa
ge
d-b
and
occ
upan
cy
"ex
cita
tion
ener
gy
of
sem
iconduct
ors
[eV
]
"P
void
frac
tion
of
par
ticl
e
#ca
taly
stef
fect
iven
ess
fact
or
#over
pote
nti
al[V
]
$i
deg
ree
of
cover
age
of
the
surf
ace
of
com
ponen
ti
%st
retc
hin
gfr
equen
cies
(IR
)[c
m
1]
% ist
oic
hio
met
ric
coef
fici
ent
&den
sity
[g/m
L]
&cat.
pel
let
den
sity
of
the
cata
lyst
[g/m
L]
'to
rtuosi
ty
(in
terf
acia
lte
nsi
on
)0
work
funct
ion
[eV
]
*ac
tive
cente
rson
the
cata
lyst
surf
ace
XV
III
Abb
revi
atio
ns
1 Intr
od
uct
ion
1.1
Th
eP
hen
om
eno
nC
atal
ysis
Cat
alysi
sis
the
key
toch
emic
altr
ansf
orm
atio
ns.
Most
indust
rial
synth
eses
and
nea
rly
all
bio
logic
alre
acti
ons
requir
eca
taly
sts.
Furt
her
more
,ca
taly
sis
isth
em
ost
import
ant
tech
nolo
gy
inen
vir
onm
enta
lpro
tect
ion,
i.e.
,th
epre
ven
tion
of
emis
sions.
Aw
ell-
know
nex
ample
isth
eca
taly
tic
conver
ter
for
auto
mobil
es.
Cat
alyti
cre
acti
ons
wer
eal
read
yuse
din
anti
quit
y,al
though
the
under
lyin
gpri
nci
ple
of
cata
lysi
sw
asnot
reco
gniz
edat
the
tim
e.For
exam
ple
,th
efe
rmen
tati
on
of
sugar
to
ethan
ol
and
the
conver
sion
of
ethan
ol
toac
etic
acid
are
cata
lyze
dby
enzy
mes
(bio
cata
-
lyst
s).
How
ever
,th
esy
stem
atic
scie
nti
fic
dev
elopm
ent
of
cata
lysi
sonly
beg
anab
out
200
yea
rsag
o,a
nd
its
import
ance
has
gro
wn
up
toth
epre
sentday
[2].
The
term
cat
alysi
sw
asin
troduce
das
earl
yas
1836
by
Ber
zeli
us
inord
erto
ex-
pla
invar
ious
dec
om
posi
tion
and
tran
sform
atio
nre
acti
ons.
He
assu
med
that
cata
lyst
s
poss
ess
spec
ial
pow
ers
that
can
infl
uen
ceth
eaf
finit
yof
chem
ical
subst
ance
s.
Adef
init
ion
that
isst
ill
val
idto
day
isdue
toO
stw
ald
(1895):
aca
taly
stac
cele
r-
ates
ach
emic
alre
acti
on
wit
hout
affe
ctin
gth
eposi
tion
of
the
equil
ibri
um
.O
stw
ald
reco
gniz
edca
taly
sis
asa
ubiq
uit
ous
phen
om
enon
that
was
tobe
expla
ined
inte
rms
of
the
law
sof
physi
cal
chem
istr
y.
Whil
eit
was
form
erly
assu
med
that
the
cata
lyst
rem
ained
unch
anged
inth
eco
urs
e
of
the
reac
tion,
itis
now
know
nth
atth
eca
taly
stis
involv
edin
chem
ical
bondin
g
wit
hth
ere
acta
nts
duri
ng
the
cata
lyti
cpro
cess
.T
hus
cata
lysi
sis
acy
clic
pro
cess
:
the
reac
tants
are
bound
toone
form
of
the
cata
lyst
,an
dth
epro
duct
sar
ere
leas
ed
from
anoth
er,
regen
erat
ing
the
init
ial
stat
e.
Insi
mple
term
s,th
eca
taly
tic
cycl
eca
nbe
des
crib
edas
show
nin
Fig
ure
1-1
[T9].
The
inte
rmed
iate
cata
lyst
com
ple
xes
are
inm
ost
case
shig
hly
reac
tive
and
dif
ficu
lt
todet
ect.
Inth
eory
,an
idea
lca
taly
stw
ould
not
be
consu
med
,but
this
isnot
the
case
in
pra
ctic
e.O
win
gto
com
pet
ing
reac
tions,
the
cata
lyst
under
goes
chem
ical
chan
ges
,
and
its
acti
vit
ybec
om
eslo
wer
(cat
alyst
dea
ctiv
atio
n).
Thus
cata
lyst
sm
ust
be
regen
-
erat
edor
even
tual
lyre
pla
ced.
1
Ind
ust
ria
lC
ata
lysi
s:A
Pra
ctic
al
Ap
pro
ach
,S
eco
nd
Ed
itio
n.
Jen
sH
agen
Co
py
rig
ht!
20
06
WIL
EY
-VC
HV
erla
gG
mb
H&
Co
.K
GaA
,Wei
nh
eim
ISB
N:
3-5
27
-31
14
4-0
-
Apar
tfr
om
acce
lera
ting
reac
tions,
cata
lyst
shav
ean
oth
erim
port
ant
pro
per
ty:
they
can
infl
uen
ceth
ese
lect
ivit
yof
chem
ical
reac
tions.
This
mea
ns
that
com
ple
tely
dif
-
fere
nt
pro
duct
sca
nbe
obta
ined
from
agiv
enst
arti
ng
mat
eria
lby
usi
ng
dif
fere
nt
cat-
alyst
syst
ems.
Indust
rial
ly,
this
targ
eted
reac
tion
contr
ol
isoft
enev
enm
ore
impor-
tant
than
the
cata
lyti
cac
tivit
y[6
].
Cat
alyst
sca
nbe
gas
es,
liquid
s,or
soli
ds.
Most
indust
rial
cata
lyst
sar
eli
quid
sor
soli
ds,
wher
eby
the
latt
erre
act
only
via
thei
rsu
rfac
e.T
he
import
ance
of
cata
lysi
sin
the
chem
ical
indust
ryis
show
nby
the
fact
that
75
%of
all
chem
ical
sar
epro
duce
d
wit
hth
eai
dof
cata
lyst
s;in
new
lydev
eloped
pro
cess
es,
the
figure
isover
90
%.
Nu-
mer
ous
org
anic
inte
rmed
iate
pro
duct
s,re
quir
edfo
rth
epro
duct
ion
of
pla
stic
s,sy
n-
thet
icfi
ber
s,phar
mac
euti
cals
,dyes
,cr
op-p
rote
ctio
nag
ents
,re
sins,
and
pig
men
ts,
can
only
be
pro
duce
dby
cata
lyti
cpro
cess
es.
Most
of
the
pro
cess
esin
volv
edin
crude-
oil
pro
cess
ing
and
pet
roch
emis
try,
such
aspuri
fica
tion
stag
es,
refi
nin
g,
and
chem
ical
tran
sform
atio
ns,
requir
eca
taly
sts.
En-
vir
onm
enta
lpro
tect
ion
mea
sure
ssu
chas
auto
mobil
eex
hau
stco
ntr
ol
and
puri
fica
-
tion
of
off
-gas
esfr
om
pow
erst
atio
ns
and
indust
rial
pla
nt
would
be
inco
nce
ivab
le
wit
hout
cata
lyst
s[5
].
Cat
alyst
shav
ebee
nsu
cces
sfull
yuse
din
the
chem
ical
indust
ryfo
rm
ore
than
100
yea
rs,
exam
ple
sbei
ng
the
synth
esis
of
sulf
uri
cac
id,
the
conver
sion
of
amm
onia
to
nit
ric
acid
,an
dca
taly
tic
hydro
gen
atio
n.
Lat
erdev
elopm
ents
incl
ude
new
hig
hly
se-
lect
ive
mult
icom
ponen
toxid
ean
dm
etal
lic
cata
lyst
s,ze
oli
tes,
and
the
intr
oduct
ion
of
hom
ogen
eous
tran
siti
on
met
alco
mple
xes
inth
ech
emic
alin
dust
ry.
This
was
sup-
ple
men
ted
by
new
hig
h-p
erfo
rman
cete
chniq
ues
for
pro
bin
gca
taly
sts
and
eluci
dat
-
ing
the
mec
han
ism
sof
het
erogen
eous
and
hom
ogen
ous
cata
lysi
s.
The
bri
efhis
tori
cal
surv
eygiv
enin
Tab
le1-1
show
sju
sthow
the
close
lyth
ede-
vel
opm
ent
of
cata
lysi
sis
linked
toth
ehis
tory
of
indust
rial
chem
istr
y[4
].
21
Intr
odu
ctio
n R (R
ea
cta
nt)
Cat.
Cat.
R
P (P
roduc
t)F
ig.
1-1
Cat
alyt
iccy
cle
Tab
le1-1
His
tory
of
the
cata
lysi
so
fin
du
stri
alp
roce
sses
[4]
Cat
alyt
icre
acti
on
Cat
alys
tD
isco
vere
ro
rco
mp
any/
year
Sulf
uri
cac
id(l
ead-c
ham
ber
pro
cess
)N
Ox
Ds
orm
es,
Cle
men
t,1806
Chlo
rine
pro
duct
ion
by
HC
loxid
atio
n
CuS
O4
Dea
con,1867
Sulf
uri
cac
id(c
onta
ctpro
cess
)P
t,V
2O
5W
inkle
r,1875;
Knie
tsch
,1888
(BA
SF
)
Nit
ric
acid
by
NH
3oxid
atio
nP
t/R
hnet
sO
stw
ald,
1906
Fat
har
den
ing
Ni
Norm
ann,
1907
Am
monia
synth
esis
from
N2,H
2Fe
Mit
tasc
h,H
aber
,B
osc
h,1908;
Pro
duct
ion,1913
(BA
SF
)
Hydro
gen
atio
nof
coal
tohydro
carb
ons
Fe,
Mo,S
nB
ergiu
s,1913;
Pie
r,1927
Oxid
atio
nof
ben
zene,
nap
hth
alen
e
toM
SA
or
PS
A
V2O
5W
eiss
,D
owns,
1920
Met
han
ol
synth
esis
from
CO
/H2
Zn
O/C
r 2O
3M
itta
sch,1923
Hydro
carb
ons
from
CO
/H2
(moto
rfu
els)
Fe,
Co,N
iF
isch
er,
Tro
psc
h,1925
Oxid
atio
nof
ethyle
ne
toet
hyle
ne
oxid
eA
gL
efort
,1930
Alk
yla
tion
of
ole
fins
wit
his
obuta
ne
togas
oli
ne
AlC
l 3Ip
atie
ff,P
ines
,1932
Cra
ckin
gof
hydro
carb
ons
Al 2
O3/S
iO2
Houdry
,1937
Hydro
form
yla
tion
of
ethyle
ne
to
pro
pan
al
Co
Roel
en,
1938
(Ruhrc
hem
ie)
Cra
ckin
gin
afl
uid
ized
bed
alum
inosi
lica
tes
Lew
is,G
illi
land,
1939
(Sta
ndar
dO
il)
Eth
yle
ne
poly
mer
izat
ion
,
low
-pre
ssure
Ti
com
pounds
Zie
gle
r,N
atta
,1954
Oxid
atio
nof
ethyle
ne
toac
etal
deh
yde
Pd/C
uch
lori
des
Haf
ner
,S
mid
t(W
acker
)
Am
moxid
atio
nof
pro
pen
eto
acry
lonit
rile
Bi/
Mo
Idol,
1959
(SO
HIO
pro
cess
)
Ole
fin
met
athes
isR
e,W
,M
oB
anks,
Bai
ley,
1964
Hydro
gen
atio
n,
isom
eriz
atio
n,
hydro
form
yla
tion
Rh-,
Ru
com
ple
xes
Wil
kin
son,1964
Asy
mm
etri
chydro
gen
atio
nR
h/c
hir
al
phosp
hin
e
Know
les,
1974;
l-D
opa
(Monsa
nto
)
Thre
e-w
ayca
taly
stP
t,R
h/m
onoli
thG
ener
alM
oto
rs,Ford
,1974
Met
han
ol
conver
sion
to
hydro
carb
ons
Zeo
lite
sM
obil
Chem
ical
Co.,
1975
!-o
lefi
nes
from
ethyle
ne
Ni/
chel
ate
phosp
hin
e
Shel
l(S
HO
Ppro
cess
)1977
31.
1T
he
Ph
enom
enon
Cat
alys
is
-
Tab
le1-1
(co
nti
nu
ed)
Cat
alyt
icre
acti
on
Cat
alys
tD
isco
vere
ro
rco
mp
any/
year
Shar
ple
ssoxid
atio
n,
epoxid
atio
nT
i/R
OO
H/t
artr
ate
May
&B
aker
,U
pjo
hn,A
RC
O,
1981
Sel
ecti
ve
oxid
atio
ns
wit
hH
2O
2ti
taniu
mze
oli
te
(TS
-1)
Enic
hem
,1983
Hydro
form
yla
tion
Rh/p
hosp
hin
e/
aqueo
us
Rhne-
Poule
nc/
Ruhrc
hem
ie,
1984
Poly
mer
izat
ion
of
ole
fines
zirc
onoce
ne/
MA
OS
inn,K
amin
sky,
1985
Sel
ecti
ve
cata
lyti
cre
duct
ion
SC
R(p
ow
erpla
nts
)
V,W
,T
ioxid
es/
monoli
th
~1986
Ace
tic
acid
Ir/I
/R
uC
ativ
a-p
roce
ss,B
PC
hem
ical
s,
1996
1.2
Mo
de
of
Act
ion
of
Cat
alys
ts
The
suit
abil
ity
of
aca
taly
stfo
ran
indust
rial
pro
cess
dep
ends
mai
nly
on
the
foll
ow
-
ing
thre
epro
per
ties
:
A
ctiv
ity
S
elec
tivit
y
S
tabil
ity
(dea
ctiv
atio
nbeh
avio
r)
The
ques
tion
whic
hof
thes
efu
nct
ions
isth
em
ost
import
ant
isgen
eral
lydif
ficu
ltto
answ
erbec
ause
the
dem
ands
mad
eon
the
cata
lyst
are
dif
fere
nt
for
each
pro
cess
.
Fir
st,
let
us
def
ine
the
above
term
s[6
,7].
1.2
.1
Act
ivit
y
Act
ivit
yis
am
easu
reof
how
fast
one
or
more
reac
tions
pro
ceed
inth
epre
sence
of
the
cata
lyst
.A
ctiv
ity
can
be
def
ined
inte
rms
of
kin
etic
sor
from
am
ore
pra
ctic
ally
ori
ente
dvie
wpoin
t.In
afo
rmal
kin
etic
trea
tmen
t,it
isap
pro
pri
ate
tom
easu
rere
ac-
tion
rate
sin
the
tem
per
ature
and
conce
ntr
atio
nra
nges
that
wil
lbe
pre
sent
inth
e
reac
tor.
The
reac
tion
rate
ris
calc
ula
ted
asth
era
teof
chan
ge
of
the
amount
of
subst
ance
nA
of
reac
tant
Aw
ith
tim
ere
lati
ve
toth
ere
acti
on
volu
me
or
the
mas
sof
cata
lyst
:
!!
!"#$%&'%()*
"+#'",-+.-')#!%
",)&%)!')#'
$"/+*%"&!)')/0-'
*)--"'1*
%#*
"/2
$34$3"&*"/56$34$3%
(1-1
)
41
Intr
odu
ctio
n
Kin
etic
acti
vit
ies
are
der
ived
from
the
fundam
enta
lra
tela
ws,
for
exam
ple
,th
at
for
asi
mple
irre
ver
sible
reac
tion
A!
P:
("7
(#
!$%,#&7%
#389%
k=
rate
const
ant
f(c
A)
isa
conce
ntr
atio
nte
rmth
atca
nex
hib
ita
firs
t-or
hig
her
ord
erdep
enden
ceon
adso
rpti
on
equil
ibri
a(s
eeS
ecti
on
5.2
).
The
tem
per
ature
dep
enden
ceof
rate
const
ants
isgiv
enby
the
Arr
hen
ius
equat
ion
:
k=
k 0e
(Ea/R
T)
(1-3
)
Ea
=ac
tivat
ion
ener
gy
of
the
reac
tion
k 0=
pre
-exponen
tial
fact
or
R=
gas
const
ant
As
Equat
ions
1-2
and
1-3
show
,th
ere
are
thre
eposs
ibil
itie
sfo
rex
pre
ssin
gca
taly
st
acti
vit
y,i.
e.,
as:
R
eact
ion
rate
R
ate
const
ant
k
A
ctiv
atio
nen
ergy
Ea
Em
pir
ical
rate
equat
ions
are
obta
ined
by
mea
suri
ng
reac
tion
rate
sat
var
ious
conce
n-
trat
ions
and
tem
per
ature
s.If
,how
ever
,dif
fere
nt
cata
lyst
sar
eto
be
com
par
edfo
ra
giv
enre
acti
on,
the
use
of
const
ant
conce
ntr
atio
nan
dte
mper
ature
condit
ions
isoft
en
dif
ficu
ltbec
ause
each
cata
lyst
requir
esit
ow
nopti
mal
condit
ions.
Inth
isca
seit
is
appro
pri
ate
touse
the
init
ial
reac
tion
rate
sr 0
obta
ined
by
extr
apola
tion
toth
est
art
of
the
reac
tion.
Anoth
erm
easu
reof
cata
lyst
acti
vit
yis
the
turn
over
num
ber
TO
N,
whic
hori
gi-
nat
esfr
om
the
fiel
dof
enzy
mat
icca
taly
sis.
Inth
eca
seof
hom
ogen
eous
cata
lysi
s,in
whic
hw
ell-
def
ined
cata
lyst
mole
cule
s
are
gen
eral
lypre
sent
inso
luti
on,
the
TO
Nca
nbe
dir
ectl
ydet
erm
ined
.For
het
eroge-
neo
us
cata
lyst
s,th
isis
gen
eral
lydif
ficu
lt,
bec
ause
the
acti
vit
ydep
ends
on
the
size
of
the
cata
lyst
surf
ace,
whic
h,
how
ever
,does
not
hav
ea
unif
orm
stru
cture
.For
ex-
ample
,th
eac
tivit
yof
asu
pport
edm
etal
cata
lyst
isdue
toac
tive
met
alat
om
sdis
-
per
sed
over
the
surf
ace.
The
num
ber
of
acti
ve
cente
rsper
unit
mas
sor
volu
me
of
cata
lyst
can
be
det
er-
min
edin
dir
ectl
yby
mea
ns
of
chem
isorp
tion
exper
imen
ts,
but
such
mea
sure
men
ts
requir
eg
reat
care
,an
dth
ere
sult
sar
eoft
ennot
appli
cable
topro
cess
condit
ions.
Alt
hough
the
TO
Nap
pea
rsat
trac
tive
due
toit
sm
ole
cula
rsi
mpli
city
,it
should
be
use
dpru
den
tly
insp
ecia
lca
ses.
Inpra
ctic
e,re
adil
ydet
erm
ined
mea
sure
sof
acti
vit
yar
eoft
ensu
ffic
ient.
For
com
-
par
itiv
em
easu
rem
ents
,su
chas
cata
lyst
scre
enin
g,
det
erm
inat
ion
of
pro
cess
par
a-
51.
2M
ode
ofA
ctio
nof
Cat
alys
ts
-
met
ers,
opti
miz
atio
nof
cata
lyst
pro
duct
ion
condit
ions,
and
dea
ctiv
atio
nst
udie
s,th
e
foll
ow
ing
acti
vit
ym
easu
res
can
be
use
d:
C
onver
sion
under
const
ant
reac
tion
condit
ions
S
pac
evel
oci
tyfo
ra
giv
en,
const
ant
conver
sion
S
pac
eti
me
yie
ld
Tem
per
ature
requir
edfo
ra
giv
enco
nver
sion
Cat
alyst
sar
eoft
enin
ves
tigat
edin
conti
nuousl
yoper
ated
test
reac
tors
,in
whic
hth
e
conver
sions
atta
ined
atco
nst
ant
spac
evel
oci
tyar
eco
mpar
ed[6
]
The
spac
evel
oci
tyis
the
volu
me
flow
rate
V 0,
rela
tive
toth
eca
taly
stm
ass
mcat:
:;)!%$%/"!1'0
!!"
%
The
conver
sion
XA
isth
era
tio
of
the
amount
of
reac
tant
Ath
athas
reac
ted
toth
e
amount
that
was
intr
oduce
din
toth
ere
acto
r.For
abat
chre
acto
r:
(7!"7!250"C
)
Appli
cabil
ity
lim
ited
wid
e
Act
ivit
ylo
ssir
rever
sible
reac
tion
wit
hpro
duct
s
(clu
ster
form
atio
n);
pois
onin
g
sinte
ring
of
the
met
alcr
yst
alli
tes;
pois
onin
g
Cata
lyst
pro
per
ties
Str
uct
ure
/sto
ichio
met
rydef
ined
undef
ined
Modif
icat
ion
poss
ibil
itie
shig
hlo
w
Ther
mal
stab
ilit
ylo
whig
h
Cata
lyst
separa
tion
som
etim
esla
bori
ous
(chem
ical
dec
om
posi
tion,
dis
till
atio
n,
extr
acti
on)
fixed
-bed
:unec
essa
ry
susp
ensi
on
:fi
ltra
tion
Cat
alyst
recy
clin
gposs
ible
unnec
essa
ry(f
ixed
-bed
)or
easy
(susp
ensi
on)
Cost
of
cata
lyst
loss
eshig
hlo
w
Tab
le1-4
show
sin
more
det
ail
that
the
key
reac
tions
of
hom
ogen
eous
cata
lysi
s,
such
ashydri
de
elim
inat
ion
and
oxid
ativ
ead
dit
ion,
corr
espond
todis
soci
ativ
ech
e-
mis
orp
tion
inhet
erogen
eous
cata
lysi
s(s
eeS
ecti
on
2.1
).
The
hope
of
incr
easi
ng
the
separ
abil
ity
of
hom
ogen
eous
cata
lyst
sby,
for
exam
ple
,
fixin
gth
emon
soli
dsu
pport
shas
not
yet
bee
nre
aliz
ed.
The
aim
of
man
yre
sear
ch
pro
ject
sis
tom
ainta
inth
ehig
hse
lect
ivit
yof
hom
ogen
eous
cata
lyst
sw
hil
eat
the
sam
eti
me
explo
itin
gth
ead
van
tages
of
easi
erca
taly
stse
par
atio
n.
The
mai
npro
-
ble
ms
are
stil
lca
taly
stb
leed
ing
and
the
rela
tivel
ylo
wst
abil
ity
and
hig
hse
nsi
tivit
y
topois
onin
gof
the
het
erogen
ized
com
ple
xes
.
An
inte
rest
ing
inte
rmed
iate
bet
wee
nhom
ogen
eous
and
het
erogen
eous
cata
lyst
s
are
the
met
alcl
ust
erca
taly
sts.
Inm
any
reac
tions
that
requir
ese
ver
alac
tive
cente
rs
of
the
cata
lyst
,it
isfo
und
that
het
erogen
eous
cata
lyst
sar
eac
tive,
whil
ehom
oge-
neo
us
cata
lyst
sgiv
eze
roco
nver
sion.
The
reas
on
isth
atcr
yst
alli
tes
on
am
etal
sur-
face
exhib
it
