OsciilfaYms in Cafalytic Raciicns

I. IXTRODUCTION ....................................... 107

a. SUSVEY OF SX?ERCIEXAL 'XORE .................... 109
IS. TZGEL-ZXC2.f. S T T C E S ............................... El
A. Xzacdon a S i q i e Toroua P d c l e ,............ 122
a. Beaction on an a r d CatJlyzic scL'i3ce ............. a-i
C. T?ie ?roblati of a C a t d p t in a C X R . ................ 136
D. T e t e t l d V e r s u s Expenmertral Besuits ............. 143
N. OSCILUTOXY STA'IZS IX TZlE G&uIIE4yTLEss
B u C T O R .....................,......*............... 144
Equa~ons,Norions, and Theorems .................. 145
to the Oxtdarion of CO .................... 149
A.
B. hpplicarfnn
V. C O N C L G D I X G W ............................... 165
SmOLS ............................................ 166
BEF-C= ........................................ 169

L DITBODU~ON
T b paper deals wifb rhe of h o w i a d g a amcaxnang open
cazalmc r e m a systams whtch, though &posed to consmnc concii-
Uons, ambit sustvned oscaJla&ry statas. Such behamor arouses

107
GSCILLiTIONS N CAT-lLTTIC RE.4CTIOS 109
 (c) Ni foil

asymbrrla uaad fn tMs column are d e a d aa blloara, a, a a u -

OUB flow stlrred unk reactorr b, conrtrmously fed rtcii- (re-
cycle) reactor: c, f k e d bed reactor with single c a u l y s t particle em-
bedded in laper of inart particles, 03 recycle; d. flow past sin&
 3 Tg: SO-d7O.C. Conversmon:
30-425
(a) 60 (a) See Flg. 2(a)

@) 2 a 20 0)C02,g:
- see Fig. 3(3).
T, : 2' C pedi-b-*&
1 Conversion: 7 0 4 5 %

15 T,-Tg: 30-14O'C

i Tg: 157-160'C for TF =

157'C. Conversaon: 63-
7 0%
0.05 r0 1 AmpUtude: -40% of m e w
reaction rate

UO'C. 1.3Eo co in air

L50-270'C. O-lgco u'8 to 150 See Figs. 1, 2@), 3@), 5,

in* and6

(a) 1 to G U (a) See T i p . 3jc) and 4

(b)3 to 45 @) See Figs. 3(c) and 4

(c) 6 b 30 (c ) T,: 294406.C

t
 t i*w

- a min-
Tim

FIG. 1. Ekunples of 'aeariy osclltdnns: (a) wlt!a

ondarion of H2 in a spherical catalyst pellet (3.14% Ht in air) [8, 9 1;

i n a s , 254'C; T -
@) with ofidadon of CO on plathum bil in a C S T B (feed of 1.75% CO
8 mln) [la;.

h r e a s e or decrease b i b w e d by a U m s span of rel;rripsly slow changes.

In t!m case depicted h Fig. 1, for exampla, tbe rnevnurd C q CoEcen-
tratlon as the s u n o f a perlod changed from Its mtntmrmrvaLte to a
maamurn in h u t 15 sec. It then slowly b a y e d back to t b mlnrmnm
over a fame spaa of ;ibDuf l20 sac. A mora preciae mazbmdcal de-
acripaon of m1pndan oscilladolrr Is glpm b a later pare of tb,ta paper. )
Perto& hmng a nmra symmetric s l u e , aach p. Wee shown ln Fig. 2,
have a h h e n reported. ObeerPatioru of much mom Lntereadng and
compllcared penodic bobmior hvs t#en rrponed in some msumces.
For exsmple, la both the oridatton of H2 (rmuotbermal) L3, 9, ~ 9 ;
and of CO (bahermal) La, 9, 17, U], there arm c 1 1 ~ c t e r i z e dby a
numkmr of peaks on a singis cycle and mtgnt be ~~y a e a c r h d in
t imr
,
+,
I
I
I
I
 T-
IC
I
1
I
I
I
1
1
'

FIG. 5. Oddation of CO on pl7rfnum fail (in Gatherma3 CSTX at

329'C, 1.92% CO in air m feed) showmg &e ae.xsunce of oscillatory
a d x a l e sfafes (between dashed oercicd Lines) [173. L x s Lid-
cate pes-to-pesk amplitudes.

a d zuass and the passage of f l u d to downslrean particles, be sui9cient

synchronazc the penods of the indivxdual particies? The quesDon can-
not be axmvercd with cercilny at tlus time, but those studies uned in
Table 1 wmch involved a packed section of particles in the reactor (En-
aces 1, 5, and 7) did not seem to yield my o a c i h m r y behanor in the
reactor ouzput whch w u cbsacterlstically different from that ob-
semmd in scaaies with singie pprticles o r cataiytic ails.
h three of the studies listed in Tabh 1 for th6 oxidation of CO (6n-
mer 3, 7 , and 8) a d in one case for the oxlddatlon of H, [19:, tbe 08-
cillarorp s u f ~was Mt a mume staze. That 1s to say, that omr some
of Conrtttbpe there c o e d an oscFtlarory stata and a stable
Urndependent st3te. F m 5 depicu ttus situt&7nfmm &sa m-
ported by Pllcbta and Scinnlrr (17:. hperlments conducted by these
 7

i1
ETG. 6.
-00 of CO o n plaUm.un foil in a C* a2 233*C, 1.34% CO in au m
feed [ 17 1. hrrows indicate peak-ro-peats amplimdes.
CSCLLATXjX'S I24 CATALPTIC REACTIONS 123

1 = L2, ... , n

Bormdarp conditions:

"i aT
z ) = & ---,=o
a2 az
124
 *We refer 0ctasslonaUy tbughorn this secdon t n "y)proOldmlurlt
zn.erhobs of analpla or solution witbut fPrthcr description of them.
The raierence ia o so-called 'lunpuq" methods wMch in effect con-
vert the orq#aal dstribursd problem to a lumped one. renaerhg it
mom a m e d e b analysis. Five -reor lumpmg methods have
been described and applied b the i n q a t t i c l e stabillty problem.
(See, for example, Fiefs. 23, W-29.) In their stmpkst versions,
l'lnm@rq't rnsrbadr would convert each of t b two partial dlflcrcn-
tlatequubru L b e d tnllable ? t o asingle otdfpvp differentialequa-
tion In time. To Uusuara. tbr, second entry in Table 2 given rhe
"kalumpedt' form of the fLnt enay. The lrrmping uz thrs case PII~LI)~
use o i *he Lzst-order o & g o d collocation tecbplque [ Z j. Nodm
t h p t o d y t a n d t . + l a r e & a n g e d . MostImportantly, r l s c b n g e d
from a s p a s h l deri~otloeterm b a bear W a c term.
126 SESECUCH .%XD SCS?IIITZ

Prohiem x2

4. solp.J;1)us m c l e (uniform
pazzlde temperaaae) wltb
w i e r resrstances (see
1-3 cl’cl,g
Ts/T
g
descrqmon LD. Part DI-B)
5. Sane 39 i mt3 negllhible
mius m i e r ressupce
dfiniteryeofchenu-
1 - XL
sorpdon (see description
in P 3 x m-B

6 . Gradientless CSTR
l-3 cs’cI, F T%
G S C I L U T I O N S IY C.ITALF!C REACTIONS L27

t 3 Ca L J+l

:'Dl
1

t'3,

s /k
U b 17 X,CC
-!
I
6 ,L
S P

M
&T

t'
UA T
C
a k + 1+-
PCpTF Y O VPC
P
is - : d x s well ceiow u v t y md hence below ;he c z ~ a c dv d u . (.A rei-
sonable z s t l z u of L, ior a ?omus piaa3m csval::sr is 0.016/d, m e r e
d is ihe aver3qee?ore diameter in cecrimeters L l S j. F o r a pre di-
meter ox 1030 -1, Lc would be 16OC.) The 2wers '5y 3lavzcek a d co-
xor:ucs aiso somr aut . a r k critacd V ~ L U ?o i L i2gac c s on 2%
T h e i r 30&u 5 . Par suificiendy smail values o i 2 . sscdlations
ux sbwn TO be mpossihie ior h e case oi 3 i = 3h o r br &re 3i
and Sin tegaxdsss oi the a a p a a e of L.
X u m e n c i sinulariona S & O W ~d c a i a s e d o s c t l h m q 3 0 h x n l S
for Lnaplte vdues o i 31 and Sh have been presezxeci as U u s t r J t l o n s
in 3 a&? of icssuslcbs. Sevenl public3clons by Y?ancek a d co-
mrk;ers ,$, 25, 31. 32: ixiucie such simuiacions ior a s p b n c d
3 ~ q c i eby 3 ,:afierJ, of me&& of soiucton sll mth ;Y > 1 and L < 1.
;C 3ze iixazc& s t o w e d s u s i i e d o s c d a t i o a x o u z a 3 %+con-
Tetsio-, 5 ~ x L~e n *L-,-ee
2 s m d g states ensreti. O t i O i s were reporred
ior spcr,-.cd p c . i d e s with L = 0.1 by Lse azc h s s 133 3 (who alSo
s t a d k d che line= ~ U F U l i t yproblem by Galarm's merhods) and by
HeUinc!cx BK al. 04:. T k laaer r e p e a ~ e dc& srmul3r;oas oi Lee t n d
LLSS,WLO used 3 qhz-cifcreace r n e b d , LD SLOW&at ' l u m p i q " by
L-SL-OEXZ s r h ~ q r scoi!oczcc~:
i g v e r e s o d i y SCFLWC :SULKS.
-.
I q u r e 7 ?rerenu .he results oi one oi L& 3m-~Larioas coct3ired
m h e piper 'T Lee a d U s :33;. The brge - J ~ ~ ~ U O 1D3 Sthe :en-
p e r v l u e ?ro&iz b u g n the pamcle are particuiariy mreresung b
W s a (1) they smw temperature excmiorrs well beyond the adiaatic
'kzmperarure Ase, and (3) the simulated temperature near t3e particle
suriace reacfies a very large value. In dorernentioncd a e r s e n t s
by Beusch e t d. 18, 9 1 the temperawe through tbe parcicle (935
nearly ~ 0 n . s ~Nonce ~ . &o tbar b e passage thmqn profiles 3,
..
4. . , 9 consumes only about 6% of the total cycle tupe, inhc-
tbar hes e particular osclllarions are of tba r e k u t i o n type.
The assumptions regarding the values of Bi and Sh were relaxed
IDa study by Hlavacek and W i c e k [30], wha also considetsd the
&ecr of reactlon order and oi a change rn molar density with reac-
-an. The suuiy was marrrly concerned wlth wtratber rhesc p--
ewrs axxi effects. when properly accouwed for, w c J d lead fD os-
ciyaroxy states for reaListic vdueta of L and JY, Th! principal find-
ings were as follows. (1) The critical v a h of L passed tbmtagh a

-
-
birr s t i l l mmed l a 8 thn unitp, a the n r t o SWBi a-
creased Imm uniry. For example. WtthJv = 2, SWBl = 10, and a
0 or 1, the cntical value of L below whwh osdllatoxy s w s could ex-
12% 0.304. I€, for the same situation, BI and Sh were taken lo be
U l i h t C , the d t l c a l v d w of L was oplp 0.075. (2) Increasmg the
 I-'-Pmflla

2
I
t
O.I*IZO
amzo
3 1

7 T TC
Q : 1.1
0.+5

I J
0 0.2 0.4 0.5 0.3 1C
.
z, D u n r m w l i a ~ Affiior h r i t i o n

XC. 7 . i ) cycle
~ of predictad temperature oscrllariona m a
spnencal porous i1arncl0 slmubred for 3 flrst-rcer .irr!muus-cype
rmctlon by a mte-difference method (1000 g n d p o w ) ; Lee and Lass
c33 :.
omer of reamon fmm one ta two decraaaed the critical d u a of L.
(3) Volrune con&zction with rcacrion bmaaed t b crftical d u e of
L, but &t effacc waa s d .
A numetrcal solutlon of the governrng pania). drfferensiatad equa-
& o m presented rn a RC~SXS p w r by Binder and CJveln [35] for
Si r Sh s&wed s u s t v n s d osciUationa about a =qua urrstable r a t e in
a spnencal panicle. Here, as in all of the prevynclly cited cases, t b

-
set of parameter valua urvolved In the oscillatory s t a t e would not
U d y apply ta realistic situaaons ( P y 8, L = 0.1. SWB1 = 5). es-
pecrallyfor k = 0.
Slncs fhs restnaace to b a s ~ a n r r p o r within
c a catalyst ptu&cle
LS usually much s d a r t b n tbe~BlcLezppl resistance, o w u q u) the
k g t particia thermal conductivity, tbs system 0quadona may be sun-
p U e d so~~lewnas K tbo uumpdon u made that tha temperarrve of the
p a r d c l e is &rm througntaut. The exparlmontll measuremenrs by
130 SHEPITCCH .L?D SCz?IITZ

1. A

Tht pet effect in the dimezuronless equations is the replacement of x ,

lp the rau fzqreseloaby x,/(l r K,x$. They 'aok Bi and Sn to he
Lrrrlnite, and uskg an, appmrtmatP method of solmon found t b t rhe
critical value of L berm wbxh oscillation^ were possrbie tncreaaed
39 either 11, o r Y increased. The upper knit of the crltacal value waa
unly. The authors contend that if dl effecrs, induding b %=-Ace m-
*hbitronerfecrr u Lanpur-iILMhelwood eppe of rate expressions,
volume conzracnon witb reacrOn, and mte unequal d u e s of ai and
Sb -re accormred for. the3 *hm i o n problem mth a single re-
acuon scep would lead v) oscillatory wlutions ior r e a s o m l e values
oi L. Thay citad Zkie ethyLene hydrogenation r8acQt.m (I < $v c 2.7;
Le = 9 C 2 3 ~ ~ a n ~ l C t n w M c h s u c h c o ~ t i o o s m i ~ p ~
brrr thcy pmsenrcd LY) simuladona for it.
a d cmspp.& u two papem [3a, 391 considered 'mtb
-US
-
tbn surface c;lpacit?ncs and yisorptba enrhalpp effects e%ecrs wphich
have besn negllecred rn all pnzvlously cited ~Olmes. Tbe a u b r s maan-
rarntkat tbe surface capzcitaca is accudlp much larger tban tba capa-
d l l l r s of the mid volume in a typical porous p m f l t . ( merm
 C. The Problem of 3 Camifst In a CSTS

There have been ~ r z s r n g i yfew theoretlcd s d e s of os&-

tory stares ior the problem of a clralysr in a well-mixed vessel al-
b u g n it closely resexzbles the classic CSTR pmblem with nomog-
eneeous reacuon. That classic problem has received exfellsive Reat-
ment through the past cwo decades 133. Some theoretical work, con-
ducted LD conpnction wlth e ~ e r i m e n asoldlee
l of baclmwred clulytlc
reactors, was described earlier Ln Part D of ths paper. h few of.&=

-
are dted bcrc, a d Parc SV elakmmw furrhar on this pmhlem.
9 o r s d J L x e k ;5l! studied the case 01 3 single porous cara-
lyst particle m a CSTR, assumrag the s u m of the panicle to be um-
form and paeuav-sready. T h y 3Lso = w e d *&x an exorherrmc re-
amon, of order U, of rhc hrreolus type occurred EL pmacie and
 i

. ; * 1.0 il-oJ/L
I r I

I n l

!FIG. 9. Skeccbes of b e dtfferent classes of p h s e piors ior the

cases I9dtc3red on the abscissas in Figs. 8 and 10. The -1 u des-
ignates unsrabie steady s u t e s ; 9, stable steady states; slc, s u b l e LLm-
i t cycles: and ulc, u n s u e limit wcles. Cppal, a y , and Poore (42;.

Figrue 10 is s l m i i a r to Fig. 8 LEI that i t summarazes steady-state,

stability, and oscrllafory fe3frrres in t b homogeneous reaction model
strr;tied by Uppal, Ray, and Poore. The difference between tlae two fLg-
aires LS that in Fig. 10 the parameter represenred on the absclssa Ls
-
tb6 residence dme a parameter convenaently -pukred
r n e d p . (The group Ca on the abbrcassa ui Fig. 8 is not a param-
expen-

emr wkch can be changed in uqrenmearJ b d e p d e d y of a l l othclr ) .

bp O d y tb k W mta h 8m8-e- RaEtOf. OOB
Jh-8 a rhr m g U r n g and - d fe-S a-
Mbimd by any ane of the sketchr ~ 1 Fig. 1 10. Nouce thp m some of
*br= 3 (a s e p a z z Ul.lt?Ebd closed m e ) e~29ui. Notice also
 FIG. LO. SketEhes of muversion v-s residence t h e sb-
characznstics for e.mtherruc
S t & a f i y - B t Y e , stability, and 0scZll;itorp
reactann mth ht-order A r r b m u s m d c s 10 a CsfII. t'ppal, Ray,
and R o t a [U:.

b t tbs same rections A, B, etc. are W c a e d &ag tne absci9888,

reierring as beiore to the different types of phase planes of Fig. 9. It
is ForerpstFng to e m the three Bgnres, lneptng in mind the llkely
procedures of an experrmeprer and to &cover that same sitmunus
(sraarty and o s c i l l a a r y stares) may be missed emrely in an experi-
me- Supposo, for e-xaxzple, p a a m e w weru such that Fig. 1O(C)
applhd. h an experiment in which oaly rhs residence times were
cbpnsed, the staxes (steady and 0aCill;rtorg) w k c h a;xUt on the twla
arould pmnaaly never be replized. Much further discusaton 19 pas-
sible mgardbg these resuits, but space for it LS not justiffed here.
The papers by Uppal. Ray, idPoor8 contarn mu& more infoma-
tton and includs a mtmber of cornputar simulatbns.
 Sesides a e s of a uuque s a b l e s w , such as h s e along sec-
'tons labeled A ui F l g . 8 and 10, sitaations amrch have actually wen
o n s e n d xa &.perlmenrswith caralydc reaczions (not dl mth reac-
tor3 oi * h CSI'R we) resemole those along sectloas labeled E (m
s w i e staces mttr =a sustaned osd!~tiorrs)[ 8 - C ! , a (a uzllque un-

-
s w l e sxam mth sustained oscUlat~ons;see references in Part XI).
F ( d u p l e steaay stares with sustaszed oscrLktions about a hgn-
conversion -table srar.e; sea references m P m It), and C (mul-
a p l e steady 9f3~eswith only the iow canversion s u m W e ; no BUS-
OSCULUULS) [U:. ObserPatiOm O f ts4k CO- = 08cil-
Latory stazu wera r e p o d by Jiracak a d H o d [:53 3. Additional
refererrcea to those experimental obaorwtionn o f steaciy-swc nul-
dplldty and mstanillri8s in b& caralyUe and noncaralytlc oysans
mch did mt repon. any mstaaned oscrllarory berravlor are pven rn
rwm~paqer .by S c k n i t z C33.
ie-ag m.gutuaes oi IT rates. &Fur-&rzaore, oscalkuions
u v e been o o s e m d Wtth b e same reactions m both i s o t f r e d ma
lolllsothertnai expennents and UI systems wittr vast difkrecces m
rhe r W v e upaatance of the crr;Jytlc suaface for chemasovtbn,
suco as pomus paracles and wires o r forls. Also, some of tbe ex-
acnmenral s u e s have pekied very compliwed penodic beruvior
wmca suqie-step -tic models (i.e., models ~ a s e don the assump-
eion of a srngfe rate-detemuzug nep) are probably mcapmle of de-
senbang. Tatran together, these kcu strongly suggest thar t&e re-
sults of t.&eoretluls t u d l a w b c h k v e employed single-step Ldnedc

'0 dau, -
models have m bear!! on t b experimental obsemations reported
ar least for K, and CO oxidation. Tba most recent litara-
fpre dted above mdica.tes that most researehen i n this m a of sardy
are of that same ophon. It is not possible to support such a view re-

--
3zrding the oecillatrons reported by Hqp [Sl for mnrsotberm3i X@
aecompositlon thc only ofber reactton for w h c n oscillations have
been ooaerPed becanse o e c W o n s with chat reactlon have nor been
suadied unner such diverse c n p n d i t i o ~ . It may M e e d prove to b an
IV. CSCILWTORY STATES IN TEE
GIMDIENTLESS REACTOR
T b ~ W OXU~ c U OR%~ iSrpd %, 1 a z ~ ,~ S p e C t i W l y ,t
b m~tt3fe
of cnemtsorption of species Ai and tbe fate of conversmn of species
d i r e d y from the y phase. &L -pie of tb latzer type con-
versmn would be an Eley-Ridad step ia which A, in the gas pkaae re-
acLs by collision wlfb other reactants on the suri3ce.
A balance on t b same speaes L I ~the &misorkd phase is
 In o n l e t ta retain the second+rder nature, and .hence to retain rbe
paasibiliry of oscillvorp soluzb~ns,the msuicrion is m3de k t F, and
F2 rat be linearly rekted.
In order that 3 solvdon sausfymg t!ae steady-sua form o f Eqs. (14)
ad (15)be sable, it-is nacessarp and suificieot tiaa~tka e i g e n d u s of
tbe mamx B have negative red p a n s :

This, in tura, requirrs tb;rr the determinant 01 the nauis be pasittve

andtbetracencgativr. Tbuis
 In t&a sectton Jle the0re.Uca.l method8 for investl- oscillvrrrg
states alscusaed in Section A are applied for ilkrscrsim and infa--

-
t h e purposes to a sarcry of the osidatloa of CO in an i s o e h e d p-
dtendcss reawr a situation m w w e l l known to gim oarcllatarp states
over some nngea of conditions. Our procedure m rhts s w was to
cornporn four &rent models for tba system and to consider a num-
ber o f s p e d c u e s for each one. Each model coamned two depen-
dent or " W c " vaaables, x, and +. T3a models differed basically
in the de~iirdt~~m oi the nvo d e s , aa is described Later. The spe-
d cases wese b.rmulated by invoking different sexa of smnptiona
and rasrrtctions. The metbds of anal- followed nearly directly
from those ouzlined ln the p r s a u s s s c t i o a For each case tba ma-
tclr poen by Eq. ( 1 6 ) and t h determinant aad mce in Eqs. (17)and
(U) were constrncted h m the far0 descrlblng dFfferePaal equations
krr x, and q. As w i l l be seen, rn some canes the ca~acitaacemamx
wasnotaragonal. InmnooftbaCYIeudidtkis&ctEq. (L?), butthe
trace LII such cam6 was mom ccmpltcvad rb?n the erpttrsion glpm LD
Eq. (U).T?M dyau for suswaed oeciUatorg s w e s ynounted to
of 0,. h ttza second model (see Table 4). wMch is based on tbe u-
*-son tha: oxppn caemrsorptwn and surface reacttons 3pe the rn-
p ~ wm t steps, s2representr; the surfme coverage of oxygen. Mode!
s Bat.? rases of CO adsorpaon and s e e r e
3 s T d c S a f c o u ~ ~br
zcnon; the second crpa3mtc m l e ISthe surface coverage of CO.
Model 4 (see Table 6) aesczibes a s g s t e m Lo wmch two sutes of chemi-
wr& Co exist, o d p one of wmch LS reac*Jve. Zxperanental studies
of the chemisorption of CO haye revealed tbc exBten~eof m chepu-
sorDed iormrr on pletrmlm t~ the temperaam mnges fndicated for ex-
p m e n r s with CO oadanon UI Table I (601. The two forms are
chmmnnly temed "UEear" and "briciged"; the latter is the acfi7e
brS. b a d d 4, X i fly- b0 b -0 C00e-S O f ths
brLdged s t l t e .
The sepiua&~cases, bned UI the bomm portton of the tabie for
anp OIIB of the modela, were all deollced from thr, gcnenJ morms of that
maad by empLoylpg tha ldclltinnll rpoumptiplrs and nsrrktAom Ustad.
We shall mt demote space hela to dtsarssion In derail each seprvate
 Nott:e tku Cases (e) 3nd {f) of %del 1 admat oscU3torp solu-
dons, brrt fn the fLRt oi U s e we Spud that tba side W o n , Reac-
don (5), nrnsr be lars W v e to the maan reactaon. Tbts obviously
is rmc zhs case in ewerimem. C u e ( f ) introduces the mtim that the
-vation energy of reardon depends on sLzr23ce composition. Depen-
dences of thrs are well !umm to cut, especially for clrermsorp-

-
rbn and deaorptbn steps. Such dependencies have also been used to
dtsmta Surface reacaon. steps aee, br example, Ref. 62 -the usual
erplaaadon be= to terms of mnrmrformitp of the activity of SAUS (her-
rmgeoeity) o r in terns of l o t e ~ c t i o n sof Chemisorbed speclea. Al-
tbu@ oscillatory states are possible in Case ( f ) in Table 3, we found
tbat the required rnqrdtude of P wzs large, so Luge in fact rbat the
c o n t z l b ~ o nof fi to the yfiwrioa energy seemed unreaLFstlc. The
town we reached was thr tbs mecbvnsttc model descnbed Ln
Lbs tap parr of Table 3 shows very lflila promise of being able to do-
scribs tha orcilkmrp oxdatloo oi CO. Consequently tIaa general ap-
plicability of some commonly accoeprad r s a forms wUch are based on
both0, d CO bslrrg LTJ Ehamlaarption equalibnum far thu nactloo ts
cUnpd.
 A
n
x
n

N
2 7
4 -

'; Y

C*

X
I
-
4

II
None

L = I

1. = 1

L / I

Oscllialory olirlee of typo I.' (see Ylge. 8 nntl 9) arc p t ~ ~ i L l u

but ordy c01 uiiraallutlcully lnrgu rulu of Ilcuclloii ( 5 )
 n
a
II
n
I

.
-
+
U
 i 3
3
- -
Q
CI
, ?-

P
z

2
M- =

I
.
II
II
 L
a

m
n
*
ma n

<
- m
d
4
?
11 t
6
11 In
4
a
m + E3

*-
+ m

e?.
Equaktne
 Smce Xodel 3 o ~ r some s p o s a i U t g for expplwug susutned os-
callanoos, we jmsent a d d f t r o d ~ s u l t sof *hstudy of i t ior Cases (b)
a d ( c ) wt!a P,, ui. vl, and v, all zem. Thus only one new paameter
M, LS added III tkis case o those conwried ~ 1 Case 1 (a) o i t;?e s-8
modei. The value of quand5es the e x ~ n of
t 'te depndence of the
w % c e c o v e w e of O2 o n the suxkce reactmn velocitg. W e found the
a l of nt. &ve wrzlda osclllvorp states are possbla, to be
c ~ ~ c value
relarlvelp s d , vvylng beween 1 and 6 dependmg on wherher Case
(b)or (cJ ~9 chosen and wnether tbe chermsorbea -0. is assumed
to DB LU the dlssoclated or uPdissociared form. (us = 1 causes a chanp
in the acrfvation enem of oniy 1 k U m o l e at 500.K for x2 = 1.) The
ar Case @) are presented LII Figs. ll.

-
results of s o m e d-ns
L2, d 13. F i w U sbo- ~aCi.Uabrp~ t l r e ~ hm t b 4-
tlple-etue regame, wMle Fig. 12 shows 0 - q Bfafeo on a curve
$&t COW only unique s d y m.These similar in fors ta
tha shmn in Reaons Vb and VI Ln Fig. 8. Experlmeazd
cumus shawn rn Figs. 5 and 6 rearmrhla cbe theoretical a r m s , buz
rmponanr qualitative dlftCTences, such the W o n of tbe ampAi-
tode of oadladopb with space vbiocaty, are mdent, An example of
&
' o x b v axweraloc oi CS ior a reslcence t l n e of LO sea t9
smwn !n Fig. l2(b). T L s oscruvOrg s w e , o b w d by numerical
solutloo of the differexid ~ ~ o n sbows s , sharp chnges u1 CO con-
version, bat t&e form is ZDE similar @ &at of tbe experLmerrP1 came
s k n m LII FIg. 1. ( h c a d e d y , we S o c m e d opt some s ~ m u l a d o ~
far a model wtuch iacluded an e a b l p y balance. S m d z temperamre
splkis slrntlaf to b e e shown In Fig. 1 were obramed, but *boecrl-
larbns xt CO comersmnmre oniy slimy ~I&XUM.) All such quali-
features, Fncludng the s h e of oecilLauaas a d the eifect of the
spa- veincity, were not burid ta be sensitme to tbe set of patuneten
ck~sen. Rumexmore, m distincr dlffereaces were found bcrween

-
Cases (b) and (c).
Figure 13 presenrs Wt cycles tn the phase plaae for Case @).

cussed in rhs Q-US -

C w b 4 (k 0) sham a true reLzfatlon oecUuon of tbe type dis-
secdon. Tbe Wt cycle br % 0 COMISU

-
of horizons "firmen" SUePrarad by relanveiy slow traotl sloop the
cprprr W d t 0. CurPer 2 a d 3, computd hr mnzsro ozluce of
&, also ertrrbit a relamion- in che sense that tha stata changes
very rapidly Vong 90- Sacdona aad relatively 3lowlp along others.
(Nodcs cha time on Curve 3.) Tbs steady-awe solution ior
the c u e sbpwn irr Fig. 13 is untque and upecahie. The llmit cycles
 FIG. E. Steady 3nd osn'!latnry states for the same case described

-
in +&a p a o n of Fig. LL. except apk3,0/C1,F * 0.0088 sec-'; a&/
C,, F = 0.07 sec-1: C, 0.1; K, = 0 . S i m W n a @) is %r t * 10
SeC.
I c..

l 412
2 a io
3 at6
4 0
 T h u g 3 much tbeotetlcal work on % w e d o s n l l r ? stares in
hetemgeneous c;stalydc reacdons has been published, them 19 pres-
d y 30 satisi3ctory expiauuinn for gcpertsenul ooservartons of 08-
cillamxy phemmena. .%E the sumey of lttemmrn in this revfew re-
~ recedy have eanbmced p r ~ h f - m l v m g
veals, t h e o r e c c i a ~untll
a singla h ~ ! a e ~ u - t p preaction,
e or other s a l e - a t e p reaction mod-
els, e s a r n h n g a p l e b r z of varlatioas of them. Exper?menkl In-
famuation now available (mainly far CO and 8, oddatbn) makes It
midens that more sapmsdcared k&eUc models am requrred. Such
nod& 3pparensly must account for Fnflcacres in t b surface pmc-
esses aua for m o r e than OM rata-dere- step. For r8aCIions
wnich exhibit oedllatory states, thcrr?iOra, soldles in whach heareti-
crl and e r p e r u n d work am Crosdy llrJred may prom fo be vaLu-
ads rn disc- w n g rival kinetic models. To this
po~Jlbllltp,one secction of rbis review was demoted to a sumy of vazi-
ous models for ttre oadatlon of CO LD an ~sorhermalm c r r t l a s s re-
2ctor. 'Emugh the appUcaUan of well-known m&ds of mybematical
arrplysls coupled *th eme~%~~emtal Wccmatiolq m e f of rbe models
A surface area of noonporous ca t al p t parude
-+ h e s masfar area of CSTR
Greek Spmbola
 169

(11 T. Rrrrrsawa, H. -
, a n d t Endoh, Kq%aaIcDgzka, s,
949 (1969).
(21 C. Nicolis and J. P o m w , C b e n . Rev.,n. 365 (19'73).
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la] P. Hugo, 4th European Symwstum on Chemcd Beactton En-
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*,
V. Hlavacek, Id. Sdaicek and X. Jaarek, J. CarA., g, 31
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V. Hkvacev and Y. Wica~,
-
h d , 29, 805 (1974).
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V. Hkoacek, Jd 3dyek. and= Kumcek, Collect. Czech
Chem. Chmmnn., 35, 2134 (1970).
V. Raxuac d U. Mare& 4th Zraobean Svmwsium 021 chepu-
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J. C. lL b e ana D. L-8, N C ‘ Z 3 . . 2,X!l (1970).
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1790 (1970).
-
J. Boralt a d 7 . Jimcek. Bid., 2 6 , L720 (1971).
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Nenv Jersey, 1962.