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Calcote - Are Ions Important in Soot Formation

Calcote - Are Ions Important in Soot Formation

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4 9 4
E n e r g y& F u e ls1 9 8 8 ,2 ,4 9 4 - 5 0 4
A reI o n sIm portanti n Soot Form ation??
H .F . C a lc o te ,*D .B . O ls o n ,a n d D. G. K e il
A eroC h em
Research Laboratories, Inc., Princeton, N ew Jersey
0 8 5 4 2
Received N ovem ber2 , 1987.
Revised M anuscript Received April 14, 1988

T h e postulates of th e ionic m echanism of soot form ation in flam es are sum m arized, an d som e of the evidencefor the ionic m echanism is reviewed. The m echanism assum esthatthe chem i-ion C3H3+ re a c ts p ro g re s s iv e ly w ith a c e ty le n e a n d d ia c e ty le n e a n d o th e r s m a ll m o le c u le st op ro d u c e la rg e io n s t h a t u ltim a te ly le a d t o s o o t p a rtic le s . T h e e v id e n c e is e x a m in e d u n d e r t h e fo llo w in g h e a d in g s :

1 .

Io n C o n c e n tra tio n ;2 . R e a c tio n R a te s ;3 . C o n firm a tio n of Io n s ;4 . L o c a tio n of Io n s in F la m e ;5 . C h a n g e s w ith E q u iv a le n c e R a tio ;6 . P ro p e n s ity of Io n st o G ro w ;7 . F u e l E ffe c ts ;8 . C h e m ic a l A d d itiv e E ffe c ts ; 9 .E le c tric F ie ld E ffe c ts a n d E le c tro n In je c tio n ;1 0 . A e s th e tic s . T h is e v id e n c e le a d s t o a n a ffirm a tiv e answ er to the question raised in the title.

In tr o d u c tio n

M any chem ical m echanism s have been proposed for th e form ation of soot in flam es b u t m ost of these have been re je c te d . T h e io n ic m e c h a n is m h a s n o t b e e n w id e ly e m - braced; it is considered

a c o m p e tito r t o

fre e -ra d ic a l m e c h a n is m s , w h ic h h a v e re c e iv e d t h e m a jo r a tte n tio n . I t seem s tim ely to review the evidence for the ionic soot form ation m echanism . W e first review th e postulates of this m echanism

and place it in the context of the total process for th e form ation of soot. T h e evidence is then discussed under1 0h e a d in g s .

P o stu la te s
Figure1 serves to place the ionic m echanism

in the a p p ro p ria te c o n te x t w ith t h e o th e r s te p s in v o lv e d in th e fo rm a tio n of so o t in fla m e s. T h is is d o n et o m ake it clear th at there are tw o distinct stages in th e form ation of soot w here charged species m ay be im portant:

(1)fo rm atio n
of t h e in itia l s o q t p re c u rs o r s p e c ie s , w h ic h le a dt o in c ip ie n t
soot; (2 ) th e fin a l s ta g e s w h e re th e c o a g u la tio n ofs m a ll s o o t
particles is inflhenced by the charge(s) on the particles.
T h i s is a n im p o r ta n t d is tin c tio n b e c a u s e t h e tw o s ta g e s
o f soot form ation are frequently confused when the sig-
n ific a n c e o f io n s is b e in g d is c u s s e d .

Som e of the early evidence for th e ionic m echanism w as certainly based on p h e n o m e n a in v o lv in g p a rtic le c o a g u la tio n , a n d s o m e of t h e criticism of th e ionic m echanism relates to th at evidence.

In Figure1 , th e precursor of soot is th e propargylium io n , C 3 H 3 + .T h e s o u rc e of th is io n is n o t c o m p le te ly c le a r, b u t it is th e dom inant ion in fuel-rich hydrocarbon flam es.

T w opossible sources of this ion are generally considered:
(1 )
o rt h e c h e m i-io n iz a tio n re a c tio n , w h ic h d o m in a te s io n
form ation in stoichiom etric and fuel-lean flam es
C H+0-. C H O ++ e-
(2 )
follow ed by severalreactions pathst o produce' C3H 3+,
e .g .
C H O ++C H 2- C H 3+ +C O
(3 )
C H 3 ++ C 2H 2- C 3H 3'
+H 2
(4)
C H *+ C 2H 2- C 3H 3++ e-
a n d /o r
'P r e s e n te d
a tthe Sym posium
on A dvances in Soot Chem istry,
1 9 4 th N a tio n a l M e e tin g o f t h e A m e ric a n C h e m ic a l S o c ie ty , N e w
O rleans, L A , A ugust 30-Septem ber
4, 1987.
0887-0624/88/2502-0494%01.5QIQ
C H O ++ H zO- H 3 0 ++ C O
(5)
H 3 0 ++ C 3H 2
C 3H 3++ H 2O
(6 )

Recently Eraslan and Brown2 have dem onstrated, in m odeling studies of fuel-rich system s, that the chem i- io n iz a tio n re a c tio n2 ,w h e n t h e C H ra d ic a l is e le c tro n ic a lly e x c ite d , is re s p o n s ib le fo r io n iz a tio n in v e ry ric h h y d ro - carbon flam es. T hey confirm ed th e series of reactions 3 -6 a s im p o rta n t in p ro d u c in g C 3 H 3 +fro m C H O + . R e a c tio n

1does not seem to be significant in th e m echanism
fo r
form ing C 3H 3+in fuel-rich flam es.2

T h e r e a r e t w o i s o m e r i c s t r u c t u r e s o f C 3 H 3 + ,a m o r e s ta b le c y c lic s tr u c tu r e , c y c lo p ro p e n y liu m , a n d a lin e a r structure; propargylium . M easurem ents of ion-m olecule re a c tio n ra te s fo r th e s e tw o isom ers near room tem perature dem onstrate th at reactions of th e Iinear isom er are fast, g e n e ra lly e q u a lt o the Langevin rate, w hile the rate coef- ficients for the cyclic isom er are ~ m a lle r.~ ? ~

E y le r a n d

associates5recently determ ined th a t th e m ajor lo w -p ressu re re a c tio n c h a n n e l of lin e a r C 3 H 3 +w ith C 2 H zis n o t a c o n - d e n s a tio n re a c tio n , a s s h o w n in F ig u re1 ,a lth o u g h th e y c o n firm e d th e ra p id c o n d e n s a tio n re a c tio n s of C 3H 3+w ith C4H 2.H ow ever,in a study at a higher pressure( 4 0 - 1 0 0 Pa),Sm ith and Adam #

did observe rapid condensation
re a c tio n s b e tw e e n
C 2 H 2 a n d
lin e a r C 3 H 3 + . T h u s t h e

q u e s tio n of th e p ro d u c ts of re a c tio n of th e p ro p a rg y liu m io n w ith a c e ty le n e re m a in s o p e n . T h e v a lid ity of e x tra p - o la tin g n e a r-ro o m -te m p e ra tu re

m easurem ents
to high
tem peratures is not clear.
W hich isomer ofC 3H 3+i s
form ed in reactions such as( l ) ,(4 ),a n d(6 ) is a ls o n o t
know n.R e a c tio n s1,4,a n d 6 a re e x o th e rm ic fo r p ro d u c in g
either isomer,1 0 0 -1 5 0
k J /m o l fo r p ro p a rg y liu m
a n d
200-250
k J /m o l fo r c y c lo p ro p e n y liu m .
A t flam e te m -
p e ra tu re s t h e tw o is o m e rs s h o u ld b e in e q u ilib riu m .F o r
(1 ) C a lc o te ,H. F.I n Z o n -M o le c u le R e a c tio n s ; F ra n k lin ,J .L . , E d .;
P le n u m :
New York, 1972;V o l.2 ,p 6 7 3 .
( 2 ) E r a s l a n , A . N .; B r o w n ,R .C . s u b m itte d fo r p u b lic a tio n in C o m b u st.
F la m e .
(3) Eyler,J .R . In The C h em istryo f Com bustion Processes; Sloane,
T .M ., Ed.; A dvancesi n C hem istry Series 249,A m erican Chem icalS o -
c ie ty : W a s h in g to n , D C ,1 9 8 4 ; p 4 9 .
(4) Sm yth,K . C.;L i a s ,S .C .; A usloos,P . C om bust.Sci. T echnol. 1982,
28,1 4 7 .
(5 )O zturk,F .; B aykut, G .; A oini,M .; E yler,J .R .J .P h ys. C hem . 1987,
9 1 ,4 3 6 0 .
(6) S m ith , D .;A dam s, N . G . Znt.J . M ass Spectrom . Zon Processes
1 9 8 7 ,76,3 0 7 .
0
1988 A m e ric a n C h e m ic a l S o c ie tv
Ionic M echanism
o fS o o tF o rm a tio n
,".....
....1 .
A--\
E n e r g y& F u e ls , V o l.2 ,N o.4 ,1 9 8 8
4 9 5
T IM E ,
m s
0
5
10
P
I 1
1
I
I
I
I
I
I
I
I
I1 ~ 2 0 0 0
C lH 5 +
-C P C -E -C X -
J
M ,
F ig u r e1 .
F ro m
c h e m i-io n s t o s o o t.
exam ple,a t 2000K th e concentration of th e propargylium
io n s h o u ld b e = 0 .2 %

of th et o t a l C 3 H 3 +c o n c e n tra tio n . T h e rate of isom erization of C3H 3+at flam e tem peratures is clearly im portant to th e establishm ent of th e postulated m echanism .

In th e ionic soot form ation m echanism , th e precursor ions react w ith neutral species,e.g., acetylenes,t op r o d u c e la rg e r io n s :

(7 )
(8)
(9)
These ions then sequentiallyadd sm allneutral species,e.g.,
acetylenes, to produce increasingly larger ions, e.g.:
C 7H 5++C 2H z- C gH 7+
(1 0 )
C gH 7++C 2H 2- C llH g +
(1 1 )
C g H 7 ++ C 4 H 2- C 13H g'
(1 2 )
C 13H 9++ C 4H 2-
C 1 7 H ll+
(1 3 )
C 1 7 H ll++ C 4H 2-
C 1 9 H ll+
+
C Z H Z
(1 4 )
C 1 7 H ll++ C 2H 2-
C 1 9 H ll+
+
H Z
(1 5 )
M ajor features of this m echanism
are the large rate
c o e ffic ie n ts fo r io n -m o le c u le reactions7+'
and th e ease w ith
w h ic h io n s

T hus th e form ation of cyclic structures does n o t represent a significant energy barrier as it does for free-radical m echanism s.

I n a d d itio n to re c o m b in a tio n w ith p o s itiv e io n s , s o m e of th e e le c tro n s p ro d u c e d in re a c tio n2p ro d u c e n e g a tiv e ions by electron attachm ent to large m olecules;these re- actions are favored by low tem perature and increasing m o le c u la r w e ig h t. A s t h e p o s itiv e io n s g ro w la rg e r, th e ir re c o m b in a tio n r a te c o e ffic ie n ts fo r re a c tio n w ith e le c tro n s o r n e g a tiv e io n s in c re a s e , t h u s re m o v in g t h e p o s itiv e io n s

C 3H 3++ C 2H 2
-w
C 5H 3++ H 2
C 3H 3++C 4H 2- C 7H 5'
C 3H 3++C 6H 2
+
C gH S+
(7)B ow ers, M . T ., E d . G as P h a se Zon C h em istry ; A cadem ic:
N ew
(8)A u s l m , P .,E d. K in e tic so f Z o n -M o le c u le R e a c tio n s ; P le n u m : N e w
Y o r k ,1 9 7 9 ; V o l.1 a n d2 .
Y o rk ,1 9 7 9 .
(9)Lias,G . L.; Ausloos,P . Zon-M olecule Reactions, Their Role in
R a d ia tio n
C h e m is try ; A m e ric a n C h e m ic a l S o c ie ty :
W a s h in g to n , D C ,
1975.
(10)Talrose, V. L.; V inogradov,P . S .; Larin,I . K . In G as P hase Zon
C hem istry; B ow ers, M . T ., E d ., A cadem ic: N ew Y ork,1 9 7 9 ; V ol.1 ,p305.
(11)A ueloos, P.; L ias,S .G . In Zon-M olecule R eactions; Franklin,J .
L ., E d .; P le n u m :
N e w Y o r k ,1 9 7 2 ; V o l.2,p 7 0 7 .
Y
l a 0 0
w3
1 6 0 0
2aY
a
1400
+
1200
0'
I
*
I
I
0
1
2
3
4
5
D IS T A N C E
A B O V E
B U R N E R ,c m
F ig u r e2 .C o m p a riso n of to ta l io n c o n c e n tra tio n a n ds o o t c o n -
centration profiles in low
p r e s s u r e(2 .6 7k P a ) ,
=
3 .0a c e ty -

le n e /o x y g e n fla m e(5 0 cm /s unburned gas velocity). T he tem - perature,ion profiles,and tim e axis are from AeroChem .14 T he soot profiles are from H ow ard e t a l."

and have been reduced b

a n d fo rm in g e ith e r la rg e n e u tra l m o le c u le s o r s m a ll n e u tra l s o o t p a rtic le s . T h e r e is , in fa c t, n o d is tin c tio n b e tw e e n a la rg e m o le c u le a n d a s m a ll s o o t p a rtic le .1 2

T h e sm all n e u tra l p a rtic le s c o n tin u e to g ro w , a n d a s th e y b e c o m e la rg e r, th e ir w o rk fu n c tio n is a s s u m e d to a p p ro a c h t h a t of b u lk g ra p h ite .

A ts u ffic ie n tly h ig h te m p e ra tu re s , th e s e

p a rtic le s b e c o m e th e rm a lly io n iz e d a n d p la y a m a jo r ro le in the final steps of the process, Figure 1,of coagulation a n d a g g lo m e ra tio n .

In this paper we review the evidence for th e sequence o f r e a c t i o n s s t a r t i n g w i t h C 3 H 3 +a n d p r o c e e d i n g t h r o u g h w h a t is te rm e d in F ig u re1as "incipient sootions". This s e t of re a c tio n s h a s b e e n la b e le d " th e io n ic m e c h a n is m " .

5 0 %s o the charged soot and ion concentrations agree a t 3 .5 cm .E
E v id e n c e
1 .Io nC o n c e n tra tio n .

T he m ost frequently raised c ritic is m of th e io n ic m e c h a n is m of s o o t fo rm a tio n h a s b e e n t h a t t h e c o n c e n tra tio n of io n s is to o s m a ll t o p la y a m a jo r ro le in so o t fo rm a tio n .

Ion concentrations have been
m easured by A eroChem 13J4and D elfau and associates15J6
in lo w -p re s s u re a c e ty le n e /o x y g e n fla m e s .

M a n y p e o p le h a v e c o n trib u te d to o u r u n d e rs ta n d in g of a p re m ix e d , s o o tin g , a c e ty le n e /o x y g e n fla m e o n a fla t-fla m e b u rn e r a t

2 .7 kPa, an equivalence ratio of 3 .0 , and an unburned gas
flo w v e lo c ity of5 0 cm /s.

This has com e to be know n as th e s ta n d a rd fla m e . Io n c o n c e n tra tio n s m e a su re d in th is flam e are show n in Figure2a lo n g w ith n e u tr a l s o o t c o n - centrations, charged soot concentrations, and th e flam e te m p e ra tu re . T h e io n c o n c e n tra tio n in th is fla m e is su f-

(12)C a lc o te , H .F . C o m b u s t. F la m e1 9 8 1 ,4 2 , 215.
(13)C alcote, H .F . ; K eil, D .G . C om bust. F lam e, in press.
(14)K e il, D . G .; G ill,R . J .; O lso n , D . B .; C a lc o te , H .F . T w e n tie th
S y m p o siu m (In te rn a tio n a l)o n C o m b u stio n ; T h e C o m b u stio n In s titu te :
P itts b u rg h , P A ,1 9 8 5 ;p 1 1 2 9 .
(15)D elfau,J . L.; M ichaud, P.; B arassin, A. Com bust. Sci. Technol.
1979,20,1 6 5 .
(16)M ichaud,P .; Delfau,J . L.; Barassin,A.Eighteenth Sym posium
(Z n te rn u tio n a l)o n C o m b u stio n ; T h e C o m b u stio n In s titu te : P itts b u rg h ,
PA ,1981;p 443.
(17)H o w a rd ,J . B .; W e rs b o rg ,B . L .; W illia m s ,G . C . F a r a d a y S y m p .
C hem .SO C .
1973,7 ,1 0 9 .
4 9 6
E n e r g y&F u e ls , V o l.2 ,N o.4 ,1 9 8 8

ficient to account for th e form ation of th e observed soot. S im ila r m e a s u re m e n ts a r e n o t g e n e ra lly a v a ila b le in o th e r flam es.

T h e m a g n itu d e of t h e io n c o n c e n tra tio n m a y , in fa c t,
n o t b e re le v a n t.1 8

U n d e r c o n d itio n s w h e re t h e io n s a n d soot particles overlap in th e sam e region of th e reacting system , the im portant question has m ore to do w ith re- a c tio n ra te s th a n w ith c o n c e n tra tio n s . I n th is s itu a tio n , in w h ic h t h e o b s e rv e d io n c o n c e n tra tio n is s m a lle r t h a n th e s o o t c o n c e n tra tio n , t h e r a te of io n re c o m b in a tio n m u s t be large com pared to the rate of ion form ation.

2 .
R e a c tio n R ates. Ion-m olecule reaction rate coef-

fic ie n ts a re g e n e ra lly s e v e ra l o rd e rs of m a g n itu d e g re a te r than those of neutral species,w hich, of course,m eans th at t h e io n c o n c e n tra tio n s n e e d n o t b ea s greata s the neutral concentrations to generate a product at the sam e rate. Io n -m o le c u le ra te c o e ffic ie n ts fo r o b s e rv e d fla m e io n s h a v e been m easured only near am bient te m p e r a tu r e ~ .~ J ~

T he

L angevin theory,"pZ1 w hich does not predict a tem perature d e p e n d e n c e fo r io n s re a c tin g w ith n o n p o la r m o le c u le s , h a s b e e n w ell te s te d a t a m b ie n t te m p e ra tu re s a n d is g e n e ra lly c o n s is te n t w ith e x p e rim e n ts .

I t should be recognized,

how ever,th at th e Langevin theory accounts only for th e r a te of p ro d u c tio n of a n io n -m o le c u le c o m p le x a n d n o t fo r h o w i t b r e a k s u p ; 2 w 2 2 t h u s , a t h i g h e r t e m p e r a t u r e s t h e d o m in a n t d isso c ia tio n p a th s m a y b e d iffe re n t fro m th o s e a t ro o m te m p e ra tu re , le a d in gt o a sm aller rate of increase in io n -m o le c u le s iz e t h a n in d ic a te d b y s im p le a p p lic a tio n of L angevin theory. T hus room -tem perature rate coeffi- c ie n ts m u s t b e u s e d w ith c a u tio n a t fla m e te m p e ra tu re s .

E v id e n c e t h a t io n -m o le c u le re a c tio n s a r e ra p id a t fla m e tem peratures com es from m easurem ents of ionization in p re m ix e d

n o n s o o tin g
h y d ro c a rb o n /o x y g e n
o r
h y d ro -
c a rb o n /a ir fla m e s.' T h e la rg e n u m b e r of d iffe re n t io n s a ll
occur nearly a t th e sam e position in th e flam e.'

T he ac- cepted explanation is th at th e charge of th e original che- m i-io n ,C H O + ,is transferred to neutral species via ion- m o le c u le re a c tio n s .l.2 3 T h e s e io n -m o le c u le r e a c tio n s m u s t be very rapid for this to occur.N o a lte rn a tiv e m e c h a n is m has been proposed.

T hese reactions have, in fact, been
used to identify th e neutral species p r e ~ e n t . ~ ~ * ~ ~
Ion concentrations in atm ospheric pressure flam es are
ty p id y1 0 'o -1 0 1 2 io n s /c m 3 .'*
T y p ic a l ra te c o n s ta n ts fo r
d is s o c ia tiv e re c o m b in a tio n a r e a b o u t
cm 3/s.'J0
B e-

cause of the rapid rate of ion recom bination, the rates of io n fo rm a tio n m u s t b e re la tiv e ly h ig h t o m a in ta in th e o b s e rv e dc o n c e n tra tio n ^ .^ ^

R ates of chem i-ion form ation
in atm ospheric pressure flam es have been reported to be
1 0 '3 -1 0 '7io n s/(cm 3
s ).2 8 9 2 9
I t is interesting to note th a t
th is is sim ilar to th e rates rep o rted for nucleation of soot
C a lc o te e ta l.
(18) C alcote, H .F . InS o o tin C o m b u s tio n S y s te m s a n d I t s T o x ic
P r o p e r tie s ;Lahaye,J ., Prado,G .,Us.; Plenum : N ew York, 1983;p 197.
(19) A nicich, V . G .;B lake,G .A .; K im ,J .K .; M cE w an,J .M .; H untress,
W . T ., J r .J.P h ys. C hem . 1 9 8 4 ,8 8 ,4 6 0 8 .
(20) Patrick,R . ; G o ld e n , D .M .J.C h e m . P h y s . 1 9 8 5 ,8 2 , 7 5 .
(21) M eot-N er,M .In GasPhase Ion Chem istry; Bow ers,M . T .,E d.;
A c a d e m ic : N e w Y o r k , 1 9 7 9 , V o l.1 , C h . 6 .
(22) C hang,J.S . ;G o ld e n , D .M .J.A m . C h em .S O C .1 9 8 1 ,1 0 3 , 4 9 6 .
(2 3 ) C alcote, H .F . ; M iller, W .J . In R e a c tio n s U n d e r P la s m a C o n d i-
tio n s ; V e n u g o p a la n , M ., E d .; W ile y :
N ew Y ork, 1971; V ol. 11, p 327.
(24) G oodings,J. M .; T a n n e r ,S . D .; B o h m e , D .K .C a n .J. C h e m . 1 9 8 2 ,
6 0 ,2 7 6 6 .
(25) B ohm e,D .K.;G o o d in g s ,J . M .; N g , E .In t.J.Mass Spectrom .Ion
P h ys.1 9 7 7 ,2 4 , 3 5 5 .
(26) M acL atchy,C .S . C o m b u s t. F la m e 1979,36, 171.
(2 7 ) C a lc o te , H .F .I nF u n d a m e n ta l S tu d ie s
ofI o n s and Plasm as;
AG ARD Conference ProceedingsN o.8 ; N A TO : Paris,France,1 9 6 5 ; Vol.
1 .
(28) P eeters,J.; V inckier, C .; V an T iggelen ,A .O rid. C om bust.R eu.
1969, 4, 93.
(2 9 ) L a w to n ,J . ;W e in b e r g ,F .J .E le c tr ic a l A s p e c tso f C o m b u s tio n ;
C la r e n d o n : O x fo r d , E n g la n d , 1 9 6 9 .
N E U T R A L
S P E C IE S
C H A R G E D
S P E C IE S
2 5
/
lo t
0
1
2
3
4
5
6
7
D IS T A N C E
A B O V E
B U R N E R .
c m
F ig u r e3 .N e u tra l s o o t p a rtic le a n d c h a rg e ds o o t p a rtic le d ia m -
etersi n sam e acetylene/oxygen flam ea s Figure2 : HW W , ref1 7 ;
BHW ,ref3 2 ;H , ref3 3 and3 4 ;PH ,re f 3 5 . U nless n o ted , m ean
d ia m e te rs a re num ber m eans. V alues for ions w ere tak en fro m
re f1 4 .
p a rtic le s ,iO '4 -iO '6
particles/ (cm 3s ).~ O ~ ~ '

Figure2 also show s evidence that the rates of ion- m o le c u le re a c tio n s a r e s u ffic ie n tly ra p id in fla m e s t o a c - c o u n t fo r s o o t fo rm a tio n ;a s th e io n c o n c e n tra tio n d e c a y s by recom bination, the soot concentration increases. T he rates of ion decay and soot particle increase are com parable w ithin the accuracy of the data. W e note, how ever,that s o o t p a rtic le s w e re id e n tifie d 1 7 o n ly a s th o s e t h a t c o u ld b e d e te c te d b y u s in g a n e le c tro n m ic ro s c o p e ; i.e ., th e ir d ia m - eter exceeded1 .5 nm .

Several available sets of data on neutral soot particle d ia m e te rs a n d p o s itiv e ly c h a rg e d s o o t p a rtic le d ia m e te rs a re p re s e n te d in F ig u re3for th e standard C zH 2/O Zflam e. These data have previously presented

a dilem m a; th e neutral particles appear to grow faster than the charged particles, b u t in th e early p art of th e flam e, th e charged p a rtic le s h a v e a la rg e r d ia m e te r th a n th e n e u tra ls . T h is observation seem s to relate m ore to particle grow th and th e rm a l io n iz a tio n of s o o t p a rtic le s th a nt os o o t n u c le a tio n ; nevertheless, th e phenom enon occurs in th e flam e a t ju st t h e p o s itio n w h e re t h e in itia l io n c o n c e n tra tio n is fa llin g a n d th e c o n c e n tra tio n s of n e u tra l a n d c h a rg e d p a rtic le s a r e in c re a s in g . P re v io u s c a lc u la tio n s '2 * 3 6

(see,how ever, ref
3 4a n d 3 6 ) attributed the appearance of charged soot

p a rtic le s a t a b o u t2cm dow nstream from the burner to therm al ionization of th e neutral particles. T h e assum p- tion w as m ade that the neutral particles w ere produced firs t a n d th e n th e rm a lly io n iz e d to a p p ro a c h e q u ilib riu m . T h is a s s u m p tio n is d iffic u lt to ra tio n a liz e if th e c o n c e n - tra tio n of c h a rg e d p a rtic le s e x c e e d s th e c o n c e n tra tio no f n e u tra l p a rtic le s a t sm a ll d is ta n c e s (F ig u re3 ) w h e re th e

(30) H arris,S.J .C o m b u s t. F la m e 1986,6 6 ,211.
(31) H aynes, B .S . ; W agner,H .G.P r o g .Energy Com bust.Sci. 1981,
7 ,2 2 9 .
(32) B onne,U.; H om ann,K . H .; W agner, H . G .Tenth Sym posium
(I n te r n a tio n a l) o n C o m b u s tio n ;T h e C om bustion In stitu te
P ittsb u r g h ,
PA, 1965;p 503.
(33) H om ann,K.H.B er. B u n sen -G es. P h ys. C h em . 1979, 83, 738.
(34) H om ann,K.H .; S tr o e fe r , E . InS o o tin C o m b u s tio n S y s t e m a n d
I t s Toxic P roperties;Lahaye,J ., Prado,G ., Eds.;Plenum : New York,
1983;p 217.

(35) P rado,G.P.;H ow ard,J . B . In E v a p o r a tio n -C o m b u s tio no f F u e ls ; Z u n g ,J . T . E d .; A d v a n c e s in C h e m is tr y S e r ie s 1 6 6 ; A m e r ic a n C h e m ic a l S o c ie ty :

W ashington, D C , 1978; p 153.
(3 6 ) H o w a r d ,J . B .; P r a d o ,G . P . C o m b u s t. S c i. T e c h n o l. 1 9 8 0 ,2 2 ,1 8 9 .

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