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The postulates of the ionic mechanism of soot formation in flames are summarized, and some of
the evidence for the ionic mechanism is reviewed. The mechanism assumes that the chemi-ion C3H3+
reacts progressively with acetylene and diacetylene and other small molecules to produce large ions
that ultimately lead to soot particles. The evidence is examined under the following headings: 1.
Ion Concentration; 2.Reaction Rates; 3. Confirmation of Ions; 4. Location of Ions in Flame; 5.Changes
with Equivalence Ratio; 6. Propensity of Ions to Grow; 7.Fuel Effects; 8. Chemical Additive Effects;
9. Electric Field Effects and Electron Injection; 10. Aesthetics. This evidence leads to an affirmative
answer to the question raised in the title.
Introduction
Many chemical mechanisms have been proposed for the
CHO+ + HzO - H30+ + CO (5)
formation of soot in flames but most of these have been H30+ + C3H2 C3H3+ + H2O (6)
rejected. The ionic mechanism has not been widely em-
braced; it is considered a competitor to free-radical Recently Eraslan and Brown2 have demonstrated, in
mechanisms, which have received the major attention. It modeling studies of fuel-rich systems, that the chemi-
seems timely to review the evidence for the ionic soot ionization reaction 2, when the CH radical is electronically
formation mechanism. We first review the postulates of excited, is responsible for ionization in very rich hydro-
this mechanism and place it in the context of the total carbon flames. They confirmed the series of reactions 3-6
process for the formation of soot. The evidence is then as important in producing C3H3+from CHO+. Reaction
discussed under 10 headings. 1 does not seem to be significant in the mechanism for
forming C3H3+in fuel-rich flames.2
Postulates There are two isomeric structures of C3H3+,a more
Figure 1 serves to place the ionic mechanism in the stable cyclic structure, cyclopropenylium, and a linear
appropriate context with the other steps involved in the structure; propargylium. Measurements of ion-molecule
formation of soot in flames. This is done to make it clear reaction rates for these two isomers near room temperature
that there are two distinct stages in the formation of soot demonstrate that reactions of the Iinear isomer are fast,
where charged species may be important: (1)formation generally equal to the Langevin rate, while the rate coef-
of the initial soqt precursor species, which lead to incipient ficients for the cyclic isomer are ~ m a l l e r . ~Eyler
? ~ and
soot; (2) the final stages where the coagulation of small soot associates5recently determined that the major low-pressure
particles is inflhenced by the charge(s) on the particles. reaction channel of linear C3H3+with C2Hzis not a con-
This is an important distinction because the two stages densation reaction, as shown in Figure 1, although they
of soot formation are frequently confused when the sig- confirmed the rapid condensation reactions of C3H3+with
nificance of ions is being discussed. Some of the early C4H2. However, in a study at a higher pressure (40-100
evidence for the ionic mechanism was certainly based on Pa), Smith and Adam# did observe rapid condensation
phenomena involving particle coagulation, and some of the reactions between C2H2 and linear C3H3+. Thus the
criticism of the ionic mechanism relates to that evidence. question of the products of reaction of the propargylium
In Figure 1, the precursor of soot is the propargylium ion with acetylene remains open. The validity of extrap-
ion, C3H3+.The source of this ion is not completely clear, olating near-room-temperature measurements to high
but it is the dominant ion in fuel-rich hydrocarbon flames. temperatures is not clear. Which isomer of C3H3+ is
-
Two possible sources of this ion are generally considered:
+
CH* C2H2 C3H3++ e-
or the chemi-ionization reaction, which dominates ion
(1)
formed in reactions such as (l),(4), and (6) is also not
known. Reactions 1,4,and 6 are exothermic for producing
either isomer, 100-150 kJ/mol for propargylium and
200-250 kJ/mol for cyclopropenylium. At flame tem-
formation in stoichiometric and fuel-lean flames peratures the two isomers should be in equilibrium. For
CH + 0 -. CHO+ + e- (2)
(1) Calcote, H. F. In Zon-Molecule Reactions; Franklin, J. L.,Ed.;
-
followed by several reactions paths to produce' C3H3+,e.g.
CHO+ + CH2 CH3+ + CO
Plenum: New York, 1972; Vol. 2, p 673.
(2) Eraslan, A. N.; Brown, R. C. submitted for publication in Combust.
and/or
CH3+ + C2H2 - C3H3' + H2
(3)
(4)
Flame.
(3) Eyler, J. R. In The Chemistry of Combustion Processes; Sloane,
T. M., Ed.; Advances in Chemistry Series 249, American Chemical So-
ciety: Washington, DC, 1984; p 49.
(4) Smyth, K. C.; Lias,S. C.; Ausloos, P. Combust. Sci. Technol. 1982,
28, 147.
( 5 ) Ozturk, F.; Baykut, G.; Aoini, M.; Eyler, J. R. J. Phys. Chem. 1987,
'Presented at t h e Symposium on Advances in Soot Chemistry, 91, 4360.
194th National Meeting of the American Chemical Society, New (6) Smith, D.; Adams, N. G. Znt. J. Mass Spectrom. Zon Processes
Orleans, LA, August 30-September 4, 1987. 1987, 76,307.
A--\
,".........
1.
0 5
TIME, m s
10
P I 1 1 I I I I I I I I I1~2000
Y
la00
w
3
1600 2
a
Y
a
1400
+
1200
ClH5+ -CPC-E-CX-
J
M,
-
CgH7+ (10) in the final steps of the process, Figure 1, of coagulation
and agglomeration.
CgH7+ + C2H2
-
CllHg+ (11) In this paper we review the evidence for the sequence
of reactions starting with C3H3+and proceeding through
CgH7+ + C4H2 C13Hg' (12)
-
what is termed in Figure 1as "incipient soot ions". This
set of reactions has been labeled "the ionic mechanism".
C13H9+ + C4H2
-
C17Hll+ (13)
Evidence
C17Hll+ + C4H2 + CZHZ
-
C19Hll+ (14)
1. Ion Concentration. The most frequently raised
C17Hll+ + C2H2 C19Hll+ + HZ (15) criticism of the ionic mechanism of soot formation has been
that the concentration of ions is too small to play a major
Major features of this mechanism are the large rate role in soot formation. Ion concentrations have been
coefficients for ion-molecule reactions7+' and the ease with measured by AeroChem13J4and Delfau and associates15J6
which ions Thus the formation of cyclic in low-pressure acetylene/oxygen flames. Many people
structures does not represent a significant energy barrier have contributed to our understanding of a premixed,
as it does for free-radical mechanisms. sooting, acetylene/oxygen flame on a flat-flame burner at
In addition to recombination with positive ions, some 2.7 kPa, an equivalence ratio of 3.0, and an unburned gas
of the electrons produced in reaction 2 produce negative flow velocity of 50 cm/s. This has come to be known as
ions by electron attachment to large molecules; these re- the standard flame. Ion concentrations measured in this
actions are favored by low temperature and increasing flame are shown in Figure 2 along with neutral soot con-
molecular weight. As the positive ions grow larger, their centrations, charged soot concentrations, and the flame
recombination rate coefficients for reaction with electrons temperature. The ion concentration in this flame is suf-
or negative ions increase, thus removing the positive ions
(12)Calcote, H. F. Combust. Flame 1981,42, 215.
(7)Bowers, M. T., Ed. Gas Phase Zon Chemistry; Academic: New (13)Calcote, H. F.; Keil, D. G. Combust. Flame, in press.
York, 1979; Vol. 1 and 2. (14)Keil, D. G.; Gill, R. J.; Olson, D. B.; Calcote, H. F. Twentieth
(8)Auslm, P., Ed. Kinetics of Zon-MoleculeReactions; Plenum: New Symposium (International) on Combustion; The Combustion Institute:
York, 1979. Pittsburgh, PA, 1985;p 1129.
(9)Lias, G. L.; Ausloos, P. Zon-Molecule Reactions, Their Role in (15)Delfau, J. L.; Michaud, P.; Barassin, A. Combust. Sci. Technol.
Radiation Chemistry; American Chemical Society: Washington, DC, 1979,20,165.
1975. (16)Michaud, P.; Delfau, J. L.; Barassin, A. Eighteenth Symposium
(10)Talrose, V. L.; Vinogradov, P. S.; Larin, I. K. In Gas Phase Zon (Znternutional) on Combustion; The Combustion Institute: Pittsburgh,
Chemistry; Bowers, M. T., Ed., Academic: New York, 1979;Vol. 1,p 305. PA, 1981;p 443.
(11)Aueloos, P.; Lias, S. G. In Zon-Molecule Reactions; Franklin, J. (17)Howard, J. B.; Wersborg, B. L.; Williams, G. C. Faraday Symp.
L., Ed.; Plenum: New York, 1972;Vol. 2,p 707. Chem. SOC. 1973,7, 109.
496 Energy & Fuels, Vol. 2, No. 4, 1988 Calcote et al.
ficient to account for the formation of the observed soot.
Similar measurements are not generally available in other NEUTRAL S P E C I E S
CHARGED SPECIES
flames.
25 /
The magnitude of the ion concentration may, in fact,
not be relevant.18 Under conditions where the ions and
soot particles overlap in the same region of the reacting
system, the important question has more to do with re-
action rates than with concentrations. In this situation,
in which the observed ion concentration is smaller than
the soot concentration, the rate of ion recombination must
be large compared to the rate of ion formation.
2. Reaction Rates. Ion-molecule reaction rate coef-
ficients are generally several orders of magnitude greater
than those of neutral species, which, of course, means that lot
the ion concentrations need not be as great as the neutral
concentrations to generate a product at the same rate.
Ion-molecule rate coefficients for observed flame ions have
been measured only near ambient t e m p e r a t u r e ~ . ~The
J~
Langevin theory,"pZ1 which does not predict a temperature 0 1 2 3 4 5 6 7
D I S T A N C E A B O V E BURNER. c m
dependence for ions reacting with nonpolar molecules, has
been well tested at ambient temperatures and is generally Figure 3. Neutral soot particle and charged soot particle diam-
consistent with experiments. It should be recognized, eters in same acetylene/oxygen flame as Figure 2: HWW, ref 17;
BHW, ref 32; H, ref 33 and 34; PH, ref 35. Unless noted, mean
however, that the Langevin theory accounts only for the diameters are number means. Values for ions were taken from
rate of production of an ion-molecule complex and not for ref 14.
how it breaks up;2w22thus, at higher temperatures the
dominant dissociation paths may be different from those particles, iO'4-iO'6 particles/ (cm3 s ) . ~ O ~ ~ '
at room temperature, leading to a smaller rate of increase Figure 2 also shows evidence that the rates of ion-
in ion-molecule size than indicated by simple application molecule reactions are sufficiently rapid in flames to ac-
of Langevin theory. Thus room-temperature rate coeffi- count for soot formation; as the ion concentration decays
cients must be used with caution at flame temperatures. by recombination, the soot concentration increases. The
Evidence that ion-molecule reactions are rapid at flame rates of ion decay and soot particle increase are comparable
temperatures comes from measurements of ionization in within the accuracy of the data. We note, however, that
premixed nonsooting hydrocarbon/oxygen or hydro- soot particles were identified17only as those that could be
carbon/air flames.' The large number of different ions all detected by using an electron microscope; i.e., their diam-
occur nearly at the same position in the flame.' The ac- eter exceeded 1.5 nm.
cepted explanation is that the charge of the original che- Several available sets of data on neutral soot particle
mi-ion, CHO+, is transferred to neutral species via ion- diameters and positively charged soot particle diameters
molecule reactions.l.23 These ion-molecule reactions must are presented in Figure 3 for the standard CzH2/OZflame.
be very rapid for this to occur. No alternative mechanism These data have previously presented a dilemma; the
has been proposed. These reactions have, in fact, been neutral particles appear to grow faster than the charged
used to identify the neutral species p r e ~ e n t . ~ ~ * ~ ~ particles, but in the early part of the flame, the charged
Ion concentrations in atmospheric pressure flames are particles have a larger diameter than the neutrals. This
t y p i d y 10'o-1012ions/cm3.'* Typical rate constants for observation seems to relate more to particle growth and
dissociative recombination are about cm3/s.'J0 Be- thermal ionization of soot particles than to soot nucleation;
cause of the rapid rate of ion recombination, the rates of nevertheless, the phenomenon occurs in the flame at just
ion formation must be relatively high to maintain the the position where the initial ion concentration is falling
observed concentration^.^^ Rates of chemi-ion formation and the concentrations of neutral and charged particles
in atmospheric pressure flames have been reported to be are increasing. Previous calculations'2*36 (see, however, ref
10'3-10'7 ions/(cm3 It is interesting to note that
s).28929
34 and 36) attributed the appearance of charged soot
this is similar to the rates reported for nucleation of soot particles at about 2 cm downstream from the burner to
thermal ionization of the neutral particles. The assump-
tion was made that the neutral particles were produced
(18) Calcote, H. F. In Soot in Combustion Systems and Its Toxic first and then thermally ionized to approach equilibrium.
Properties; Lahaye, J., Prado, G., Us.; Plenum: New York, 1983; p 197.
(19) Anicich, V. G.; Blake, G. A.; Kim, J. K.; McEwan, J. M.; Huntress, This assumption is difficult to rationalize if the concen-
W. T., Jr. J.Phys. Chem. 1984,88,4608. tration of charged particles exceeds the concentration of
(20) Patrick, R.;Golden, D. M. J. Chem. Phys. 1985, 82, 75. neutral particles at small distances (Figure 3) where the
(21) Meot-Ner, M. In Gas Phase Ion Chemistry; Bowers, M. T., Ed.;
Academic: New York, 1979, Vol. 1, Ch. 6.
(22) Chang, J. S.;Golden, D. M. J. Am. Chem. SOC.1981, 103, 496.
(23) Calcote, H. F.;Miller, W. J. In Reactions Under Plasma Condi- (30) Harris, S.J. Combust. Flame 1986, 66, 211.
tions; Venugopalan, M., Ed.; Wiley: New York, 1971; Vol. 11, p 327. (31) Haynes, B. S.;Wagner, H. G.Prog. Energy Combust. Sci. 1981,
(24) Goodings, J. M.; Tanner, S. D.; Bohme, D. K. Can. J. Chem. 1982, 7, 229.
60, 2766. (32) Bonne, U.;Homann, K. H.; Wagner, H. G. Tenth Symposium
(25) Bohme, D. K.;Goodings, J. M.; Ng, E. Int. J.Mass Spectrom. Ion (International) on Combustion;The Combustion Institute Pittsburgh,
Phys. 1977,24, 355. PA, 1965; p 503.
(26) MacLatchy, C. S. Combust. Flame 1979, 36, 171. (33) Homann, K. H.Ber. Bunsen-Ges. Phys. Chem. 1979, 83, 738.
(27) Calcote, H. F. In Fundamental Studies of Ions and Plasmas; (34) Homann, K.H.; Stroefer, E. In Soot in Combustion S y s t e m and
AGARD Conference Proceedings No. 8; NATO: Paris, France, 1965; Vol. Its Toxic Properties; Lahaye, J., Prado, G., Eds.; Plenum: New York,
1. 1983; p 217.
(28) Peeters, J.; Vinckier, C.; Van Tiggelen, A. Orid. Combust. Reu. (35) Prado, G.P.;Howard, J. B. In Evaporation-Combustion of Fuels;
1969, 4, 93. Zung, J. T. Ed.; Advances in Chemistry Series 166; American Chemical
(29) Lawton, J.; Weinberg, F. J. Electrical Aspects of Combustion; Society: Washington, DC, 1978; p 153.
Clarendon: Oxford, England, 1969. (36) Howard, J. B.; Prado, G. P. Combust. Sci. Technol. 1980,22,189.
Ionic Mechanism of Soot Formation Energy & Fuels, Vol. 2, No. 4, 1988 497
k+ = ad2 ( 4amek2F'
h3 ) X
Y
2000
J 2100 g
1500 2 1000 24
1700
w
U
1500
1000
z 1300 2
500
i ‘qH2
w
:
0
1Ol2
/1 PCAH
, IONS
108
E I
I
I
-4 -2 0 2 4 6
-1 0 1 2 3 4
FUEL AIR
FUEL AIR
DISTANCE FROM FUELlAlR BOUNDARY, mm
DISTANCE FROM F U E L l A l R BOUNDARY, mm
Figure 6. Profiles 15 mm above a Wolfhard Parker slot burner Figure 7. Comparison of reactant products and soot (an arbitrary
supporting an atmospheric pressure methane/air diffusion flame. scaling factor of location in a methane/air diffusion flame.
Fuel velocity = 9.7 cm/s. Air velocity = 19.4 cm/s. Temperature Data were taken from Figure 6. As in Figure 6, the dotted curves
and positive ions (concentration measured with Langmuir probe, represent the extremes based on assumed ion masses of 39 and
baaed on lo00 amu and 39 amu assumed ion mass-resulting range 1000 amu.
indicated by dotted lines) profiles were measured at AeroChem.*
Other profiles were adapted from Smyth et al.& The profile for that the limiting reaction have a very high activation en-
C4Hzrepresents experimentalprofiles at 9 mm scaled to 15 mm
by the acetylene ratio at the two heights. PCAH is a visible-la- ergy. Soot is located between the peak concentrations of
ser-induced fluorescence profile approximately scaled with a acetylenes and ions, just where expected if these were the
constant factor based on the ratio of C14HB to C8& concentrations two critical reactants as described by the ionic mechanism,
in the low-pressure flame of Figures 2 and 4. For the soot curve, and no unusual phenomena were occurring to distort the
see text. picture. This point is better shown in Figure 7, where
Further evidence of a similar nature comes from ob- relative global rates for the proposed processes are ap-
servations in diffusion flames at one atmosphere. We have proximated as products of reactant concentrations and
measured46ion concentrations in the same methanelair plotted against lateral distance in the flame for comparison
flame on which Smyth et a1.46 made a number of mea- with the observed soot profile. The flow streamlines in
surements. Our temperature profiles agree with theirs. this flame are from the air to the fuel suggesting
The data for this diffusion flame are summarized in Figure a net transport to the left in Figure 7.
6, and the rationale for the estimates of concentrations is An important question with respect to soot formation
summarized in the caption. The soot concentration profile is, “Why does inception stop?” Harris has recently sug-
was not measured by Smyth et al., but they determined gested30 that the falloff in oxygen concentration may be
the position of the soot maximum in the flame from la- responsible due to its promotion of the formation of
ser-induced ionization. Similarly, they estimated the high-energy species that are important for soot formation
concentrations of polycyclic aromatic hydrocarbons, and that disappear as the oxygen disappears; see, e.g.,
PCAH, from laser-induced fluorescence. We confirmed Figure 4. He suggested that the production of excess H
the radial location of the soot maximum by 633-nm laser atoms may be responsible for the effect. An even more
extinction measurements at a slightly higher position in obvious explanation for the termination of soot inception
the flame. We estimate from our measurements that the would be the termination of ion formation, which involves
maximum volume fraction of soot was about 5 X lo+, 0 atoms in their formation (see reaction 2) and the rapid
which, for 20-nm-diameter particles, would correspond to decrease in ion concentration (see, e.g., Figure 2). It is a
about 1O1O particles/cm3. We scaled their relative laser long-established fact that ions show a sharp peak in the
induced ionization curve to this estimate of the maximum flame front of hydrocarbon flame^.^^,^^
soot number density in Figure 5. 5. Changes with Equivalence Ratio. Dramatic
The location of soot, Figure 6, with respect to the pos- changes in ion concentrations occur in premixed flames
sible reactants is more consistent with an ionic mechanism at the threshold for soot formation (Figure 8). Small flame
than with a mechanism involving acetylene reacting with ions become large ions as the equivalence ratio is increased
a polycyclic aromatic hydrocarbon. To shift the peak through the threshold soot point. This simple observation
acetylene-PCAH rate to correspond to the location of the would be consistent with an ionic mechanism of soot
peak in the soot curve would require the involvement of formation; there are, however, complications. Why does
a third reactive species such as hydrogen atoms30*47*48 or the concentration of ions increase at higher equivalence
ratios beyond the soot threshold? This observation has,
~~ ~
in fact, been used to argue against the ionic mechanism;
(45) Calcote, H. F.; Keil, D. G., to be submitted for publication in the increase in ion concentration with equivalence ratio
Combust. Flume.
(46) Smyth, K . C.; Miller, J. H.; Dorfman, R. C.; Mallard, W. G.;
Santoro, R. J. Combust. Flame 1985,62, 157.
(47) Frenklach, M.; Clary, D. W.; Gardiner, W. C., Jr.; Stein, S. E. (48) Frenklach, M.; Warnatz, J. Combust. Sci. Technol., in press.
Twentieth Symposium (Intermtiom0 on Combustion; The Combustion (49) Calcote, H. F. Combust. Flame 1957,1, 385.
Institute: Pittsburgh, PA, 1985; p 887. (50) Wilson, H.A. Rev. Mod. Phys. 1931, 3, 156.
500 Energy & Fuelsj Vol. 2, No. 4, 1988 Calcote et al.
10.0
PI)
5
0
r
0
c
2
0
U
a
z
I-
8 1.0
z
0
0
z
0
5
3
-
I
X
4
I
Figure 8. Variation of maximum ion concentration with Figure 10. Maximum total ion concentrations as a function of
equivalence ratio in a low-pressure acetylene/oxygen flame. Total equivalence ratio: circle, maxima closest to burner; square, second
ions are Langmuir probe measurements. Profiles of individual maxima. The soot threshold is indicated by shading. C2H2(02
ions, identified by mass in amu, were measured with flame ion flames a t 2.7 kPa pressure and 50 cm/s unburned gas velocity.
sampling mass spectrometry. The ratio of total ions to the sum
of the individual currents a t 4 = 2.0, where mass 39 dominates,
provided a calibration of the mass spectrometer against the
Langmuir probe result for lighter masses. Similarly, >300 amu,
representing all heavy ion masses between 300 amu and the high
mass cutoff of the mass spectrometer, was calibrated against the
Langmuir probe at = 2.9. Shading indicates the threshold for
soot formation.
1 2 3 4
EQUIVALENCE RATIO
--
-50 E
a
I-
s4
- 25
0 1 2 3 4 5
RADIAL DISTANCE, cm
without CCI, with CCI,
I 1 I 1 I I
10' 10'0 10" 10'2
Figure 12. Effect of CC14on cation profiles and soot formation cs+ CONCENTRATION, cm-3
in a C2H2/02spherical diffusion flame: 0.53 kPa, 0.35 mol % of
CC14 added. C2H2inlet tube a t 0.0 cm. Figure adapted from Figure 14. Effect of CsCl additive concentration on soot for-
Miller.74 mation in an acetylene/oxygen diffusion flame. Figure adapted
from Bulewicz et a1.68
-
N0N S00TIN G SOOTING
simultaneously completely altered the ionic structure of
10-8 the flame (Figures 12 and 13). The ion concentrations
were measured with molecular-beam ion mass spectrom-
etry. The chlorine from the additive formed compounds
that attached electrons producing large concentrations of
negative ions, e.g.
CC14 + e- - + CC13 C1-
+ - +
2
(20)
P
C12 e- C1- C1 (21)
+ -
10-11