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494 Energy & Fuels 1988,2, 494-504

Are Ions Important in Soot Formation??


H. F. Calcote,* D. B. Olson, and D. G. Keil
AeroChem Research Laboratories, Inc., Princeton, New Jersey 08542
Received November 2, 1987. Revised Manuscript Received April 14, 1988

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.

0887-0624/88/2502-0494%01.5QIQ0 1988 American Chemical Societv


Ionic Mechanism of Soot Formation Energy & Fuels, Vol. 2, No. 4, 1988 495

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,

Figure 1. From chemi-ions to soot.

example, at 2000 K the concentration of the propargylium


ion should be =0.2% of the total C3H3+concentration. The 0'
I * I I
rate of isomerization of C3H3+at flame temperatures is 0 1 2 3 4 5
clearly important to the establishment of the postulated DISTANCE ABOVE BURNER, c m

mechanism. Figure 2. Comparison of total ion concentration and soot con-


In the ionic soot formation mechanism, the precursor centration profiles in low pressure (2.67 kPa), = 3.0 acety-
lene/oxygen flame (50 cm/s unburned gas velocity). The tem-
ions react with neutral species, e.g., acetylenes, to produce perature, ion profiles, and time axis are from AeroChem.14 The
larger ions: soot profiles are from Howard et al." and have been reduced b
50% so the charged soot and ion concentrations agree at 3.5 cm.E
C3H3+ + C2H2 -w C5H3+ + H2
C3H3+ + C4H2 - C7H5'
(7)
(8)
and forming either large neutral molecules or small neutral
soot particles. There is, in fact, no distinction between a
large molecule and a small soot particle.12 The small
C3H3+ + C6H2 + CgHS+ (9) neutral particles continue to grow, and as they become
These ions then sequentially add small neutral species, e.g., larger, their work function is assumed to approach that of
acetylenes, to produce increasingly larger ions, e.g.: bulk graphite. At sufficiently high temperatures, these
C7H5+ + C2Hz - particles become thermally ionized and play a major role

-
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

particle diameters are the smallest; the extent of thermal CO


ionization is very sensitive to particle diameter.12 The rate H,

of thermal ionization is also sensitive to particle diameter, C2H2


H,O -
so that for the small neutral particles the rate of ionization co2
is slow compared to the experimentally observed rate. The
rate law for charging particles with an initial charge ( z -
1)e is defined by
dN$/dt = k5N6-l
where the rate coefficient, k+, is given by the modified
Richardson equation for small p a r t i c l e ~ ~ ~ , ~ * :

k+ = ad2 ( 4amek2F'
h3 ) X

Here d is the particle diameter, meis the electron mass,


k is Boltzmann's constant, T is the absolute temperature,
h is Planck's constant, e is the electron charge, 6 is the
work function of the material, and C, the electrical capacity
of the particle, is given by 27rcod for a spherical particle
(to is the dielectric constant of free space).
On the basis of neutral soot concentrations, Figure 2,
and diameters, Figure 3, we calculate a rate of ionization
at 2.25 cm above the burner of 2 X 10" charged parti-
cles/(cm3 s). From the slope of the "charged-soot" curve
at this point, Figure 2, we obtain a greater rate of 6 X 10"
charged particles/ (cm3s). Similar considerations show that
between 2.5 and 3.0 cm, however, the calculated rate ex-
ceeds the observed rate and equilibrium controls the
concentrations. Assuming the data are sufficiently accu-
rate for these calculations to be meaningful, we can con- 5
0 5 10 15 20 25
clude that the rate of thermal ionization of neutral particles DISTANCE, m m
early in this flame is too small to account for the observed Figure 4. Concentration profiles of selected neutral and ionic
rate of charged particle appearance, leading to the con- species. The OH profile was adapted from ref 42. Neutral profiles
clusion that ion-neutral equilibrium early in the soot zone were calculated from published mole fraction profiles. CzHzand
is approached from the direction of excess charged par- O? profiles were adapted from Figure 11 in ref 40 and are in-
ticles. This is further evidence that charged species are distinguishablefrom those of Delfau and V ~ v e l l e(DV).
~ ~ Other
profiles adapted from Bittner and Howard&(BH) included C10H8,
involved in the formation of soot. It also demonstrates that Cl2H8,and CI4HB.Profiles of CO, Hz, COz, HzO, C3H3,C3H4,and
the large ions are not derived from neutral soot particles. C&15were adapted from DV. Profdes for C4Hzand C4H4,reported
The difference in slopes of the neutral and charged by both BH and DV, are, respectively, similar in shape and
particle diameters in Figure 3 may be due to a faster rate magnitude (less than a factor of 2 difference) and were averaged
of ion recombination for large ions than for small ions. The for presentation here. The corresponding profiles for CBHG were
equation for the rate coefficient of ion-electron recombi- also averaged although they were significantly different. From
BH, the C6H6 maximum occurs at 7 mm while DV show the
n a t i ~ n , ~k,,' is, assuming that all electrons stick
k , = ad2 c, ( + &)
I
maximum at 4 mm. Also, DV found lower mole fractions by as
much as a factor of 10. Selected ion profiles are adapted from
AeroChem.13 Shading indicates where the yellow emission first
appears.
where E, is the average electron velocity at the electron and are not derived from the neutral particles. Not only
temperature T,, assumed to be the gas temperature, and is this evolution of charged particles further evidence for
the other symbols are defined above. the ionic mechanism of soot formation but it also makes
Increasing the particle diameter from 5 to 10 nm in- very awkward any explanation of the source of ions being
creases the rate coefficient of recombination from about the thermally ionized particles or large m o l e ~ u l e s . ' ~ ~ ~ ~ ~ ~ ~
2X to about 6 X cm3/s. Thus the larger charged We have recently13identified a large number of heavy,
particles are neutralized more rapidly than the smaller polyaromatic hydrocarbon ions in a sooting, C2H2/02/Ar
ones. The observation that the neutral particles grow flame (4 = 3.0; 2.7 kPa; 50 cm/s; 3% Ar) similar to that
faster than the charged particles is consistent with the size in Figure 2. Ions with carbon numbers up to 45 were
dependence of recombination coefficients and is incon- observed, and all can be represented as polyaromatic ions
sistent with the size dependence of thermal ionization rate similar to those given in Figure 1. Absolute ion concen-
constants, evidence that the observed charged particles are tration profiles were determined for this flame, some of
derived from the chemi-ions produced early in the flame which are shown in Figure 4 along with absolute concen-
trations of neutral species as measured by Bittner and
(37) Sodha, M.S.;Guha, S. Ado. Plasma Phys. 1971,4, 219.
(38) Newman, R.N.;Page, F. M.; Wolley, D. E. In Euaporation-Com-
bustion of Fuels; Zung, J. T., Ed.; Advances in Chemistry Series 166; (39) Homann, K. H. Twentieth Symposium (International) on Com-
American Chemical Society: Washington, DC, 1978; p 141. bustion; The Combustion Institute: Pittsburgh, PA, 1985; p 857.
498 Energy & Fuels, Vol. 2, No. 4, 1988 Calcote et al.
CARBON ATOMS
Table I. Rate Constants for Reaction of Neutrals with Ions 0 5 10 15 20 25 30 35 40 45
To Produce Larger IonsI3
- O
10IOk,cm3/s
from
reactants characteristic Langevin: experimentally
neutral ionbVc timesd est obsd
CzHz C3H3+ 0.0007 11 10,l
%HZ C14H11+ 0.0007 9 > 15
(%HZ C45H17+ 0.0007 9
C4H2 C3H3++ 0.02 13 1o e
ClHP C14Hll 0.02 10
C4H2 C4H3t 0.02 12 7.4h Figure 5. Occurrence of carbon a n d hydrogen atoms in flame
C3H4 CH+ 0.4 8 1l e ions.13
C4H4 C:Hi: 0.9 12 1l h
CBH6 3 16 14,15e*f
C3H3
@,i cantly to ion growth in this flame. These observations
ClZHB C3H3’ 300 19
CloHs C H ” 400 17 7f support the view of a series of rapid ion-molecule growth
C14H8 (Hit 1000 19 6.i reactions, involving the addition of small neutral species
to ions, taking place in the flame and eventually leading
Estimated with Langevin’s theory using polarizabilities calcu-
lated from refractive indices and the Lorentz-Lorenz equation.
to soot formation.
Ion in “estimated” and “observed” reactions. Linear C3H3+as- 3. Confirmation of Ions. All of the individual ions
sumed. dIndependent of ion.13 “myth e t al.4 f E ~ l e r 8Eyler
.~ and involved in the postulated mechanism, up to mass 557,
associates6 report a much lower rate coefficient for this reaction. have been observed in sooting f l a m e ~ . ~ ~ The J ~ Jcar-
~,~~
T h e higher rate coefficients are supported by recent measurements bon-hydrogen content of these ions is identified in Figure
by Smith and Adams.6 hAnicich e t al.19 ‘For l-methyl- 5. The carbon-hydrogen ratios require that the molecular
naphthalene, CllHlo.
structures be highly condensed aromatic rings. The
Howard@in the same flame using the same burner design presence of larger ions prior to the appearance of soot has
and by Delfau and Vovelle41in a similar flame without the also been confirmed, without identification of the indi-
Ar. The OH profile is from L a ~ r e n d e a u . ~ With
~ only a vidual The data in Figure 5 demonstrate that the
few exceptions, all of the ion concentration profiles ex- hydrogen content remains constant as the number of
hibited13 peaks at about the same location in the flame, carbon atoms increases, until at some specific number of
0.8-1.0 cm. This was true for both odd and even carbon carbon atoms the number of hydrogen atoms increases by
number species, with the profiles for heavier species, >400 2. This observation dictates the possible reactions that
amu, being broader than for the lighter ions. This ob- can be employed in any ionic mechanism. As expected,
servation indicates either that the ions are in equilibrium the ratio of carbon to hydrogen increases with increasing
with each other or that they are related by a series of rapid molecular weight. The highest ratio observed is still less
reactions, since a bottleneck would tend to delay the for- than 3 while the ratio in soot is about 10. Thus the largest
mation of heavier ions in the reaction sequence and they observed ions are far from being soot particles.
would be observed further downstream from the burner. 4. Location of Ions in Flame. The relative position
From the shapes of the profiles, we estimated charac- at which ions and soot occur, Figure 2, in a flame is not
teristic times for formation of ions,13 T , and related these in itself evidence of the order of production of ions before
to a bimolecular rate coefficient and the concentration of soot in the reaction sequence; the order of appearance
the reactant in excess [n], i.e., the neutral reactant, through would be reversed if the rate of production of soot from
the expression ions were fast compared to the rate of production of ions.
However, when the species peak considerably far apart in
k[n] = T In 2
the flame, such as do ions and neutrals in Figures 2 and
Since the concentrations of the neutral reactants were 4,it seems safe to assume that the first peak precedes the
known, the rate coefficients could be calculated. second in reaction sequence as well as in order of ap-
The estimated rate constants derived from the pearance. This assumption is further warranted when
“characteristic times” for various assumed reactions are there is no clear pathway for proceeding from soot particles
given in Table I, along with Langevin estimated and some to moderately sized ions.ls With these caveats, the ap-
experimentally observed rate constants. The required rate pearance of ions in the flame preceding the appearance of
constants involving acetylene and diacetylene as the neu- soot is evidence for ions being the precursors of soot and
tral growth species are considerably lower than the Lan- is further evidence that the ions are not produced from
gevin or experimental values, indicating ion growth reac- the soot particles.
tions involving these species are potentially important in In this regard, it is interesting to note that both Homann
this flame. In fact, both allene and vinylacetylene also and Wagner44and Bittner and Howard40observed mass
appear as viable reactants; the rate coefficients from the spectrometrically a group of large neutral molecules with
characteristic times are smaller than the Langevin or mass greater than 500 amu occurring at exactly the same
measured rate coefficients. These are the major processes position in the flame at which the total ion concentration
included in the ionic soot formation mechanism (Figure peaks. Both of these groups identified these species as the
1). Reactions of larger neutral species such as the poly- precursors of soot formation. Could they have been ob-
aromatic hydrocarbons in Table I with small ions to gen- serving the peak in ion concentration reported in Figures
erate large ions would require such large rate constants 2 and 4?
that this route can be eliminated as contributing signifi-
~~ (43) Olson, D.B.; Calcote, H. F. Eighteenth Symposium (Interna-
(40) Bittner, J. D:; HGardTJ. B I n Particulate Carbon: Formation tional) on Combustion; The Combustion Institute: Pittsburgh, PA, 1981;
During Combustion; Siegla, D. C., Smith, G. W., Eds.; Plenum: New p 453.
York, 1981; p 109. (44) Homann, K.H.;Wagner, H. G. Eleuenth Symposium (Interna-
(41) Delfau, J. L.; Vovelle, C. Combust. Sci. Technol. 1984, 41, 1. tional) on Combustion; The Combustion Institute: Pittsburgh, PA, 1967;
(42) Laurendeau, N. M.,personal communication, 1986. p 371.
Ionic Mechanism of Soot Formation Energy & Fuels, Vol. 2, No. 4,1988 499

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

1.5 2.0 2.5 3.0 3.5 4.0


0.1
I
,
g I
1 2 3 4
EQUIVALENCE RATIO, 4 EQUIVALENCE R A T I O , 6

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

Figure 11. Variation of recombination coefficients with equiv-


alence ratio. Same flames as Figure 10 (data from ref 14).
Figure 9. C1&ll+(239 amu) ion profiles in an acetylene/oxygen
flame: 2.1 kPa; 50 cm/s unburned gas velocity; soot threshold Of additional interest is the manner in which the global
equivalence ratio = 2.4. second-order recombination coefficient, calculated from
was attributed to ionization of neutral particle^.^*^^ It has downstream ion concentration decays,14 varies with
been demonstrated above that thermal ionization of soot equivalence ratio (Figure 11). This rate coefficient is
particles cannot explain the formation of moderately sized about 2 X lo-' cm3/s in a stoichiometric flame, a typical
ions, Le., less than mass 1O00, as shown in Figure 8. It has, value for small ions,l decreases to about 0.1 of this value
in fact, been shown that the second rise in total ion con- just before soot is observed, rises to a maximum at about
centration with equivalence ratio is due to the formation the same point in the flame as where the second ion con-
of a second maximum in the ion concentration vs distance centration peak exceeds the first peak (Figure lo), and
profile14and that this maximum is comprised of the same then falls again to an even lower value. Both decreases
ions as the first maximum; see, e.g., Figure 9. The source in recombination coefficient must be due to the formation
of this second maximum is unknown but appears to be of negative ions (recombination rate coefficients for pos-
related to soot formation. In Figure 10 the concentrations itive and negative ions are much smaller than for positive
of total ions in the two maxima are plotted together. The ions and electrons); such ions have, in fact, been observed
hatched area indicates the equivalence ratio in the flame in sooting flames by Homann and Stroefer.% Multicharged
where soot is first observed. particles may also play a role.52 Exactly why the recom-
bination rate coefficient reaches a minimum at about C#J =
(51) Wagner, H. G. Seventeenth Symposium (International) on
Combustion; The Combustion Institute: Pittsburgh, PA, 1979; p 3. (52)Bradley, D.; Jamel, M. A. M. Combust. Flame 1984, 58, 115.
Ionic Mechanism of Soot Formation Energy & Fuels, Vol. 2, No. 4, 1988 501
2.0 and then increases again is not clear. The answer will Table 11. Effect of Chemical Additivesn on the
have to await further study or computer modeling of the Concentration of Small Ions in Flames'O
process in which all of the rates are included. Electron ratios of ion concn with and without additive
attachment increases at lower temperatures and for larger additive H,O+ CHO+ C,H,+ C,H,O+ C,H,+
molecular species. Nevertheless, the big changes in ionic
character of the flame at the soot threshold, if not the Na 1.0 0.9 0.9 1.0 1.0
Ca 0.7 0.7 0.6 0.5 0.7
result of soot formation (see above), may very well be the Ba 0.4 0.4 0.4 0.4 0.5
cause of soot formation.
6. Propensity of Ions to Grow. The ionic mechanism Additive concentration 25 ppm.
assumes that small ions grow to larger ions by the addition
of small molecular species such as acetylene, poly- of carbon atoms in the fuel.
acetylenes, and other small hydrocarbon species. This is 8. Chemical Additive Effects. The same additives
consistent with the known facts of ion-molecule reac- have been observed to both promote67@or inhibit the
tion~.~+J~4- Most of these reactions are exothermic, and formation of soot, and the results have been interpreted
the rates of reaction are proportional to the exothermicity as affecting either the nucleation or the coagulation step;
of the reaction.57 see Figure 1. Much of the confusion arises because of the
7. Fuel Effects. Soot is only found in those flames of number of possible roles an additive can play69 and the fact
carbon-containing fuels that also produce ions. Diffusion that these roles can vary with the experimental conditions,
flames of all organic substances except methyl alcohol, e.g., the concentration of the additive. For our purposes
formaldehyde, and formic acid produce soot;5s all organic in this paper we present evidence that under some con-
substances except formaldehyde and formic acid produce ditions the additive alters the nucleation step where the
ions in flame-ionization detectors, and methyl alcohol effect is consistent with the ionic mechanism of soot nu-
flames have very low ion concentration^.^^^^^ Inorganic cleation.
carbon-containing molecules such as carbon monoxide,58 Some of the first evidence for an ionic mechanism of soot
carbon disulfide, mixtures of carbon disulfide and hydro- formation was the observation of the effect of chemical
genF2and cyanogen61do not produce soot. Of these gases additives with low ionization potentials on soot forma-
only cyanogen flames produce ions, and they are different tion.68*70,71 Strong correlations are observed between an
from those in hydrocarbon flames.23i62 These observations additive's effect on soot formation and its ionization po-
are consistent with the ionic mechanism of soot formation. tential.6s.70Alkaline-earthmetals are a special case because
Another indication of a correlation between fuel struc- the level of ionization is greater than anticipated by
ture effects on soot formation and flame ionization can be thermal equilibrium; ions are produced by chemi-ioniza-
t i ~ n , e.g.
~*
gleaned from the correlation made by Takahashi and
Glassmane3in premixed flames between the equivalence
ratio for soot formation and the number of carbon bonds.
They observed that the tendency to soot increases with
Ba + OH - BaOH+ + e- (16)
Thus alkaline-earth metals may have a greater effect on
the number of carbon bonds. This is reminiscent of several flame ionization than predicted from their ionization po-
observations made on the tendency of compounds to tential.
produce ions under various conditions. In flame-ionization The effects of additives on soot nucleation are based on
detectors for gas chromatography, the magnitude of the two processes as suggested by Addecutt and N ~ t t (1) : ~ ~
signal produced is correlated with the number of carbon the transfer of charge from a chemi-ion, M+, to a metallic
atoms in the molecule.59@ Bulewicz and Padley62found atom, A, e.g.
in premixed fuel/oxygen flames that the electron current
increased with the number of carbon atoms in the mole- M+ + A + M + A+ (17)
cule. Interestingly acetylene is off their correlation very
much as in the correlation of Takahashi and Glassman. where M+ is a hydrocarbon ion, such as C3H3+,or (2) an
B u l e w i ~ has
z ~ also
~ ~ ~correlated the response in a flame- increase of the concentration of electrons due to thermal
ionization detector to the heat of reaction of the fuel to ionization of easily ionized metals. This would increase
C02+ Hz, which, of course, also increases with the number the rate of dissociative recombination of chemi-ions:
A + A+ + e-
-
(18)
(53)Dheandhanoo, S.;Forte, L.; Fox, A.; Bohme, D. K. Can. J. Chem.
1986,64,641. M+ + e- products (19)
(54) Schiff, H. I.; Bohme, D. K. Astrophys. J. 1979,232,740.
(55)Knight, J. S.;Freeman, G. G.; McEwan, M. J.; Anicich, V. G.; Either of these mechanisms would remove the precursor
Andress, W. T., Jr. J. Phys. Chem. 1987,91,3898. chemi-ion from the system and thus reduce the number
(56)Kebarle, P.; Haynes, R. M.; Searles, S. In Ion-Molecule Reactions of soot nuclei produced. Reaction 17 will be important
in the Gas Phase, Advances in Chemistry Series 58;American Chemical
Society: Washington, DC, 1966;p 210. under conditions such that the equilibrium concentration
(57)Ausloca, P.; Jackson, J.-A. A.; Lias, S. G. Int. J.Mass Spectrom. of M+ is lower than that of A+. In fact, the rate coefficient
Ion Phys. 1980,33,269. for reaction 17 is so much greater than for reaction 18 that
(58)Gaydon, A. G.; Wolfhard, H.G. Flames, Their Structure, Radi-
ation and Temperature, 4th ed.; Chapman and Hall: London, 1979;
Chapter VII.
(59)Sternberg, J. C.; Galloway, W. S.; Jones, D. T. L. In Gas Chro- (67)Feugier, A. Combustion Institute European Symposium; Wein-
matography; Brenner, N., Jones, J. E., Weiss, M. D., Eds.; Academic: berg, F. J., Ed.; Academic: London, 1973;p 406.
London, 1962;p 231. (68)Bulewin, E. M.;Evans, D. G.; Padley, P. J. Fifteenth Symposium
(60) Goodings, J. M.; Ng, C.-H.; Bohme, D. K. Int. J.Mass. Spectrom. (International) on Combustion; Reinhold: New York, 1977;p 1461.
Ian Phys. 1979,29,57. (69)Howard, J. B.; Kausch, W. J., Jr. Prog. Energy Combust. Sci.
(61)Abers, E. A.; Homann, K. H. 2.Phys. Chem. 1968,58,220. 1980,6,263.
(62)Bulewicz, E. M.; Padley, P. J. Ninth Symposium (International) (70)Addecutt, K. S. B.; Nutt, C. W. Presented at the Symposium on
on Combustion; Academic: New York, 1963;p 638. Deposit, Wear, and Emission Control, 158th National Meeting of the
(63)Takahashi, F.;Glassman, I. Combust. Sci. Technol. 1984,37,1. American Chemical Society, New York, Sept 1969;Paper A69.
(64)Scanlan, J. T.; Willis, D. E. J. Chromat. Sci. 1985,23,333. (71)Bartholome, E.; Sacksse, H. 2.Elektrochem. 1949,53,326.
(65)Bulewicz, E. M. Nature (London) 1966,211,961. (72)Schofield, K.; Sugden, T. M. Tenth Symposium (International)
(66)Bulewicz, E. M. Combust. Flame 1969,13,214. on Combustion; The Combustion Institute: Pittsburgh, PA, 1965;p 589.
502 Energy & Fuels, Vol. 2, No. 4, 1988 Calcote et al.
SOOTING I ' ' 1
I I
PRO-SOOT I

--
-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

C12 e- C12- (22)


10-12
0 1 2 3 4 5
These anions reduced the rate of recombination of cations,
0 1 2 3 4 5
RADIAL DISTANCE, cm
which normally disappear via dissociative reactions such
without CCiq with CCi4 as
Figure 13. Effect of CC14on anion profiles and soot formation C12H3+ + e- ---+ products (23)
in a C2H2/02spherical diffusion flame. See Figure 12.
When the additive is present, the cation can disappear only
equilibrium concentrations of A+ may be approached via
reaction 17 rather than reaction 18.l The metal ion, A+,
may also be produced in greater than equilibrium con-
centrations by reaction 17.l Thus the specific mechanism
by reactions with anions such as
C12H3+ + C1- - products (24)
Recombination coefficients for dissociative ion-ion re-
by which an additive is effective will be determined by the combination reactions, such as reaction 24, in flames are
relative equilibrium concentrations of A+ and M+ and the about an order of magnitude lower than for those ion-
time available to approach equilibrium. electron reactions such as reaction 23.75*7s Thus the
Reaction 17 is well documented in nonsooting flames.l positive ion concentration is increased, and this increase
Addecutt and N ~ t tin, a~ study
~ of the effect of chemical can, assuming the ionic mechanism of soot formation, be
additives on soot formation, observed, by molecular beam responsible for the increase in observable soot.
mass spectrometry, the effect of 25 ppm of Na, Ca, and Bulewicz et aLB studied the effect of metal additives on
Ba on the small ions in a flame at approximately 1970 K. soot formation in flames and have given a detailed inter-
Under these conditions Na was only slightly ionized while pretation of their results which is in complete accord with
Ca and Ba were both fully ionized. The results, Table 11, the ionic mechanism of soot formation. A number of
indicate an effect of Ca and Ba on the concentrations of chemical additives were added to the fuel side of an
small ions. Goodings et al.73did a similar experiment in acetylene/oxygen diffusion flame, and soot was collected
which they demonstrated that hydrocarbon ion concen- on a glass-fiber filter and weighed. The soot particle size
trations up to mass 120 amu were suppressed by the ad- was determined by electron microscopy of samples taken
dition of CsC1. It is not possible, for either of these sets at 2 cm, for about 1ms, above the burner, and the total
of data, to distinguish which of the above two mechanisms positive ion concentration was determined with a Lang-
(e.g., reaction 17 or reactions 18 and 19) is operative; it does muir probe. Flame temperatures were in the range of
demonstrate an additive effect on chemi-ion concentration, 1400-1800 K.
for the same additives and in the same order in which they
The same additive acted as a prosoot or an antisoot
affect soot formation.70 additive (Figure 14), depending upon the total ion con-
Miller74observed that the addition of carbon tetra- centration due to the additive. With increasing additive
chloride to a spherical low-pressure diffusion flame concentration, the total quantity of soot increased and then
transformed a nonsooting flame into a sooting flame and with a greater concentration of additive the quantity of
soot decreased so that at a little over 1O1O cesium ions/cm3
(73)Goodings, J. M.; Graham, S. M.; Karallas, N. S. Int. J. Mass.
Spectrom. Ion Processes 1986,69, 343.
(74)Miller, W.J. Eleventh Symposium (International)on Combus- (75)Burdett, N.A.; Hayhurst, A. N. Second European Symposium
tion, "he Combustion Institute, Pittsburgh, PA, 1967;p 252;unpublished on Combustion; The Combustion Institute: Pittsburgh, PA, 1975;p 55.
work, AeroChem TP-151,1967. (76)King, I. R. J. Chem. Phys. 1962, 37, 74.
Ionic Mechanism of Soot Formation Energy & Fuels, Vol. 2, No. 4, 1988 503
the amount of soot produced was the same as without the quantity of soot produced in a flame or deposited on an
additive. At this additive concentration the particle electrode are sometimes quoted as evidence of an ionic
number density reached a maximum. Beyond this con- mechanism of soot nucleation. This evidence is somewhat
centration of additive the number density, total mass of ambiguous and will be the subject of a future publication;
soot, and the soot particle size all decreased, indicating that it is mentioned here only for completeness.
the dominant effect of the additive was on the nucleation Weinberg and associates have demonstrated dramatic
step rather than on the coagulation step. In other flames effects of electric fields on soot f o r m a t i ~ n , ~which
*~~@ they
the dominant effect of additives is on coagulation, see e.g., have interpreted as due to both an effect on soot nucleation
Haynes et al.I7 and on coagulation. Both enhancement and suppression
Bulewicz et a1.68explain both the prosoot and the an- of soot concentrations were demonstrated. Similar results
tisoot effect by means of an ionic mechanism. The reader have also been obtained by o t h e r ~ . ~ l - ~ ~
is referred to their paper for the detailed arguments. Both Bowser and WeinbergE4and Saloojae5have dem-
Briefly, the antisoot effect is due to charge transfer from onstrated that the injection of electrons into flames, from
the precursor hydrocarbon ion, M+, to the metal atom as small coated wires placed in the flame, can markedly alter
in reaction 17. They point out that in their flame, thermal the quantity of soot produced. The effect, enhancement
ionization of the metal atom, reaction 18, would be too slow or suppression, is dependent upon the location of the wire
to produce electron concentrations above the natural flame in the flame and the quantity of electrons introduced.
level so that reaction 19 would not be effective in reducing Whether this effect occurs on the nucleation step or on the
the concentration of hydrocarbon flame ions. The prosoot coagulation step is not clear.
effect was explained by arguing that small concentrations 10. Aesthetics. The ionic mechanism of soot formation
of additive may, in fact, maintain the level of M+ at a is aesthetically pleasing: it is simple; and it does not have
higher value throughout the flame than when no additive any “ad hoc” assumptions.
is present. Consider the potassium range of concentration
from prosooting to antisooting, similar to the cesium levels Summary
used in Figure 14, which vary from about lo1(‘to 1014at-
oms/cm3. At about 1600 K, the equilibrium concentration In responding to the title question, a number of obser-
of K+ varies from about lo8 to 1O’O ions/cm3 (function of vations have been examined. Some of these have been
solution molarity). The natural flame ionization concen- found to be consistent with an ionic mechanism, albeit not
tration is about 1O’O ions/cm3, several orders of magnitude a proof, and others are strongly supportive of an ionic
above equilibrium levels. When the concentration of K mechanism and in fact difficult to explain without invoking
is 1014 atoms/cm3 and the concentration of M+ is 1O1O an ionic mechanism of soot nucleation. Clearly much
ions/cm3, it is clear that reaction 17 can proceed at a information is missing, and some of the published data
significant rate, thus reducing the concentration of M+. used in the arguments are of questionable validity. Below
At this high level of additive concentration the equilibrium we summarize some of the data and arguments used in
concentration of K+ cannot be exceeded. On the other examining the title question and then indicate the infor-
hand, when the K concentration is only 1Olo atoms/cm3, mation that is most needed to place the ionic mechanism
the M+ concentration can be only negligibly reduced in the on a sound footing.
time available. However, the equilibrium level of K+, The data and arguments in support of an ionic mecha-
which is only about loEions/cm3, may be significantly nism of soot formation are as follows:
exceeded because the recombination rate is slow compared 1. Ion concentrations measured in the “standard” flame,
to the rate of charge transfer from chemi-ions, reaction 17 an acetylene/oxygen flame at 2.7 kPa and 50 cm/s un-
(see, e.g., ref 1). Further downstream the slow decay of burned gas velocity, are sufficient to account for the soot
K+ maintains a higher level of total ionization, and at this concentrations observed.
point Bulewicz et al.m suggest that the reverse of reaction 2. The rates of ion formation and soot formation in
17 maintains the concentrations of M+. In the absence of flames seen to be of the same magnitude; however, there
this reaction, M+ would have decayed because dissociative are no really comparable measurements in the same flame,
recombination of molecular ions is about 2 orders of except in the “standard” flame.
magnitude faster than recombination of atomic ions, which 3. Ion-molecule reaction rates involved in the ionic
must decay by a three-body process.78 Thus new ionic mechanism of soot formation have been demonstrated to
nuclei are available at later stages in the combustion be fast at the high temperatures of sooting flames by
process to grow to incipient soot particles. measuring the characteristic times for the ions to appear
The prosoot action of higher ionization elementsm (e.g.: in the standard flame.
Pb, 7.42 eV; Mg, 7.64 eV; Cr, 6.76 eV; Co, 7.06 eV; Mn, 7.43 4. Ion-molecule reactions involving large ions reacting
eV; and even Li, 5.39 eV) are also explained by the above with small neutrals are demonstrated to be possible can-
argument. Their equilibrium ionization levels are very low,
and their ionization potentials are somewhat less than
those for hydrocarbon ions, so a concentration above the (79)Weinberg, F. J. In Soot in Combustion Systems and Its Toxic
Properties; Lahaye, J., Prado, G., Eds.; Plenum: New York, 1983;p 243.
equilibrium concentration is expected. Clearly this analysis (80)Hardesty, D.R.;Weinberg, F. J. Fourteenth Symposium (Inter-
merits more detailed modeling in which all of the simul- national) on Combustion; The Combustion Institute: Pittsburgh, PA,
taneous reactions can be accounted for more quantita- 1976;p 907.
(81)Heinsohn, R.J.; Becker, P. M. In Combustion Technology, Some
tively. It is, however, at this stage of development con- Modern Deuelopments; Palmer, H. B., Beer, J. M., Eds.; Academic: New
sistent with the ionic mechanism of soot formation. York, 1974;Chapter IX.
9. Electric Field Effects and Electron Injection. (82)Lester, T. W.; Wittig, S. L. K. Sixteenth Symposium (Interna-
tional)on Combustion; The Combustion Institute: Pittsburgh, PA, 1977;
The sometimes dramatic effects of electric fields on the p 671.
(83)Wittig, S.L. K.; Lester, T. W. In Euaporation-Combustion of
Fuels; Zung, J. T., Ed.; Advances in Chemistry Series 166;American
(77)Haynes, B. S.;Jander, H.; Wagner, H. G. Seventeenth Sympo- Chemical Society: Washington, DC, 1978; p 167.
sium (International)on Combustion; The Combustion Institute Pitts- (84) Bowser, R. J.; Weinberg, F. J. Nature (London) 1974, 249,339.
burgh, PA, 1979;p 1365. (85)Salooja, K. C. Combustion Institute European Symposium;
(78) Ashton, A. F.; Hayhurst, A. N. Combust. Flame 1973, 21, 69. Weinberg, F. C., Ed.; Academic: London, 1973;p 400.
504 Energy & Fuels, Vol. 2, No. 4, 1988 Calcote et al.
didates for ion growth, but the opposite reactions, small best available reaction rate coefficient information to de-
ions reacting with large neutrals, are eliminated as pos- termine the extent to which such an ionic model is con-
sibilities for producing large ions. This is largely the result sistent with experimental data and to better define the
of the concentration of reactive species in sooting flames. unknowns in the mechanism. We are currently pursuing
5. Data on neutral and charged soot particle diameters this course.
through a sooting flame have in the past presented a di- 2. The structure of the ion C3H3+,the assumed pre-
lemma, because the neutral particles seemed to be growing cursor in the mechanism, should be determined as it is
at a faster rate than the charged particles. Within the produced in a flame; Le., is the linear or cyclic isomer
accuracy of the data, these observations are interpreted produced?
as indicating that, for small particles, equilibrium between 3. The rate at which the equilibrium between linear and
ionized and neutral particles is approached from the side cyclic C3H3+proceeds needs to be determined at the tem-
of excess ionized particle. This is consistent with an ionic perature of sooting flames.
mechanism of soot formation. 4. The rate coefficienb of ion-molecule reactions at high
6. All of the ions proposed in the ionic mechanism, up temperatures are very badly needed. There is a dearth of
to mass 557, have been identified in sooting flames. data on the effect of temperature on ion-molecule reaction
7. The location of the peak in ion concentration with rates.
respect to the peak in soot concentration, in both premixed 5. The measurement of the concentration and the
and diffusion flames, is consistent with an ionic mechanism identification of large negative ions in sooting flames are
of soot formation. very important. There is evidence of the presence of large
8. Soot formation ceases in a premixed sooting flame negative ions; they could make a difference in equilibrium
at about the same location in the flame as that at which considerations of the sources of large hydrocarbon ions in
ions are no longer being formed by chemi-ionization. flames.
9. The character of the ions observed in flames with 6. More detailed and quantitative data on the concen-
various fuel/oxidizer ratios changes at the equivalenceratio tration and size distribution of both small neutral and
at which soot first appears in premixed flames. ionized soot particles are very important to an under-
10. Ions have a thermodynamic propensity to grow. standing of the mechanism of incipient soot formation.
11. There is a correlation between the tendency of fuels 7. Determination of the effect of chemical additives on
to produce soot and their tendency to produce ions. soot formation and ionization would help unravel the
12. The effect of some chemical additives on soot for- mechanism of soot formation as well as have practical
mation in premixed and in diffusion flames can be readily implications.
explained by assuming an ionic mechanism of soot nu- The answer to the question raised in the title seems to
cleation. be “yes”.
13. The ionic mechanism of soot nucleation is aesth-
etically pleasing; it is simple, and it does not require any Acknowledgment. This paper is based on work funded
“ad hoc” assumptions. by the Air Force Office of Scientific Research under
The research and information needed to place the ionic Contract F49620-83-C-0150and National Science Foun-
mechanism of soot formation on a sounder basis are as dation Grant CBT-8502122. We gratefully acknowledge
follows: the assistance of Helen Rothschild in reducing the data
1. A theoretical model should be developed by using the and preparing the figures.

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