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Real-time observation of metastable polymeric

species formed from precursor soot
Article in Chemical Physics Letters October 2004
Impact Factor: 1.9 DOI: 10.1016/j.cplett.2004.08.126

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Washington State University
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Chemical Physics Letters 397 (2004) 324328

www.elsevier.com/locate/cplett

Real-time observation of metastable polymeric species

formed from precursor soot
Ryan P. Rodgers, Peter T.A. Reilly *, William B. Whitten, J. Michael Ramsey
Laser Spectroscopy and Microinstrumentation Group, Oak Ridge National Laboratory, P.O. Box 2008, MS 6142,
Oak Ridge, TN 37831-6142, USA
Received 13 August 2004; in nal form 27 August 2004
Available online 16 September 2004

Abstract
Micrometer-sized precursor soot particles were formed by pyrolysis of pure atmospheric-pressure acetylene in a ow tube reactor. Real-time analysis of both the gas and particle phases of the reactor euent was performed with an ion trap-based aerosol mass
spectrometer. O-line analyses were also performed on the lter-collected reactor euent. The real-time particle mass spectra
revealed the presence of a polymeric mass distribution starting near 1000 Da and continuing to greater than 1750 Da. The spacing
between the polymer peaks is approximately 70 Da. Comparison of real-time and o-line analyses reveals the metastable nature of
the polymer-like high mass species.
2004 Elsevier B.V. All rights reserved.

1. Introduction
Precursor soot as its name implies is an integral step
in the formation of mature soot. It forms during pyrolysis of hydrocarbons and has been observed in ames
[1,2] and during the commercial production of carbon
black used in the production of tires [3]. Though precursor soot was observed more than 50 years ago [4], its
very existence is still controversial with most critics suggesting it results from sampling artifacts.
Though the origins of the controversy have never (to
our knowledge) been put in print, it probably is due to
the analysis of the composition of precursor soot. Precursor soot is an oil containing polycyclic aromatic
hydrocarbons (PAHs). These same PAHs have been observed to reside in the gas phase of pyrolytic processes.
The controversy arises because the boiling points of
the vast majority of the components of the condensed
species are well below the formation temperature of

Corresponding author. Fax: +1 865 574 8363.

E-mail address: reillypt@ornl.gov (P.T.A. Reilly).

0009-2614/$ - see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2004.08.126

the precursor soot. It is therefore logically concluded

that these components cannot physically condense at
atmospheric pressure at those temperatures. Hence, it
can and has been argued that precursor soot does not
exist it must result from sampling-induced condensation of the gas phase species.
However, the above arguments against the existence
of precursor soot are not supported by the denitive
work performed by Sweitzer and Parker (members of
the carbon black industry) in the 1950s [3]. In these
experiments, a white mist was observed to form inside
a huge furnace (used to industrially produce carbon
black) when the hydrocarbon fuel was passed through
the furnace. The white mist was sampled and found to
be an oil of low boiling PAHs upon analysis. The observed mist evolved into mature soot (carbon black) as
the temperature of the furnace was raised. Since there
was no sampling involved in this experiment, the mist
was not formed by sudden cooling of the vapor phase
PAHs. Consequently, a high temperature stable form
of hydrocarbon must exist that is a precursor to soot.
Hence, precursor soot must exist in high temperature
environments.

R.P. Rodgers et al. / Chemical Physics Letters 397 (2004) 324328

The above arguments suggest an apparent contradiction or paradox. However, in reality, they are an indication that some very interesting chemistry is occurring
during the pyrolysis process. In this work, we present
compelling evidence for the existence of precursor soot
by examining in real time the gas and particle phases
of the same pyrolytic process. We show, for the rst
time, the existence of transient high mass polymer-like
species that could not be produced by gas phase condensation. This evidence will be used to provide a rational
explanation of the chemistry of precursor soot.

325

0.22 lm pore size) for further o-line analysis. The euent was completely extracted from the lter with methylene chloride and analyzed by several techniques.
GCMS was used to identify the low mass components
(<300 Da). Laser desorption/ionization time-of-ight
mass spectrometry (LD-TOF) was used to evaluate the
high mass extract components (>200 Da). The extracted
euent was also deposited on C18-coated, 5-lm silica
beads by solvent evaporation. These beads are standard
packing for liquid chromatography columns. The beads
were analyzed individually with our aerosol mass spectrometer by sprinkling them into the inlet to yield a
direct comparison between real-time and o-line particle
analysis.

2. Experimental
Pure atmospheric pressure acetylene was passed
through a 3.85-mm ID, 45-cm long quartz tube reactor
at a constant temperature (700 C). The ow through
the reactor was laminar at 40 ml/min. Upon exiting
the reactor, the euent was rapidly diluted and cooled
by mixing with a 4 l/min ow of pure room temperature
nitrogen. A portion of the diluted euent was then sampled into our aerosol mass spectrometer. The details of
the conguration and operation of the aerosol instrument have been published elsewhere [5].
Individual particle mass spectra were obtained by
ablating each detected particle as it passed through the
center of the ion trap with a focused pulse from a
308-nm laser (1 J/cm2). Gas phase mass spectra of the
diluted euent were obtained by deliberately mistiming
the laser pulse to miss the detected particle. Gas phase
mass spectra were also obtained by electron impact ionization for the sake of comparison and validation.
The diluted euent was collected on hydrophobic
polyvinylidene uoride membrane lters (Millipore,

3. Results and discussion

166

The gas phase species from the diluted euent of the

700 C reactor were examined in real time by laser and
electron impact ionization mass spectrometry. The results of this study are presented in Fig. 1a, b, respectively. Both ionization techniques yield similar spectra
with the primary dierences in the degree of hydrogenation and the intensities of the PAH ions in the mass
spectral distributions. These dierences can be explained
by dierences in the ionization energies and crosssections of the two techniques. Ionization by electron
impact leaves the ions with greater internal energy than
the laser ionization process and therefore results in more
fragmentation. The consistent dierence in the degree of
hydrogenation of the ions by the dierent ionization
techniques suggests the presence of labile hydrogen even
in the gas phase species. There is no ion signal exceeding

100

202
216

180

154
141
150

200

250

300

350

400

450

50

100

150

Electron Impact Ionization

of Gas Phase Species

500
(b)

192
202

178

115
128
141
152

63
74
89

165

50

115

74
87

61

(a)

Laser Ionization
of Gas Phase Species

200

250

300

350

400

450

500

m/z
Fig. 1. Comparison of the gas phase ion distributions created by laser ionization (a) and electron impact ionization (b) of the diluted gas phase
species from 700 C pyrolysis of atmospheric pressure acetylene.

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R.P. Rodgers et al. / Chemical Physics Letters 397 (2004) 324328

temperature, the particles must have been produced by

some other process. Moreover, we have also performed
experiments at higher temperatures where the dierences
in the mass spectral distributions of the gas and particle
phases become much more pronounced. Consequently,
the suggestion of rapid condensation of the gas phase
species producing our results is not credible.
Given the dierences between our real-time results
with the o-line measurements from other techniques,
we thought a direct comparison of real-time and o-line
techniques would be prudent. After the euent was collected on a lter and extracted with methylene chloride,
5 lm, C18-coated silica beads were deposited in the
extractant. These beads are routinely used to pack liquid
chromatography columns. The solvent was then evaporated driving the euent species into the C18 matrix on
the silica beads. The beads were then dropped into our
aerosol mass spectrometer where they were analyzed.
The averaged results of our o-line measurement are
shown in Fig. 2b. Once again, the primary dierence is
the greater degree of hydrogenation seen in the real-time
measurement. The remarkable similarity between the
two techniques suggests that we have a credible o-line
technique.
Unfortunately, ion traps have a limited dynamic
range in terms of the masses that can be stored. Consequently, the high mass species are not as readily observed under the same conditions as the lower mass
species. However, they can be observed in a separate
experiment without the low mass species. The high mass
range was scanned for both the real-time and o line
measurements. The averages from these measurements
are shown in Fig. 3a, b, respectively. It is here that the
dierences between the two measurements become obvious. On the left-hand side of the real-time mass spectrum, the tail end of the PAH distribution can be
observed. Out of that distribution, a fullerene distribu-

100

Real-Time Analysis
of the Particle Plus Gas Phase

200

250

300

150

400

450

500
(b)

202
215

180

154

86
98
110
100

350

Off-Line Analysis
of the Extracted Effluent
from the C18 Matrix

74
50

(a)

181
193
203
216

150
166

61

50

154

76
90

6264

167

the noise level above 216 Da in any of the gas phase

spectra.
Fig. 2a shows the averaged particle mass spectrum in
the ever-present gas phase background. No attempt was
made at background subtraction. Comparison of the
particle and gas phase laser ionization spectra in Figs.
1a and 2a show similar ion distributions with three fundamental dierences. First, the local distributions
around each PAH mass line are broadened. This type
of broadening has been observed before [5] and results
from rapid hydrogen transfer and exchange. Because
hydrocarbon radicals can readily rearrange their carbon
skeletal structure, any given hydrocarbon formation is
just as likely to lose hydrogen as gain it as indicated
by the symmetric distribution around each peak in the
mass distribution (see Fig. 2b). The rate of transfer or
the density of hydrocarbon radicals is indicated by the
width of the distribution around each of the mass peaks
in the spectrum (see [5]). Second, the ion distribution
proceeds beyond 216 Da. Third, there is an overall increase in the degree of hydrogenation as seen by the
mass shift of most intense peaks in the particle phase
spectrum. Given the similarity in the ion distributions
of the gas and particle phases, it could be suggested that
the particles that we observe in our experiment might
actually result from the dilution process creating a
supersaturation (due to the rapid change in temperature) and causing rapid condensation of the gas phase
species. Sampling-induced condensation has often been
suggested to explain the presence of particles containing
low-boiling PAHs from high temperature environments
such as ames. However, the observed mass shift between the gas phase PAHs and the condensed phase
PAHs (compare Figs. 1a and 2a) negates this supposition because it would require that the gas phase PAHs
condense along with hydrogen to yield the observed
mass shift. Since hydrogen does not condense at room

200

250

300

350

400

450

500

m/z
Fig. 2. Comparison of the averaged mass spectra from real-time measurement of single particles plus gas phase species in the euent (a) with the
lter-collected euent deposited on liquid chromatography column packing beads (b). It is a direct comparison of real-time and o-line techniques.

R.P. Rodgers et al. / Chemical Physics Letters 397 (2004) 324328

500

700

900

1300

1500

1700
(b)

Off-Line Extractant
Mass Spectrum
From C18 Particles

PA

1740

1670

1597

1458

1388

1248

1100

1318

1178

1109

1045

C70

C60

C50

C40
300

(a)

Real-Time
Particle Mass Spectrum

1528

PA

327

Polymer
Fragments?

300

500

700

900

1100

1300

1500

1700

m/z
Fig. 3. Comparison of the averaged high mass spectra from real-time measurement of single particles plus gas phase species in the euent (a) with
the lter-collected euent deposited on liquid chromatography column packing beads (b). It is a direct comparison of real-time and o-line
techniques.

150

LD-TOF
of Extractant

350
364
378

242
252/4
266
276
290
302
316
330
340

202

230

217

desorption/ionization time-of-ight (LD-TOF) mass

spectrometry on the same extractant sample that was
used in the C18 o-line measurements. A few drops of
the extractant were deposited on a stainless steel probe.
The solvent was allowed to evaporate and the probe was
inserted into the spectrometer and pumped down. A focused nitrogen laser was used to desorb and ionize the
sample. The averaged mass spectrum is shown in Fig.
4. The observe LD-TOF distribution does not look at
all similar to our C18 o-line measurements in Figs.
2b and 3b. However, it does look similar to the distribution observe by Dobbins and coworkers [2]. In the

181

tion emerges showing the typical 24 Da mass separation

and C60 being the most intense peak. Above 1000 Da, a
polymer-like distribution of ions appears with a very
regular 70 Da peak separation. The width of the local
distribution around each polymer mass appears to be
very broad and becoming sharper toward higher mass.
These ions have never been observed in any pyrolytic
process, to our knowledge.
Turning our attention to the o-line measurement, we
observe very dierent results. First, the fullerene distribution is not present. This is not surprising since fullerenes are not particularly soluble in the C18 matrix. What
is surprising is the loss of the structure in the polymerlike distribution. The ion intensity is still there, but the
distribution has been completely scrambled. Since the
C18-coated particles are a packing material standard
used in liquid chromatography columns, a catalytic
process converting the high mass hydrocarbon species
into something else at room temperature in this medium
is unlikely. This suggests that the polymeric structures of
the high mass species are metastable! Further examination of the o-line spectrum reveals signicant ion intensity in the vicinity of 500 Da that is not observed in the
real-time spectrum. We speculate that these ions are
fragments of the metastable polymeric species.
Observation of the metastable nature of the high
mass polymer-like species suggested that other o-line
techniques do not observe these species because they
rearrange before the measurement is made. To check
this hypothesis and have a valid comparison with other
o-line techniques, we later decided to perform laser

250

350

450

550

650

750

m/z
Fig. 4. The averaged laser desorption time-of-ight mass spectrum of
the lter-collected euent extract that has been deposited on a
stainless steel probe.

328

R.P. Rodgers et al. / Chemical Physics Letters 397 (2004) 324328

LD-TOF spectra, we speculate that the most intense low

mass species are absent or greatly diminished by evaporation that occurs in the vacuum during pump down.
No ion intensity was observed in the high mass region
above 1000 Da.
The polymer-like high mass species must have degraded into PAHs and perhaps other evaporable low
mass species. This is the reason that these high mass species are not observed by typical o-line measurements.
Why do we see large mass species in the C18 o line
measurements and not in the LD-TOF measurements?
Time and perhaps the nature of the desorption media.
The C18 measurements were done the same day the
euent was collected whereas the LD-TOF experiments
were done a couple months later on the same sample.
Additionally, it is conceivable that the stainless steel
probe surface may have facilitated rearrangement
whereas the C18 matrix did not.
The above comparisons may explain the previously
described apparent paradox. It is clear that the chemical
nature of precursor soot in high temperature environments is very dierent from that measured under room
temperature conditions. In pyrolytic environments, precursor soot is not an oil of low boiling PAHs. It is probably not a polymer either. The reason for this suggestion
comes from acknowledging the rapid hydrogen transfer
and exchange observed in real-time PAH distributions.
Rapid hydrogen transfer and exchange results in a large
concentration of radicals in the precursor soot. Radical/
neutral reactions are very rapid and preserve the radical.
Consequently, a system of radicals continuously rearranges its carbon skeletal structure by making and
breaking carbon bonds. Such a system is best thought
of as one big molecule whose substructure is continually
changing. It therefore cannot be thought of as a polymer
because a polymers substructure does not change.
So why do we see a polymer-like distribution in the
mass spectrum? Our guess is that the metastable structure results from the rapid cession of hydrogen transfer
and exchange upon cooling of the particle. The radicals
are then rapidly eliminated by radicalradical recombination. The resulting structure is not thermodynamically
stable at room temperature and probably neglects rules
of aromaticity for the expedience of radical elimination.
This is a good reason for the existence of the short-lived
metastable species. The nature of the polymer-like structure still eludes us. We have tried many combinations,
but still cannot account for the 70 Da (C5H10) peak separations. We are reasonably sure that the metastable
structure evolves into the more stable PAHs observed

in the low mass region as the polymeric structure rearranges itself in order to obey the rules of aromaticity.
Consequently, the creation of precursor soot is another
path to the production of PAHs in pyrolytic processes.

4. Conclusion
Comparison of real-time and o-line measurements
has permitted the nature of the chemistry of precursor
soot to be revealed. Observation of the metastable polymer-like mass distribution yields conclusive proof that
precursor soot in the high temperature environment is
chemically dierent from that observed at room temperature. The polymer-like high mass species indicate that
precursor soot in the high temperature environment is
polymeric with its substructure in a continuous state
of ux due to the presence of hydrocarbon radicals. This
is what gives precursor soot its remarkable high temperature stability and phenomenal growth rate. The metastable high mass species apparently evolve into the small
(low boiling point) PAHs typically observed from pyrolytically condensed hydrocarbon species when the temperature is reduced. These observations support the
existence of precursor soot and help elucidate its
chemistry.

Acknowledgements
Research Sponsored by the Division of Chemical Sciences, Geosciences, and Biosiences, Oce of Basic Energy Sciences, US Department of Energy, under
Contract DE-ACo5-00OR22725 with Oak Ridge
National Laboratory, managed and operated by UTBattelle. We also thank Dr. Christopher L. Hendrickson
and other members of the Marshall group who helped
obtain our LD-TOF data.

References
[1] R.A. Dobbins, H. Subramaniasivam, in: H. Bockhorn (Ed.),
Formation in Combustion, vol. 59, Springer, Berlin, 1994, pp.
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[2] R.A. Dobbins, R.A. Fletcher, W. Lu, Combust. Flame 100 (1995)
301.
[3] C.W. Sweitzer, G.L. Heller, Rubber World 134 (1956) 855.
[4] W.G. Parker, H.G. Wolfhard, J. Chem. Soc. (London) (1950) 2038.
[5] P.T.A. Reilly, R.A. Gieray, W.B. Whitten, J.M. Ramsey, Combust.
Flame 122 (2000) 90.