United States
Environmental Protection
Agency
Environmental Sciences Research EPA-600/3-80-029
Laboratory         February 1980
Research Triangle Park NC 27711
Research and Development
Computer
Modeling of
Simulated
Photochemical
Smog
Final Report

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                 RESEARCH  REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

      I.   Environmental Health Effects Research
      2.   Environmental Protection Technology
      3.   Ecological Research
      4.   Environmental Monitoring
      5.   Socioeconomic Environmental Studies
      6.   Scientific and Technical Assessment Reports (STAR)
      7   Interagency Energy-Environment Research and Development
      8.   "Special" Reports
      9.   Miscellaneous Reports

This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on the effects  of pollution on  humans, plant and animal spe-
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ences. Investigations include formation, transport, and pathway studies to deter-
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                                EPA-600/3-80-029
                                                February 1980
COMPUTER MODELING OF SIMULATED PHOTOCHEMICAL SMOG
                   Final Report
                        by

  D. G. Hendry, A. C. Baldwin, and D. M. Golden
                SRI International
               333 Ravenswood Avenue
           Menlo Park, California 94025
            Contract No. 68-02-2427
                 Project Officer

                 Marcia C. Dodge
   Atmospheric Chemistry and Physics Division
   Environmental Sciences Research Laboratory
  Research Triangle Park, North Carolina 27711
      ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
          OFFICE OF RESEARCH AND DEVELOPMENT
         U.S. ENVIRONMENTAL PROTECTION AGENCY
     RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711

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                               DISCLAIMER

     This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for
publication.  Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection
Agency, nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
                                    ii

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                                ABSTRACT

     The chemistry by which hydrocarbons affect photochemical smog
formation has been investigated using computer modeling techniques.
Detailed chemical kinetic mechanisms for the atmospheric reactions of
toluene, m-xylene, propene, ethene, formaldehyde, and acetaldehyde were
constructed from available experimental and chemical kinetic data.
These mechanisms were used to simulate smog chamber data from both the
Statewide Air Pollution Research Center at the University of California
at Riverside and the outdoor facility at the University of North Carolina
at Chapel Hill.
     In general, the simulations predict the experimentally observed
time-concentration for NO, N02, and hydrocarbons quite well.  The rate
of buildup of ozone is also well predicted, although the maximum con-
centrations of ozone as well as the time to reach the maxima are over-
predicted 30%-50% in many cases.
     This report was submitted in fulfillment of  contract number
68-02-2427  by SRI International under the sponsorship of the U.S. Environ-
mental Protection Agency.   This report covers a period from 1 September 1977
to 31 August 1979,  and work was completed as of 30 November 1979-
                                   iii

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                                CONTENTS
Abstract	     iii
Figures	     vi
Tables	     vii

   1.  Introduction  	      1
   2.  Conclusions and Recommendations 	      5
   3.  Approach	      8
          Smog Chambers	      8
          Light Intensity Calculations 	      9
          Chamber Characteristics  	      9
          Modeling Technique  	     10
   4.  Aromatic Hydrocarbons  	     11
          Contribution of Aromatics to Total Atmospheric
          Hydrocarbons 	     11
          Reactions of Aromatic Hydrocarbons 	     12
          Products of Reaction of Aromatic Hydrocarbons  ....     14
          Toluene-OH Reactions 	     20
          Reactions of Cresol	   26
          NO Oxidation and NOX Consumption in Toluene Reaction  .     26
          Mechanism for Modeling Toluene Smog Chamber Data ...     29
          Toluene Simulation Results 	     34
          Mechanism for Modeling m-Xylene Smog Chamber
          Experiments	     42
          m-Xylene Simulation Results  	     45
   5.  Alkenes	     51
          Mechanism	     51
          SAPRC Data Set	     52
          UNC Data Set	     62
   6.  Alkanes	     65
          Mechanism	     65
          SAPRC Data Set	     65
          UNC Data Set	     65
   7.  Aldehydes	     74
          Mechanism	     74
          SAPRC Data Set	     74
          UNC Data Set	     74
References	     80
Appendices
   A.  Simulation of Aromatic Hydrocarbon Chamber Runs  	     85
   B.  Simulation of Alkehe Chamber Runs	     139
   C.  Simulation of n-Butane and Aldehyde Chamber Runs   ....     185

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                                FIGURES






Number                                                             Page




   1   Simulation of SAPRC Toluene Run EC-266  	    41




   2   Simulation of UNC Toluene Run 8.16.78 Red	    43




   3   Simulation of UNC Toluene Run 9.14.78 Red	    44




   4   Simulation of SAPRC m-Xylene Run EC-344 	    48




   5   Simulation of SAPRC Propene Run EC-277  	  .    56




   6   Simulation of SAPRC Ethene Run EC-156 	    57




   7   Simulation of UNC Propene Run 6.16.78 Blue	    63




   8   Simulation of UNC Ethene Run 11.19.78 Red	    64




   9   Simulation of SAPRC Butane Run EC-309 	    69




  10   Simulation of UNC Butane Run 2.27.78 Red	    73




  11   Simulation of SAPRC Acetaldehyde Run EC-253 	    76




  12   Simulation of SAPRC Formaldehyde Run EC-252 	    77




  13   Simulation of UNC Acetaldehyde Run 8.08.78 Red	    78




  14   Simulation of UNC Formaldehyde Run 9.14.77 Red	    79
                                    v±

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                                 TABLES
Number                                                             Page

   1   Atmospheric Reactions of Toluene 	     13

   2   Reported Rate Constants for Reaction of OH Plus Aromatic
       Hydrocarbons 	     14

   3   Observed Products from SAPRC Chamber Run EC-273  ....     15

   4   Fraction Methyl Attack by OH for Several Aromatic
       Hydrocarbons 	     18

   5   Atmospheric Reactions of Cresols 	     27

   6   Analysis of Selected SAPRC Smog Chamber Experiments  .  .     28

   7   Toluene Mechanism  	     36

   8   Inorganic Reactions  . 	     38

   9   Summary of Initial Conditions for Smog Chamber
       Experiments for Toluene and m-Xylene 	     39

  10   Comparison of Experimental and Simulation Results for
       Toluene and m-Xylene Chamber Experiments 	     40

  11   m-Xylene Mechanism	     46

  12   Propene Mechanism  	     53

  13   Ethene Mechanism	     55

  14   Summary of Initial Conditions for Smog Chamber
       Experiments for Propene  	     58

  15   Comparison of Experimental and Simulation Results for
       Propene Chamber Experiments  	     59

  16   Summary of Initial Conditions for Smog Chamber
       Experiment for Ethene	     60

  17   Comparison of Experimental and Simulation Results for
       Ethene Chamber Experiments 	     61

  18   n-Butane Mechanism	     66

                                  vii

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19   Summary of Initial Conditions of Miscellaneous Smog
     Chamber Experiments  	     70

20   Comparison of Experimental and Simulation Results for
     Miscellaneous Chamber Experiments  	     71

21   Aldehyde Mechanism	     75
                                 viii

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                               SECTION 1
                            INTRODUCTION

     To assist the United States Environmental Protection Agency in
developing models to describe the chemistry of photochemical smog forma-
tion,  SRI International has continued to develop explicit mechanisms
describing the chemistry of individual hydrocarbons.1  This report
discusses our efforts during the past two years to develop mechanisms
describing the chemistry of aromatic hydrocarbons and simple alkenes
and  alkanes.  EPA-supported smog chamber data from the Statewide Air
Pollution Research Center  (SAPRC) at the University of California,2
Riverside, and the outdoor facility at the University of North Carolina3
have been used to test and verify these models.
     Considerable effort has been made to develop detailed models to
describe the photochemical smog chemistry of individual hydrocarbons.
Demerjian, Kerr, and Calvert^ and Niki, Daby, and Weinstock5 were the
first  to work on problems of developing detailed mechanisms.  Hecht,
Seinfeld, and Dodge6 investigated constructing a more compact mechanism
while  maintaining important details generalizing certain reactions.
.Whitten et al.7 have also worked on developing detailed mechanisms,
but  with the goal of developing a method to generalize the reactivity
of a wide variety of hydrocarbons.  The most recent effort to update
the  complex chemistry of propene and n-butane, besides our own effort,
is the work of Carter et al.8 who have applied the mechanisms to modeling
SAPRC  data.
     Our general approach to developing the kinetic models has been
to use critically evaluated kinetic data for each of  the reactions
wherever possible.  Where data on specific reactions  were not available
or not at the appropriate temperature and pressures,  we have used  thermo-
chemical techniques to estimate the desired rate constants.  Whenever
thermochemical data were used to predict rate constants, error bounds

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were determined for both the thermochemical estimates and the resulting
rate constants.  If needed, we varied the estimated rate constants
within these error limits to optimize the agreement between computed
and experimental concentration-time    profiles.  This type of procedure
can artificially compensate for other inaccuracies in the model and
reduce the reliability of the model for application to conditions
at atmospheric concentrations of reactants.  When rate constants
were varied to optimize agreement between simulated and experimental
results, the mechanisms for different hydrocarbons were considered
together and the rate constants of concern were adjusted as a group.
In this way we used the maximum possible data base to guard against
fortuitous compensations obscuring deficiencies in the mechanisms.
     The major effort in model development during the last two years
has been on the toluene mechanism.  The experimental data base has
been enlarged since our report two years ago,1 but the product balances
in chamber experiments still account for less than 30% of the carbon
for the most complete product analyses.  The major changes
in the toluene mechanism have been made based on the following new
experimental data.
     (1)  A smog chamber study of o-xylene has shown that one
          reaction channel, accounting for 18% of the reaction of OH
          with o-xylene, gives biacetyl as a product.9  A similar type
          of ring cleavage reaction has been assumed for toluene
          where glyoxal and methylglyoxal are formed.  There are
          no data from smog chamber experiments that these compounds
          form, but they would readily polymerize and react with hy-
          droxylic compounds and may be extremely difficult to quan-
          titatively measure or even detect using direct gas chromatography
          techniques.
     (2)   New laboratory data on the reaction of benzaldehyde plus
          OH indicate that only the following reaction is important

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                     CHO             0=

                           + OH —*-  fVj I   + H20


          with no evidence of ring addition of the type observed for
          alkyl-substituted aromatic hydrocarbons.10
     (3)   Laboratory data have been reported for the chemistry of
          peroxybenzoyl nitrate (PBzN).1*  The reactions that have
          been evaluated are

                  PhC(0)02« + N02 —*-  PhC(0)02N02

                      PhC(0)02N02 —»-  PhC(0)02« + N02

                   PhC(0)02» + NO —*-  PhC(0)0« + N02

                         PhC(0)0« 	*- Ph» + C02

These data fix the role of PBzN in the  toluene mechanism and, together
with data on the reaction of OH and benzaldehyde, clarify the role of
benzaldehyde in the overall toluene mechamism, although the fate of
Ph» is still unknown.
     The major change in the mechanisms for alkenes is the observation
of Herron and Huie12 that the reaction of alkene plus ozone does not
form free radicals as readily as was originally thought.  For ethene,
the reported reactions are

                     CH2-CH2 + 03 —*-  CH20 + CH202
                                  207
                           CH202     > H2 + C02
                           CH202  70%> H20 -I- CO

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                                  107
                           CH2Oa    »  2H-  + C0
Thus the interaction of ethene and 03  gives a pair of radicals  only
10% of the time rather than the 100% that had been assumed  earlier
by most modelers.

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                               SECTION 2

                    CONCLUSIONS AND RECOMMENDATIONS

     Models have been developed to describe the participation of toluene,
m-xylene, ethene, propene, and n-butane in the formation of photochemical
smog.  Each model uses the best kinetic data available and is chemically
consistent with the others.  Some adjustment of unknown rate constants
was necessary to give good agreement between the smog chamber experiments
and the simulations.  Although this has been especially true for the
models for the aromatic hydrocarbons, it was also necessary to a lesser
extent for ethene, propene, and n-butane.  The amount of adjusting of
parameters has been kept to a minimum, and although better overall
agreement could undoubtedly be obtained by further fitting, it would
not necessarily improve the predictability of the model under atmospheric
conditions and would certainly obscure the deficiencies of the models.
     A toluene mechanism has been developed that reflects the chamber
data observation that approximately three NO are oxidized and one NO
                                                                    3C
is consumed for each toluene molecule reacted.  The mechanism has
been applied to 31 SAPRC and 2 UNC toluene runs.  In the simulation
of the SAPRC data, the average time to N02 maximum was 4(±26)% greater
than observed, and the N02 maximum concentration was 8(±6)% higher.
The simulated ozone maximum came 32(±28)% later than observed, and the
maximum concentration was 47(±39)% larger-.  The data for ozone reflect
the tendency to predict the correct initial ozone formation rate but
not to predict the leveling off in the ozone formation at the maximum.
This phenomena is not unique to toluene and appears to be related to an
overprediction of H02" once the NO  is essentially totally consumed.
                                  A
     A model for the reaction of m-xylene was constructed based on
the toluene model and taking into account both the higher reactivity
of m-xylene and the additional methyl group in the parent hydrocarbon.

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Using the four SAPRC m-xylene runs to test the model, we found the
simulated time to the ozone maximum 36(± 44)% high and the maximum
ozone concentration 17(± 16)% high.
     With minor changes in kinetic models describing the photochemical
smog chemistry of ethene, propene, and n-butane, proposed earlier,1
both new SAPRC and UNC smog chamber experiments for these hydrocarbons
have been simulated with relatively good results.  The modeling of
the outdoor UNC chamber requires no modification of the homogeneous
mechanisms used for SAPRC data, although some changes in heterogeneous
processes were made as would be expected.  It is only necessary to
account for diurnal and seasonal effects on light intensity at each
wavelength as well as the random variation of temperature and cloud
cover.  In all cases it was necessary to use initial nitrous acid as
an adjustible parameter.  In the case of the propene experiments, where
there is the best data base, the ozone  maxima  are overestimated by
31(±37)% in the SAPRC experiments  (13 runs) and  18(±35!X%  in the
UNC experiments (17 runs) .  The ethene and n-butane mechanism overestimates
ozone similarly.
     To improve our ability to model photochemical smog and increase the
accuracy  of  our current mechanisms,  we  recommend that  the following informa-
tion  be obtained:
     (1)  Analyze the loss mechanisms of relevant species at the
          point of experimental ozone maximum to determine what reactions
          and rate constants can cause the observed discrepancies in
          the ozone maximum and the time to ozone maximum.
     (2)  Obtain complete product analysis for the toluene smog chamber
          experiments as well as product analyses for other aromatic
          hydrocarbons.
     (3)  Determine rates and pathways for photolysis of the critical
          photoactive intermediates that are proposed in the toluene
          mechanisms.
     (4)  Determine mechanisms of the reactions of alkenes with ozone.
     (5)  Determine alternative decomposition pathways for peroxynitrates.

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(6)   Determine effect of beta-OH-substituents  on rates and products
     of cleavage of alkoxy radicals.

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                               SECTION 3
                                APPROACH

 SMOG CHAMBERS
      In this report  explicit chemical mechanisms for the formation
 of photochemical  smog  in  the photooxidation of hydrocarbon-NO
                                                             X
 mixtures are validated against smog chamber experiments.  Two sets
 of data are used:  one  from the Statewide Air Pollution Research Center
 (SAPRC)2 at the University of California-Riverside and another from
 the University of North Carolina  (UNC).3  Both data bases consist
 of concentration-time  profiles from the irradiation of static mixtures
 of a hydrocarbon  and NO .  Data are available for a number of hydrocarbons,
                       -A.
 at various hydrocarbon/NO and N0/N0a ratios.
                          j£
      The SAPRC data  are obtained  under conditions of constant temperature
 (mostly at ^ 300  K), constant light intensity, and constant spectral
 distribution.  The data are thus  relatively easy to simulate, but
 somewhat different from real atmospheric conditions.  The UNC data,
 on the  other hand, are obtained using solar irradiation.  Therefore,
 during  the experiments, the temperature and the solar intensity and
 spectral distribution  change as the sun rises and sets.  In addition,
meteorological variables  such as  cloud cover produce an additional
variation on each  run.  These data are more difficult to simulate because
of  these  added variables, but are more representative of the real
atmospheric conditions.   The UNC  chamber also has a much lower
surface-to-volume  ratio than the  SAPRC chamber, which should minimize
heterogeneous effects.
     In  simulation of  the SAPRC data, once the temperature and light
intensity dependent rate  constants are calculated for a particular
run, they remain constant throughout that run.  The necessary experimental
parameters are reported by SAPRC  and there is little doubt that these
processes are well represented in the model.  In simulation of the UNC
                                   8

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data, many rate constants vary with time during the run because  of
the changes in temperature and light intensity.  This makes the  simulations
more complex and is a possible source of error.  In general, however,
we feel that the variations of temperature and light are well represented
in the model, within the limits of the reported experimental parameters,
and that this is not a significant source of error.

LIGHT INTENSITY CALCULATIONS
     For the SAPRC runs, the light intensity distribution is computed
from the relative light intensity at 12 wavelengths between 300  and
500 nm and from the experimentally determined value of the N02 photolysis.
Photo rates for compounds are then computed from the reported cross
section and quantum yields plus the computed light intensity spectrum.
     For the UNC experiments, which rely on solar radiation, the photo
rates are computed hourly using the procedure of Schere and Demerjian.*3
These calculations correct for location and difference in distribution
during the day.  To correct for cloud cover, hourly averaged total
solar radiations were compared with clear day values, and the ratio
was used to reduce all photo rates accordingly.  The UNC chamber has
an aluminum floor that reflects the solar radiation and enhances the
light intensity, primarily from 3 to 6 PM.  To correct for this
effect, we increased the computed photo rates by a factor of 1.125 during
this interval.

CHAMBER CHARACTERISTICS
     In addition to light intensity differences, both facilities  were
characterized with regard to ozone decay.  A decay constant of 1 x 10" 3
min"l was used for the SAPRC runs and a value of 4 x 10~ * min~ *  was
used for the UNC chambers.
     Dilution rates for the chambers also vary.  For the SAPRC chamber
the value is approximately 3 x 10~u min~l and for the UNC chamber
the value is 1 x 10" * miri"1.

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     Our earlier analysis1 of the SAPRC data concluded that there is
a source of either OH or H02» radicals from the chamber walls equal
to a rate of 2.0 x 10~ u ppm miri" x.  We have continued  to include this
source of radicals in the simulation of all SAPRC data.  There is no
evidence for such a source of radicals in the UNC experiments.

MODELING TECHNIQUE
     The simulations of the concentration-time profiles of various
species were obtained from the given mechanism and the appropriate
starting concentrations using the computer program CHEMK of Whitten
and Meyer.1'1'  This program constructs the differentials describing
the rate of change in concentration of each species of the input
mechanism.  The actual numerical integration of these differentials
is then performed by the Hindmarsh15 version of the Gear16 integration
method.
                                    10

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                               SECTION 4
                        AROMATIC HYDROCARBONS

CONTRIBUTION OF AROMATICS TO TOTAL ATMOSPHERIC HYDROCARBONS
     Single-ring aromatic hydrocarbons make up a substantial fraction
of the hydrocarbons found in urban and nonurban atmospheres.  Calvert1
reported that in Los Angeles, California (1973) 23% of the carbon
present as hydrocarbons, excluding methane, is in the form of aromatic
compounds.  A report for Manhattan, New York (1969), indicates that
32% of the organic carbon is from aromatic compounds.18  Measurements
of hydrocarbons in various non-urban areas of sourthern Florida (1976)
indicate that 20% to 30% of the carbon is found in aromatic compounds.19
Based on the Los Angeles data,17 the aromatic hydrocarbons are composed
of about one-third toluene and one-third xylene isomers, with the
remaining third composed of, in decreasing order, benzene, sec-butylbenzene,
ethylbenzene, and n-propylbenzene.  The Florida study indicated this
same general distribution of compounds but identified additional minor
amounts of di- and tri-alkylbenzene.19
     Calvert17 analyzed the distribution of hydrocarbons based on their
reactivity toward OH and showed that, in the Los Angeles case, aromatic
hydrocarbons contribute up to about 20% of the total reactions of OH
with hydrocarbaron.  The xylene isomers contribute 12.5% to the total
OH-hydrocarbon reactions, more than any other compound detected in the
atmosphere.  Toluene, the second most important aromatic compound, is
the sixth most important compound overall and accounts for 5.1% of all
OH-hydrocarbon reactions.  The only compounds contributing more than
toluene are propene (6.3%), isobutene (8.1%), isopentane  (8.4%), 1-heptene
(7.5%), and the xylenes (12.5%).
     The aromatic compounds found in the urban atmosphere are considered
to come largely from gasoline in which they are used to increase the
octane rating.  Gasoline in the Los angeles basin is composed  largely
                                   11

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 of aromatic hydrocarbons  (30%-40%)  and  Includes 6%  to 8%  toluene.
 Therefore, it is not surprising  that aromatics make up a  large  fraction
 of the hydrocarbons in the  urban atmosphere.  In recent years the aromatic
 component of gasoline has been increased so as to maintain  the octane
 rating because the use of tetraalkyl lead compounds has been restricted.
 Since additives to enhance  the  octane   rating are not likely to be
 developed and produced in sufficient quantitites to significantly affect
 the use of aromatics in gasoline, aromatics will continue to be a major
 component of the atmosphere for  some time.

 REACTIONS OF AROMATIC HYDROCARBONS
      Table 1 summarizes the atmospheric reactants that we believe could
 react with aromatic hydrocarbons, along with approximate concen-
 trations of these reactive  species  and  the best estimates of rate constants
 for their reaction with toluene.  From  these data, only the reaction with
 OH is expected to be important.   Collision with aerosol particles is
 considerably faster, but  adsorption is  expected to be very inefficient
 (< 10" * per collision)  and  thus  should  not compete with the reaction of
 OH.
      Reaction with 0(3P)  could account  for 0.1% as much reaction as OH;
 even under conditions favoring 0(3P) this percentage would not  be greater
 than 1%.   The limit for the photolysis  rate is about the  same as the
 0(3P)  rate.   The photo  rate is a limit  because we do not  know the cross
 sections  in the solar region or  the quantum yields; we have used liberal
 estimates  in  both cases to  define an upper limit.
     For aromatic hydrocarbons besides  toluene, we  expect the reaction
 rates with  the  various  atmospheric  species to parallel those for toluene.
 Therefore,  only their reactions  with OH are of interest.  Table 2  summarizes
 the  rate constants  for  OH reactions for a variety of aromatic hydrocarbons
as reported by  four  sources.  The values reported by Davis et al.,20»21
Perry et al.,22  and  Hansen  et al.23 were obtained using resonance
fluorescence  to monitor OH  decays,  and  in the case  of Doyle et  al.28
the values were  obtained by measuring the rate of disappearance in  smog
                                    12

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              TABLE 1.  ATMOSPHERIC REACTIONS OF TOLUENE
Species
0(3P)
OH
H02«(ROa»)
03
NO 2
N02*
NO 3
02(XA)
hv
Particulate
Cone , ppm
10- 8
10' 7
icr3
0.1
0.1
< 10""
10" 6
* 10- 5
—
^WsC
k, ppm" l miri" 1
1.
9.
2.
5.
1.
4
< 3
< 2
« 7
* 1CT
1
4
5
0
0
x
X
X
X
6 (
x 102
x 103
x icr7
x 10- 7
x 10" 8
10- 5
icr2
10" 3
ID- s
i
(Reference)
(24)
(20, 22, 23)
(25)
(26)
(a)
(a)
(27)
(a)
(b)

Ttol'
9
1
4
2
1
2
> 3
5
» 1
a, 0
.0
.1
.0
.0
.0
.5
.3
.0
.4
.2
min
x 10s
x 103
x 1011
x 107
x 109
x 108
x 107
x 107
x 10"

^Estimated.
 Assumes a < 2 x 10"22 molec"L cm"2 from 290-400 nm and a quantum yield
 of unity.
^Particles cm"3 average particle of 0.1-ym diameter.
 Collisions s" l.
chamber experiments relative to the disappearance of n-butane, which is
known to react solely with OH.  The agreement between the two methods
is as good as the agreement between the reported values obtained by
resonance fluorescence, about ± 15%.  The exception is that, for toluene,
the average of the three resonance fluorescence values agrees within 5%
while the second method gives a value about 30% less than the mean of
these values.
                                   13

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 TABLE  2.   REPORTED RATE CONSTANTS FOR REACTION OF OH PLUS AROMATIC
           HYDROCARBONS
Compound
Benzene
Toluene
o-Xylene
m-Xylene
p-Xylene
1,2,3-Mesitylene
1,2,4-Mesitylene
1,3,5-Mesitylene
Perry
(Ref. 22)
1.20
6.40
14.3
24.0
15.3
33.3
40.0
62.4
Hansen
(Ref. 23)
1.24
5.78
15.3
23.6
12.2
26.4
33.5
47.2
Doyle
(Ref. 28)
< 3.8
4.2
12.8
23.2
12.3
23.0
33.0
52.0
Davis
(Ref. 20, 21)
1.59
6.11
12.4
20.5
10.5
—
—
—
 PRODUCTS OF REACTION OF AROMATIC HYDROCARBON
     All attempts to determine the toluene reaction products in controlled
 smog chamber experiments have failed to account for large fractions of
 the reacted hydrocarbon.  Table 3 summarizes data for a typical experiment
 reported from the SAPRC facility.2  Early in the experiment, less than
 20% of the carbon from the consumed toluene is accounted for.  PAN, CO,
 and benzaldehyde account for most of the detected products.  The cresol
 isomers account for only a small portion of the consumed toluene.  They
 form early in the reaction and the amount detected stays constant until
 late in the reaction when it decreases slightly.  Later in the reaction,
 the carbon accounted for increases to 22%, but most of the increase is
due to CO, which accounts for 67% of the found carbon.  Some of the CO
may result from wall decomposition of products that are present from
previous runs.   In this case the observed CO values would be considerably
larger than they should be.
     O'Brien and coworkers29 of Portland State University have investigated
the reaction of toluene at concentrations of toluene and NO  about 10
                                                           X
times higher than those at SAPRC.  They observed low yields of benzaldehyde
                                   14

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                             TABLE 3.  OBSERVED PRODUCTS FROM SAPRC CHAMBER RUN EC-273
                                                                              Time,  min
                                                                         JL2JL
                          .180.
240
300
360
Toluene, ppm


A Toluene, ppm


PAN


CHZ0


AcH


CO


o-Cresol


m-Cresol


p-Cresol


Benzaldehyde (+ trace of benzylnltrate)


Nltrotoluenes


Consumed toluene accounted for as products, % carbon


  As CO, % carbon

              a
  As products,   % CH3
0.587    0.423    0.383   0.334    0.309    0.284    0.255


         0.155    0.197   0.247    0.272    0.298    0.327


0.000    0.024    0.032   0.031    0.029    0.028    0.028


0.002    0.006    0.004   0.009    0.009    0.013    0.017


0.001    0.002    0.004   0.006    0.007    0.007    0.008


0.33     0.38     0.37    0.47     0.57     0.63     0.67


0.0005   0.0027   0.0026  0.0024   0.0027    0.0018   0.0014


0.0003   0.0001   0.0001  0.0002   0.0001    0.0001   0.0001


0.0047   0.0053   0.0056  0.0052   0.0054    0.0040   0.0048


0.0009   0.0097   0.0111  0.0118   0.0158    0.0123   0.0116


0.0000   0.0010   0.0008  0.0008   0.0010    0.0008   0.0009


         17.6     15.1    18.2     23.5     22.4     22.1


          4.6      2.9     8.1     12.6     14.4     14.8


         2.39     24.8    20.2     20.2     15.8     14.7
 Includes PAN and AcH but not CH20,  which only in part Is from the CH9-group.

-------
 (^ 4%) and o-cresol  (6%) and several nitrogen-containing compounds:
 benzylnitrate  (1.6%), m-nitrotoluene (3.8%), and p-nitrotoluene (1.65%).
 Including these nitrogen-containing products, which are expected to be
 more prevalent in these experiments because of the higher concentration
 of NO  , and CO, 27% of the consumed toluene is accounted for.  A limit
     X
 of less than 1% is set on the amount of ring cleavage products in the early
 stages by these workers.  At very long reaction times significant CO formation
 occurs, a result supporting the high CO data in the SAPRC run summarized
 in Table 3.
     Jefferies, Fox, and Kamen of University of North Carolina have
 carried out some runs with toluene in their outdoor smog chamber.3
 Although they have not yet made an extensive study of the products, it
 is clear that CO formation occurs in the reaction.  At 60% conversion     (
 of the toluene, about 9% of the consumed carbon is converted to CO.
     To summarize these smog chamber studies of toluene, one must conclude
 that gas phase products account for about 20%-26% of the carbon consumed.
 After  the N02 maximum, much of the carbon found is of low molecular
 weight products CO, PAN, CH20, which can be formed only by ring cleavage.
 Because it is impossible to use these data to construct a clear picture
 of the toluene mechanism for modeling purposes, it is important to
 consider other studies beside the smog chamber data.
     In their determination of the rate constants of OH with aromatic
hydrocarbons,  Perry et al.22 found an unusual temperature dependence
for the OH decay with all aromatic compounds.  They concluded that two
reaction paths are important, one of which is reversible at elevated
temperatures.   The two pathways are
                          CH3
OH+
                                       HOH
                                   16

-------
                OH +
                                                                    (2)
At high temperatures (85° to 200°C) where reaction (2) was readily
reversibly, the decay of OH was governed by reaction (1).  They found
for this reaction log (ki/cm3  molec"1 sec"1) = -11.3 (± 0.05) - 900(± 1000)/RT;
thus at 30°C kx = 1.1 x 10" 12 cm"  molec"x s"1.  Because of the extrapola-
tion, ki nay range from 0.65 to 1.9 x 10"12.  At 30°C they found a much
faster decay constant, which is ki + ka and equals 6.4(±0.64) x 10" 12.
Therefore, ka = 5.3 x 10" 12 cm3  molec"1 s~ x and WCkj. + k2) = 0.16
(range:0.11 toO.20).  Thus, attack at the methyl group under atmospheric
conditions accounts for about 16% of the OH reaction, with the large
uncertainty due to the value range of kn.  The possibility that the
reversibility of reaction  (2) is important at atmospheric conditions is
ruled out by the lack of a pressure effect on the observed decay content
at 30°C.  Values of ki/(kj + ka) for several aromatic hydrocarbons are
listed in Table 4.
     To determine the stable products from reactions (1) and (2) under
atmospheric conditions and thereby evaluate the ratio kx/Ckj. + k2) by
a more direct method, we investigated the OH-aromatic reaction in our
own laboratory.10  A low pressure flow system is used to generate OH,
which is then allowed to react with various aromatic hydrocarbons.
The products are determined by sampling the gas stream with solid phase
absorbance and by condensing the organics, followed by gas chromatography
and/or field ionization mass spectroscopy.  These results indicate that,
at the high ratios of Oa/N02 found in the atmosphere, the benzyl radical
formed in reaction (1) gives benzaldehyde by the proposed mechanism
                           CH202«        CH20»          CHO
                                 NO
o   -  ro   ^  ro
                                                                       (3)
                                   17

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TABLE 4.  FRACTION METHYL ATTACK BY OH FOR SEVERAL AROMATIC HYDROCARBONS
                   Hydrocarbon
                                                                  k2)
Perry et al.(23)   Hendry et al.(10)
        Benzene
        Toluene
        o-Xylene
        m-Xylene
         p-Xylene
         1,2,3-Trimethyl benzene
         1,2,4-Trimethyl  benzene
         1,3,5-Trimethyl benzene
   0.05
  (0.01-0.13)
   0.16
  (0.11-0.23)
   0.20
  (0.10-0.35)
   0.04
  (0.02-0.04)
   0.07
  (0.04-0.14)
   0.035
  (0.02-0.12)
   0.03
  (0.02-0.06)
   0.02
  (0.02-0.04)
< 0.05
  0.15 ± 0.02
  0.15 ± 0.02
  0.021  ±  0.006
 aRate constant kx  includes  abstraction of  aromatic ring hydrogens in this case.
  In other cases this  added  process  is  relatively unimportant because of the
  much larger values of kj, and  k2.
 and  the adduct formed in reaction (2)  gives  o-,  m-,  and p-cresols by the
 reaction
                          H
                                            CE-.
                              + 0:
      + H0a«
   (4)
                                    18

-------
From the ratio of products, it is possible to estimate the ratio k
+ ka).  These values are also included in Table 4.  Comparison of these
values with those reported by Perry et al., shows that they are in
excellent agreement.
     These results suggest that the initial products from the reaction
of toluene should be ^ 15% benzaldehyde and 85% cresol.  This conclusion
contrasts strongly with the smog chamber results discussed above where,
at best, about 6% benzaldehyde and about 5% total cresol isomers are
observed early in the run  (see Table 3).  Other laboratory results
complicate the issue even  further.  Heuss and Glasson30 found, in their
smog  chamber  study of toluene, that benzaldehyde accounted for 19%
of the products, a value agreeing well with laboratory measurements
mentioned above.  However, the only other products reported were 3%
formaldehyde  and 4% PAN.   Kopczynski et al.31 conducted experiments
on mixtures of aromatics including toluene and reported no evidence of
benzaldehyde, although toluene was a relatively small fraction of the
mixture.
      Hoshino  et al.3^ attempted to determine the atmospheric products of
OH plus toluene by photolyzing HONO and a large excess of toluene in
air.  These results indicate that 70% of the detected products are cresol or
products that would have been expected to give cresol if the OH-toluene
adduct were not partially  trapped by the high concentration of N02; 30%
of the products are benzaldehyde or benzylnitrate, which would have given
benzaldehyde  in the absence of high N02.
      Akimoto  et al.33 determined the toluene products from photolysis
of N02-toluene mixtures under conditions where they suggest 0(3P) is
the reactive  species.  However, because of the high N02 concentration
(11-174 ppm), a very high  fraction of 0(3P) reacts with N02 by the reaction

                           0 + Ntf2 —*- NO + 02                       (5)

Thus  it is possible that OH is the dominating reactant species in these  re-
actions.  The ratio of products resulting from methyl-attack versus the  sum
of methyl attack and ring  attack (corresponding to ki/(kj. + k2) ranges
                                   19

-------
from 0.16 to 0.30, overlapping the value expected for OH reactions from
the laboratory experiments.
     Nojima et al.3£* investigated the products resulting from photolyzing
toluene (2000 ppm) in the presence of air containing 50-1000 ppm NO.
The reaction mechanism could involve OH, although the conditions may
favor wall reactions.  They found only 11% of the consumed toluene
as benzaldehyde, cresol, m-nitrotoluene, p-nitrotoluene, and nitrated
cresols.  With 50 ppm NO and after one hour, they found ^ 0.5% glyoxol
and 3% methylglyoxol, which are indicative of ring cleavage.  Because
of the severity of the reaction conditions, it is not possible to tell
if these last two products are formed directly or by secondary reaction
of the benzaldehyde and cresols products.
     Strong evidence for direct ring cleavage of aromatic rings by OH
comes from recent SAPRC chamber data for o-xylene reported by Darnall
et al.9  They found that biacetyl formation occurs very early in these
runs, consistent with 18 ± 2% of the xylene-OH reaction giving this
product  directly.  They found that the biacetyl photolyzes rapidly,
generating acetyl radicals, which are converted to PAN.  Complete product
analyses are not given and these two products account for only about
12% of the carbon from the consumed xylene.  However, based on this
data, the reaction of toluene would be expected to give methyl glyoxal
(pyruvaldehyde) to approximately the same extent as biacetyl in the o-xylene
experiment.

TOLUENE-OH REACTIONS
     From the data of Perry et al.22 and Kenley et al.,10.35 the first
step of the OH toluene reaction is
                                    20

-------
     OH +
                                               + H20(+33 kcal/mol)  (6)
                                              OH  (+ 24 kcal/mol)    (7)
The isomer distribution of the last product is 81% ortho, 14% para,
and 5% meta.10  The benzyl reacts by the following series of reactions
                       CH2»
                     o
+ 0:
                            (8)
                       CH202»
             CH20«
                      O
+ NO
O
+ N02
(9)
                       CH202»
             CH202H
                             + H02«
            O
                       CH20»
              CHO
                                                + H02«
                           (10)
                                       (11)
                                   21

-------
                     :H2o«
                  12ON02
                    o
   + N02
o
                     (12)
                     CH20-
                 CHO
                    O
   + N02
 o
+ HN02
(13)
 Under  normal atmospheric conditions, reaction (11) dominates the other
 reactions  involving PhCH20».  The chemistry of the OH adduct formed
 in reaction  (7)  is as follows
                              0
                                         CH;
               O
           + H02«
                     (14)
                                          CHS
                                     0-
                                                   (+ 8 kcal/mol)    (15)
                   CH3
                 G
-OH
      N02
From the data of Kenley et al.,35 the ratio of  rate  constants for
reaction (14) and reaction (16) is 2.3 x 10" \   Since  k^   is expected
to approximate 3 x 109 M~1 s"1, kn  must be approximately 1.0 x 10s M" *
                                 O2
                                   22

-------
s~l.  This value compares with 3.9 x 10s tf~1  s~ x  for  the  similar  reaction
of methoxy plus 02
                                                36
                       CH30« + 02
              CH20 + H02-
(17)
The second reaction with oxygen  [reaction  (15)]  to  form the organic  peroxy
radical is expected to be just % 1 x  109 M~l  s~ i.   The heat of  reaction
is estimated to be 8 'ccal/mol; thus the back  reaction may  be approximated
by the expression

                          log k-ls =  15.0  - 8,000/RT
                               k30o =  1.5 x  109  s"1
The  fate  of  this  peroxy  radical  is  determined by what  can  compete with
its  decay back to carbon radical and  oxygen.  Possible competing reactions
are
                  .0-0
                  •0-0
                               + NO
N)H.
                                             NDH
                         + N02
                                     N0200 CH3
                                              *N)H
(18)
                                                                    (19)
                  •0-0  CH3
                                             'H
                                                                    (20)
                                    23

-------
      The reaction with NO is  expected  to  proceed  rapidly with  a  rate
 constant of k = 1 x 10* IT1  s~ x.   Thus at even NO =  0-1 ppm (4 x 10~9  M),
 k[NO] = 4s"1.  The reaction with  N02 is expected  to  proceed at a rate
 similar to reaction (18); however,  in  this case the  product is expected
 to decompose back with a rate constant of 10"2 s~ l such that further
 reaction is unlikely.37
      Reaction (20) has been  suggested  by  Darnall  et  al.9 as the  major
 reaction leading to ring cleavage in the  reaction of o-xylene.  However,
 the addition of peroxy radicals to conjugated dienes has an activation
 energy of 10 kcal/mol.25  Thus the activation energy for reaction (20)
 is expected to be 10 plus ;the increase in strain  energy, which is
 another  5-10 kcal/mol.  Thus assigning an A  factor  reflecting the  large
 loss of entropy gives the maximum rate constant for  reaction (20) as

                              log  k < 12 - 15000/RT

                            k(3oo)  < 10 s"x

      Thus none of three reactions of the  organic  peroxy radical  that
 we can visualize is fast enough to compete with its  decomposition back
 to OH-toluene adduct and oxygen  [reaction (-15)].  This leads  us to
 the conclusion that the only  reaction  the toluene-OH adduct should
 undergo in the atmosphere is  reaction  (14) to the corresponding  cresol.
 This conclusion is consistent with our laboratory data,10  except that
 only traces of cresols are found  in smog  chamber  experiment.  Thus
 either we have not anticipated all the possible homogeneous reactions
 of the toluene-OH system or very  rapid reactions  of  the cresols  and
possibly  benzaldehyde account for the  large degree of ring cleavage observed
 in      smog chamber runs.
      If we assume that the reactions of cresol and benzaldehyde  are
 only with OH,  a simple consecutive model  may  be assumed where  the OH
 radical concentration is constant.  The concentrations of  toluene,
 cresol,  and  benzaldehyde as function of time  may  be  approximated by
 the  expressions38
                                    24

-------
                              [Tol] =  [Tol]oe"kTol[OH]t

                                      f
-kTc
                                      Cres    Tol
                                     f k    [Tol]    •     [OH]t         f
                     [Benzaldehyde] =  ° Tol_    °(e"kTol     -e~kBenzC°H]t)
                                      oenz    Tol
where k's are rate constants for reaction of OH with toluene  (9.0 x 103
ppnf l miri"1)22 cresol  (6.9 x 10* ppm~ * min~1),39 and benzaldehyde
(2.0 x 10* ppnf1 min"1),1*0 and f  and f, are the fractions of reaction
of toluene plus OH to  give cresol (0.85) and benzaldehyde (0.15).
Assuming an OH concentration of 2 x 10~7 ppnf l, 1 ppm toluene will be
reacted to the extent  of 0.103 ppm after 60 min, and the concentration
of cresol and benzaldehyde would be 0.057 and 0.014 ppm, respectively,
or 55% and 13% of the  consumed toluene.  The remaining 32% would be
cresol and benzaldehyde reaction products.  After 300 min these expressions
indicate 0.417 ppm toluene reacted (^ 42%) and concentrations of cresol
and benzaldehyde of 0.067 and 0.034 ppm or 16% and 8% of the consumed
toluene, respectively.
     The data in Table 3 indicate much lower concentrations of cresol
and benzaldehyde, especially early in the reaction.  Thus we must again
conclude that there are alternative pathways by which toluene reacts
or alternative pathways by which the cresols and possibly benzaldehyde
react.  In the case of the cresols, the rates of the alternative pathways
would have to be 10 times faster than the cresol plus OH reaction.
The reported rate constant for the OH-cresol reaction is close to diffusion
control so it is impossible for it to be 10 times faster.  It is important
for us to consider what cresol reactions might compete favorably with
the OH reaction and whether or not they can account for the cleavage
of the aromatic ring and thereby formation of PAN and other low molecular
weight products.
                                   25

-------
 REACTIONS OF CRESOL
      Since cresol isomers  are  anticipated based  on  thermochemical and
 kinetic reasoning but are  not  found,  it  is important to consider what
 reactions ofcresol can be  important.   Table  5 lists typical concentrations
 of various atmospheric species,  their rate constant with cresol, and
 their lifetimes.   From the table we  see  that the reactive species 0(3P),
 H02» (R02«), and 03 are considerably less important than the reaction
 with OH.  We know less about N02,  N03, and 02(1A), but from our estimates
 it does not appear that any of these species will account for the observed
 discrepancy.  Similarly, direct  photolysis appears  to be unimportant
 because of the weak adsorption in  the solar  spectrum.
      The only process that is  faster than reaction with OH is collision
 of cresol molecules with particulate.  Collision with walls in a chamber
 will proceed at an even faster rate.   If the cresol has no affinity
 for absorption to the surface,  there should be no effect.  However,
 because cresols are highly polar,  they would be  expected to be readily
 absorbed and because they  are  susceptible to oxidation, further reaction
 may occur.  Thus  it appears that if  toluene  is converted largely to
 cresols, then cresols at least must  be rapidly reacting on the chamber
 walls.   This possibility should  be carefully investigated.
 ANALYSIS  OF NO  OXIDATION AND NO   CONSUMPTION IN TOLUENE REACTIONS
                               X
      We analyzed  several toluene  runs  reported by  SAPRC to  determine
 both  the  amount of NO being oxidized per  toluene consumed and  the  amount
 of NO disappearing  per toluene consumed  during the  time leading up
      X
 to the NO  maximum and for the comparable length of time following  the
          ^v
 NO  maximum.  Table  6 gives these results.
  A
      During the time required to  reach the N02 maximum, an  average of
 2.7 net NO  molecules are oxidized to form N02 and  03 for each  consumed
 toluene.  After the  NO  maximum,  the value falls to  1.8.  Conversion
                      X
of toluene  to benzaldehyde is expected to require  2  NO per  toluene,
whereas conversion to cresol requires  only 1 NO per  toluene.   Thus the
additional  oxidation of NO must occur  upon cleavage  of the  ring and/or

                                   26

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               TABLE 5.  ATMOSPHERIC REACTIONS OF CRESOLS
Species
0(3P)
OH
H02»(R02«)
03
N02
*
N02
Oa(lA)
hv
Particulate
. Estimated.
Assumes a
yield and
Cone . , ppm k
10" 8
10- 7
10"s
0.1
0.1
< 10" *
10" 5 <
—
10sC
- > 2 x 10" 2a molec"x
average summer light
«^*M * * ••* mff^m*** s^s* «^ ^ *»4™ ^ ^ 1
, ppm" l min
8.6 x 102
6.9 x 10fc
2.5 x 10" 2
8.8 x 10"*
1.0 x 10"s
10
1 x 102
10" s
ID- sd
cm" 2 from
intensity. ^
l-L f* € f\ 1 	 IIWH
(Ref) T •
(41)
(39)
(42)
(39,43)
(a)
(a)
(a) >
(b)

290-400 ran and
it
ft -1 r*mf*4~ n -*•
• l/k[conc] , min
1.2 x
1.4 x
4.0 x
1.1 x
1 x
1.0 x
1.0 x
1.0 x
0.2
a unit
10s
10 2
106
10"
10 9
105
103
10s

quantum
 ,i ax. i_a.^.^.c<3 *-«*  y


 Collisions s" *.
upon further reaction of the products.  The proposed mechanism must  take



this into consideration.



     The consumption of NO  averages about 1.0 NO   per  toluene reacted
                          x                      x

up to the NO  maximum and about 1.2 after.  Much of this  loss  of NO



is due to the reaction
                         OH + N02
WO-.
(21)
The data in Table 6 indicate that  20%-40%  of  the loss  is due to this



reaction in the interval up to  the N02 maximum in most cases.  After



the W2 maximum, about 45% of the  NO  is lost by this  reaction.  PAN
                                    2t


accounts for only a small fraction of the  NO   loss:  about 8% up to the
                                            X
                                    27

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                       TABLE 6.  ANALYSIS OF SELECTED SAPRC SMOG CHAMBER EXPERIMENTS

Hydrocarbon
Hydrocarbon, ppm
NO, ppm
N02, ppm
HC/NOx
kx
(AND + A03)/4HC
t -tN°>
o max
tN02 _ NOa
max max
AND /iHC
t -tN°*
o max
N02 2tN°2
AHN03/AHC(from OH -
t -tNO'
o max
max max
APAN/AHC
t -tNO*
o max
tN02 _ 2 N02
max ~ max
Difference (%)b
co max
max max
EC-327
Toluene
0.573
0.357
0.096
1.26
0.40

2.58
2.27

0.85
1.67
t- N02)a
0.83
0.98

0.06
0.17

•v 0(0)
0.52(31)
EC- 340
Toluene
0.537
0.333
0.096
1.25
0.39

2.86
3.05

0.78
1.86

0.51
0.96

0.04
0.17

0.23(29)
0.73(39)
EC-266
Toluene
1.196
0.432
0.060
2.40
0.35

2.21
1.69

1.28
0.91

0.28
0.37

0.07
0.21

0.93(52)
0.33(36)
EC-78
Toluene
0.210
0.069
0.032
2.95
0.16

3.73
1.40

1.09
0.85

0.41
0.41

0.14
0.22

0.54(49)
0.22(26)
EC-85
Toluene
1.92
0.431
0.092
3.67
0.16

1.96
0.72

1.15
0.81

0.20
0.23

0.09
0.09

0.86(75)
0.49(60)
EC- 344
m-Xylene
0.486
0.520
0.154
0.72
0.39

2.67
2.88

0.94
2.18

0.42
0.53

0.22
0.61

0.30(32)
1.04(48)
EC-314
Propene
1.046
0.684
0.246
1.12
0.48

1.37
0.88

0.32
0.81

0.24
0.44

0.03
0.24

0.05(16)
0.13(16)
 Rate of formation of HON02 estimated from average [N02] and [OH];  the latter concentration was
.estimated from the hydrocarbon disappearance.
"Difference - (AND /AHC) - AHN03/AHC - APAN/AHC;% = 100 x Difference/(ANO /AHC).
                                                  28

-------
N0x maximum and about 16% after the N02 maximum.  This leaves 50%-70%
of the NO  loss before the N0a maximum and 40% after the maximum that
         X
is unexplained and must be taken into consideration by the mechanism.

MECHANISM FOR MODELING TOLUENE SMOG CHAMBER DATA
     Although uncertainty remains as to what initial products are formed
from the direct addition of OH to toluene, the chamber data clearly
indicate that at  least 25% and possibly as much as 90% of the consumed
toluene cleaves during or shortly after reaction by some mechanism.
Thus any attempt  to model the data must recognize this fact as well
as the observation made above regarding molecules of NO oxidized  and
NO  consumed per  reacted toluene.  However, any proposed mechanism
  X
will at best be a simplification of what may be a much more complex
process.
     For our current modeling effort we have assumed that 15% of the
toluene-OH  reaction  is described by methyl abstraction, reactions  (6), and
 (8)-(13).   The remaining 85% is assumed to react by the following reactions
                              n
                              0
                                  14.3%
            + H02«
(22)
                                  14.3%
                                         CH3C(0)CHO +  CJ
                      H02»   (23)
                                  14.3%
CH3C(0)CHO
                                                               H20    (24)
                                  28.6%
                                         HC(0)CHO 4- C5H603  + H02-      (25)
                                    '%  HC(0)CHO + C5HS06»  + H20     (26)
                                    29

-------
The fraction of the first pathway was assigned based on the observation
of cresol.  The remaining reactions were divided to give glyoxal 2/3
of the time and methylglyoxal 1/3 of the time.  This  ratio represents
statistical cleavage of the ring.
     In each of reactions (23) through (26), a fragment is proposed
that we have no experimental evidence for, but is included to balance the
C, H, and 0.  Obviously in reality each fragment could be composed of
several compounds.  For simplicity we assume fragments C<,H<,03 and C3H603
in reactions (23) and  (25) to be

               HC(0)CH=CHC(0)OH and HC(0)C(CH3)=CHC(0)OH

The fragments ChE306* and C3HS0S« in reactions (24) and (26) are assumed
to be complex acyl peroxy radicals

           H02C(0)CH=CHC(0)02» and H02C(0)C(CH3)=CHC(0)02«

     We have proposed that these reactions occur without oxidation of
NO to N02; however, variations could be written for reactions  (23) and
(25) where NO is oxidized to N02 without change in the overall modeling
results if OH were formed in place of H02».  There would be no change
in the overall conversion of NO to N02 because the fate of H02» is to
oxidize NO except when NO  is extremely low.
                         X
     The peroxy radicals formed in reactions  (24) and  (26) are assumed
to react further.  However, for simplication CSH506» has been  assumed
to be identical to C<,H306», which reacts as follows

                     C<,H306» + NO —*- N02 + HC(0)CHO + CO + C02 + H02»    (27)

                    C4H306» + N02  7-*- C«,H306N02                       (28,-28)

                        C<,H306N02 *—*- to wall                         (29)
                                   30

-------
Reaction (29) thus becomes a mechanism by which NO   is removed  from
                                                  x
the  system.   The rate of NO  loss depends on the N0/N02 ratio.
                            X
Initially when the N0/N02 ratio  is high, little NO   is lost, but by
                                                  X
the time the N0x maximum is reached,  this process is a major NO loss
process.

Reactions of Glyoxal
    Reactions  (25) and  (26) generate- glyoxal.  The glyoxal reactions
used in the simulation are hydrogen  abstraction by OH

                    HC(0)CHO + OH  - *-HCO» + CO + HOH               (30)

and photolysis 1+5

                    HC(0)CHO + hv  — *- H2CO + CO                     (31)

The rate constant used for reaction  (30) is 2 x 104  ppnf 1 miri" l , which
is the same as  for simple aldehydes.1*0  The rate constant for  reaction  (31)
has been adjusted to  optimize the  prediction of formaldehyde;  this has
led to a value of 0.01 times the N02 photolysis rate.

Reactions of Methylglyoxal
     Reactions  (23) and  (24) form  methylglyoxal .  As for glyoxal we  have
assumed reactions with OH and solar  radiation, although  radical formation
is assumed to  result  from photolysis
                   CH3C(0)CHO + OH -^CH3C(0)02-  + CO + HOH        (32)

                   CH3C(0)CHO + hv -24- CH3C(0)02«  + CO + H02»        (33)
                                                                  "•3 3
The assumed value of k32  is  2 x 10"  ppm" l min"1.1*0   The value  of  k;
has been adjusted to optimize both total radicals entering  the system
and PAN formation; this value is about  0.04  times that for  N02 photolysis.
A minor alternative photo reaction is possibly
                                   31

-------
                 CH3C(0)C(0)H + hv  —*-  CH3C(0)H + C0«                (34)

 and may be responsible for the small  amount  of acetaldehyde that is
 often reported in the SAPRC data.   We have not included  this reaction
 in our mechanism because of its very  minor role and  the  uncertainties
 surrounding it.

 Reactions of Benzaldehyde
      Both photolysis and reactions  with OH have been considered  for
 the reaction of benzaldehyde.   For  the  reaction with OH,  we have assumed
 the following mechanism.

                        PhCHO + OH  —*-PhC(0)« + HOH                (35)

                      PhC(0)» + 02  TT-*~  PhC(0)02«                    (36)

                   PhC(0)02« +N0a^=±:  PhC(0)02N02                  (37)

                    PhC(0)02» + NO   —*-  PhC02«  + N02                  (38)

                            PhC02»  —*-  Ph« + C0a                    (39)

                          Ph« + 02  —*-  Ph02«                        (40)

                        Ph02» + NO  —*-  PhO»  +  N02                    (41)

                        PhO» + N02  —*-  N02-PhOH or PhON02           (42)

                         PhO« 4- 02  —»»  2HC(0)C(0)H + CO  + C02 + H02»  (43)

     The  reaction with OH is assumed  to abstract only  the aldehydic
hydrogen.  Addition to the aromatic has been shown to  be unimportant
(< 10% of total  reaction)  in low pressure reaction product studies.10
Reaction  (42)  is  based on the observation of Niki'4'6 who  observed formation

                                    32   ,

-------
of nitro phenol in controlled experiments when benzoyl radicals were
generated in the presence of 02 and N02.  Reaction  (43) is included
to account for ring cleavage, which is expected to be important and
may include participation of NO.
     To estimate the importance of benzaldehyde photolysis, we have
made use of the two SAPRC experiments with added benzaldehyde (EC-337
and -339).  Simulation of these runs with our mechanism suggests that
benzaldehyde photolysis  is not an important source of radicals in the
system and further that  the disappearance of benzaldehyde is due largely
to reaction with OH.  To slightly improve the simulation of the
benzaldehyde decay curve, we have included the reaction

                            PhCHO  —*- Benzene + CO                  (44)

Using a rate constant of 2 x 10* ppm"i miri"1 for reaction (35), we
determined the best value for k<,4 to be  4 x 10"3 miri" 1.

Reactions of Cresol
     The important reaction of cresol is with OH (see Table 5).  The mechanism
assumed in the simulation is

                     CH3PhOH + OH  ^£*. CH3C6H3(OH)2 + H02«           (45)

                     CH3PhOH + OH  —>- CH3PhO»  +  H20               (46)

                     CH3PhO» + 02 —*- CH3C6H<,(0)02-                 (47)

               CH3C6H4(0)02« + NO  —*- CH3CSH4(0)0- + N02            (48)
                      CH3C6H*(0)0-  -VCH3C(0)02«  + HC(0)CHO  +      (49)
                                        stable  products
Reaction (45)  has been substantiated by product analysis of OH + o-cresol
at  low pressure.47  The rate constant for the sum  of reactions (45) and

                                    33

-------
 (46) was  obtained  from Atkinson et  al.39  for  o-cresol  and  the  relative
 values  from Perry  et  al.1*8

 Reactions of C^EuOa
      The  species  C4H<,03  and C3H603  formed  in  reactions  (23)  and  (25)
 are  assumed  to  be aldehydes and  therefore  reactive  like other  aldehydes.
 For  simplicity  C5H603  is assumed to be  identical  to CAH*03.  The reactions
 with OH are

                       C<,H«,03 + OH J2^C<.H305- +  HOH                (50)
                                                                   *
 The  rate  constant for  reaction (50) was assumed to  be 2.0  x  10**  ppm~ l
 min, the  same as  other aldehydes.   The  following  photolysis  reaction
 was  assumed .

                       C4H«03 4- hv —*~  C<,H303» +  H02»                (51)

 The  reaction was  assigned a rate constant  0.03 times the value for N02
 photolysis.
      To simplify  the mechanism,  the C«,H30S» formed  in reactions  (50)
 and  (51)  was  assumed to  be identical  to Cj,H306» formed  in  reaction (24).

 TOLUENE SIMULATION RESULTS
 SAPRC Data
      The  toluene  mechanism, which is  summarized in  Table 7,  was applied
 to the  complete set of SAPRC toluene  smog  chamber runs.  The list of
 the  necessary inorganic  reactions is  given in Table 8.   The  data for
 peroxynitric  acid has  been undated from our last  report in accord with
new  data  of Baldwin and  Golden.51   Initial concentrations  for  each ex-
periment  are  given in  Table 9, and N02  and 03 maxima and times to maxima
are  given in  Table 10.   Ozone  decay rates, radical  flux rates, and dilution
rates were as discussed  earlier.   Plots showing comparisons  of simulation
and experimental  data  for  the  species monitored in  each run are given in
                                    34

-------
Appendix A.  Figure 1 compares the simulation ceoncentrat ions of NO, N02,
03, and toluene as well as the products PAN, formaldehyde, benzaldehyde,
and cresol for EC-266.  Qualitatively the general agreement between the
simulation and experiment is quite good in the initial stages.  The agree-
ment is much improved over previous attempts, which were made with a much
smaller data base, especially less product information.

     Looking more carefully at figure 1, we  see  that the simulation
slightly overpredicts the rate of NO oxidation before the N02 maximum
and that the amount of the N02 at maximum is slightly larger  (^ 10%)
than observed.  The toluene and  N02 decay is too slow after the N02
maximum, indicating insufficient OH radical  concentration.  Despite
these  differences, the simulation of ozone formation agrees well in the
first  part of  run but does not level off as  early as experimentally
observed and the final value  is  overpredicted by 50%.  The fact that the
ozone  agrees early  in the run with  insufficient  reaction of toluene means
that each  consumed  toluene eventually oxidizes too many molecules of
NO.  This may  mean  that more  of  the toluene  fragments are less reactive
than the model assumes or are trapped on the walls of the chamber.
With regard to the  products,  the formaldehyde is overestimated and the
PAN is underestimated.  Benzaldehyde and cresol  are slightly  overestimated.
     From  the  data  in Table 10,  the average  of all runs indicates that
the N02 maximum averages 8% high and comes 4% later than experimentally
observed.  The average ozone maximum is 47%  high and comes 32% later
than observed.  The initial stages  of ozone  formation generally match
the experimental very well, but  the formation fails to level  off at the
proper point.   This effect is not unique to  toluene but is observed in
many runs  for  other hydrocarbon  and in principal could be due to a wide
variety of factors.

UNC Data
     Two toluene runs were made  in  the outdoor UNC chamber.   The data
are included at the bottom of Tables 9 and 10.   Figures 2 and 3 are plots
showing the comparison of simulation and measured  concentrations of NO,

                                    35

-------
TABLE 7
           TOLUENE MECHANISM
NO.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
_
17
18
19
20
21
22
23
24
25
26

27
28
29
30

31
32
33
34
35
36
37
38
39
40
Activation
A Factor* Energy K
PhCH, + OH
PhCH., + OH
CH3C8HSOH
CHjCgHjOH
CH3C8HSOH
CH3C8H5OH
CH3C,H5OH
CH3C8HSOH 4- N02
PhCHjOj' 4- NO
PhCH202' 4- NO2
PhCH202N02
PhCH20'
PhCH20' 4- N02
PhCH20' 4- N02
PhCHO + OH
DWOTh A. h
PhC(0)02' + NO
PhC(0)O2' 4- N02
PhC(0)02N02
PhC(0)O'
Ph02' +• NO
PhO' + NO2
PhO'
CH.,C8H4OH 4- OH
CH C H OH 4* OH
CH3CeH4O1' 4- NO

C*H,O«- 4- NO
C,H,06. + NO
C*Ht09 4- OH
C,H«0S + OH

C*H<,O9 4- hv
C,H«0, 4- hV
CtH,0.-+ N02
C,H,0«. 4- NO2
C^H jOQNU2
C^HgOgjlVOg
CSH30«NO,
CjHjO.NO,
CH3C(0)CHO + OH
CH,C(0)CHO 4- hV
2»
-
2^
?>
Q
°*
-«
-
-
— * •
-
°*
-
-
2»
^
-s
-
-
-
-
-
-
-
-
2s

-
-
£»
Q
•«
oa
z
I*
-
-
-
-
PhCH,02' 4- H20
CH3C8HSOH
CH3CgH4OH 4- H02'
CH-,C(O)CHO + Ci,CtO,+. HO,
CH3C(O)CHO 4- C^H,06-
HC(0)CHO +C,R«O, + HO,'
HC(0)CHO 4- CjH.Os •
CH,C8H4N02 4- H20
PhCH,0' 4- N02
PhCH202N02
PhCH20,' 4- N02
PhCHO 4- H02 '
PhCHO 4- HNO2
PhCH2ON02
PhC(0)02- 4- H20
puu 4. prj
Iran, T ^u
PhC(O)0' 4- N02
PhC(0)02N02
PhC(0)02' 4- N02
PhO,- 4- C02
PhO' 4- N02
PhONO, (or NO,-C8H4OH)
2HC(0)CHO 4- CO 4- HO2-
CH3CgH3(OHX, + HO,'
CHjC8H40' 4- H20
NO, 4- CH3C(0)O,' 4- HC(O)CHO
H,0 4- 2 CO 4- C02
N02 4- HC(O)CHO 4- CO 4- C02 4- H02'
N02 4- HC(0)CHO 4- CO 4- C02 + H02'
CtH90<.
C,HS0« •

C»H,0.. 4- HO,-
C,H,0,. 4- HO
C4H30,NO,
C3HjO«NOi
C^HjO, • 4. NO,
wall
1.6 x
7.4 x
*1.5 x
*1.S x
*1.5x
*3.0 x
*3.0 x
2.0 x
1.0 x
7.8 x
103
103
10s
10s
10s
10s
10s
10*
10*
10s
*1 .25x10" 1.16 x 10*
*1.3 x
1.5 x
3.0 x
2.0 x

3.7 x
2.5 x
*9.5 x
*5.2x
1.0 x
6.0 x
*1.0 x
6.9 x
6.9 x
1.0 x

7.5 x
7.5 x
2.0 x
20 x

- •

2.5 x
2.5 x
10s
10*
103
10*

10*
10*
10t8 1.3 x 10*
10T
10*
103
10s
10*
10s
10*

10s
103
10*
10*


-
103
103
*1.02 xlO18 1.35 x 10*
*3.0 x
10-2S
C,HS0S. + NO, *1.02 x!0ts 1.35 x 10*
-
2*
2>
wall
CH3C(0)02- 4- CO 4- H,0
CH3C(0)0,-4- CO 4- HO, '
*3.0 x
2.0 x
-
10-"
10*
-
                                                continued ....
             36

-------
Table 7    Toluene Mechanism (concluded)
No.
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65

CH3C(0)02' + NO 22
CH3C(0)02- + SO, -
CH3C(0)02W>2 _
CH302- + NO -
CH30' + 02 -
CH30' + N02 -
CH30' + NO2 -
CH20 •*• OH -
CH20 + hv -
CH20 + hv -•
HC(0)CHO + OH -
HC(0)CHO + hv -
CHjCHO •(• OH -*
CH,CHO + hv -
PhCH202' + HO2' -
PhCH20- + H02 -
Ph02' + HO,' -
PhO- + H02- -
PhC(0)02' + H02- -
PhC(0)0' + H02- -
CHjOj' + H02' -
CH3C(0)O2- -t- H02' -
2CH;,C(0)02- 22
2CH,02- -
CHaCgH^OH + 0, -

NO2 + CH3O2' + C02
CH3C(0)02N02
CH3C(0)02' + N02
CHjO- + N02
CH2O + H02'
CH20 + HN02
CH3OH02
H02- + CO + H20
H2 + CO
2H02' + CO
B02' + CO * CO + H20
2H02' + 2CO
CH3C(0)O2' + H20
CH3C(O)02- + HO,'








2CR,02 ' + 2CO.,
CH20 + CH3OH
OH
Activation
A Factor* Energy K
7.5 x 103
2.5 x 103
*1.02 x 1018 1.35 x 10*
1.0 x 10*
2.0 x 10s
2.2 X 103
2.0 x 10*
2.0 x 10*
	

2.0 x 10*

2.0 x 10*

2.0 x 103
2.0 x 103
2.0 x 103
2.0 x 103
2.0 x 103
2.0 x 103
2.0 x 103
2.0 x 103
2.0 x 102
2.0 x 102
1.0 x 103
   Units are ppm~'  oin'1  except those narked  * are min~*.
  b
bln UNC chamber run, rate constant for reactions  36 and 38 is 7 x 10'3 nin'1.
                                                       37

-------
                     TABLE 8.  INORGANIC REACTIONS
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
— •^••••a*-" "i 	
'units in ppm
ppnf 2 min~ .
Reaction
0(3P) 4- 02 4- M
0(3P) 4- N02
03 + NO
0(*D) + M
O(XD) + H2o
O3 + OH
03 + H02
03 + N02
N03 -i- NO
N03 4- N02(4- M)
N2O«+ H O
z 3 T na\J
N20S(+ M)
NO 4- N02 4- H20
2HNO2
N02 4- OH(4- M)
NO 4- OH(4- M)
NO 4- H02
N02 + H02
. HO2NOZ
TT/X . IT/"\
riUj 4- nU2
CO 4- OH
NO -f- hv
03 -t- hv
0,+. hv
HONO + hv
Hi02 + hv
' 1 miri" l except
- 03 4- M
-* NO 4- 02
- N02 + 02
-* O(3P) + M
- 20H
- H02 4- 02
- OH 4- 202
- N03 + 02
- wall
- 2N02
- N205(+ M)
- 2HNO3
- N02 4- N03(4- M)
- 2HONO
- NO + N02 4- H20
- HNO3(4- M)
- HONO (+ M)
-» N02 + OH
- H02N02
- H02 + N02
- H«02 4- 02
•*• HO + CO
-»• NO -i- O( P)
•*• 0( JD) + Oa
-»• O( 3IO fc 02
-»• OH + NO
-»• 2OH
Mto-^A^^^B«*M^.^«^B«^.B^^B^P^HVW^H«^^B^«B«
-------
TABLE 9.
SC No.
83
82
85
81
265
266
264
80
84
271
79
269
327
340
273
77
78
335
272
86
336
270
337
339
331d
338d
328
334
329
330
UNC8.16.78R
UNC9.14.78R
344f
343f
345f
346f
SUMMARY OF INITIAL CONDITIONS FOR SMOG CHAMBER EXPERIMENTS FOR TOLUENE AND
Toluene
5.63
1.88
1.92
1.96
1.07
1.20
1,16
1.02
0.97
1.15
0.98
0.57
0.57
0.54
0.59
0.28
0.21
1.00
0.58
1.09
1.01
0.58
0.96
0.54
1.99d
0.95d
0.57*
0.99e
0.56e
0.57e
0.56
0.32
0.49f
0.49f
0 .48f
0.49f
NO
1.36
0.68
0.43
0.41
0.44
0.43
0.42
0.40
0.39
0.19
0.08
0.40
0.36
0.33
0.096
0.52
0.069
0.35
0.40
0.41
0.34
0.41
0.32
0.34
0.35
0.35
0.36
0.35
0.35
0.20
0.60
0.24
0.52
0.21
0.22
0.20
N02
0.66
0.34
0.099
0.094
0.048
0.060
0.056
0.095
0.080
0.029
0.019
0.074
0.096
0.096
0.014
0.058
0.032
0.092
0.080
0.08
0.10
0.05
0.12
0.10
0.112
0.100
0.096
0.10
0.10
0.09
0.088
0.057
0.15
0.066
0.059
0.059
H2CO
0.00
0.001
0.00
0.00
0.012
0.010
0.008
0.00
0.007
0.004
0.011
0.003
0.00
0.005
0.002
0.003
0.00
0.010
0.017
0.161
0.303
0.178
0.009
0.002
0.006
0.008
0.015
0.015
0.001
0.009
0.00
0.00
0.00
0.009
0.002
0.006
ACH
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.001
0.00
0.00
0.30
0.00
0.00
0.00
0.00
0.00
0.00
0.001
0.001
0.001
0.001
0.002
0.002
0.00
0.00
0.001
0.001
0.00
0.001
BAL
0.016
0.00
0.005
o.OO
0.00
0.00
0.00
0.00
0.032
0.00
0.00
0.00
0.000
0.00
0.00
0.00
0.00
0.002
0.009
0.00
0.00
0.003
0.172
0.187
0.00
0.001
0.00
0.00
0.00
0.00
0.00
0.00
0.000s
0.002s
0.000s
0.000s
HONO
0.000
0.01
0.001
0.02
- _
0.001
—
0.02
0.001
0.00
—
0.000
0.000
0.003
0.000
0.001
0.001
0.000
0.001
0.001
0.000
0.000
0.000
0.000
0.01
0.003
0.003
0.006
0.002
0.006
0.010
0.004
0.000
0.000
0.000
0.000
m-XYLENEa
Tol/N0x
0.80
1.85
3.67
3.90
2.22
2.43
2.42
2.05
2.06
5.33
9.86
1.20
1.26
1.25
5.34
0.48
2.07
2.24
1.21
2.24
2.30
1.24
2.15
1.21
4.27
2.14
1.25
2.22
1.22
1.94


0.73
1.77
1.71
1.89

kN02
0.16
0.16
0.16
0.16
0.35
0.35
0.35
0.16
0.16
0.37

0.35
0.40
0.39
0.37
0.16
0.16
0.39
0.35
0.16
0.39
0.35
0.39
0.39
0.40
0.39
0.40
0.39
0.4O
0.40

- -
0.39
0.38
0.39
0.39
       are ppm.  Standard conditions include in addition:
 103 ppm HaO was used; chamber temperature 302 K.
 Amount of HONO used in simulation.
"jCnits are rain" *.
 Plus 2.04 ppm n-butane.
pPlus 0.096 ppm propene.
 m-Xylene run, no toluene present.
*Me thylb enzaldehyde.
2 x 10* ppm HtO except for EC-83 where only 1.8 x
                                                      39

-------
TABLE 10. COMPARISON OF EXPERIMENTAL AND  SIMU1ATIOH RESULTS FOR TOLUENE AND m-XYLEHE CHAMBER EXPERIMENTS
EC No.
83
82
85
81
265
266
264
80
84
271
79
269
327
340
273
77
78
335
272
86
336
270
337
339
331
338
328
334
329
330
UITC8.16.78B
UNC9.14.78R
344
343
34S
346
E X
O3-inax
ppn
> 0.42
> 0.36
0.27
0.26
0.39
0.40
0.42
0.34
0.23
0.30
0.096
0.30
0.38
0.35
0.22
> 0.01
0.092
0.40
0.41
0.30
0.39
0.37
0.32
0.22
0.52
0.48
0.52
0.41
0.40
0.34
> 0.27
> 0.31
0.59
0.28
0.40
0.38
PERI
Bin
> 360
> 360
240
180
220
220
220
255
360
90
120
> 360
360
360
80
> 360
195
225
340
330
165
330
255
> 360
120
240
360
180
310
180
> 750
> 770
180
75
75
60
MENTAL
NOj-ma
PP»
1.37
0.61
0.35
0.34
0.30
0.30
0.29
0.31
0.27
0.14
0.063
0.26
0.26
0.25
0.064
JO. 24
0.066
0.27
0.30
0.34
0.27
0.27
0.26
0.24
0.33
0.30
0.30
0.29
0.28
0.19
0.40
0.18
0.45
0.19
0.19
0.12
X
nln
270
180
120
75
90
90
90
105
140
30
30
140
135
120
30
300
45
75
100
120
60
100
105
195
45
75
105
60
100
60
490
490
45
30
25
35
S
0, -max
ppn
> 0.42
> 0.25
0.46
0.48
}
>0.60
)
> 0.35
0.33
0.40
	
0.30
0.39
> 0.40
0.25
> 0.01
0.16
0.69
0.68
0.48
0.65
0.52
0.58
> 0.38
0.98
0.98
> 0.96
0.73
> 0.56
0.57
> 0.30
> 0.18
0.70
0.40
0.40
0.41
I M U L A
rain
> 360
> 360
300
250

310

> 360
> 360
150
	
> 360
> 360
> 400
110
> 360
250
330
> 400
> 400
210
> 360
360
> 400
270
380
> 400
330
> 400
330
> 720
> 720
180
100
85
120
T I 0 N
N02-i
ppn
1.40
0.67
0.36
0.36

0.33

0.33
0.30
0.144
- -
0.29
0.27
0.26
0.07
0.26
0.064
0.30
0.33
0.34
0.29
0.29
0.29
0.29
0.36
0.34
0.34
0.31
0.30
0.20
0.38
0.16
0.45
0.19
0.20
0.17
nax
rain
200
190
95
60

90

100
130
50
	
160
140
135
35
3OO
60
55
80
100
40
100
115
150
55
100
110
80
125
70
540
520
45
25
30
30
                                                       40

-------
      M»»ei«S Mvf.  MH.

       MR       •     |

       till      .     I
                                                      J li juti it
                                                   II 1          J 14
                                                                   II
                                  I)
                                  1
              rft I II
             "      If
           *  •   •
          I            II
                    5       .
     I     I           I
     •        •     I!          •
   I         |
  >          I   I >



'            Il"'l .             '               "
      H1I II  II     III .III-  I •) .,| .	I. if.   .     .
                                           t »

                                                                                           li •
                                                                                           «        rccc ccccccc cc re cc c
                                                                                          *  >c trrrc    •              c ccccccccc ccc cccc re
                                                                                         « re                                           c tccccccticc c c ccc
                                                                                        • •>      IM       m      ttt      us
                             tlHl IKIWHCSt

                                                                                                            is»      ;••      nt      too       is-      «••
                                                                                                                tint IHIMUTCH
ii      s»rclts  uri.  SIM.
 i li    IM.     •    i
                             ii 11
                             •   I II
                                    I I
                                        lit!
                                              I III
                                                  ill ri
                                                        ii ii
                                              •     •       III III Illl
                                                                                                                                           • •      **
                 <•      us      iii      in      ft
                              IIME
                                                                                                    in       IVS      1*0      ?7*      /II

                                                                                                                IIHt fHIMIlltSI
                         Figure  1.   Simulation of  SAPRC  Toluene  Run  EC-266.

-------
N02, 03, toluene, and CO for these runs.  In both cases the agreement
between simulation and experiment   is quite good.  In these runs the
initial HN02 was varied to obtain the desired initial NO decay.   In both
cases after the N0a maximum, the decay of N02 is slightly slower than
observed  as was often also observed in the SAPRC runs.  The ozone buildup
is  low  in one case and high in the other.  Unfortunately, it is not
possible to make any generalization regarding the source of this discrepancy
with just these two experiments.
MECHANISM FOR MODELING m-XYLENE SMOG CHAMBER EXPERIMENTS
     The m-xylene mechanism was based on the toluene mechanism with
the following changes:
     •  The total rate constant for the reaction of OH with m-xylene
        is 3.6 x 10" ppm"1 min" l (see Table 2).
     «  The ratio of methyl attack to total reaction for OH + m-xylene
        is 0.083 (see Table 4).
     •  The xylene-OH adduct was assumed to react by reactions parallel
        to reactions (22) through (26), the same as for toluene; however
        the proportions assumed were 14.3:28.6:28.6:14.3:14.3, respectively,
        to account for the additional methyl group in xylene.  The reactions
        for xylene are:
                    + 03
                            14.3%
                               (22')
                                     CH3C(0)CHO + CSH603  + H02»     (23'
                                     CH3C(0)CHO +  C9HS06«  + HaO    (24')
                                     HC(0)CHO + C6H803 + H02«
                               (25')
HC(0)CHO + C6H706» + H20
                                   42
                                                                    (26

-------
            till  I  I I  l«ll  *•*•
                        III till ••
                               !!••
                                           I •           »*•
                                                    •* » 7??»?y«***»y>

                                            •      •*  f»          **tt9
                                             •     ft              »  n
   •  r
    • *
   •»»
  • •
 •»  •!
 r
r     • i
r      • i
        • i
                                                                       r n
                                                                       '  t i
                                                                       ••  i  I
                                                                         ••   if
                                                                          •» i
                                                                           9-
                                                                          »  ••
                                                                         j    •
                                                                         j >•
                                                        i            J ii
                                                         n         in
                                                        •  n     mi
                                                        •   II   Ml
                                                             HI I
                                                            •I •"•III
                                                         1UIIK    Illll
                                                        iiif    ••••••••• »i ii  ii i i
                                         !•« l»l*IITffM
                                                             It.
                                                                                                Illl  III* IIMIOII*
                                                                                                                  I fl»ll
                                                                            •lit*
III
       Illlll
            t Illl
                Illll
                   • I  II I
                      • Ml t
                                                                                                       *•       IM      tflfe       Utt       *»*      *«»       ftJt      '*•
                                                                                                                           fl**i
U)
                                  •     •
                                     er
                           : f«cc«crcreer«
                   vq      IMA       ?ii      IAD
                                                                       M KM



                                                     I M


                                                     sa      \4o      AJO      IM
                                                                                                                                                        * it      ??•
                                    Figure  2.   Simulation of  UNC  Toluene Run 8.16.78  Red.

-------
          01      I
«, 1
     Illl  I I 1*1 I «l l«| i*
                      •nun*
                            in*
                              in
**'      •   t   .   . lint.lt
  • > > > i i i itr i t
                                   t*          ...        |i      t
                                    I        •  mm f»  ..
                                     I*      t i       it «•*      11
                                     I    •'«               it*   »
                                      ii »                •   •»» it
                                      " I*                   it   »»
                                     »•   i                  »      i »
                                   »•     i             ID.
                                 «f       I •            »
                                »»           i          i )         •
                              '•'             I      fit              •
                                              >||   j)
                                                in
                                            i >•      III I
                                  111 111 J«1J >        •  • l*lllll| Illl I I
                               l|Nt
                                                           •»•      III
                                                                                    iff  I r I ( I*
                                                                                                  III I IMItl   •
                                                                                                           HIM
                                                                                                               ITU
                                                                                                                    III   •
                                                                                                                       III
                                                                                                                      I  •

                                                                                                                       till
                                                                                                                                      MM
                                                                                                                                       • urn
                                                                                                                                            i i
                                                                                 • .•>•»»«...»•.».«•.»,...

                                                                                   •        ••      !»•
                                                                                                              tl-f
                                                                                                                  Ml      «»•      »«•
                                                                  C C
                                                         CCC
                                                    CCC
                                                CC
                                      CC C
                                         ccc
                                            C C
                                              CCC
    tier  c c-c        •         cccccccc
             ccc crc c cccccc cc
                           Figure  3.    Simulation  of UNC Toluene  Run 9.14.78  Red,

-------
        Since the fragments  in reactions  (23' )-(26' ) have  an  additional
        CH3, reactions  (27)-(29),  (50), and  (51)  are changed  accordingly

        C3H506« + NO  — *- N02 +  CH3C(0)C(0)H + CO + C02 +  H02«      (2/ )

        C5H506» + N0a  ^±! CSH50SN02                                (28' )

        C5HS06N02  — *-  wall                                         (29' )

        CSH603 + OH  — *- CSH50S- + HOH                              (5C)' )

        C5H603 + hv  — *- CSHS0S- + H02»
        The intermediates C6H80 3 and CSH603 are assumed to be identical,
and C6H706»  and  C3HS03«  are  the  same  as  CSHS06».
     The data in Table 6  calculated for  xylene run EC-344 indicate  that
32%-48% of the NO   loss  is due to  reactions between the organic fragments
                 X
and NO .  This percentage is  similar  to  that observed for toluene, so
      X
no changes were  made  in  reactions  (27) through (29) .
     The reactions  of methyl  benzaldehyde and dimethylphenol were assumed
to be identical  to  those  of benzaldehyde and cresol, which are formed
in the toluene mechanism.  The complete  m-xylene mechanism is given in
Table 11.

m-XYLENE SIMULATION RESULTS
     The results from four SAPRC runs are available to develop and test
the m-xylene mechanism (Table 11) .  Three of these runs are under nearly
identical conditions.  The concentration data for these experiments are
included in Table 9;  N02  and  03 maxima and times to maxima are given
in Table 10.  Figure  4 plots  the simulated and observed concentrations
for EC- 345 as an example.  Plots of all  four experiments are given in
Appendix A.

                                    45

-------
Table 11   n-XYLENE MECHANISM
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Activation
A-Factor Energy K
CH3PhCH3 •)• OH
CH3PhCH3 + OH
(CH,)2C8H4OH
(CH3)2C8H4OH
(CH3)2C8H4OH
(CH3)2C8H4OH
(CH3)2CSH4OH
(CH,)2CSH,OH + N02
Ca,PhCH202- + NO
CH,PhCH202 + N02
CH3PhCH202H02
CH3PhCH20'
CHjPbCHgO' + N02
Ca,PhCH20- + S02
CHjPhCHO + OH
CH-jPhCHO + hv
CH3PhC(O)O2- + NO
CHjPhCCOjO,- + NO,
CH3PhC(0)02N02
CH3PhC(0)O-
CH3Ph02' + NO
CH3PhO- * N02
CHjPhO-
(CH3)2CBH3OH + OH
(CHa)2C6H3OH +• OH
\Cu 
-------
Table 11   m-Xylene Mechanism (concluded)
No.
41
42
43
44
45
46
47
48
49
50
51
52
S3
54
55
56
57
58
59
Activation
A-Factora Energy K
CHjO- +
CH20
CH20
CH20
HC(O)CHO
HC(0)CHO
CH,CHO
CHjCHO
CHjPhCHjOj' +
CH,PhCH2O- +
CH,Ph02- +
CHjPhO- +
CH,PhC(0)02- +
CHsPhC(0>0- +
CH,02- +
CHjC(0)02- +
acH,c(<
N02 - CH3ON02
+ OH •» HO2- + CO •»• H20
+ hv - H2 + CO
+ hv - 2H02' + CO
+ OH - H02- + CO + CO + H20
+ h^ -• 2HO ' + 2CO
+ OH -z CHjC(0)02' + H,0
+ hv - CHjCCOOj- + HO2-
H02- -
HO," -
H02- -
H02- -
H02- -
H02- -
H02- -
H02- -
3)02- - 2CH302- + 2C02
2CH,02- - CH20 + CH3OH
(CH,),C8H4OH
+ 0, - OH
2.0 x
2.0 x


2.0 x
- -
2.0 x

2.0 x
2.0 x
2.0 x
2.0 x
2.0 x
2.0 x
2.0 x
2.0 x
2.0 x
2.0 x
1.0 x
104
104


104

10"

103
103
103
103
103
103
103
103
102
102
103
  *Units are ppn~l  min"1  except those marked * are min"1.
                                                       47

-------
                                   I •
                                     9
                                     I
                                        n
                                         a i m it n i /«*>/<  t • i   i
                       '*      IK      i«      111     t/t
                                 1 1 "I IMWICtl
                                                                                                       IIMIIU
                                                                                                     »««    II III
                                                                                                                                1 I 1 I  I
*•
00
 *«•• •!*! M  •  «  * »t   *   *


/Ag     >*•     tM     !*•     *»•
                                                                                                     crcccrtccrcc
                                                                                                            c cue cc c t  t  c   ccc ec t e c  c
                                                                                                   |s«
                                                                                                                 '•*•      ••«      la I     «•»
                                        Figure  4.   Simulation of  SAPRC m-Xylene Run EC-344.

-------
VO
                                        •    *

                        Figure 4.  Simulation of SAPRC m-Xylene Run EC-344 (concluded).

-------
     All the simulated and observed concentration profiles agree very
well.  The experimental ozone for run EC-343 does not agree with parallel
runs EC-345 and EC-346, and this is reflected in the simulated values.
The model greatly overpredicts the PAN decay after the maxima.
This effect appears to be due to overpredicting the peroxy radical-radical
interactions, which in turn, may be due to errors in the computed NO
and NO2 values.
     The success in applying the toluene mechanism to the xylene reaction,
with only the changes indicated, confirms the general nature of the toluene
and xylene mechanism.  The basic assumption that cleavage of the aromatic
ring does occur to give o-dicarbonyl forces one to expect more methylgly-
oxal instead of glyoxal in the xylene experiments than in the toluene
experiments.  Since methylglyoxal is a radical source and glyoxal is
not, m-xylene is expected to be more reactive in oxidizing NO than toluene,
not only because of the larger OH rate constant, but also because of
the larger radical input from the increased amount of methylglyoxal.
This dual effect is apparent in the modeling results.
                                   50

-------
                               SECTION 5
                                ALKENES

MECHANISM
     In our previous report we modeled data reported by SAPRC for the
hydrocarbons propene, ethene, 1-butene, and trans-2-butene.  In this
report the mechanisms have been slightly updated and the temperature
dependence of reactions having a significant activation energy has been
included.  Using the revised mechanisms we have modeled SAPRC data for
propene and ethene, including one propene run at higher and one run at
lower than the standard  (300 K) temperature.  We also modeled UNC data
for ethene and propene,  using the temperature-dependent mechanism to
simulate the experimentally observed temperature changes.
     The complete mechanisms for ethene and propene are given in Tables 12
and 13, respectively.  The only significant changes from our previously
reported mechanisms are  as follows:
     •  The ozone-alkene mechanism has been modified to be consistent
        with the experimental results of Herron and Huie.12  They found
        that the ozonolysis of ethene formed formaldehyde and Criegee
        biradical, which decomposed to give 20% radical products.  Thus
        we represent this reaction as:

                     CH2=CH2 + 03  —*- CH20 + 0.2H02»

        Similarly for propene:

                   CH3CH=CHa + 03  —*- 0.5CH20 + 0.5CH3CHO + 0.2H02-

        Although in this case the production of radicals may be higher,1*9
        this mechanism assumes that the two possible Criegee biradicals
        formed in the propene case are equally likely  to be formed  and
                                   51

-------
        that the two carbon biradical decomposes to radical products in
        the same ratio as the one carbon biradical.
     •  The temperature dependence of the critical rate constants have
        been added.  This includes the decomposition of peroxyacyl
        nitrates50 and peroxyalkyl nitrates,51 the reactions of alkoxy
        radical,52 and the reactions of 0(3P), OH, and 03 (Table 8).
     In accordance with the experimental results of Niki et al.,51+  the
 OH-substituted alkoxy radicals formed by OH addition to propene and
 ethene are assumed to decompose faster than they react with oxygen.
 Earlier,  based on thermochemical estimates1'8'52 we assumed that for the
 ethene case the  reaction with oxygen was nearly identical with decomposi-
 tion.  The reason for this inconsistency is an unresolved question  at
 present.  Thus the reactions of the OH-substituted alkoxy radicals  may
 be more  complex  than the present mechanism indicates.

 SAPRC DATA SET
     Simulations are presented for 13 propene and 6 ethene chamber  runs
 performed at the SAPRC facility (see Appendix B); typical propene and
 ethene results are shown in Figures 5 and 6.  Initial conditions are
 given for the propene runs in Table 14, and 03 and N0a maxima and time
 to  each  maxima are given in Table 15.  Similar data for the ethene
 results are given in Tables 16 and 17.  In all the simulations a standard
 heterogeneous input of 2 x 10"4 ppm min~ l of H02 radicals is used,  although
 input of  OH at the same level gives the same results in cases tested.
 In  general the simulations reproduce the experimental results wifch
 reasonable accuracy.  The only discernible systematic trend is that the
 maximum ozone concentration is overpredicted 31(±18) % on the average for
propene and 23(±21)% for ethene.
     Two propene experiments were reported at other than the standard
 temperature.   The increase in the reactivity observed at higher  temperature
 (312 K,  EC-316) is well simulated by the homogeneous mechanism.  The
 run at lower than standard temperature  (289.5 K, EC-215) shows a much
decreased reactivity, which is not predicted by the model.  It is
difficult to draw meaningful conclusions based on one experiment, but the
                                    52  ,

-------
TABI£  12   PBOPENE MECHANISM
No,
1
2
3
4
5

6

7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31

32
33
34
35
36


CHa=CHCH3 + OH "2
CHa«CHCH3 4- 0(SP) *
CH2-CHCH3 + 0('P) ->•
CH2-CHCH3 4 0(3P) -»
CHa-CHCH3 4 03 •*
-*
CH2=CHCH3 4 03 -••
•*•
CHi-CHCH3 4 N03 *
HOCHaCH(6a)CH3 4 NO -
CH3CH262 4 NO *
CH36a + NO •*
CH3C(0)6a 4 NO *
CH3CHaC(0)62 4 NO •*
CHa(OH)02 4 NO +
HOCH,CH(6)CH3 2»
HOCHaCH(6)CH3 4 Oa •»•
CHjCHjO 4 Oa •*
CHjO 4 Oa ->
CHaOH 4 Oa •*
CHaOH + 0, *
CHa(OH)0 + 02 *
CH3CH2CHO +• hv •*
CHjCHO + hv ^
CHaO 4 hv *
CH20 + h\) ->•
HOCH2C(0)CH3 +• hv -»
CHsCHaCHO + OH 21
CH3CHO -t- OH +2
CH20 + OH 2J
HO, + NOa *
HOaNOa •*
CHa(OH)6a + NO, •+

CH,(OH)OaNOa *
CH,(OH)CH(6a)CH3 + N02 *
CHa(OH)CH(02N02)CH3 *
CH3C(0)02 + NOa *
CH3C(0)02NOa *


HOCH2CH2(6a)CH3
CHjCHjCHO
CH362 + CH3C(0)62
CH3CHa62 + HOa
CH3CHO + CO
CHSCHO + HOa*
CH20 + CO
CH, 0 + H02 •
CH3CHaCHO -I- N02
HOCHaCH(6)CH3 + N02
CH3CH26 + N02
CH36 -t- N02
CH362 + N02 + C02
CHjCHaOa + NO, + CO,
CH2(OH)6 + N02
CHjCHO +• CHjOH
HOCH2C(0)CH3 + HOa
CHsCHO + HOa
CHaO + HOa
CH2(OH)62
CH20 •+• H02
HC(0)OH + HOa
CH3CH262 + C0a + HOj
CH362 -1- CO, + HOa
CO + H2
CO +• H02 4- HOj
CH3C(0)62 + CHaOH
CH3CH2C(0)62 + H20
CH3C(0)62 -*• HaO
HOa 4- CO
H02N02
H02 + NO,
CH2(OH)02N02

CH2(OH)6a 4 N02
CHa(OH)CH(OaN03)CH3
CHa(OH)CH(62)CH3 -t- N02
CH,C(6)02N02
CH3C(0)62 + N02

A Factor*
6.00 x 103
1.8 x 103
1.8 x 103
1.8 x 103
6.0 x 10~l
1.5 x 10-3
6.0 x 10~3
1.5 x 10-3
7.8
1.0 x 10*
1.0 x 10*
1.0 x 10*
5.4 x 103
5.4 x 103
1.0 x 10*
*3.00 x 10"
*6.7 x 10'
*2.0 x 103
*2.0 x 10s
*1.2 x 102
*1.2 x 103
*1.4 x 10s





2.0 x 10'
2.0 x 10*
2.0 x 10'
2.0 x 10s
*7.80 x 10"
7.8 x 103
*
1.60 x 10"
7.8 x 103
*1.60 x 10"
1.5 x 103
*1.02 x 10"

Activation
Energy K
-5.40 x 102














7.76 x 103















1.04 x 10*


1.16 x 10*

1.16 x 10*

1.35 x 10*
continued. . . .
             53

-------
Propene Mechanism  (concluded)
37                   CH»CHJC(0)0, ••• NOa  *




38                      CH,CH,C(0)0,NO,  »




39                           CH,6 + NO,  *




40                           CHjO + NOa  +




41                        CH,CH,6 + NO,  ->•




42                        CHjCHjO + NOa  +




43                CHa(OH)CH(6)CH, + NOa  ->•




44                CHa(OH)CH(6)CH, •(• NOa  -v




45                          CH36, + NOa  -*




46                             CH,0,NO,  ->•




47                   CH,CH,C(0)6, + BOa  ->




48                      CH,C(0)6a + HO,  *




49                      CH,(OH)6, -I- HOa  +




50                CH,(OH)CH,CH,6a + HOa  -*




51                       CHjCHaOa •*• HOa  -+




52                CH,C(0)6, + CH,C(0)6a  ->-




53    CH,(OH)CH,CH,6, + CH,(OH)CH,CH,6,  ->
                                              CH,CH,C(0)0,NO,




                                              CHSCH,C(0)6, + HO,




                                              CH,ONO,




                                              CH,0 + HNO,




                                              CHjCHjONO,




                                              CH,CHO + HNO,




                                              CH,(OH)CH(ONO,)CHj




                                              CHa(OH)C(0)CHs + HSO,




                                              CHjOjNO,




                                              CH30, + NO,




                                              CH3CH,C(0)OOH




                                              CH3C(0)OOH




                                              CH,(OH)OOH




                                              CH, (OH)CH,CHaOOH




                                              CH3CH,OOH




                                              CBsOi + CH,6, + 2CO,




                                              CHa(OH)CH,CH,6 + CH, (OH)CH,CH,6 -I- 0,
  1.5 x 103




 *1.02 x 10"  1.35 x 10*




  2.0 x 10*




  2.2 x 10s




  2.0 x 10*




  2.2 x 10s




  2.0 x 10*




  2.2 x 103




  7.8 x 10s



*1.60 x 101"  1.16 x 10*




  4.0 x 103




  4.0 x 10s




  4.0 x 10*




  2.0 x 103




  2.0 x 103




  2.4 x 103




  2.5 x 10a
 Units pprn"1 min~* except * rain"1 .
                                                    54

-------
                                    TABLE 13   ETHENE MECHANISM
Ho.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
IS
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
A Factor
CH2CH2 + OH -*
CH2CH2 + 0(3P) -
CH2CH2 + 0(3P) -
CH2CH2 + BO, -
CH2CH2 + 03 -
HOCH2CH262 + NO -
CH362 * NO -
CH3C(0)62 +• NO -
HOCH2CH26 + 02 -
CH36 + 0, -
CH2O + hv -.
CH,O + hv —
CH3CHO + hv -*
CH20 + OH -*
CH3CHO + OH -*
HOCHjCHO + OH -
CH,02 + H02 -
HOCH2CH262 + H02 -
CHjC(0)62 + HO2 -
CH3C(0)62 + N02 -
CH3C(0)02K02 -
H02 + N02 -
H02N02 -
CH362 +- N02 -
CH302N02 -
HOCH2CH262 + N02 -
HOCH,CH202H02 -
CH3C(O)0., + CH3C(0)02 -
CH362 +• CH,02 -
HOCH2CHj62 + HOCH2CH2Oa -
HOCH2CH26 -2
CH2OH + 02 -
HOCH2CH202
CH3CHO
CH..6.J + H02 + CO
CH3CHO •(• NO2
CH20 * H02
CH20 + CO
HOCH2CH20 + N02
CH30 + N02
CH.,6, + NO, + C02
HOCH2CHO + H02
CH,0 + HO,
H02 + H02 + CO
CO + H2
CH3O2 + CO + H02
CO + HO2 + H2O
CH3C(0)62 + H20
CH20 + H02 + CO
CHjOOH +• O2
HOCH2CH2OOH + O2
CHjC(0)OOH + O2
CH3C(0)02N02
CH3C(0)02 + NO,
H02N02
H02 + N02
CH302NO,
CH302 + N02
HOCH2CH202ND2
HOCH2CH262 + N02
CH.,62 + CH,02 + 2C02 + 02
CH36 + CH36 + 02
HOCH2CH20 + HOCH2CH26 + 02
CH20 + CH,OH
CH20 -f H02
3.26
4.07
4.07
1.4
2.66
1.06
1.0
1.0
5.4
*
1.0
*2.0



2.0
2.0
2.0
2.0
2.0
4.0
1.5
*1.02
2.0
*7.80
7.8
*1.60
7.8
*1.60
2.4
2.0
2.0
*l.O
*1.2
x 103
x 103
x 103

x 10'
x 104
x 104
x 103
x 103
x 103



x 10"
x 104
x 104
x 103
x 103
x 103
x 103
x 10"
x 103
x 101S
x 103
x 10"
x 103
x 10"
x 103
x 102
x 102
x 10s
x 103
Activation
Energy K
-3.85 x 102
5.65 x 10Z
5.65 x 102

2.56 x 103
2.56 x 103















1.35 x 104

1.04 x 10"

1.16 x 104

1.16 x 104





Units ppn"1 ain"1 except * min'
55

-------
         S1CIH KM.  sin.
         Ml     •    X

         M»     •    *


         tl

        I  t

       »•   t
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    (
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                                         r   t  r  r r    r
l>       » m>M i
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                         IM      lit      its     l'«      »»

                              fl«C IMfHUfCSI
                                         Figure 5.    Simulation of SAPRC Propene  Run.

-------












I.H







• M





I.I <
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«, •»" r o
t •
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                                  TlPC INIHUVCSI
                                                                                        •>      «i      in     Hi     in     »••      911
                                                                                                          IIMC IKIWIffft
                                         Figure  6.   Simulation of  SAPRC  Ethene  Run EC-156.

-------
         TABLE 14  SUMMARY OF INITIAL CONDITIONS FOR SMOG CHAMBER EXPERIMENTS FOR PROPENE
So.
256
257
276
277
278
279
314
315
316
317

318
319
320
12.26.77R
1.10.78R
2.27.78R
3 .06 .78R
3 .31 .78R
6. 16 .788
7. 01 .788
7.24.78R
7.24.788
7.30.78B
8.05.78R
8.05.788
8 .06 .78R
8.15.78R
8.16.78R
10.03.788
10.12.788
Propene
0.11
0.112
0.54
0.56
1.02
1.14
1.06
0.97°
1.07d
0.49®
f
0.51
0.50B
0.54
O.99
1.08
1.32
1.26
1.27
0.67
0.51
0.99
0.49
0.42
0.28
0.51
0.56
0.48
0.52
0.45
0.44
NO
0.520
0.530
0.410
0.098
0.366
0.730
0.684
0.664
0.735
0.236

0.172
0.100
0.222
0.28
0.32
0.37
0.39
0.39
0.42
0.61
0.78
0.80
0.40
0.21
0.43
0.43
0.43
0.62
0.35
0.36
N02
0.044
0.032
0.106
0.010
0.128
0.244
0.246
0.276
0.246
0.281

0.331
0.430
0)290
0.12
0.14
0.12
0.12
0.091
0.21
0.32
0.18
0.17
0.084
0.052
0.145
0.121
0.109
0.070
0.14
0.12
CH,0
0.042
0.371
0.016
0.005
0.017
0.017
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
HONO
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.020
0.020
0.005
0.000
0.004
0.001
0.015
0.020
0.020
0.010
0.030
0.030
0.030
0.030
0.020
0.010
0.010
RH/NOX
0.19
0.86
1.06
S.22
2.04
1.17
1.16
1.03
1.09
0.93

1.02
0.95
1.05
2.48
2.35
2.69
2.47
3.09
1.06
0.55
1.03
0.51
0.88
1.07
0.89
1.02
0.89
0.75
0.92
0.92
"NO,
0.30 j
0.30
0.35
0.35
0.35
0.35
0.55
0.55
0.55
0.55

0.55
0.55
0.55
_ _
	
	
	
	
- -
_ _
	
	
- -
	
- .
- -
- -
- -
- -
- -
 Units In ppm.
 Units in min
 Temperature, 289.5  K.
 Temperature, 312.0  K.
'initial PAN, 0.072  ppm.
 Initial PAN, 0.149  ppn.
Initial PAN, 0.036  ppm.
                                               58

-------
TABLE IS  COMPARISON OF EXPERIMENTAL AND SIMULATION RESULTS  FOR PHOPENE CHAMBER EXPERIMENTS
No.
256
257
276
277
278
279
314
315
316
317
318
319
320
12.26.77R
1.10.78R
2.27.78B
3.06.78R
3.31.78R
6.16.78R
7.01.78B
7.24.78R
7.24.78B
7 .30 .788
8.05.78R
8 .05 .788
8.06.78R
8.15.78R
8.16.78R
10. 03 .788
10.12.788
E X
0,-max
opm
0.020
0.066
0.37
0.31
0.63
0.68
0.73
0.34
0.95
0.61
0.68
0.76
0.64
0.38
0.36
0.59
0.65
0.82
1.02
0.56
1.20
0.29
0.78
0.62
0.77
0.50
0.91
0.73
0.41
0.46
PERI
min
> 360
> 360
> 360
135
195
> 360
> 360
> 360
> 360
> 360
> 360
255
330
700
700
570
540
480
> 720
820
680
> 720
> 720
720
700
> 600
> 650
> 720
700
> 720
MENTAL
NO, -max
ppm
0.21
0.30
0.37
0.085
0.39
0.71
0.67
0.61
0.72
0.40
0.42
0.46
0.40
0.31
0.37
0.38
0.44
0.42
0.49
0.68
0.81
0.66
0.37
0.25
0.48
0.51
0.47
0.53
0.38
0.37
min
> 360
195
135
30
60
105
90
135
75
75
45
30
60
525
460
540
420
370
420
470
370
540
450
300
350
280
360
450
520
510
o,-.
ppm
0.007
0.066
0.67
0.46
0.79
0.89
1.10
0.53
1.40
0.60
1.00
1.11
0.95
0.23
0.19
0.88
0.90
1.17
1.11
0.77
1.47
0.60
0.92
0.61
0.87
0.63
1.00
0.87
0.49
0.39
S I M U L A T
nax
min
> 360
> 360
> 360
180
240
> 360
> 360
> 360
> 360
> 360
> 360
> 360
> 360
720
720
720
> 720
> 720
> 720
> 840
720
> 720
> 720
720
720
> 720
> 720
> 720
> 720
> 720
ION
N02-max
ppm
0.19 >
0.32
0.39
0.088
0.40
0.76
0.69
0.65
0.74
0.38
0.40
0.45
0.41
0.27
0.27
0.33
0.34
0.36
0.48
0.70
0.76
0.73
0.36
0.23
0.45
0.46
0.43
0.53
0.37
0.35
min
360
240
120
45
90
120
120
160
120
140
45
30
60
480
600
480
420
420
480
480
420
520
420
360
400
400
360
420
480
540
                                             59

-------
TABLE 16  SUMMARY OF INITIAL CONDITIONS FOR SMOG CHAMBER EXPERIMENT FOR ETHEHE
No.
142
143
156
285
286
287
6.16.78R
8.21.78R
9 .19 .78R
10 .17.788
10 .18 .78R
11.19.78R
11.20.78R
Ethene
0.95
2.03
1.99
1.95
3.76
4.00
1.98
0.695
0.940
1.37
1.56
1.89
2.20
NO
0.32
0.39
0.38
0.79
0.71
0.40
0.42
0.80
0.57
0.37
0.34
0.42
0.42
NO,
0.16
0.11
0.12
0.22
0.24
0.12
0.21
0.18
0.12
0.12
0.11
0.034
0.030
HONO
0.050
0.050
0.050
0.000
0.000
0.000
0.004
0.000
0.003
0.010
0.000
0.006
0.010
RH/NOX
1.98
4.06
3.98
1.93
3.96
7.69
3.14
0.71
1.36
2.79
3.47
4.20
4.89
*N02
0.33
0.33
0.33
0.39
0.39
0.39

- -
	
	
	
	
~ ~
Units la ppm.
                                      60

-------
TABLE 17  COMPARISON OP EXPERIMENTAL AND SIMULATION RESULTS FOR ETHENE CHAMBER EXPERIMENTS
No.
142
143
156
285
286
287
6.16.78R
8.21.78R
9.19.78K
10.17.78B
10.18.78R
11 .19 .78R
11.20.78R
EXPERIMENTAL
Oj-max N0z-max
ppo min ppm min
> 0.78
1.09
1.05
> 0.84
1.08
0.96
1.10
0.012
1.03
0.44
0.71
0.79
0.75
> 360
210
195
> 360
180
135
480
> 720
700
> 600
690
630
630
0.30
0.38
.36
0.71
0.76
0.45
0.48
0.37
0.51
0.39
0.31
0.43
0.42
105
60
45
160
70
45
320
670
430
480
500
460
480
S I M U L
0,-raax
ppm nin
1.15
1.08
1.08
> 1.00
1.50
1.30
2.04
0.024
0.61
1.38
1.14
1.23
1.32
> 360
180
180
> 360
200
140
660
720
720
720
720
720
720
A T I 0 N
NO z -max
ppm min
0.38
0.45
0.44
0.71
0.75
.45
0.52
0.54
0.47
0.36
0.35
0.39
0.41
60
25
25
190
100
45
420
720
600
420
540
550
480
                                             61

-------
large magnitude of the change for only a ten-degree change in temperature
suggests a nonhomogeneous effect.

UNC DATA SET
     UNC has reported data for propene and ethene.  The results are also
shown in Appendix B, typical runs are shown in Figures 7 and 8.  Starting
conditions are given in Table 14, and the 03 and N02 maxima and times
to maxima given in Table 15.  The results are, in general, good; no
systematic discrepancies between computed and experimental data are
apparent except for the ozone.  The computed ozone values average 18(± 35)%
for the propene runs and 78(+ 80)% for ethene.  Note that the apparent
discrepancy for N02 rate in some runs is due to the experimental measure-
ment including PAN as N02.  Substraction of the computed PAN concentra-
tion produces good agreement in all cases.  A small initial amount of  ,
nitrous acid was assumed in the simulations to achieve the correct overall
rate of reaction.  The amounts are also given in Table 14.
                                   62

-------
     0.1*
U)
    O.I
SMxm tin. sin.
to • »
not • i



< 1 I
• I 11
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MH*M N • 2
XX • 1
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i* • • It
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• It N 1
11 •!
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jin t i a « 11111111.1 ii i . . <
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II It
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• *
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• M IMNMIIMI
M IM tie l»0 «H MO 410 HO
, iim mmuicn
irccifl «•»'• «""•
ru • *
1.0




0.11


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0.0


IrKKI tin. II*. o .
01 • 0 •
r • ' • o
o
0
•
ou
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• a
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• 0

999 99
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IINC IHIMMVfVI


             •0     110
                         no     no
                            tint IHINUIISI
                         Figure 7.   Simulation of UNC Propane Run 6.16.78 Blue,

-------
••H
t.*<
          IWCItl KM. ||«.

          w      ;    j
     mi *i IM i i  i mm i
              •  •  •  •  inn
                         •  • I
                             I«M
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                  in      ttt
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                              tilt IMIMItftl
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                                                                              wrcm UM.  UK.
                                                                              01     •    I
                                                                                                                                        I •
                                                                                                                                    M,
                                                                                      IM      til      Ml     «•«
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                                                                                                                               Ml     »M      ft*
t.M*
 .»4
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                     tin.
    net  11«i 11  t'tt ml fttttt
                                    in t*
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                                                     it
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                                                                               I.M
                                                                               •.n
' M      IM      *»*      >•«      »*•      *»«      •'•      '**
                     lir 	
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                                                                                                        III      Ml     «••
                                                                                                            IIM IKIMIIfll
                                                                                                                           I..............................

                                                                                                                               •41      *M      IM
                            Figure  8.   Simulation of  UNC Ethene  Run 11.19.78 Red.

-------
                               SECTION 6
                                ALKANES

MECHANISM
     Both SAPRC and UNC have reported data on butane-NO  systems.  The
butane mechanism is given in Table 18.  The major change from our previous
report,1 besides addition of the activation energy terms, is the reduction
of reaction (16) in the table.  This change improves the simulation of
the butanone data as well as the agreement of the rate constant with
values for similar reactions.

SAPRC DATA SET
     The results for six SAPRC butane chamber runs are shown in Appendix C.
Initial conditions are given in Table 19, and the N02 and 03 maxima and
the time to these maxima are given in Table 20-  A typical result is
shown in Figure 9.  In all the simulations a standard heterogeneous
radical input of 2 x 10"'' ppm miri" * of H02 radicals is assumed.   In general
there is good agreement between the computed and experimental results.
In common with the propene set, there is a systematic tendency to
overpredict ozone.
     The results for the two nonstandard temperature runs (EC-308, 288.5 K;
EC-309, 311.5 K) are similar to the results for the propene experiments.
The increased reactivity at higher temperatures is adequately simulated,
whereas the decrease in reactivity at low temperature is not, probably
because of heterogeneous effects.
     In summary these results are similar to the bulk of our previous
work in tthe SAPRC butane-NO  data set.
                           A
                                   65

-------
TABLE 18   n-BUTANE MECHANISM
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36

CH3CH,CH,CH3 +
CH3CH,CH,CH3 +
CH3CH,CH*CH3 + 0(
CH3CH,CH2CH,6, +
CH3CH,CH(6,)CH3 4
CH3CH,CH,C(0)6, 4
CH3CH,C(0)6, +
CH3C(0)6, +
CH3CH,(6,)C(0)CH3 4
HOCH,CH,CH,CH262 4
CH3CH,CH262 4
CH,,CH2Oi 4
CHjOj 4

OH
OH
'P>
NO
NO
• NO
NO
NO
• NO
• NO
• NO
• NO
• NO
CH3CH2CH(0)CH3
CH3CH,CH,CH,0
CH3CH,CH(6)CH3 4
CH3CH,CH,CH26 4
CH3CH,CH,0 4
CHjCHiO 4
CH36 4
CH,0 4
CH,0 4
CH3CHO 4
CH3CH,CHO 4
CH3CH,CH,CHO 4
CH3CH2CH2CHO 4
CH3CH2C(0)CH, 4
CH20 4
CH3CHO 4
CH3CH2CHO 4
CH3CH,CH,CHO 4
CH,CH2C(0)CH3 4
CH3CH,CH2C(0)6, 4
CH3CH,C(0)6, 4-
CH3C(0)6, 4-
HOCH,CH,CH,CH,6, 4-
• 0,
• o,
" 0,
• 02
• 0,
• hv
• hv
• hv
• hv
• hv
• hv
• hv
• OH
• OH
• OH
• OH
• OH
• HO,
HO,
HO,
HO,

u,
0,
0,
+
+
0,
0,
0,
02
*
*
*
+
0,
0,
*
+
+
+
+
20,
-*•
20,
20,
20,
+
202
->•
0,
0,
0.
2*
•*
*
*
+

CH3CH,CH,CH,0, 4- H,0
CH3CH,CH(6,)CH3 4- H,0
CH3CH2CH,CH,6, 4- OH
CH3CH,CH,CH26 4- N02
CH3CH,CH(6)CH3 4- N02
CH3CH262 4- N02 4- CO,
CH3CH,6, 4- NO, 4- CO,
CH36, 4- NO, 4- C02
N02 4- H02 4- CH3C(0)C(0)CH3
HOCH,CH,CH2CH,6 4- NO,
CH3CH,CH,6 + NO,
CH3CH,6 4- NO,
CH,6 4- NO
CH3CH,02 4- CH3CHO
CH,(62)CH,CH,CH,OH
CH3CH,CH(0)CH3 4- HO,
CH3CH,CH,CHO 4- HO,
CH3CH,CHO 4- HO 2
CH3CHO 4- HO,
CH,0 4- HO,
HO, 4- HO, 4- CO
H, 4- CO
CH362 4- HO, 4- CO
CH3CH,6, 4- HO, 4- CO
CH3CH2CH26, 4- HO, 4- CO
CH3CHO 4- C,H»
CH3C(0)62 4- CH3CH26,
CO 4- H02 4- H,0
CH3C(0)6, 4- H,0
CH3CH,C(0)6, 4- H,0
CH3CH,CH,C(0)6, 4- H,0
CH3CH(6,)C(0)CH3 4- H,0
CH3CH,CH,C(0)OOH 4- 0,
CH3CH2C(0)OOH 4- 0,
CH3C(0)OOH 4- 0,
HOCHjCHjCHjCHjOOH + 02
A Factor
8.87 x 103
1.36 x 10*
6.4 x 10l
1.0 x 10*
1.0 x 10*
5.4 x 103
5.4 xlO3
5.4x 103
5.4x 103
1.0 x 10*
1.0 x 10*
1.0 x 10*
1.0 x 10*
* 1.05 x 10"
* 1.51 x 1013
*5.15 xlO'
* 1.02 x 10"
1.02 x 10*
* 1.02 x 10'
* 1.63 x 10"







2.0 x 10*
2.0 x 10*
2.0 x 10*
2.0 x 10*
5.2 x 103
4.0 x 10'
4.0 x 103
4.0 x 103
2.0 x 103
Activation
Energy
8.20 x 10*
4.30 x 10 a











7.35 x 103
3.87 x 103
1.76 x 103
2.01 x 103
2.01 x 103
2.01 x 10s
2.01 x 103
















             66

-------
 Table 18.   n-Butane Mechanism (continued)
 37

 38

 39

 40

 41

 42

 43

 44

 45

 46

 47

 48

 49

 50

 51

 52

 53

 54

 55

 56

 57

 5E

 59

 60

 61

 62

 63

 64

 65

 66

 67

 66

69

 70

71


72
          CHsCH(02)C(0)CHj 4- HOj


           CH3CH,CH(6a)CH3 + H02

            CH,CH,CH,CHaO, + H0a


                CH,CH,CH,da + H02

                   CH,CH,6a -I- H0a


                      CH,6a + HO,


           CH3CH2CHjC(0)Oj + N02


               CH3CH2C(0)62 + N02

                 CH3C(O)6a +N0z


               CH3CHiCH2C(0)OaNOa

                  CHiCH2C(0)02HO,

                     CH3C(0)OatlOa

                       CH36 + H0a

                       CH36 + N02

                    CH3CH26 + K02

                    CH3CH26 + N02

                 CH3CH2CHaO + NO 2

                 CH3CHaCHa6 +> N02

              CH3CH2CH2CH26 -I- H0a

              CH,CB2CH1CH>6 -I- N02

             CH3CH2CH(6)CH3 + NO,

             CH,CH2CH(6)CH3 + NO,

                        HOi + N0a

                           H02N02

                      CH362 + N02

                         CH302N02

                   CH3CH262 + H0a

                      CH3CH202N02

                CH9CH2CH262 -t- N02

                   CH3CHaCH202N02

             CH3CHaCH2CH26a + N02

                CH3CH2CH2CH202N02


            CH3CH2CH(02)CH3 + N03

               CH3CH2CH(02N02)CH3

CH3CH2CH(Oj)CH3 + CH3CH2CH(62)CH3


  CH,CH2CH2CHj6, + CH,CH,CH2CH26,
CH3CH(OOH)C(0)CH3 + Oa


CH3CHaCE.(CH. )OOH -t- 0,

CH3CH2CH2CH2OOH + 02

CH3CHaCHaOOH + 02

CHjCHjOOH + 02

CH,OOH + 02


CH3CH2CH2C(0)02N02


CH3CH2C(0)02N02

CH,C(0)02KOa


CH3CH2CH2C(0)Oa + N0a

CHaCH2C(0)02 + N02

CH3C(0)62 + N02

CH3ON02

CHjO + HNOa

CH3CH2OKOa

CH,CHO + HNO,

CH9CHaCH2ON02

CH3CHaCHO + HN02

CH3CH2CH2CH2ON02

CH,CH2CH2CHO + HNOa

CH,CHaCH(ONOa)CH3

CH3CH2C(0)CH3 + HN02


H02N02

H0a + N0a

CH302N02

CH36a + NO,

CH3CH202N02

CH3CH26a + N02

CH3CH2CH2OaNOa

CH3CHaCH262 + N02

CH3CH2CH2CH202N02

CH3CH2CHaCHaOa + N02

CH3CH2CH(02N02)CH,


CH3CH2CH(62)CH3 + N02


CH3CH2CH(6)CHs + CH3CH2CH(6)CH3  + 02


 CHsCHaCHaCH,0 * CH3CH2CHaCHsO -I- 02
   2.0 x 103

   2.0 x 103

   2.0 x 103

   2.0 x 103

   2.0 x 103

   2.0 x 10*

   1.5 x 103

   1.5 x 103

   1.5 x 103

 *1.02
               1.35  x 10*

 *1.02 x 10"   L35  x 10*
 *
  1.02 x 10la   1.35  x 10*

   1.5 x 10*

  4.4  x 103

  1.5  x  10*

  2.9  x  103

  1.5  x  10*

  2.9  x  103

  1.5  x  10*

  1.5  x  103

  1.5  x  10*

  1.5 x  10*

  2.0 x  103
*
  7.80 x 10>s   1.04 x 10*


  7-8 x  103
A
  1.60  x  10le   1.16 x 10*

  7.8 x  103
*
 1.60 x  10"   1.16 x 10*

  7-8 x  IQ3

 1.60 x  10"  1.16 x  10*

  7-8 x IQ3
*
 1.60 x 1018  1.16 x  10*


  7.8 x 103

  1.6 x  IQ18  1.16 x  10*


  2.0 x 103


  2.0 x  102


        continued .   . .
                                                   67

-------
Table 18.  n-Butane Mechanism (concluded)
   73             CH9CHaCHa6a  + CHjCHjCHjOj   ->  CHjCHjCHjO + CHjCHjCHjO + 02           2.0 x 102




   74                   CH,CH,6, + CH,CHa6a   -f  CH,CHa6 + CH,CH,6 -1-0,                 2.0 x 10*




   75                         CH36a + CH,0,   -»•  CH,6 + CH»6 + 0,                       2.0 x 102




   76                 CH3C(0)6, -t- CHSC(0)6»   +  CH,6» + CH,6, + 2COa + Oa              2.4 x 103




   77                     CHa(0)CHjCHaCHaOH   °2  CHa(OH)CH2CHaCH(OH)6a                *9.51 x 1012  3.27 x 103




   78            CHa(OH)CHaCHaCH(OH)6, + NO   +  CHa(OH)CHaCH2CH(OH)6 •(- NO,             1.0 x 10*




   79          CHa(OH)CHaCH3CH(OH)6, +  HO,   *  stable  product                         4.0 x 10s




   80                  CH,(OH)CHaCHaCH(OH)6   3*  CH(OH) (6a)CHaCH2CH(OH) a              *9.51 X 1011  3.27 X 103




   81         CH(OH)(6a)CHaC2i,CHa(OH)a + NO   *  CH(OH) (6)CH,CHaCH(OH),                 1.0x10*




   82        CH(OH)(62)CHaCHaCHa(OH)a + HO,   *  stable  product                         4.0 x 103




   83           .     CH(OH)(6)CH,CHaCH(OH)a   °a  CH(OH)aCHaCH,C(OH)a6a                *4.76 X 1011  2.31 X 103




   84            CH(OH)aCHaCHaC(OH)a6a -t- NO   -*•  CH(OH) jCHjCHjCCOWO                    1.0x10*




   85           CH(OH)zCHaCHaC(OH)26a 4- HOa   *  stable  product                         4.0 x 103




   86                  CH(OH),CHaCHaC(OH)a6   $2  C(OH)1(6>)GH2CH,C(OH),               *4.76 x 10"  6.44 x 103




   87           C(OH)a(6a)CHaCHaC(OH)3 + NO   ->•  C(OH) j(6)CHaCHaC(OH)3                  1.0x10*




   88          C(OH),(Oa)CH2CHaC(OH)9 -f HOa   •*  stable  products                        4.0 x 103
        ppm"1 min~l, except * units rain'1.
                                                      68

-------
        (.11
                 tmrn  nn.  JM.
                  oj      .    o
                  "o      •    *
                  mt     >    i
                                                                                  Ill '   IMCIIl  MM.  »l«.

                                                                                     M   Mil     •   •
                       11 ti mm! ii i       •  i
                   • tnt         •    i lint            •
              * ii i     iii    i      tut i
           •  t i                      • • a     tit  •
••>•     «    i                           M      > in 11
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       in                             o                 i
      >t                              o        •          m
    it                                •      •                ii
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            II «
                                                                         nt
                                                                                       1.1
                                                                                       1.1
                   I    • H       10

                          *  *co
                      •  I   • Ml
                        •  «•  mm
                      • • a    «•••••

           |M «q«00 * *                NMM<« *• MKMUIMMMI I ••«""!•
        J^^I^^MUMI wmmmm m\ fj • •in •• •• ^••••_LB j -• jjji-m-ai r • j  x»*»-» >-B^4M mmmmm im-mtmmmmmm • .•• • «0 ••!•

           *        «t       «•      lit      IK      t»l      tri

                                      tIM MIMIffll
                                                                                                                                      M
                                                                                                         ill      III
                                                                                                             ilia
                                                                                                                         III      110      Mt
       4.ia>
a>
       ll.it
                  MN

                  «H
                       u»l.  UN.
                                                       U

                                                       t
                                                *     »
                     I    t
               «     *
           II          I                MM*

         U         I               • •» MUM

        I                    WWWW »

      U              «» • •• *

   111 1 HIM II II H II II «• IHW  •     *    • I



   •        49       «0      111      III

                               IIM IMMUIIII
                                                   rt »

                                                  ill      in
                                                              t »
                                                                  •if      M*
                                              Figure  9.    Simulation  of SAPRC  n-Butane  Run  EC-309.

-------
TABLE 19  SUMMARY OF INITIAL CONDITIONS OF MISCELLANEOUS SMOG CHAMBER EXPERIMENTS*
No.

304
305
306
307
c
309
7.21.78R
7.22.78R
2.27.78R

250
251
252
255
9.14.77R
9. 15.788
9.21.78B

253
254
12.26.77B
8 .08 .78R
Subst .
n -Butane
4.28
4.30
6.44
6.44
4.05
4.31
1.83
2.09
3.37
CH,0
0.33
0.19
0.36
0.33
1.05
2.00
1.97
A0H
0.546
0.472
1.91
0.46
NO

0.349
0.078
0.147
0.083
0.305
0.203
0.189
0.432
0.189

0.011
0.080
0.392
0.006
0.293
0.211
0.190

0.011
0.085
0.29
0.42
NO,

0.117
0.020
0.040
0.019
0.178
0.272
0.054
0.116
0.077

0.012
0.033
0.103
0.010
0.104
0.057
0.067

0.009
0.027
0.117
0.095
HONO

0.000
0.000
0.000
0.000
0.000
0.000
0.020
0.020
0.020

0.000
0.000
0.000
0.000
0.000
0.000
0.000

o.ooo
0.000
0.000
0.000
RH/NOX

9.18
43.9
34.4
63.1
8.39
9.07
7.53
3.81
12.7

14.3
1.71
0.73
20.63
2.64
7.46
7.67

27.3
4.32
4.69
0.89
"NO,"

9.43
0.43
0.43
0.43
0.43
0.43
- _
	
- -

0.30
0.30
0.30
0.30
_ _
	
- -

0.30
0.30
- -
"
bUnits In ppm.
 Units in oin~*.
 Temperature, 288.5 K.
 Temperature, 311.5 K.
                                        70

-------
TABLE 20  COMPARISON OF EXPERIMENTAL AND SIMULATION RESULTS FOR MISCELLANEOUS CHAMBER EXPERIMENTS







7
7
2




9
9
9


12
8
No.
304
305
306
307
308
309
.21.78R
.22.78R
.27.78R
250
251
252
255
.14.77R
.15.788
.21.788
253
254
.26.778
.08.78R
E X
03-nax
ppm
0.36
0.40
0.54
0.42
0.04
0.56
0.72
0.13
0.72
0.21
0.25
0.02
0.15
0.62
0.55
0.74
0.125
0.20
0.039
0.51
PERI
min
> 435
> 360
> 405
> 390
> 360
360
> 720
> 720
680
360
315
> 360
315
> 720
630
630
> 360
> 360
700
770
MENTAL
NO. -max
ppm
0
0
0
• o
0
0
0
0
0
0
0
0
-
0
0
0
.
0
0
0
.32
.077
.15
.078
.28
.36
.22
.43
.27
.22
.08
.20
-
.28
.22
.25
.
.06
.33
.42
min
180
90
100
60
345
90
400
660
300
330
30
180
	
30O
300
300
..
90
660
470
o,
ppm
0.98
0.76
0.99
0.84
0.35
0.91
0.84
0.19
0.62
0.21
0.063
0.013
0.18
0.52
0.93
1.25
0.14
0.16
0.60
0.75
S I M U
-max
min
> 435
> 360
> 400
> 390
> 360
> 360
> 720
> 720
> 720
230
360
> 360
240
720
650
660
> 360
> 360
720
780
L A T I ON
NO -max
ppm
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.35
.075
.15
.08
.35
.35
.20
.42
.22
.012
.07
.20
.01
.30
.21
.22
.013
.082
.28
.34
min
170
60
90
60
220
160
480
660
600
0
60
170
0
360
300
300
90
180
360
480
                                               71

-------
UNC DATA SET
     The results for the selected UNC butane  runs are shown in Appendix C.
Initial conditions are given in Table 19 and results summarized in
Table 20.  A typical result is shown in Figure 10.  The results are
generally  in good agreement.  A small variable amount of initial nitrous
acid was used to increase the overall reaction rate of the simulations
to match the experimental data.  The amounts used are listed in Table 19.
                                   72

-------






o.*v»

i
u
It

i
1
1.
I
ft
* **•!«
1
1
t
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>
*
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p* * p I

n •
I
D
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fj-'N H H I. hfclWftN* fc* * g
ft M*N * g
N*N
MN I I«II
* » I I f Q
Nil
* t n
• H» t • }
1 0
t t
2 N 0 «J
I*N n t »•**
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2 It • N 0 1
X M» * N 1
J.'f? J 1 / 22f222* # • 10
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** *
* 0 II
CM *
Q UN tt
nn o OOWIQI * HHhHM NN }? ttiwin? ttxtn
I1" 211 119 420 929 A10 Ml MO
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/

P « ' '» '
rn » e
crrcrcc
ccc
cc
* »>r» » c
• » »» cc
* •» c
99 C
rr »
•
• 9 T-
9 '
9 r
•
e
» e •
I* C
• » c
P • •
•c • • *
• c »
C 9 •
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C f
C f
t 9
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t c» »
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                           119     420
                               Tlir IMIKU1CSI
                                  Figure 10.   Simulation of  UNC n-Butane Run  7.27.78 Red.

-------
                               SECTION 7
                               ALDEHYDES

MECHANISM
     Both SAPRC and UNC have reported experiments for acetaldehyde and
formaldehyde chamber experiments.  The aldehyde mechanisms are subsets
of the alkane and alkene mechanism, but are given explicitly in Table 21
for convenience.

SAPRC DATA SET
     The six SAPRC aldehyde runs have been modeled and are shown in
Appendix C.  Initial conditions are in Table 19 and the results are
summarized in Table 20.  Typical results for acetaldehyde and formaldehyde
are shown in Figures 11 and 12.  Aldehydes present a difficult analytical
problem and there is considerable scatter in their concentration
measurements.  However, in general the results are in good agreement.

UNC DATA SET
     The UNC aldehyde chamber runs are given in Appendix C.  Initial
conditions are in Table 19 and results are summarized in Table 20.  A
typical result for acetaldehyde is shown in Figure 13, and for
formaldehyde in Figure 14.  As in the SAPRC data set there is considerable
scatter in the hydrocarbon measurement, but in general the results are
in agreement.
                                   74

-------
   TABLE 21
                                             ALDEHYDE MECHANISM
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Activation
A-Factora Energy
0
CHjCHO + hv •*•*
CHaO > hv *
CHaO + liv •*
OUCHO + OH +*
CHaO + OH ->•
CH3C(0)6a + SO »
CH3C(0)6a + N02 *
CH3C(0)OaNOa *
CHjOa + NOa •*
CH362N02 •*
CH36a + NO ->•
CH30 ••• Oa •*
CH36 + NOa -*•
CH30 + NOa *
CH»C(0)6a +• CH3C(0)6a *
CH3C(0)Oa + HO, *
CH36 + HOa *
CH302 -t- CO + HOa
CO + HO, + HOa
CO
CH3C(0)6a -I- H,0
H02 + CO+ HjO
CH362 -I- NOa + CO,
CH3C(0)0,NO,
CH3C(0)63 + NO,
CH30,NOa
CH362 + N02
CHjO + NOa
CH20 + HOa
CH3ONOa
CHaO + HNOa
CH36a + CH36a + 2COa
CH3C(0)OOH
CH3OOH


2.0 x
2.0 x
5.4 x
1.5 x
1.02 x
7.8 x
*1.6«
1.0 x
*2.0 x
2.0 x
2.2 x
2.4 x
4.0 x
2.0 x


10*
10*
103
103
1018 1.35 x 10*
103
10" 1.16 x 10*
10*
103
10*
103
103
103
103
^nits in ppm"1 min"1, except
* min
     "1
                       75

-------
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                                REFERENCES
 1.  D. G. Hendry, A. C. Baldwin, J. R. Barker,  and D.  M.  Golden,  "Computer
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 2.  J. N. Pitts, Jr., et al., "Mechanisms of Photochemical Reactions in
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 3.  H. E. Jeffries, D. L. Fox, and R. M. Kamen,  "Outdoor  Smog Chamber
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11.  D. G. Hendry and R. A. Kenley, "Abstracts of Papers," Part II,  178th
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14.  G. Z. Whitten and J. P. Meyer, "CHEMK: A Computer Modeling Scheme
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                                    80

-------
15.   A. C. Hindmarsh, "GEAR:  Ordinary Differential Equation Systems
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                                    81

-------
 33.   H.  Akimoto,  M.  Hoshino,  G.  Inone,  M.  Okuda,  Bull.  Chem.  Soc.  Japan,
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 34.   K.  Nojima, K.  Fukaga,  S.  Fukui, and S. Kanno,  Chemosphere,  3^,  247
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 35.   R.  A.  Kenley,  J.  E.  Davenport, and D. G. Hendry, J.  Phys. Chem.,  82,
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 36.   J.  R.  Barker,  S.  W.  Benson, and D. M. Golden,  Int. J.  Chem. Kinetics,
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 37.   D.  G.  Hendry and  R.  A. Kenley, "Atmospheric  Chemistry  of Peroxy-
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 38.   S.  W.  Benson,  The Foundation  of Chemical Kinetics, McGraw-Hill Book
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 39.   R.  Atkinson, K. R. Darnall, and J. N. Pitts, Jr.,  J. Phys.  Chem.,
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 40.   H.  Niki, P..O.  Maker,  C.  M. Savage, and C. P.  Breitenbach,  J.  Phys.
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 41.   R.  Atkinson  and J. N.  Pitts,  Jr.,  J.  Phys. Chem.,  79,  541  (1975).

 42.   J.  A.  Howard, Adv. Free  Radical Chemistry, 4^,  49 (1972).

 43.   D.  G.  Hendry,  "Chemical  Kinetic Data  Needs for Modeling  the Lower
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 44.   D.  G.  Hendry,  "Atmospheric  Reaction Products of Organic  Compounds,"
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 45.   C.  S.  Parmenter,  J.  Chem. Phys., 41,  658  (1964).

 46.   H.  Niki,  P.  D.  Maker,  C.  M. Savage, and L. P.  Breitenbach,  "FTIR
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 47.   D.  G. Hendry, unpublished data.

 48.   R. A. Perry, R. Atkinson, and J. N. Pitts, Jr., J. Phys. Chem., 81,
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                                   82

-------
51.  A. C. Baldwin and D. M. Golden, J. Phys. Chem., 8:2, 644 (1978).

52.  A. C. Baldwin, J. R. Barker, D. M. Golden, and D. G. Hendry, J.
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     for Atmospheric Chemistry - 1977," NBS Special Publication 513,
     1977.
                                    83

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                   Appendix A




SIMULATION OF AROMATIC HYDROCARBON CHAMBER RUNS
                        85

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       TABLE A-l.   PHOTOLYSIS RATE CONSTANTS FOR TOLUENE AND m-XYLENE CHAMBER RUNS (in min"1)






     EC No.     N02	HN02	H30a	OaQD)	03(3P)     H2CQ(rad)     H3CO(molec)




      77-86     0.16   4.5 x 10" 2   3.3 x 10" *    6.0 x 10" *   6.6 x 10""   5.6 x 10""    8.0 x  10~4




     266-272    0.35   0.11         7.7 x 10" *    1.2 x 10"3   1.7 x 10"3   1.2 x 10"3    2.2 x  10~3




     273        0.37   0.12         8.2 x 10""    1.3 x 10"3   1.8 x 10"a   1.3 x 10"3    2.4 x  10"3




**    327-340    0.40   0.12         7.8x10""    7.9xlO~"   1.6xlO"3   7.8x10""    2.5xlO"3




     343-346    0.38   0.11         7.6 x 10" *    1.0 x 10"3   1.6 x 10"3   8.2 x 10~"    2.4 x  10"3

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       FIGURE  A-8    SAPRC  EC-85
                                                                                                                      H?CII
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-------






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       FIGURE  A-9   SAPRC  EC-86

-------
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        FIGURE  A-10   SAPRC  EC-266

-------
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        FIGURE  A-ll    SAPRC  EC-269
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                                                                                                                 HUH P  K     *PP P n P f f f »  ******
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-------
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       FIGURE  A-12   SAPRC  EC-270

-------
                   SPTCICS OPT. si*.
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       FIGURE A-12   SAPRC  EC-270

-------
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-------
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               FIGURE  A-13   SAPRC  EC-271

-------






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-------
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      FIGURE A-14   SAPRC EC-272

-------
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                                                                                                                                                                                 «•        ISO        »lt

-------
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      Figure  A-15   SAPRC  EC-273

-------
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-------
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FIGURE A-16   SAPRC  EC-327

-------
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-------
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FIGURE  A-17  SAPRC EC-328

-------
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-------
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FIGURE A-18   SAPRC  EC-329

-------
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FIGURE  A-19   SAPRC  EC-330
                                                                                       FIPI.  SIM.
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-------
                             CXPT,  SIM.
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        FIGURE A-19    SAPRC  EC-330

-------
                 tin.  SIM.

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I        sprcics  fid.  SIM.


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                                                                                                                                        MM

-------
         H?ca    .   H
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FIGURE A-20   SAPRC EC-331

-------
             SPICKS
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-------
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-------
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-------
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-------
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-------
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-------
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-------
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-------
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-------
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-------
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-------
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-------
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-------
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-------
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FIGURE A-32   SAPRCE EC-345

-------
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     FIGURE  A-33  SAPRC  EC-346

-------
            Appendix B




SIMULATION OF ALKENE CHAMBER RUNS
                139

-------
TABLE B-l.  PHOTOLYSIS  RATE  CONSTANTS FOR PROPENE AND ALKENE CHAMBER RUNS  (in  mliT1)
EC-No .
142-143
156
256-257
276-279
285-287
314
S 315
316
317-318
319-320
NO a
0.33
0.33
0.30
0.35
0.39
0.48
0.49
0.51
0.53
0.55

9.
9.
8.
0.
0.
0.
0.
0.
0.
0.
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5 x 10" 2
5 x 1CT2
0 x 10" 2
11
12
14
15
15
16
16
H20a
6.5 x 10""
6.5 x 10" *
5.7 x IGT*
7.6 x 10""
6.5 x 10" "
1.0 x 10" 3
1.1 x 10" 3
1.1 x 10' 3
1.1 x 10" 3
1.1 x 10" 3
03(XD)
1.1
1.1
8.4
1.2
1.3
1.5
1.7
1.7
1.3
1.2
x 10" 3
x 10" 3
x 10" "
x 10" 3
x 10" 3
x 10" 3
x 10" 3
x 10" 3
x 10" 3
x 10" 3
03(3P)
1.2 x 10" 3
1.2 x 10" 3
1.2 x 10" 3
1.7 x 10"3
1.8 x 10" 3
2.2 x 10"3
2.3 x 10"3
2.3 x 10" 3
2.3 x 10" 3
2.3 x 10" 3
H2CO(rad)
9.0 x 10" *
9.0 x 10" u
8.4 x 10" *
1.2 x 10" 3
1.3 x 10" 3
1.1 x 10" 3
1.2 x 10" 3
1.2 x 10" 3
1.2 x 10"3
1.2 x 10" 3
H2CO(molec)
2.4
2.4
1.6
2.1
2.4
3.4
3.4
3.4
3.5
3.7
x 10" 3
x 10" 3
x 10" 3
x 10" 3
x 10" 3
x 1
-------
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-------
                   Appendix C




SIMULATION OF n-BUTANE AND ALDEHYDE CHAMBER RUNS
                       185

-------
                                TABLE  C- 1.   PaJTO^.Ji-  ;UT- ^^iCTAiSTS '.'OR n-BUT,':'E,  ""Ma'iliU™" 7, AND AC™7.-:.":""'.7  Cr.WT'.R RUNS (In rolif ')
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-------
                                    TECHNICAL REPORT DATA
                             (l lease read lauructions on the reverse before completing}
  REPORT NO.
   EPA-600/3-80-029
                        2.
                                                      3. RECIPIENT'S ACCESSIOI*NO.
 4. TITLE AND SUBTITLE
   COMPUTER MODELING OF SIMULATED  PHOTOCHEMICAL SMOG
   Final Report
                                                      5. REPORT DATE
                                                         February  1980
                                                      6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)

   D. G. Hendry,  A.C. Baldwin,  and  D.  M.  Golden
                                                      8. PERFORMING ORGANIZATION REPORT NO.
 9. PERFORMING ORGANIZATION NAME AND ADDRESS
   SRI International
   333 Ravenswood Avenue
   Menlo Park,  California  94025
                                                      10. PROGRAM ELEMENT NO.

                                                        1AA603   AC-27   (FY-79)
                                                      11. CONTRACT/GRANT NO.
                                                             Contract No. 68-02-2427
 12. SPONSORING AGENCY NAME AND ADDRESS
   Environmental Sciences Research Laboratory-RTP, NC
   Office of  Research and Development
   U.S. Environmental Protection Agency
   Research Triangle Park. North Carolina  27711
                                                      13. TYPE OF REPORT AND PERIOD COVERED
                                                       Ftn^l   Q/77 -
                                                      14. SPONSORING AGENCY CODE
                                                        EPA/600/09
 15. SUPPLEMENTARY NOTES
 16. ABSTRACT
        Efforts to develop chemical kinetic mechanisms  to describe the formation of
   photochemical smog are discussed.  Detailed mechanisms for the atmospheric  reactions
   of toluene,  m-xylene, propene,  ethene, formaldehyde  and acetaldehyde were con-
   structed  from available experimental and chemical  kinetic data.  These mechanisms
   were used to simulate smog  chamber data from  the Statewide Air Pollution Research
   Center  at the University  of California, Riverside  and the outdoor facility  of the
   University of North Carolina.
 17.
                                 KEY WORDS AND DOCUMENT ANALYSIS
                   DESCRIPTORS
                                               b.lDENTIFIERS/OPEN ENDED TERMS
                                                                    c. cos AT I Field/Group
   *
   *
   *
   *
   *
Air pollution
Reaction kinetics
Photochemical reactions
Mathematical models
Computerized simulation
 13B
 07D
 07E
 12A
 14B
 3. DISTRIBUTION STATEMENT

   RELEASE TO  PUBLIC

   »•••••••—••••———
EPA Form 2220-1 (9-73)
                                         19. SECURITY CLASS (ThisReport)
                                           UNCLASSIFIED
21. NO. OF PAGES

   215
                                         20. SECURITY CLASS (Thispage)
                                           -UNCLASSIFIED
22. PRICE
                                             207

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