REACTIVITY/VOLATILITY CLASSIFICATION
OF
SELECTED ORGANIC CHEMICALS;
EXISTING DATA
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
O.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARX, NORTH CAROLINA 27711
-------
REACTIVITY/VOLATILITY CLASSIFICATION
OF
SELECTED ORGANIC CHEMICALS:
EXISTING DATA
by
Hanwant B. Singh
Helen M. Jaber
John E. Davenport
SRI International
Menlo Park, California 94025
EPA Cooperative Agreement CR810346-01
Project Officer
Basil Dimitriades
Environmental Sciences Research Laboratory
U.S. Environmental Protection Agency
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
-------
NOTICE
The information in this document has been funded wholly or in part by the
United States Environmental Protection Agency under cooperative agreement
CR810346-01 to SRI International. It has been subject to the Agency's peer
and administrative review, and it has been approved for publication as an EPa
document. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
11
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ABSTRACT
This study deals with the reactivity/volatility classification of some
118 organic chemicals (including isomers and one solvent mixture) specified by
the U.S. Environmental Protection Agency (EPA). The classification system has
been developed based on existing and available information. It was clear at
the outset that little or no experimental data were available for a signifi-
cant fraction of these chemicals. In such cases we relied heavily on our
ability to make valid predictions, based on sound physico-chemical principles.
As requested by EPA, a three-tiered individual, as well as composite, classif-
ication scheme of the reactivity and volatility of these 118 chemicals was
developed. It is recognized that the degree of photochemical involvement of
chemicals cannot be rigorously compartmentalized into discrete classes;
nevertheless, a practical classification system is considered useful from a
control strategy viewpoint. The three-tiered classification system was con-
ceived as follows:
Class I (26 chemicals): These chemicals are sufficiently nonvolatile
or unreactive so that they may not participate
in photochemical smog formation.
Class II (17 chemicals): Chemicals that are borderline cases, or for
which available data are inadequate to draw
definitive conclusions.
Class III (75 chemicals): These chemicals are both reactive and volatile,
and can participate in processes of smog formation.
It is found that smog chamber data for low reactivity organic chemicals may
not be directly applicable to ambient conditions. Because of extensive
shortcomings in existing information a number of recommendations were made
to bridge current information gaps.
iii
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This report was submitted in fulfillment of Cooperative Agreement No.
CR810346-01-0 (SRI Project 4954) by SRI International under the sponsorship of
the U.S. Environmental Protection Agency. The technical work was accomplished
during the period froia October 1, 1982 to May 31, 1983.
iv
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CONTENTS
ABSTRACT iii
LIST OF ILLUSTRATIONS vi
LIST OF TABLES v1* i
ACKNOWLEDGMENT vi ^ j
1 INTRODUCTION 1
2 OBJECTIVES 3
3 GENERAL TECHNICAL APPROACH 5
Reactivity Classification 5
Volatility Classification 12
4 DATA COLLECTION AND ESTIMATION 19
Smog Chamber Data 19
Measured Rate Constant Data and
Rate Constant Estimation 20
Physical Properties and Their Estimation 22
5 REACTIVITY/VOLATILITY CLASSIFICATION AND
DISCUSSION OF RESULTS 31
Chemicals in the Class I Category 31
Chemicals in the Class II Category 36
Chemicals in the Class III Category 41
6 RECOMMENDATIONS 47
REFERENCES 51
APPENDIX
REACTIVITY/VOLATILITY DATA SHEETS AND CLASSIFICATIONS
FOR 118 SELECTED SPECIES A-l
v
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ILLUSTRATIONS
1 Correlation of Maximum Oxidant/O^ and Reactivities ... 7
2 A Sample Correlation Plot of NO2 and Hydrocarbon
Disappearance Rates 8
3 Maximum Ozone Concentrations Produced by the Propane-
NOx-Air Irradiations in an Outdoor Smog Chamber at
Various OC to N0X ratios 8
4 Relationship Between OH Rate Constant and Initial
Organic Chemical to N0X Ratio Needed for Maximum
O3 Formation 9
5 Comparison of Relative Hydrocarbon Disappearance
Rates (n-butane«l) and Hydroxyl Radical Rate Constant .... 9
6 Hydrocarbon Reactivity Vs. Oxidant Maximum 10
7 Distribution of Cg-C28 n-Alkanes and Other Select
Chemicals in the Aerosol and Gas Phase 15
8 The Relationship Between Predicted (K ) and Experi-
mental (K„) Hydroxyl Radical Rate Constants 27
9 Relationship Between OH Rate Constant and Prevailing
Mean OH Concentrations in Three Smog Chambers 37
10 Irradiation of Acetaldehyde-NOx-Air-Photochemical
System 42
11 Smog Chamber Irradiations of 2-Butoxyethanol and
Butyl Alcohol in an NOx-Air System 43
12 Smog Chamber Irradiation of a 1-Heptene-NO -Air
Mixture * ........ . 44
13 Smog Chamber Irradiation of a Toluene-NOx~Air Mixture .... 44
14 Maximum Ozone Formation as a Function of OC to
N0X Ratio for Some Biogenic Chemicals and Propene 45
v1
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TABLES
1 Distribution of Aliphatic Hydrocarbons Between
Aerosol (A) and Gas (G) Phase at Ghent 16
2 Abstraction Rate Constants For Reactions of OH
With Generalized Structures 23
3 Induction Factors for Substituents 24
4 Addition Rate Constants for Reaction of OH With
Carbon-Carbon Double Bond and Values of Induction Factors . . 25
5 Addition Rate Constants for Reaction of OH With
Aromatic Rings and Values of Induction Factors 26
6 Reactivity/Volatility Classification of Selected
Organic Chemicals 32
7 Chemicals That May Not Participate in Smog Formation
(Class I) 34
8 Estimation of Average OH Concentrations in Three
Selected Smog Chambers 35
9 Chemicals Whose Smog Participation Can Not Be
Suitably Defined (Class II) 38
vi i
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ACKNOWLEDGMENT
Thanks are due to Dr. Basil Dimitriades, EPA Project Officer, for assis-
tance and encouragement during the conduct of this study. Support provided by
Dr. Bruce Cantrell, Dr. R. Thomas Podoll, Ms. Robin Redmond, Ms. Barbara Wild-
man, Ms. Dorothy Sevela and Ms. Valeria Ramsay of SRI International is grate-
fully acknowledged.
vi ii
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SECTION 1
INTRODUCTION
Current strategies to control photochemical air pollution rely on abating
the emission of volatile organic compounds (VOCs). Because VOCs differ signi-
ficantly in their ability to produce oxidants, a strategy based on the control
of those compounds which manifest themselves most strongly in smog formation,
rather than indiscriminate control, clearly constitutes a superior technical
approach.
Three major factors determine the ozone- or oxidant-forming ability of an
organic chemical:
• Ambient concentrations (or emissions)
• The ability of the organic chemical and its intermediate products to
remain in the gas phase (volatility)
• The ability of the organic chemical to oxidize in the atmosphere (typi-
cally, by reacting with OH or O3) and the efficiency of the oxidation
products to form ozone (reactivity).
This study deals with the reactivity/volatility classification of some
118 organic chemicals (including isomers and mixtures) specified by the
Environmental Protection Agency (EPA). These compounds include the 101 com-
pounds produced in largest volume in the U.S. as well as several additional
compounds used by the paint and coatings industry. The classification system
has been developed based on existing and available information. It was clear
at the outset that little or no experimental data were available for a signi-
ficant fraction of these chemicals. In such cases we relied heavily on our
ability to make valid predictions, based on sound physico-chemical principles.
As requested by EPA, a three-tiered individual, as well as a composite, clas-
sification scheme of the reactivity and volatility of these chemicals was
developed. It is recognized that photochemical involvement of organic chemicals
1
-------
cannot be rigorously compartmentalized into discrete classes. Nevertheless,
such a classification system is a useful, practical tool from a control
strategy viewpoint. For those cases where existing information does not
allow any definitive conclusions, a research protocol that bridges many of
the shortcomings of the current information needs to be developed. It is
noted that the regulatory objective is to classify chemicals as those that
either "contribute to smog" or those that "do not contribute to smog." The
middle category is created as a practical necessity when the above assign-
ments are not possible for lack of reliable information.
2
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SECTION 2
OBJECTIVES
The overall objectives of this study are the following:
• Develop a three-class reactivity scale for a list of 118 specified
organic chemicals
• Develop a three-class volatility scale for a list of 118 specified
organic chemicals
• Develop an integrated three-class scale that takes into account both
reactivity and volatility considerations
These three-tiered scales are constituted as follows:
- Class I: Compounds that are unreactive or nonvolatile and do not
contribute to smog formation.
- Class II: Compounds that are borderline cases or for which insuffi-
cient information is available to draw definitive conclusions.
- Class III: Compounds that are reactive and volatile, and contribute
to smog formation.
3
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SECTION 3
GENERAL TECHNICAL APPROACH
REACTIVITY CLASSIFICATION
Hydrocarbon reactivity has been defined in many objective and subjective
ways. The most commonly used objective criteria are maximum ozone formation,
rate of hydrocarbon depletion, NO (or NO2) oxidation rates, and analysis, and
concentrations of photochemical products. The most common subjective cri-
terion employs eye irritation as an index of oxidants in a simulated smog sys-
tem. It is now well recognized that photochemical air pollution is not lim-
ited to effects of ozone alone, but rather to a broad category of secondary
products (EPA, 1978; Altshuller, 1982). However, ozone is a useful surrogate
for the effects of photochemical pollution, and a specific national air qual-
ity standard (0.12 ppm O3 - hourly standard not to be exceeded more than once
in a year) currently exists. Keeping this In mind, we have given most atten-
tion to the following objective parameters —
- Maximum O3 yield
- Organic chemical (OC) depletion rate
- NO (or NO2) oxidation rate
- Product analysis
It is recognized that the above objective parameters are not absolute but
are dependent on factors such as OC concentration, 0C/N0x (ppmv/ppmv unless
otherwise specified) ratio, light intensity and temperature.
The above parameters were often directly available from smog chamber stu-
dies. A wide range of OC and N0X initial concentrations had been employed in
these studies. Typical initial 0C/N0x (ppov/ppmv) ratios varied from 2 to 20,
but ratios of <1 and >100 were also encountered. Chemicals that could be
5
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shown to produce O3 concentrations in excess of 0.12 ppm with an initial OC
concentration of <4 ppm and any OC/NOx ratio have been called reactive (Class
III). OC depletion rates and NO oxidation rates were also typically reported
in most smog chamber studies. There were very few Instances where the OC
depletion rates and NO oxidation rate contradicted the results of ozone forma-
tion. In most, but not all, cases the reasons for these discrepancies could
be explained.
Figure 1 shows the relationship between reactivity based on maximum ozone
formation and the rate of NO2 formation (Dimitriades et al., 1975). Simi-
larly, Figure 2 shows the correlation of maximum OC disappearance rate and the
maximum rate of NO2 disappearance (Laity et al., 1973). Although linear rela-
tionships are not implied, it is apparent that high organic chemical reac-
tivity, high NO oxidation rate, and high O3 formation are all manifestations
of the processes that lead to smog formation.
Figures 3 and 4 further show the significance of the initial OC/NOx ratio
in ozone formation. The figures are derived from data presented by Altshuller
and Bufalini (1971) and Sickles et al. (1980). It is obvious that a chemical
can be erroneously considered nonreactive when a wide range of 0C/N0x ratios
are not considered. Since a great deal of smog chamber data has been obtained
under conditions of low initial OC/NOx ratios (2 to 10) and relatively short
irradiation times (3 to 7 hours), this aspect was especially kept in mind in
assigning reactivities. When irradiations at high 0C/N0x ratios (>20) had
also been performed, such data were decisive even when low 0C/N0x data showed
little or no reactivity.
Over the years, it has also become apparent that OC depletion is most
dependent on reaction with the hydroxyl radical (OH) (Altshuller and Bufalini,
1971; Niki et al., 1973; Darnall et al., 1976). Figure 5 shows this relation-
ship for a number of compounds whose disappearance rates have been measured in
smog chambers (Pitts et al., 1978). It is acknowledged that alkenes may react
with O3 and aldehydes may photolyze at significant rates. Nevertheless, reac-
tivity analysis is possible based on reaction with OH radicals in the absence
of smog chamber data. Although exceptions exist, irradiations with NOjj of a
mixture of n-pentane, m-xylene and trans-2-butene (Winer et al., 1979) seem to
6
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1.4 r-
• Propiofioldahyda
• 8utadian*
Methylslyrm*
• cii*Z-Bu1«n«
2-M«1IVf<- 2-but«n« •
¦ (ran»-2- Bultn*
o-Tolualdtftyd*
~ •
4,0
REACTIVITY, propyltn* tquivol«nU
5.0
6.0
SOURCE: OlMITniAOCS, at at. (1978)
Figure 1. Correlation of maximum oxidant/Og and Rjvjq_ reactivities
7
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N02 Disappearance, Max. Rate (ppb/min)
SOURCE: LAITY, *t •!. (1973)
Figure 2. A sample correlation plot of NO2 and
hydrocarbon disappearance rates
OC/NOx (ppmV/ppm)
SOURCE: SICKLES, at at. (1M0)
Figure 3. Maximum ozone concentrations produced by
the propane-NOx-air irradiations in an outdoor
smog chamber at various OC to N0X ratios
8
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-
• II!
1 INI'
iii i j j-nri:
-
[propane
-
-
-
-
-
-
Hn-BUTANE
-
-
-
-
—
-
-
-
-
-
*
sTOLUENE
•
-
I ill
I I II I
Wtpropene , , , ,
T->-T_j_ i i 1 1 II
10 100
OH RATE CONSTANT (X10-12) - Cm3molec-1j-1
Figure 4. Relationship between OH rate constant and initial
organic chemical to NOx ratio needed for maximum
O3 formation
1 1 1 iy
*
o
1,2 J-Tnm«iny4Mflran«
t-j r-~n r-
Cycwwww/r
Ji
inm t t /' •mafHyttoAtw*
fTT'Pfofftw
^ m-Xyi«n«
(A
I
Ui
%
0 5 I 10 »
RELATIVE rates of HYDROCARBON DISAPPEARANCE
IN SAPRC CHAMBER EXPERIMENTS
SOUHCE: PITTS, at al. (19781
Figure 5. Comparison of relative hydrocarbon disappearance
rates (n-butane=»1) and hydroxy I radical rate
constant
9
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$ 1011
o~
o",
<7 1010
Hi "3
1 10®
a
>
x
x •
r'*
^¦
A-'#
• • • •
10®
1 1 ' 1
l! 15 2.5
0.5 1.0
OXIDANT MAXIMUM (PPM)
SOURCE: AOAPTED FHOM PARLEY, (1978)
Figure 6. Hydrocarbon reactivity vs. oxidant maximum
10
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suggest that O3 and PAN yields depend primarily on the OH radical reactivity.
This observation is further confirmed by Akimoto and Sakamaki (1983) for the
case of propylene-NOx system. Figure 6 shows results compiled by Farley
(1978) that further support this contention.
In summary, we have depended heavily on smog chamber irradiations for our
reactivity classifications. These data have been complemented with OH reac-
tivity to better understand those cases that are exceptions to general rules.
Instances where no smog chamber data were available are identified. In such
cases, we have used OH reactivity as the primary guiding criterion, although
reactions with O3, 0, NO3 as well as photolysis are considered when appropri-
ate. Exceptions are dealt with on a case-by-case basis. These few exceptions
deal specifically with free radical scavengers, such as phenol, aniline,
naphthalene (Gitchell, 1974; 1974a), as well as instances where smog chamber
systems may not simulate ambient conditions (e.g., perchloroethylene).
Although there are exceptions, our findings on reactivity can be broadly
stated as follows:
Class I: Organics where direct (smog chamber) data shows O3
formation significantly less than 0.12 ppm, and
the chemical has a measured or calculated depletion
rate that is less than ethane.
Class II: Direct evidence shows O3 formation near 0.12 ppm or
depletion rates are 1 to 5 times that of ethane.
Class III: Chemicals where direct evidence of O3 formation in
excess of 0.12 ppm (initial conditions of 0C <4 ppm
and any 0C/N0x ratio) is available, and/or measured
or calculated depletion rates are larger than 5 times
that of ethane, or chemicals for which no direct or
indirect evidence on reactivity exists.
The reasons that led to these divisions, and the specific exceptions,
will become clear during the Discussion of Results In Section 5. We note
here that for ethane and for species 2 to 5 times as reactive as ethane,
11
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limited experimental evidence was available, but the results were not
unequivocal. Only for chemicals more than 5 times as reactive as ethane
did convincing evidence of reactivity emerge from available data. We
also point out that for low reactivity chemicals, the reaction rate con-
stants are often uncertain to within a factor of 2.
VOLATILITY CLASSIFICATION
The photochemical reactivity of ozone precursors in the atmosphere
depends in part on the gas-phase distribution of reactive species. Vapor
phase organics may be removed from the atmosphere under ambient conditions by
water droplets or suspended particulate matter (aerosols). The effectiveness
of these sinks will determine the amount of chemical available for gas-phase
reactions.
Chemical species dissolved in dilute solutions partition between the
vapor phase and the condensed phase depending on their relative vapor pressure
and solubility. The ambient phase distribution can be quantified by Henry's
law
P-HC
where P is the partial pressure of the chemical In air, C is the solute con-
centration of the chemical dissolved in solvent, and H is Henry's constant.
Henry's constant is then a temperature-dependent measure of the phase distri-
bution for a chemical at the temperature of the partial pressure and solubil-
ity given. In the absence of measured values of H, the Henry's constant can
be calculated from the saturated vapor pressure and solubility.
Phase distribution depends on the mass transfer rates of a substance
across the liquid- and gas-phase boundary layers. Llss and Slater (1974) have
suggested typical mass transfer coefficient values for O2 and H2O transfer.
Based on these parameters, a chemical with high vapor pressure and/or low
3 3-1
solubility (H > 5 x 10 atm a mol ) is 95Z controlled by liquid phase resis-
-5 3
tance, while low vapor pressure and/or high solubility (H < 1 x 10 atm m
mol"*1) results in 952 resistance by the gas phase. Chemicals have been
12
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classified as high, intermediate, or low volatility compounds on the basis of
their Henry's constants (Smith et al., 1980, 1981). This approach is not
directly applicable to the partitioning of a chemical into solution that is
already in the gas phase because the gas/liquid equilibrium time is far
greater than reaction or removal rates in the atmosphere.
Experimental determinations in polluted atmospheres have been made by
Cautreels and Van Cauwenberghe (1976, 1978) and Broddin et al. (1980) of the
distribution of organic pollutants between airborne particulate matter and the
gas phase. Eichmann et al. (1979, 1980) also conducted similar measurements
for naturally occurring n-alkanes in unpolluted marine air. The Van Cauwen-
berghe and Broddin studies found that lower molecular weight compounds with
high vapor pressures were predominantly present in the gas phase, although the
maximum molecular weight and minimum vapor pressure varied among chemical
classes. The vapor pressure limit, above which a class of chemicals parti-
tioned into the gas phase, ranged over several orders of magnitude. Chemicals
with vapor pressures above 10 ^ atm consistently were found predominantly in
the gas phase, and can therefore be classified as high volatility (Class III)
compounds. Although the overall results of Eichmann et al. are in substantial
disagreement with the Van Cauwenberghe and Broddin studies, there is agreement
that species with vapor pressures of >10 ^ atm will be found essentially in
the gas phase. Some gaseous chemicals are highly soluble in water and others
may be preferentially adsorbed by aerosols. The small amount of water content
under typical smog conditions (relative humidity <70%) and relatively low par-
ticulate abundances in the ambient atmospheres (Heicklen, 1981) are unlikely
to significantly remove the gaseous reservoir of such chemicals.
Heicklen (1981) has shown that the removal rate of atmospheric species is
related to the turnover rate of atmospheric particulate matter. In the
absence of reaction in water droplets or on aerosol surfaces, vapor pressures
-9
less than 4 x 10 atm are required for complete removal by particulate
matter. Under typical environmental conditions, chemicals with vapor pres-
—8
sures less than about 10 atm should result in nearly complete (>75%) remo-
val. These chemicals have been classified as low volatility (Class I) com-
pounds, and exhibit partitioning predominantly into the condensed phase. This
—8
cutoff of O.Q atm vapor pressure for nonvolatile species is in good
13
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agreement with the results of Broddin et al. (1980). Unfortunately, it is in
disagreement with the results of Eichmann et al. (1979, 1980) who find even
C28 alkanes (vapor pressure 7x10 atm) primarily in the gas phase. Their
results are shown in Figure 7, and clearly suggest that more than 95Z C9-C28
alkanes exist in the vapor phase. Table 1 summarizes the results of Broddin
et al. (1980) where all chemicals with vapor pressures equal to or greater
-8
than tetracosane (C24, V.P.»1.3 x 10 atm) are found exclusively in the aero-
sol phase.
-8
We have chosen the 10 atm vapor pressure as the cutoff for Class I
(nonvolatiles) primarily because it conforms with the theoretical analysis of
Heicklen (1981) as well as the experimental results of Broddin et al. (1980).
Unlike the Eichmann et al. (1979, 1980) studies, the Broddin studies are per-
formed in typical urban atmospheres. Here the aerosol composition and density
may be such that high molecular weight species can be adsorbed onto available
surfaces. Eichmann's studies were performed la remote marine atmospheres and
are not directly applicable to polluted air. From these studies it is evident
that volatility is highly dependent on the type of the aerosol mix available
for condensation and adsorption.
-8 -6
Vapor pressures between 10 and 10 atm result in varying degrees of
partitioning depending on chemical structure, functional groups, and atmos-
pheric conditions. These have been classified as Intermediate volatility
(Class II) compounds. Class II has also been designated for organlcs of
uncertain phase distribution, or insufficient information.
The volatility of each chemical has been classified as follows:
Class I: Organlcs with clearly greater percent occurrence
in the condensed phase (>75% condensed phase)
under ambient conditions (vapor pressure
<1 x 10 8 atm).
Class II: Organlcs with intermediate phase distribution in ambient
air (1 x 10"®atm < vapor pressure < 1 x 10"^ atm),
and organlcs for which volatility or phase distribution
evidence does not exist.
14
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9 II Q IS 17 19 21 23 25 27
10 7 H 1# « 20 22 24 28 n
C - numbtr at n ¦ alkrjnn —«
SOURCE: EICHMANN. «t ll. (1079)
Figure 7. Distribution of Cg-C2g n-alkanes and
other select chemicals in the aerosol
and gas phase
15
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Table 1. Distribution of aliphatic hydrocarbons between aerosol (A) and gas (G) phase at Ghent (residential), pg/1000 m3
Compound
January
A
G
February
A
G
March
A
G
July
A
G
August
A
G
September
A G
Hciadccanc
2.31
40
151
16
021
94
—
106
—
251
081
154
Hcpudccaoe
1.20
39
1 56
17
049
41
—
362
—
146
0.78
335
Octadecane
1.61
22
275
22
075
47
—
245
159
130
130
118
NwadccMt
126
3
1.00
1
0)0
1
187
38
105
13
075
16
Eicosanc
291
—
1.90
1
031
4
120
7
096
10
063
2
Hencicosanc
49)
1
311
I
0.90
2
1.79
13
1 11
6
059
—
Docosanc
9.95
—
169
—
1.96
1
2.10
1
1.51
3
1.44
9
Tricosaiw
11.73
—
1011
—
267
—
511
1
1.17
4
3.99
1
TcUacouae
19.14
—
1260
—
4.94
—
442
—
4 22
—
6.41
—
Pcntacosanc
18.51
—
9.44
—
4.07
—
795
—
8.61
—
763
—
Hexacosanc
1162
—
616
—
3.01
—
2.58
—
1.65
—
4.90
—
HcpUcosaoc
18.64
—
SIS
—
4.78
—
6.14
—
S.iS
—
581
—
Octacosanc
1726
—
410
—
295
—
1.89
—
116
—
391
—
Nonacosane
20.S4
—
617
—
559
—
659
—
784
—
8.76
—
Tfiaconttae
1649
—
246
1.20
—
0.49
—
1.91
—
2.61
—
Hcntriacomane
154)6
—
100
—
115
—
415
—
468
—
6.73
—
Douiacontanc
10.98
—
1.10
—
1.21
—
0.64
—
135
—
2.49
—
Tnlriaconunc
7.75
—
174
—
—
—
1.40
—
260
—
3.08
—
SOURCE; BROODIN, tt «l. (1MOI
-------
Class III: Organics with clearly greater percent distribution
—6
in the gas phase (vapor pressure > 1 x 10 atm).
For alkanes this scheme leads to Class I OC24 alkanes), Class II (C13-
C24 alkanes) and Class III (
-------
SECTION 4
DATA COLLECTION AND ESTIMATION
All data collected or estimated are summarized la the Appendix for each
of the chemicals of Interest. Since no measured data were available for a
large number of chemicals, estimation methods had to be employed In such
cases. All sources of data are cited and estimates clearly noted In the
Appendix. In addition, comments are Included that allow a better Interpreta-
tion of these raw data. The overall process of data collection was divided
Into three categories. These are
• Smog chamber data (Reactivity)
• Measured rate constant data and rate constant estimation (Reactivity)
• Measured physical properties and their estimation (Volatility).
In the following sections, we shall briefly discuss these data. Complete
details for individual compounds can be found in the Appendix.
SMOG CHAMBER DATA
These data provide the most direct determination of the 03-forming abil-
ity of a chemical. Smog chamber data taken between 1959-present were found
and employed in this study. All relevant references and important data are
summarized in the Appendix. Most of the data are obtained with relatively low
0C/N0X ratios (2 to 10), and simulate Irradiations of 3 to 7 hours. During
the last decade, however, it has been increasingly felt that for chemicals of
low reactivity, high 0C/N0x ratios (>20) and long irradiation times are condu-
cive to high ozone formation. Some smog chamber data were available for
approximately half of the 118 chemicals of interest. Although the sources of
these data are many (Appendix), the following are some of the prominent ones:
19
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- Stanford Research Institute (Schuck and Doyle, 1959)
- Los Angeles County (Brunelle et al., 1966)
- General Motors Research (Heuss and Glasson, 1968)
- Stanford Research Institute (Wilson and Doyle, 1970)
- Battelle Columbus Laboratories (Levy and Miller, 1970)
- Shell Oil Company (Laity et al., 1973)
- Bureau of Mines (Dimitriades et al., 1975)
- Rutgers University (Appleby, 1976)
- Environmental Protection Agency (Dimitriades and Joshi, 1977)
- MITI Japan (Yanagihara et al., 1977)
- Research Triangle Institute (Sicld.es et al., 1980)
- University of North Carolina (Jefferies et al., 1982)
The most Important initial conditions and results from smog chamber irradia-
tions are presented for each of the chemicals. A good deal of product
analysis is also based on smog chamber studies. The identified products are
summarized under comments in the Appendix. Where no product analysis is pro-
vided, it can be assumed that ozone, PAN and formaldehyde are the only identi-
fied products.
MEASURED RATE CONSTANT DATA AND RATE CONSTANT ESTIMATION
In the absence of any smog chamber data, reactivity of chemical species
with hydroxyl (OH) radical provides a useful technique for establishing their
involvement or noninvolvement in photochemical ozone formation. It is recog-
nized that a direct and quantitative relationship between OH reactivity and
ozone formation has not been established, and exceptions are known to exist.
Nevertheless, available information provides strong support for the general
validity of such relationships (Darnall et al., 1976; Winer et al., 1979; Aki-
moto and Sakamaki, 1983). In addition, these allow an independent assessment
of the depletion rates measured in smog chambers, and indirectly, an estima-
tion of the validity of experimental data. The exhaustive literature search
was therefore conducted to collect measured OH-rate-constant data at 295-300°K
20
-------
from Che literature. These data and the relevant references are Included in
the Appendix. Two of the primary sources of OH rate constant data were compi-
lations prepared by Atkinson et al. (1979) and Hampson (1980). Additional
published and unpublished data for the period 1980-1983 were also sought and
are cited. When applicable the rate constants with O3 (for alkenes), and due
to photolysis (aldehydes and ketones), are also included.
After an exhaustive survey of kinetic data, it became evident that the
measured rates were available for only about 602 of the chemicals of interest.
Thus, it was essential for us to estimate OH rate constants for the remainder
of the chemicals. The method used was an updated version of the structure
activity relationship (SAR) method developed by Hendry and Kenley (1979) and
described by Davenport in Mill et al. (1982). This OH-rate-constant estima-
tion technique included three major pathways for such reactions in the gas
phase: (i) H-atom abstraction, (ii) addition to olefinic bonds and, (iii)
addition to aromatic rings.
Each reaction path has an intrinsic reactivity constant for each reaction
ADD ADD
center, kAgsT» k0LEFIN« an<^ ^AROM* Each reactivity constant is modified by
substituents on the reaction center (a-position) and adjacent to it (B~
position), which are expressed as substituent constants a and g , respectively.
Thus, the general expression for the OH SAR is
k * k + (1)
OH ABST OLEFIN AROM
OH
P
L
i-1
i Hi MHi
q
^Hi ^
j-1
*Ej
r
+ L
1-1
aAl Al
(2)
The term n^ is the number of times a structural group appears in the molecule.
Each am is the product of an for each a-postion substituent (maximum of three
for a methyl hydrogen). Likewise, each Sjji is the product of 6u for the (up
to nine) 8-position substituents. The kg^ term is the rate constant of the
21
-------
parent hydrocarbon group without substituents. Similarly agj is" the product
of all substituent constants otg for the substituents on the jth double bond
while ia the product of the substituent constants for all substituents
on a given aromatic ring (1). Each kg or kA is the rate constant for the dou-
ble bond or aromatic structure type, respectively* Values of k, a and 0 are
based on an extensive list of published rate constants for each kind of reac-
tion or composite reaction constants that were divided into the contributory
constants for each pathway. The current best values of these SAR constants
are given in Tables 2 to 5 (from Davenport in Mill et al., 1982). For addi-
tional details on the application of these SAR constants, including examples,
the reader is referred to Hendry and Kenley (1979), Mill et al. (1981) and
Mill et al. (1982).
The validity of this OH reaction rate estimation method was tested for a
set of approximately 100 chemicals for which the estimation technique is
applicable and measured rate constants were available. Figure 8 shows these
results for alkane, alkenes, haloalkenes, aldehydes, ethers, alcohols, ace-
tates, ketones, sulfur compounds, aromatics, chlorobenzenes, and terpenes.
For lack of available constants, the estimation methodology is not strictly
applicable to alkynes, phthalates, nitrogenous compounds, and epoxides. It is
clear from Figure 8 that the estimated rate constants in general are in agree-
ment with measured values to within a factor of two (one standard deviation).
For the purposes of this study, OH rate constants were estimated for those
cases where no reliable measurement had been made. Occasionally, this was
also used to suggest potential discrepancies in measured OH rate constants.
The increase in scatter with decreasing rate constants in Figure 8 is due to
less accurate measurements in this region. These also cause SAR constants to
be less precise.
PHYSICAL PROPERTIES AND THEIR ESTIMATION
Literature data is relatively scarce for physical property information
such as vapor pressure, solubility, or ambient phase distributions. The solu-
bility of chemical in water can be estimated from the activity coefficient
where the mole fraction of chemical in water is the inverse of the infinite
dilution activity coefficient. Several methods are available for estimating
22
-------
Table 2. Abstraction Rate Constants (kH) for reactions
of OH with generalized structures
Structura*
10"
1. Primary carbon
H—CX2-(CY3,-QY, or -CY or -SY)
0.065 1 0.013
0
2. Sacondary carbonf
X
H C-(CY3)2
0.55 * 0.07
+
3. Tartlary carbon '
H C-(CY3)3
2.9 ± 0.58
4. Doubla bond^
X Y
1 ^
H—C"C
0.01 t 0.002
N Y
S. Primary carbon.
fl-doubla bond**
X Y
H—C-C*C
0.3 * 0.1
X
6. Secondary carbon.
ft-doubla bond^t
CYiY
l 1
H*"C-CeC
l
2.5 t 1.0
X
7. Tartlary carbon.
A-doubla bond**
CY,Y
1 1
H—C-OC
4.0 t 1.5
«)
8. Aldahyda*
»—C-
17 1 4
N
0
9. Marcaptan1
H S-
2.6 t 1.3
10. Craaol
H—O-C
1.7 1 0.08
Tha x'a rafar eo a aubatltuanca, Y'a to B aubatltuants. Tha subatituanta are
not nacaaaarlly identical. For axaapla, Y'a in H-CX^CYj could rapraaant two
dlffarant kioda of th« aubatlcuane troupa llatad In T«bt« 5; ona Y nay rapraaant
a CI and tha othar an H. If no X or Y la llatad, thara la no aubatituanc affact
^for that atruetura. .
Rata conatant axpraaaad aa c«3 00lac" a*1.
In addition to aaturatad carbon aoladaa, *CYj, -0Y -C-Y or -S-Y taolaclaa
can ba uaad inataad aa ahown in atruetura 1. 0
Olaflnlc or aroatttlc.
Mo 0 aubacltuanta affacta for thaaa ttructuraa (I.a., 0g ¦ 1.0 for all 6
acructuras).
23
-------
Table 3. Induction factors for substituents
Substituent, X or Y
a^(for X's)
SyCfor Y's)
-H
1.0
1.0
-F
1.0
0.3 ± 0.1
-CI
2.4 + 0.5
0.4 + 0.1
-Br
2.4 + 0.05
0.4 + 0.1
-OH
2.0 + 0.05
1.0
-O-alkyl
6.0 ±2.0
1.0
-C (alkyl)+
1.3 + 0.2
1.0
r
1.0
1.0
-N
100 ± 50
1.0
-S-
200 + 100
1.0
*See test for method of application and chapter by
Davenport in Mill et al. (1982) for examples
^Only for structures 1 through 7, Table 2.
24
-------
Table 4. Addition rate constants (kg) for reaction of OH with carbon-carbon
double bond and values of induction factors (ag)
Substituent
12 *
10 "k (per double bond)
Substituent a£
none (ethene)
7.9
1-alkyl
27.0 + 5
H - 1.0
1,1-dialkyl
50.0 + 10
F - 0.5+0.3
cis-1,2-dialkyl
60.0 + 12
CI, Br ¦ 0.7 ± 0.3
trans-1,2-dialkyl
70.0 + 14
trialkyl
80.0 + 16
tetraalkyl
150.0 + 30
vinyl or phenyl
80.0 + 20
methoxy
33.0
r 3-1-1
Rate constant expressed as cm molec s
25
-------
Table 5. Addition rate constants (k^) for reaction of OH with aromatic
rings and values of induction factors (a^)
Substituent
12 *
10 k.
A
Substituents
°A
H
2.0 +0.6
H
1.0
Alkyl
5.0 + 2
CI
0.3
Dialkyl
12 + 4
F,Br,I
< 1 "
1,2,3-Trialkyl
10 + 5
—
—
1,2,4-Trialkyl
25 + 5
—
—
1,3,5-Trialkyl
49 + 5
—
—
Methoxy
17 ± 5
—
—
OH plus alkyl
34 + 10
—
—
-C-H
II
0
< 1.0
—-
—
3 -1 -1
Race constant expressed as cm molec s
26
-------
10
i-9r
— 10"10
, !—
Log Kg -0.96 (±0.05) Log Kp+ 0.14 (±0.54)
R - 0.97
Standard error (log Kg) — 0.26
Standard error on Kg » 100.26 » 1.82
A »
*
*
*
45° LINE
*
10'
-11
10
r12
A
~
* Oj
V
a y* •
V
a *
• Alkanes
O Alkenes
A Haloalkenes
~ Aldehydes
¦ Ethers
0 Alcohols
4 Acetates
A Ketones
V Sulfur Compounds
~ Aromatic Hydrocarbons
x Chlorobenzenes
+ Terpenes
10
r13
_L
l
10
-13
10'
-12
io-
ii
10'
,-10
Kp - PREDICTED VALUE (cm3molec"V1)
10"
Figure 8. The relationship between predicted (Kp) and experimental (Kg) hydroxyl
radical rate constants
27
-------
Che activity coefficients based solely on knowledge of the molecular struc-
ture. Correlation constants for an equation that considers contributions by
solute and solvent functional groups and number of carbon atoms were developed
by Pierotti et al., (1959), and are detailed in Lyman et al., (1982) and Reid
et al., (1977).
Several correlation equations estimate vapor pressure from boiling and
melting points. One recently reviewed method for estimating vapor pressures
at below boiling point temperatures is described by Grain in Lyman et al.'s
Handbook of Chemical Property Estimation Methods (1982). The method requires
only the normal boiling point and is suitable for all organic materials over a
wide pressure range. The Lyman method has a stated maximum error of 7.1Z over
the pressure range 0.01-1 atm, 50% between 1 x 10 ^-0.01 atm, and 200Z below 1
-6
x 10 atm. The average error is <50Z which is often less than the range of
vapor pressures found in the literature.
The Lyman method uses a modification of the Watson correlation to express
the temperature dependence of A#v such that
where Ahv is the heat of vaporisation, APvb is che heat of vaporization at the
normal boiling point, and m is a constant which depends upon the physical
state. Substitution in the Clausius-Clapeyron equation and integration
results in an expression with adjustable parameters that depend on the molecu-
lar structure and the physical state at the temperature of Interest. With
further modification, the Lyman method can also be used to estimate vapor
pressures from boiling points at reduced pressure.
Henry's constants were calculated from the vapor pressure and solubility
4 -3
data given. A water solubility of 1.7 x 10 mol m was used for chemicals
which were completely misclble in water. Practically, the water solubility
22 3 "22 3
cannot exceed 10 molecules/cm , since the molecular volume is > 10 cm
(Heicklen, 1981). This is equivalent to 1.7 x 10 mol m at 25°C. For gase-
ous chemicals at 25°C, the convention is to calculate the Henry's constant for
(3)
28
-------
a total solute vapor pressure equal to one atmosphere because the solubility
data is at atmospheric pressure. Chemicals with high solubility or in the
gaseous state at ambient conditions will, therefore, not always have calcu-
lated values (Henry's constants) equal to Che saturated vapor pressure divided
by the solubility (P/C). In addition, the value on the data sheets may also
differ from expected calculated values because of rounding off differences*
Henry's law is strictly applicable only to dilute solutions (mole frac-
tion <0.001) and ideal gases where the activity coefficient is constant. For
non-ideal systems, the activity is no longer constant and the solute vapor
pressure exerted is smaller than for the pure solute. However, the magnitude
of H for non-ideal systems can be used to broadly estimate environmental par-
titioning. In this study, it is assumed that most typical smog conditions
occur during conditions of moderate-to-low humidity (<70Z RH).
29
-------
SECTION 5
REACTIVITY/VOLATILITY CLASSIFICATIONS
AND DISCUSSION OF RESULTS
The raw data, a9 well as the reactivity, volatility, and overall
classifications, are provided in the Appendix. To facilitate discussion
these assigned classifications are summarized in Table 6. Shortcomings
in data availability are also specified in this table. The overall
classification utilizes the lowest rankings of the individual reactivity
or volatility classification. We shall discuss the reasons, uncertainties,
and shortcomings of individual rankings in the following sections.
CHEMICALS IN THE CLASS I CATEGORY
These chemicals are listed in Table 7. The reason for this designation
(low reactivity or low volatility) is specified. Of the 26 chemicals ranked
as Class I, only 4 are due to very low volatility. All of the nonreactive
species have a reactivity less than that of ethane. Ethane, tested in a smog
chamber under a variety of OC-to-NOx ratio conditions, was found to yield no
more than 0.08 ppm O3 (Heuss, 1975). In the same study, propane yielded as
much as 0.14 ppm O3, suggesting that the NAAQS-O3 level of 0.12 ppm corresponds
to a reactivity level between those of ethane and propane. These data and
comparisons are not unequivocal because of the questionable comparability of
smog chamber and "real" atmospheres and of other uncertainties. However, in
the lack of more definitive data, ethane is taken to be the best choice of
"borderline" organic separating the "reactive" organics from the "unreactive"
ones.
OH-rate-constants at 25 #C relative to ethane vary from 0 to 1.0. In a
number of instances (Chemical Nos. 6, 7, 25, 26, 28, 39, 48, 53, 54, 56, 71, 77,
and 94), simulated laboratory irradiation data are available and show no O3
31
-------
Table 6. Reactivity/volatility classification of selected organic chemicals
Classification
Chemical Name
No.
Reactivity
Volatility
Overall
Acetic acid
1
III
III
III
Acetic anhydride
2
11+
III
II
Acetaldehyde
3
III
III
III
Acetone
4
III
III
III
Acetone cyanohydrin
5
11+
III
II
Acetonltrile
6
I
III
I
Acetylene
7
I
III
I
Acrylic acid
8
III+
III
III
Acrylonitrile
9
III
III
III
Adipic acid
10
lilt
III
III
Aniline
11
TT*
III
II
Benzene
12
ii
III
II
Bisphenol-A
13
111+
£
I
1,3-Butadiene
14
hi
III
III
n-Butane
15
hi
III
III
1-Butane
16
hi
III
III
Butenes
17A-C
hi
III
III
Isobutylene
18
in
III
III
n-Butanol
19
hi
III
III
2-Butoxyethanol
20
in
III
III
n-Butyl acetate
21
hi
III
III
s-Butyl acetate
22
hi
III
III
t-Butyl alcohol
23
hi
III
III
Carbon disulfide
24
ii
III
II
Carbon tetrachloride
25
i
III
I
Chloroform
26
i
III
I
Monochlorobenzene
27
ii
III
II
p-Dlchlorob«nzene
28
i
III
I
Dichloropropene (1,3 and 1,2)
29A-B
iii+
III
III
Cumene
30
in
III
III
Cvclohexane
31
hi
III
III
Cyclohexanol
32
m+
III
III
Cyclohexanone
33
in
III
III
Diechylene glycol
34
111+
+
III
III
Di-(2-ethylhexyl) phthalate
35
nr
I
I
Diisodecyl phthalate
36
iix+
I
I
Dimethyl terephthalate
37
m+
iu>
III"
III
Epichlorohydr in
38
III
III
Ethane
39
i
III
I
Ethanol amine (mono)
40A
111+
III
III
Ethanol amine (di)
40B
111+
I
I
Ethanol amine (trl)
40C
m+
II
II
Ethyl acetate
41
hi
III
III
Ethyl alcohol
42
hi
III
III
Ethyl benzene
43
hi
ii j
III
III
Ethyl chloride
44
III
II
2-E thoxyhexanol
45
iii+
III
III
Ethylene
46
hi
III
III
Ethylene dlbromlde
47
I»
III
I
Ethylene dlchlorlde
48
i
III
I
Ethyl ether
49
in
III
III
Ethylene glycol
50
iii+
III
III
Ethylene oxide
51
i
III
I
2-Ethyl hexanol
52
in+
III
III
FluoTocarbon 11
53
i
III
I
Fluorocarbon 12
54
i
III
I
Fluorocarbon 22
55
i
III
I
Fluorocarbon 113
56
i
III
I
Fluorocarbon 114
57
i
III
i
Formaldehyde
56
in
III
in
Clyc trine
59
lll
II
ii
Hexaaethy1enetetranine
60
iii+
II"
II
Heptenea
61
hi
HI
III
62
iii+
III**
III
32
-------
Table 6. (Continued)
Classification
Chemical Name
No.
Reactivity
Volatility
Overall
Hydrogen cyanide
63
I»
III
I
Isodecyl alcohol
64
Ulf
II
II
Isoprene
65
III
III
III
Isopropyl alcohol
66
ni.
III
III
n-Propyl alcohol
67
Ill1
III
III
Maleic anhydride
68
III+
III
III
Methanol
69
III
III
III
Methyl chloride
70
I»
III
I
Methylene chloride
71
I
III
I
Methyl ethyl ketone
72
III
III
III
Methyl isohutyl ketone
73
III
III
III
Methyl methacrylate
74
III
III
III
Solvent naphtha
75
III
III**
III
Naphthalene
76
II*
III
II
Nitrobenzene
77
I
III
I
n-Octyl-n-decylphthalate
78
III+
I
I
Nonylphenol (ethoxylated)
79
III+
II*
II
Perchloroethylene
80
I*
III
I
Phenol
81
II*
III
II
Phosgene
82
I+
III
I
Phthalic anhydride
83
III+
II
II
Propane
84
III
III
III
Propylene
85
nl+
III
III
Propylene glycol
86
111*
III
III
Propylene oxide
87
II5
III
II
Styrene
88
III
III
III
Terephthalic acid
89
III+
III
III
Terephthalic acid (dimethyl ester)
90,37
III
III**
III
Tetrapropylene
91
III+
III**
III
Toluene
92
III
III
III
Toluene diieocynate
93
III+
III
III
1,1,1-Tr ichloroethane
94
I
III
I
Tr ichloroethylene
95
III
III
III
Triathylene glycol
96
IIIr
III
III
Vinyl acetate monomer
97
III
III
III
Vinyl chloride monomer
98
III
III
III
m-and mixed Xylenes
99
III
III
III
o-Xylene
100
III
III
III
p-Xylene
101
III
III
III
Dimethyl succinate
102
III +
III**
III**
III
Dimethyl glutarate
103
III+
III
Dimethyl adipate
104
III+
III**
III
2-aethoxy ethanol
105
III+
III**
III
Ethylene glycol mononethyl ether
106
IIIf
III
III
Ethylene glycol monoethyl ether
107
III+
UItt
III
Diisoamyl ketone
108
in!
11*
II
Propylene glycol methyl ether
109
HIT
III
III
Dipropylene glycol methyl ether
110
III.
III
III
o,m,p Cresols
111A-C
Ill*
III
III
+No smog chamber or measured hydroxyl radical rate constant data war* available.
*Exception requiring special interpretation of data (see text).
**
Vapor pressure was estimated.
5Mo smog chamber data were available.
No vapor pressure estimate was possible.
33
-------
Table 7. Chemicals that may not participate in smog formation (Class I)
Chemical Name
NO.
Nonreactive
Nonvolatile
Conments*. +
Acetonlcrlle
6
/
Significantly less reactive than
ethane
Acetylene
7
/
/
Reactivity comparable co ethane;
Bisphenol-A
13
V.P. is 2 (-12) atm: very low
partition coefficient. Highly
reactive in gas phase
Carbon tetrachloride
25
/
Unreactlve In the troposphere
Chloroform
26
/
Reactivity less than ethane
p-dichloroben2ene
28
/
Reactivity comparable to ethane
Di-(2-ethyl hexyl) phthalate
35
~
Vapor pressure is 2(-10) atm.
Highly reactive in gas phase.
Dlisodecyl phthalate
36
~
V.P. is 4(-10) atm. Highly
/
reactive in gaa phase
Ethane
39
Too unreactlve to participate in
smog formation
Ethanol amine (dl)
40B
~
V.P. is 2(-9) atm. Very low parti-
tion coefficient. Highly reactive
/
in gaa phase.
Ethylene dlbrooide
47
Reactivity less than ethane
Ethylene dlchlorlde
48
/
Reactivity less than ethane
Ethylene oxide
51
/
Less reactive than ethane
Fluorocarbon-11
53
/
Unreactlve in the troposphere
Fluorocarbon-12
54
/
Unreactlve In the troposphere
Fluorocarbon-22
55
/
Significantly less reactive than
/
/
ethane
Fluorocarbon-113
56
Unreactlve in the troposphere
Fluorocarbon-114
57
Unreactlve In the troposphere
Hydrogen cyanide
63
/
Virtually unreactlve in the
troposphere
Methyl chloride
70
~
Significantly less reactive than
echane
Methylene chloride
71
/
Less reactive than ethane
Nitrobenzene
77
/
Less resctlve than ethane. Smog
inhibitor
n-octyl-n-decyl phthalate
78
V.P. is 9(-9) atm. Highly reactive
In gas phase
Perchloroethylene
80
/
Signlficsntly less reactive than
ethane
' Phosgene
82
/
Significantly less reactive than
ethane
1,1,1-Trlchloroethane
94
J
Significantly less reactive than
ethane
*2(-12) - 2 x 10"12; V.P. - v»por pressure
+For additional dlacuaalona *•• Appendix and text.
34
-------
Table 8. Estimation of average OH concentrations in three selected smog chambers
Chemical Name
No.
Measured Oil
rate constant, iC
(cb^ molec-! s~l)
l)iwl t r lades and
Joshi (1977)
Yanaglhara et
al. (1977)
Heuss and Glasson (1968)
Av. Dlsapp. rate
DR U/h)
oil
(uolec. cm-^)
Av. Dlsapp. rate
DR (Z/h)
oil
-1
(inolec. cm )
Av. Dlsapp. rate
DR (Z/h)
011
(molec. cci-^)
Acetic acid
1
7. 3(— 13)*
2.0
7.6(6)5
Acetonltrlle
6
4.9(-14)
0.02™
1.1(6)
Acetylene
7
1.7(-13)
6.3
1.0(8)
3.5
5.7(7)
Acrylonltrlle
9
4.1(-12)
5.3
2.3(6)
Benzene
12
1.2(-12)
3.1
7.2(6)
3.3
7.6(6)
2.2
5.1(6)
n-Butane
15
2.7(-12)
1.4
1.4(6)
7.0
7.2(6)
0.8
0.8(6)
n-Butanol
19
7.6(-12)
7.4
2.7(6)
n-Butylacetate
21
5.3<-12)t
4.3
2.3(6)
5.3
2.8(6)
Chloroform
26
l.K-13)
0.8
2.0(7)
Monochlorobenzene
27
9.0(-13)
1.5
4.6(6)
o-Dlchlorobenzene
28+
2.5(-13)
4.3
4.8(7)
Cumene
30
7.8(-12)
5.5
2.0(6)
Cycloliexane
31
6.2(-12)
5.8
2.6(6)
Ethane
39
3.1(-13)
0.5
4.5(6)
11.0
9.8(7)
Ethyl acetate
41
1.8(-12)
1.9
2.9(6)
Ethyl alcohol
42
2. 5(-12)
4.0
4.4(6)
Ethyl benzene
43
8.0(-12)
6.5
2.3(6)
4.8
1.7(6)
i-Propanol
66
5.5(-12)
3.3
1.7(6)
4.0
2.0(6)
Methanol
69
l.K-12)
1.3
3.3(6)
Methylene chloride
71
1.6(-13)
5.7
9.9(7)
1.9
3.3(7)
Perchloroethylene**
80
1. 7(-13)
Propane
84
1.9(-12)
2.0
2.9(6)
4.1
5.9(6)
Toluene
92
5.8(-12)
0.1++
8.0
3.8(6)
6.5
3.1(6)
1,1,1-Tr lchloroethane
94
1.2(-14)
2.3(7)
Trlchloroethylene
95
2.2(-12)
9.4
1.2(7)
o-Xylene
100
1-2(—11)
11.1
2.6(6)
8.7
2.0(6)
Noce: Initial Hydrocarbon (ppa) to N0X (ppa) ratios are A/0.2, 2/1 and 2/1 respectively for Dlnltriades and Joshi (1977),
Yanaglhara et al. (1977) and Heuss and Glasson (1966).
* -13
7.3(-13) • 7.3 x 10 . For source of rate constant data see Appendix.
*Rate measured for s-butyl acetate; No. 28 Is p-dlchlorobenzene, the rate constant and measured depletion rates
are for o-dlchlorobenzene.
S0H - 2.78 x 10~6 (iC'.DK)
**NoL possible because of CI atom reactions in smog chambers.
ff
In thuae experlnents, disappearance races of <0. lZ/li are probably nut quantitative.
-------
formation above chamber background levels. In these and all other unreactive
cases measured or estimated OH rate constants are utilized to arrive at Table 7.
Here we point out that even when smog chamber data are available for low
reactivity chemicals, the results may be Inapplicable. Table 8 summarizes the
depletion rates from three smog chamber studies for those chemicals whose
reactivity is exclusively with OH radicals and a measured OH-rate-constant is
available. The estimated average OH values that prevailed in these smog chambers
are listed in Table 8. Figure 9 shows a plot of the estimated OH concentration
and the OH-rate-constant for each of the chemicals. Two salient observations
can Immediately be made from the results of Table 8 and Figure 9.
• The prevailing OH concentrations in a smog chamber can vary nearly
100-fold, depending upon the chemical being irradiated.
• The prevailing OH concentrations increase as the OH reactivity
decreases.
It is also obvious from Figure 9 that this behavior is not limited to a single
study. The best available estimates of OH abundance in the boundary layer
of a polluted atmosphere is 3(±2) x 10*> molec. cm~3 (Calvert, 1976; Singh
et al., 1981). Therefore, we feel that smog chambers may not provide repre-
sentative reactivity data for chemicals with an OH-rate-constant of less than
10~12cm3moiec-ls-lj or roughly three times the rate constant for ethane. One
reason for the prevailing high OH levels during such cases is the inability
of low reactivity OCs to provide an effective OH removal process which are
probably produced as a result of chamber wall effects. We hasten to add that
the chemicals assigned Class I are less reactive than smog chamber experiments
suggest, hence their classification will not change. On the other hand, some
chemicals in Class II or III categories may more appropriately belong in Class
I.
The four nonvolatile species in Class I category all have vapor pressures
less than 10~® atm and as low as 10~^2 atn. All current experimental (Broddin
et al., 1980) and theoretical evidence suggests that these compounds would be
more than 757. partitioned in the particulate phase. In almost all of these
cases, Henry's coefficients are also sufficiently low to favor the aerosol phase.
We note, however, that all four of these species would be higly reactive if they
36
-------
J L
AMBIENT OH RANGE
3(±2)i<106molec. cm-3
/////////. ¦
• Dimitriades and Joshi (1977)
X Yanagihara et at (1977)
~ Heuss and Glasson (1968)
''''
-I l II I II I
108
10® 107
ESTIMATED AVERAGE OH (OT) molec. cm-3
108
Figure 9. Relationship between OH rate constant and prevailing mean OH
concentrations in three smog chambers
37
-------
Table 9. Chemicals whose smog participation cannot be suitably defined (Class II)
Intermediate
Intermediate
it ±
Chemical Name
NO.
Reactivity
Volatility
Comments ''
Acetic anhydride
2
/
No S.C. or kinetic daca; reactivity
slightly greater Chan ethane
Acetone cyanohydrin
5
/
No S.C. or kinetic data; reactivity
slightly greater than ethane
Aniline
11
Reactive smog Inhibitor, no S.C. data
Benzene
12
J
Carbon disulfide
24
/
Insufficient and unreliable evidence
of reactivity
Monochlorobenzene
27
J
2 to 3 times as reactive as ethane
Echanol amine (di)
40B
/
V.P. is 7(-7) atm. Highly reactive
in sas shase
Sthyl chloride
44
4
No S. C. or kinetic daca; reactivity
J
slightly greater than ethane
Glycerine
59
J
About 5 times as reactive as ethane;
/
V.P. - 3(-7) atm.
Hexameehyleneteeraoine
60
V.P. la 8(-7) ata. Highly reactive
~
in gas phase
Isodecyl alcohol
64
V.P. is 8(-7) atm. Highly reactive
in gas phase
Naphthalene
76
Reactive smog inhibitor, no S.C. data
Nonylphenol (ethoxylated)
79
No V.P. estimate possible
Phenol
SI
/
Reactive smog inhibitor
Phthalic anhydride
83
V.P. is 7(-7) atm. Low partition
coefficient. Highly reactive in gas
~
phase
Propylene oxide
87
No V.P. estimate possible
Diisoamyl ketone
108
*S.C. - smog chamber; V.P. • vapor pressure; 3(-7) • 3 x 10"7
~For additional discussion see Appendix and text.
38
-------
could exist in the gas phase (Table 7, Appendix). This i3 based on the assump-
tion that the estimated rate constants are reliable.
CHEMICALS IN THE CLASS II CATEGORY
Seventeen chemicals are designated as Class II (Table 9). Seven of these
are in this category exclusively for reasons of moderate reactivity, and four
for reasons of low volatility. One chemical (glycerine) is estimated to have
low reactivity and low volatility, and for two other chemicals no vapor pres-
sure estimate could be made. In addition, three chemicals are designated as
Class II because they appear to behave exceptionally, and data are insufficient
to draw definitive conclusions.
In general, compounds that are l-to-5 times as reactive as ethane have
been assigned to Class II, but there are some exceptions. Broadly speaking,
this category reflects chemicals that are less reactive than propane, but
more reactive than ethane. Some chemicals in this range have been assigned
to Class III because smog chamber data show that these chemicals produce
significant ozone. Specifically, acetic acid, butyl alcohol and methanol are
2.4, 2.0 and 3.5 times as reactive as ethane, respectively. The data of
Dimitriades and Joshi (1977) and Sickles et al. (1980) support significant
ozone formation for these three chemicals when the initial 0C/N0x ratio is
>20. As discussed in the previous section, the validity of such smog chamber
data can be subject to some question. In the absence of direct experimental
evidence, species l-to-5 times as reactive as ethane are designated Class II.
Typically, reliable data showing significant ozone formation became available
for species as reactive or more reactive than propane.
Other exceptions also exist. In the case of perchloroethylene, a variety
of contradictory smog chamber data was available (Appendix). Because of the
potential for high CI atom concentrations in a smog chamber system, the data
must be considered unrepresentative of atmospheric conditions. In the ambient
troposphere, CI atoms are virtually nonexistent and cannot participate in the
kind of chemistry that exists within the smog chamber air mixture (Appleby,
1976; Gay et al.f 1976). Recently, Dimitriades et al. (1983) reviewed this
issue in more detail and concluded that perchloroethylene/NOx smog chamber
data cannot be extrapolated to ambient conditions. Based exclusively
on OH reactivity, perchloroethylene is less reactive than ethane and may be
assigned to Class I.
39
-------
Carbon disulfide presents yet another anomalous case. The measured OH
rate constant indicates negligible OH reactivity (Wine et al., 1980). The
rate constant was measured In an inert atmosphere. There is unpublished evi-
dence (private communication of S. Penkett, Harwell, U.K.) that in an oxygen
atmosphere the OH rate constant is much faster. Smog chamber data of Sickles
and Wright (1979) show significant loss rate (1 to 4% hourly loss rate) but
high ozone is produced only in one case when the initial CS2/N0X ratio is 20.
When this ratio is 2, 4, and 10, no significant ozone formation occurs. In
all cases however, carbonyl sulfide and sulfur dioxide were identified as pro-
ducts. Until more conclusive information is generated, carbon disulfide is
assigned to Class II.
In addition, some chemicals chat are more than five times as reactive as
ethane have been placed in Class II because they behave exceptionally. The
cases of aniline, naphthalene, and phenol are noted. The OH-based reactivity
of these chemicals is more than 50 times that of ethane (Appendix). Limited
smog chamber runs for aniline and naphthalene (Spicer et al., 1974) show a
good deal of aerosol formation, but no ozone is produced. Similarly, phenol
irradiations fail to show significant O3 formation (Sickles et al., 1980). It
is likely that the inability of benzene to produce ozone (Table 9, Appendix)
is directly linked with the fact that phenol consitutes a dominant product of
benzene photooxidation (Hendry, 1979). Chemicals, such as aniline,
naphthalene, and phenol are well known free-radical scavengers, and have been
tested in laboratories as candidate chemicals that could inhibit smog forma-
tion (Gitchell et al., 1974; 1974a). There is evidence for one inhibitor
(Diethylhydroxyl amine) which suggests that under appropriate conditions even
inhibitors can produce large concentrations of ozone (Pitts et al., 1979;
Cupitt and Corse, 1979). Additional studies are needed to further elucidate
the Involvement of these species in the processes of smog formation which pre-
vail under more typical atmospheric conditions.
40
-------
—6 *"8
The species of intermediate volatility ( 10 -10 atm vapor pressure)
are also listed in Table 9. Except for glycerine, which is only moderately
reactive, all of the moderate volatility chemicals would be highly reactive if
they could exist in the gas phase (Table 9, Appendix). This assumes that the
estimated OH rate constants are a reliable indicator of reactivity*
CHEMICALS IN THE CLASS III CATEGORY
Of the 118 chemicals investigated during this study, 73 are designated as
Class III, i.e., chemicals that are sufficiently volatile and reactive to par-
ticipate in smog formation. To be included in this category, the following
conditions were met:
• Smog chamber data (OC concentration 0.12 ppm).
• In the absence of smog chamber data, the chemical was at least 5 times
as reactive as ethane. [Although OH reactivity is most-,important, pho-
tolysis as well as reactions with other species (O3, 0 , NO3) were
considered when applicable.]
• No significant reasons existed to disregard available smog chamber or
kinetic data.
• The vapor pressure was greater than 10 ^ atm (25°C), and Henry's coef-
ficients were moderate-to-high.
We emphasize that good and representative smog chamber data were available
for several chemicals to allow us to conclude that, in general, chemicals
which show OH—based reactivity of greater than five times that of ethane
can produce significant ozone concentrations. Propane, vhich is about
six times as reactive as ethane, is one case where substantial evidence
for ozone production exists. As stated earlier, acetic acid, t-butyl
alcohol, and methanol are only 2-to-4 times as reactive as ethane even
though smog chamber data show significant ozone formation (Dimltriades
and Joshi, 1977; Sickles et al., 1980). Here we point out that measured
OH-rate constants have been published for only methanol, although an
unpublished measurement was available for acetic acid. Additionally,
highly reactive chemicals, such as toluene diisocyanate and cresols,
Al
-------
may act as smog inhibitors by terminating free radical chains. Little con-
clusive evidence on the role of inhibitors is available in the literature.
Oiethylhydroxyl amine (DEHA), a known free radical scavenger, has been shown
to produce significant ozone (Pitts et al., 1977; Cupitt and Corse, 1979).
The reason for classification III selection for individual chemicals (Table 6)
is self-explanatory. All the data as well as comments dealing with mechan-
isms, data availability, and product analysis can be found in the Appendix. A
number of these chemicals have already been measured in the ambient gas phase
(Brodzinsky and Singh, 1982) and are known to exist in the gas phase in the
chamber atmospheres (Appendix). Figures 10-14 show results of smog chamber
irradiations for a wide variety of structurally different compounds. In all
these cases, significant ozone concentrations are encountered. These chemi-
cals include oxygenated species such as aldehydes and alcohols (Figures 10 and
11), 1-heptene (Figure 12), toluene (Figure 13), and the naturally-occurring
isoprene (Figure 14). It should also be pointed out that even the relative
ozone-forming potential of a reactive species Is dependent on many variables
including the 0C/N0x ratio and the chemical composition of the mixture
(Bufalini and Dodge, 1983).
IRRADIATION TIME (minutas)
SOURCE: KUNTZ, »t al, (1973)
Figure 10. Irradiation of acetaldehyde-NOx-air
photochemical system
42
-------
7 Butyl Alcohol
SOURCE: YANAGIHARA, ttal. (1977)
Figure 11. Smog chamber irradiations of
2-Butoxyethanol and Butyl
alcohol in a NOx-air system
43
-------
I.O
1.4
<
1.2
>
I
1.0
a.
•
J
0.8
B
i
0.6
0.4
0.2
0
•NO,
.Dilution
rN0
-Aerosol
volume
l-Heptene(xlO"')
•a«w
280
240 "g
I
200 e
4.
•
160 J
I
120 S
S
80 °
0 60 120 180 240 300 36
Irradiation Time, min
SOURCE: MILLER AND JOSEPH, (1976)
40 5
2
Figure 12. Smog chamber irradiation of
a 1 -Heptene-NOx-air mixture
0 60 120 180 240 300 36C
Irradiation Time, min
SOURCE: MILLER ANO JOSEPH, (1978)
Figure 13. Smog chamber irradiation of
a Toluene-NOx-air mixture
44
-------
o 10 20 30 «0 50 60 70 80 90 100 200
C:NOx Ratio (ppm C vt. ppm NOx); (NOx)g-0.33 pprn
SOURCE: ARNTS. at *1.(1981)
Figure 14. Maximum ozone formation as a function of OC to N0X ratio for
some biogenic chemicals and propene
45
-------
SECTION 6
RECOMMENDATIONS
For a sizable fraction of the 118 chemicals for which reactivity/
volatility classifications were sought, a severe absence of data was evident.
Smog chamber irradiations had been performed for only half of the chemicals of
interest. Hydroxyl radical rate constants had been measured for about 60% of
the chemicals. The situation with volatility parameters (vapor pressure and
partition coefficients) was also not dissimilar.
It is clear, therefore, that even preliminary experimental data are
lacking for a sizable fraction of the chemicals of interest. Further,
for those cases where some data are available, considerable judgment was
needed because of the inadequacy of the data. Thus, while we have used
our best possible judgments based on available information, the need for
additional theoretical and experimental studies is overwhelming. In the
following sections, we discuss several specific as well as general short-
comings .
1. The ozone-forming ability of hydrocarbons is known to be dependent on the
initial 0C/N0x ratio (e.g., Figures 3 and 4). The OC/NOjj ratio that leads to
maximum O3 formation is a function of the reactivity of the species (Figure
4). It is clear that the lesser the reactivity, the *reater the OC/NOX ratio
that leads to maximum O3 production. Much of the smog chamber irradiation
data are available at an OC/NOjj ratio of 2-to-5 with some studies operating at
a ratio of 20. Me feel that smog chamber irradiations should be performed at
a number of 0C/N0x ratios, with at least one irradiation at a ratio suggested
by Figure 4. Additional data are needed to develop a more comprehensive
47
-------
Figure 4. For many chemicals of moderate-Co-low reactivity, existing smog
chamber evidence obtained at an OC/NOx ratio of about 2 and showing no O3 for-
mation, is misleading.
2. Analysis of smog chamber data shows that the OH radical concentrations (a
key to smog initiation processes) vary widely from run to run. A 100-fold
variability in OH concentrations can be justified from available data. It
further appears chat the discrepancies are most severe (highest OH levels) for
the least reactive chemicals (Table 5, Figure 9). This raises serious ques-
tions about the atmospheric applicability of smog chamber data for chemicals
-12 3 -1 -1
with OH radical reaction rate constants of <10 cm molec s (figure 9).
The reason may be the inability of these less-reactive chemicals to provide an
effective sink mechanism for OH removal. Smog chamber wall effects may also
dominate the photochemical system. Therefore, we recommend chat Irradiations
of such low-reactivity species be performed in mixture with more reactive
chemicals. In such cases, the OH rate constant, when available, can provide a
better means for extrapolating to ambient conditions compared with smog
chamber data.
3. As a routine practice all smog chamber runs should be spiked with trace
quantities of a known chemical which can be independently monitored to infer
OH concentrations. This is particularly important for low-reactivity chemi-
cals since only a small fraction may react, leading to large errors in measur-
ing depletion rates. A suggested chemical for such an OH-tracer application
is trichloroethylene. At an initial concentration of 1 part per billion (ppb)
in chamber experiments, it can be monitored accurately for several hours. At
this low concentration, it is not likely to perturb ongoing chemistry (e.g.,
via cl atoms) in a smog chamber with precursors present at three orders of
magnitude higher concentrations. Alternatively, 5 to 10 ppb of propane or n-
butane may also be an adequate OH tracer. For these suggested tracers, ozone
reactions are too slow to be significant. Since most smog chamber runs are
performed at l-to-4 ppm reactant concentrations, the system is negligibly per-
turbed.
4. The classification system developed in this study would not have been pos-
sible without our ability to predict OH radical rate constants. Although
48
-------
tests with experimental data (Figure 8) are highly encouraging, these predic-
tive capabilities should be further developed and expanded. Currently, the
predictive techuique used here is not strictly applicable to chemicals such as
alkynes, nitrogenous compounds, epoxides, and phthalates. This is largely due
to the unavailability of constants on which these structure-activity relation-
ships are based. There is a great need to expand and further develop these
predictive capabilities.
5. As a category, organic acids have been studied least of all. Except for
acetic acid, no kinetic or smog chamber data were available for any of the
acids. Even for acetic acid, the OH-rate constant data have not yet been pub-
lished and may be in error.
6. A number of highly reactive free radical scavengers (such as naphthalene)
do not appear to form O3 even though they lead to high aerosol production.
The smog chamber data of this class of inhibitors (phenols, naphthalene,
nitrobenzene, aniline and possibly cresols) are too scarce to be meaningful.
Tentative evidence exists to support the contention that at least some of
these inhibitors may produce ozone upon prolonged irradiations. Irradiations
at both low and high OC/NOx ratios need to be performed to further ascertain
their photochemical role*
7. For a number of chemicals, smog chambers do not simulate the ambient atmo-
sphere. Perchloroethylene, due to Its complex CI initiated chemistry, is one
such known chemical. Trichloroethylene and other halogenated chemicals can be
expected to behave similarly. Neither their 03-forming ability nor the pro-
duct distribution can be easily extrapolated from smog chambers to ambient
conditions. Such shortcomings of smog chamber experiments should be identi-
fied in as many cases as possible.
8. A reliable, parallel, aerosol/gas sampling system does not exist. Vapori-
zation of particulate matter and condensation of vapors is known to occur when
samples are collected on a variety of filters. The development of a true
aerosol/gas sampling system is urgently needed.
49
-------
9. The available data base on ambient partitioning of chemicals is very
scarce. Atmospheric variables (such as temperature, humidity, particulate
loading and particulate composition) affect partitioning to different degrees,
but correlations do not exist to estimate the relative importance of these
factors* A large body of data may allow volatility estimates with a lot more
confidence than is possible today.
10. For a wide variety of nonvolatile materials, the vapor pressure data are
either not available, or must be extrapolated over large temperature ranges.
This shortcoming can be dealt with only when determinations are made for vapor
pressure under ambient type conditions.
50
-------
INFERENCES
Akimoto, H. and F. Sakamaki, 1983: "Correlatloa of Ozone Formation
Races With Hydroxyl Radical Concentrations in the Propylene-Nitrogen
Oxide-Dry Air System: Effective Ozone Formation Rate Constant,"
Environ. Sci. Technol., Vol. 17, pp. 94-99.
Akimoto, H., F. Sakamaki, M. Hoshino et al., 1979: "Photochemical Ozone
Formation in Propylene-Nitrogen Oxide-Dry Air System," Environ. Scl.
Technol., Vol. 13, pp. 53-58.
Altshuller, A. P., 1982: "An Assessment of Ozone as a Surrogate for
Other Products of Atmospheric Photochemical Reactions," Draft document.
Altshuller, A. P. and J. J. Bufalini, 1971: "Photochemical Aspects of
Air Pollution: A Review," Environ. Sci. Technol., Vol. 5, No. 1, pp.
39-63.
Altshuller, A. P. and I. R. Cohen, 1963: "Structural Effects on the
Rate of Nitrogen Dioxide Formation in the Photooxidation of Organic
Compound-Nitric Oxide Mixtures in Air," Int. J. Air Wat. Poll., Vol. 7,
pp. 787-797.
Altshuller, A. P., K. L. Klosterman, P. W. Leach, et al., 1966:
"Products and Biological Effects From Irradiation of Nitrogen Oxides
with Hydrocarbons or Aldehydes Under Dynamic Conditions," Air Water
Pollut., Vol. 10, No. 2, pp.81-98.
Appleby, A., 1976: "Atmospheric Freon and Halogenated Compounds," EPA-
600/3-76-108.
Arnts, R. R., B. W. Gay and J. J. Bufalini, 1981: "Photochemical Oxidant
Potential of the Biogenic Hydrocarbons," Atmospheric Biogenic
Hydrocarbons. Vol. 2, eds. J. J. Bufalini and R. R. Arnts, Ann Arbor
Science Publishers, Michigan, pp. 117-133.
Atkinson, R., S. M. Aachmann, W. P. L. Carter et al., 1982: "Kinetics of
the Reaction of OH Radicals with n-Alkanes at 299 +_ 2K," Int. J. Chem.
Kinetics, Vol. 14, pp. 781-788.
Atkinson, R., K. R. Darnall, A. C. Lloyd et al., 1979: "Kinetics and
Mechanisms of the Reaction of the Hydroxyl Radical with Organic
Compounds in the Gas Phase", Adv. in Photo Chem., Vol. 11, pp» 375- 88.
51
-------
Banerjee, S., S. H. Yalkowsky, and S. C. Valvani, 1980: "Water
Solubility and Octanol/Water Partition Coefficients of Organics.
Limitations of the Solubility-Partition Coefficient Correlation,"
Environ. Sci. Technol., Vol. 14, No. 10, pp. 1227-1229.
Barnes, I., V. Bastian, K. H. Becker, et al., 1982: "Reactivity Studies
of Organic Substances Towards Hydroxyl Radicals Under Atmospheric
Conditions," Atmos. Environ., Vol. 16, pp. 545-550.
Broddin, G., W. Cautreels and K. Van Cauwenberghe, 1980: "On the
Aliphatic and Polyaromatic Hydrocarbon Levels in Urban and Background
Aerosols From Belgium and the Netherlands," Atmos. Environ., Vol. 1A,
pp. 895-910.
Brodzinsky, R. and H. B. Singh, 1982: "Volatile Organic Chemicals in
the Atmosphere: An Assessment of Available Data," SRI Project 2222, EPA
Contract 68-02-3452, Final Report prepared for EPA by SRI International,
Menlo Park, California.
Brunelle, M. F., J. E. Dickinson and W. J. Hamming, July 1966:
"Effectiveness of Organic Solvents in Photochemical Smog Formation,"
prepared for Air Pollution Control District, County of Los Angeles.
Bufalini, J. J. and M. C. Dodge, 1983: "Ozone-Forming Potential of
Light Saturated Hydrocarbons," Environ. Sci. Technol., Vol. 17, pp. 308-
311.
Callahan, M. A., M. W. Slimak, et al., 1979: "Water-Related
Environmental Fate of 129 Priority Pollutants," EPA-440/4-79-029.
Calvert, J. G., 1976: "Hydrocarbon Involvement in Photochemical Smog",
Environ. Sci. Technol., Vol. 10, pp. 256-262.
Calvert, J. G., 1980: "The Homogeneous Chemistry of Formaldehyde
Generation and Destruction Within the Atmosphere," Report FAA-EE-80-20,
pp. 153-190.
Calvert, J. G. and H. E. Jeffries, 1977: "International Conference on
Oxidants, 1976 - Analysis of Evidence and Viewpoints, Part II. The
Issue of Reactivity," EPA-600/3-77-114.
Calvert, J. G. and J. N. Pitts Jr., 1966: Photochemistry, John Wiley and
Sons, Inc., New York.
Cammenga, H. Y., F. W. Schulze and W. Theuerl, 1977: "Vapor Pressure
and Evaporation Coefficient of Glycerol," J. Chem. Eng. Data, Vol. 22,
No. 2, pp. 131-134.
52
-------
Carter, W. P. L., A. M. Winer, J. N. Pitts, 1981: "Major Atmospheric
Sink for Phenol and the Cresols. Reaction with the Nitrate Radical,"
Environ. Sci. Technol., Vol. 15, pp. 829-831.
Cautreels, W. and K. Van Cauwenberghe, 1976: "Determination of Organic
Compounds in Airborne Particulate Matter by Gas Chromatography - Mass
Spectrometry", Atmos. Environ., Vol. 10, pp. 447-457.
Cautreels, W. and K. Van Cauwenberghe, 1978: "Experiments on the
Distribution of Organic Pollutants Between Airborne Particulate Matter
and the Corresponding Gas Phase", Atmos. Environ., Vol. 12, pp. 1133-
1141.
Conway, R. A., G. T. Waggy, M. H. Spiegel and R. L. Berglund, 1983:
"Environmental Fate and Effects of Ethylene Oxide", Environ. Sci.
Technol., Vol. 17, No. 2, pp. 107-112.
Cox, R. A., R. G. Derwent and M. R. Williams, 1980: "Atmospheric
Photooxidation Reactions. Rates, Reactivity, and Mechanism for Reaction
of Organic Compounds with Hydroxyl Radicals," Environ. Sci. Technol.,
Vol. 14, pp. 57-61.
Cupitt, L. T. and Corse, E. W., 1979: "Effect of Diethylhydroxylamlne
on Smog Chamber Irradiations", EPA-600/3-79-040.
Darnall, K. R., A. C. Lloyd, A. M. Winer, and J. N. Pitts, Jr., 1976:
"Reactivity Scale for Atmospheric Hydrocarbons Based on Reaction with
Hydroxyl Radical," Environ. Sci. Technol., Vol. 10, pp. 692-696.
Dawson, G. A., J. C. Farmer, and J. L. Moyers, 1980: "Formic and Acetic
Acids in the Atmosphere of the Southwest U.S.A.," Geophys. Res. Lett.,
Vol. 7, pp. 725-728.
Dean, J. A. (Editor), 1979: Lange's Handbook of Chemistry, 12th
Edition, McGraw-Hill Book Co., New York.
Dilling, W. L., 1977: "Interphase Transfer Processes. II. Evaporation
Rates of Chloro Methanes, Ethanes, Ethylenes, Propanes, and Propylenes
From Dilute Aqueous Solutions. Comparisons with Theoretical
Predictions," Environ. Sci. Technol., Vol. 11, No. 4, pp. 405-409.
Dilling, W. L., C. J. Bredeweg and N. B. Tefertiller, 1976: "Organic
Photochemistry: Simulated Atmospheric Photodecomposition Rates of
Methylene Chloride, 1,1,1-Trichloroethane, Trichloroethylene,
Tetrachloroethylene and Other Compounds," Environ. Sci. Technol., Vol.
10. pp. 351-356.
Dlmltrlades, B., B. W. Gay, R. R. Arnts and R. L. Sella, 1983:
"Photochemical Reactivity of Perchloroethylene: A New Appraisal",
J. Air Poll. Control Assoc., Vol. 33, pp. 575-587.
53
-------
Dimltriades, B. and S. B. Joshi, 1977: "Application of Reactivity
Criteria in Oxidant-Related Emission Control in the USA," Proceedings of
the International Conference on Photochemical Oxidant Pollution and Its
Control, EPA-600/3-77-00lb, pp. 705-711.
Dimltriades, B., G. P. Strum, T. C. Wesson and F. D. Sutterfleld,
1975: "Development and Utility of Reactivity Scales From Smog Chamber
Data," Bureau of Mines, Report of Investigations RI 8023, Dept. of
Interior, Washington, D.C.
Dimltriades, B. and T. C. Wesson, 1972: "Reactivities of Exhaust
Aldehydes," J. Air Poll. Control Assoc., Vol. 22, pp. 33-38.
Drelsbach, R. R., 1955: Physical Properties of Chemical Compounds.
Advances in Chemistry Series No. 15, American Chemical Society,
Washington, D.C.
Du Pont, 1969: "Freon Product Information Bulletin B-2," E. I. du Pont
de Nemours and Company, Wilmington, Delaware.
Eiceman, G. A. and V. J. Vandiver, 1983: "Adsorption of Polycyclic
Aromatic Hydrocarbons on Fly Ash from a Municipal Incinerator and a Coal
Fired Power Plant", Atmos. Environ., Vol. 17, pp. 461-465.
Elchmann, R., G. Ketseridis, G. Schebeske, et al., 1980: "n-Alkane
Studies In the Troposphere - II: Gas and Particulate Concentrations in
Indian Ocean Air", Atmos. Environ., Vol. 19, pp. 695-703.
Elchmann, R., P. Neuling, G. Ketseridis, et al., 1979: "n-Alkane
Studies in the Troposphere - I. Gas and Particulate Concentrations in
North Atlantic Air", Atmos. Environ., Vol. 13, pp. 587-599.
EPA, 1978: "Air Quality Criteria for Ozone and Other Photochemical
Oxidants," EPA-600/8-78-004, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina.
Farley, F. F., 1977: "Photochemical Reactivity Classification of
Hydrocarbons and Other Organic Compounds," EPA-600/3-77-001b, U. S.
Environmental Protection Agency, Research Triangle Park, North Carolina,
pp. 713-726.
Farley, F. F., 1978: "Correspondence," Environ. Scl. Technol., Vol. 12,
pp. 99-100.
Flnlayson, B. and J. N. Pitts, 1976: "Photochemistry of the Polluted
Troposphere," Science, Vol. 192, pp. 111-119.
Fluka Chemical Corp., 1982/1983 Catalog, Hauppauge, New York.
54
-------
Freier, R. K., 1975: Aqueous Solutions: Data for Inorganic and Organic
Compounds. Walter de Gruyter and Co., Berlin.
Gay, B. W., Jr., P. L. Hanst, J. J. Bufalini and R. C. Noonan, 1976:
"Atmospheric Oxidation of Chlorinated Ethylenes," Environ. Sci.
Technol., Vol. 10, pp. 58-67.
Gerrard, W., 1976: Solubility of Gases and Liquids. Plenum Press, New
York.
Gitchell, A., R. Simonaitis and J. Heicklen, 1974: "The Inhibition of
Photochemical Smog. I. Inhibition by Phenol, Benzaldehyde and Aniline,"
J. Air Poll. Control Assoc., Vol. 24, pp. 357-361.
Gitchell, A., R. Simonaitis and J. Heicklen, 1974a: "The Inhibition of
Photochemical Smog. II. Inhibition by Hexafluorobenzene, Nitrobenzene,
Naphthalene and 2,6-Di-tert-butyl-4-methylphenol," J. Air Poll. Control
Assoc., Vol. 24, pp. 772-775.
Glasson, W. A. and C. S. Tuesday, 1970: "Hydrocarbon Reactivity and the
Kinetics of the Atmospheric Photooxidation of Nitric Oxide," J. Air
Poll. Control Assoc., Vol. 20, pp. 239-243.
Gusten, H., W. G. Filby and S. Schoof, 1981: "Prediction of Hydroxyl
Radical Reaction Rates with Organic Compounds in the Gas Phase," Atmos.
Environ., Vol. 15, pp. 1763-1765.
Hampson, R. P., 1980: "Chemical Kinetics and Photochemical Data Sheets
for Atmospheric Reactions," Report No. FAA-EE-80-17.
Harris, G. W., T. E. Kleindlenst and J. N. Pitts Jr., 1981: "Rate
Constants for the Reaction of OH Radicals with CH3CN, C2H5CN and C^'CH-
CN in the Temperature Range 298-424K," Chem. Phys. Lett., Vol. 80, pp.
479-483.
Heicklen, J. 1981: "The Removal of Atmospheric Gases by Particulate
Matter," Atmos. Environ., Vol. 15, pp. 781-785.
Hendry, D. G., 1979: "Reactions of Aromatic Compounds In the
Atmosphere," National Bureau of Standards, Special Publication 557, pp.
85-91.
Hendry, D. G. and R. A. Kenley, 1979: "Atmospheric Reaction Products of
Organic Compounds," EPA-560/12-79-001.
Hendry, D. G., A. C. Baldwin and D. M. Golden, 1980: "Computer
Modelling of Simulated Photochemical Smog", EPA—600/3-80-029.
Hester, N. E., E. P. Stephens and 0. C. Tayler, 1974: "Fluorocarbons in
the Los Angeles Basin," J. Air Poll. Control Assoc., Vol. 24, pp. 591-
595.
55
-------
Heuss, J. M., 1975: "Smog Chamber Simulation of the Los Angeles Atmo-
sphere", Paper 75-16.1 presented at the National APCA Meeting, June 16-20,
1975, Boston, MA (Also, General Motors Research Report GMR-1802, February).
Heuss, J. M., and W. A. Glasson, 1968: "Hydrocarbon Reactivity and Eye
Irritation," Environ. Sci. Technol., Vol. 2, pp. 1109-1116.
Jefferies, H. E., R. M. Kamens, K. G. Sexton, A. P. Gerhardt, 1982:
"Outdoor Smog Chamber Experiments to Test Photochemical Models", Final
Report, CA 805843, Univ. of North Carolina.
Jordan, T. E., 1954: Vapor Pressure of Organic Compounds, Interscience
Publishers, Inc., New York.
Joshi, S. B, M. C. Dodge and J. J. Bufalini, 1982: "Reactivities of
Selected Organic Compounds and Contamination Effects", Atmos. Environ.,
Vol. 16, pp. 1301-1310.
Kamens, R. M., H. E. Jeffries, K. G. Sexton and A. A. Gerhardt, 1981:
"Smog Chamber Experiments to Test Oxidant Related Control Strategy
Issues" Draft Report, Grant 805726, Univ. of North Carolina.
Kleindienst, T. E., G. W. Harris and J. N. Pitts, Jr., 1982: "Rates and
Temperature Dependencies of the Reaction of OH with Isoprene, Its
Oxidation Products and Selected Terpenes," Environ. Sci. Technol.. Vol.
16, pp. 844-846.
Klippel, W. and P. Warneck, 1980: "The Formaldehyde Content of the
Atmospheric Aerosol," Atmos. Environ., Vol. 14, pp. 809-818.
Klopffer, W., G. Rippen, and R. Frlsche, 1982: "Physlcochemical
Properties as Useful Tools for Predicting the Environmental Fate of
Organic Chemicals," Ecotox. and Environ. Safety, Vol. 6, pp. 294-301.
Kuntz, R. L., S. L. Kopczynskl and J. J. Bufalini, 1973: "Photochemical
Reactivity of Benzaldehyde and Benzaldehyde-Hydrocarbon-NO Mixtures,
Environ. Sci. Technol., Vol. 7, pp. 1119-1123.
Laity, J. L., I. G. Burstain and B. R. Appel, 1973: "Photochemical Smog
and the Atmospheric Reactions of Solvents," Solvents Theory and
Practice, Advances in Chemistry No. 124, Ed. R. W. Tess, American
Chemical Society, pp. 95-112.
Lenoir, J. Y., P. Renault, and H. Renon, 1971: "Gas Chromatographic
Determination of Henry's Constants of 12 Gases In 19 Solvents," J. Chem.
Eng. Data. Vol. 16, No. 3, pp. 340-342.
Levy, A., 1973: "The Photochemical Smog Reactivity of Organic
Solvents," Solvents Theory and Practice, Advances In Chemistry Series
No. 124, Ed. R. W. Tess, American Chemical Society, pp. 70-94.
Levy, A. and S. E. Miller, 1970: "The Role of Solvents in Photochemical
Smog Formation," Final Technical Report 799, prepared by Battelle
Columbus Laboratory for National Paint, Varnish and Lacquers
Association.
56
-------
Lillian, D., H. B. Singh, A. Appleby, et al., 1975: "Atmospheric Fates
of Halogenated Compounds," Environ. Sci. Technol., Vol. 9, pp. 1042-
1048.
Lloyd, A. C., 1979: "Tropospheric Chemistry of Aldehydes," National
Bureau of Standards Special Publication 557, pp. 27-46.
Lyman, W., W. Reehl, and D. Rosenblatt (Editors), 1982: Handbook of
Chemical Property Estimation Methods: Environmental Behavior of Organic
Compounds. McGraw-Hill Book Co., New York.
Mackay, D. and W. Y. Shiu, 1981: "A Critical Review of Henry's Law
Constants for Chemicals of Environmental Interest," J. Phys. Chem. Ref.
Data. Vol. 10, pp. 1175-1199.
Mackay, D., W. .Y. Shiu, and R. P. Sutherland, 1979: "Determination of
Air-Water Henry's Law Constants for Hydrophobic Pollutants," Environ.
Sci. Technol., Vol. 13, pp. 333-337.
McAuliffe, C., 1966: "Solubility in Water of Paraffin, Cycloparaffin,
Olefin, Acetylene, Cycloolefin, and Aromatic Hydrocarbons," J. Phys.
Chem., Vol. 70, pp. 1267-1275.
Mellan, I., 1977: Industrial Solvents Handbook, Noyes Data Corporation,
Park Ridge, New Jersey.
Merck and Co., 1976: The Merck Index, 9th Edition, Merck and Co.,
Rahway, New Jersey.
Mill, T., J. S. Wlnterle, J. E. Davenport, et al., 1982: "Validation of
Estimation Techniques for Predicting Environmental Transformation of
Chemicals", Final Report, EPA Contract No. 68-01-6269, SRI
International, Menlo Park, California.
Mill, T., W. R. Mabey, D. C. Bomberger, T.-W. Chou, D. G. Hendry and
J. H. Smith, 1981: "Laboratory Protocols for Evaluating the Fate of
Organic Chemicals in Air and Water", Final Report, EPA Contract No. 68-
03-2227, SRI International, Menlo Park, California.
Miller, D. F. and D. W. Joseph, 1976: "Smog Chamber Studies in
Photochemical Aerosol-Precursor Relationships," EPA-600/3-76-080,
Environmental Sciences Review Laboratory, Environmental Protection
Agency, Research Triangle Park, North Carolina.
Miyano, Y. and W. Hayduk, 1981: "Solubility of Acetylene in Several
Polar and Nonpolar Solvents and Solvent Mixtures," Can. J. Chem. Eng.,
Vol. 59, No. 6, pp. 746-751.
Morrison, R. T., and R. N. Boyd, 1973: Organic Chemistry, 3rd Edition,
Allyn and Bacon, Inc., Boston.
57
-------
NAS, 1976a: Vapor-Phase Organic Pollutants, National Academy of
Sciences, Washington, D.C.
NAS, 1976b: Halocarbons: Effect on Stratospheric Ozone, National
Academy of Sciences, Washington, D.C.
Nlki, H., 1979: "An Evaluation of Chemical Kinetic Data Needs for
Modeling the Lower Troposphere: Reactions of Olefins with Hydroxyl
Radical and with Ozone," National Bureau of Standards Special
Publication 557, pp. 7-14.
Nikl, H., E. E. Daby and B. Winstock, 1972: "Mechanism of Smog
Reactions," in Photochemical Smog and Ozone Reactions, R. F Gould,
American Chemical Society, Washington, B.C., pp. 16-57.
O'Brien, R. J., P. J. Green, R. A. Dotty, et al., 1979: "Interactions
of Oxides of Nitrogen and Aromatic Hydrocarbons Under Simulated
Atmospheric Conditions," Nitrogenous Air Pollutants, Ed. D. Grosjean,
Ann Arbor Science Publishers, pp. 189-210.
O'Brien, R. J., P. J. Green, N. Lguyen, et al., 1983: "Carbon Balances
in Simulated Atmospheric Reactions: Aromatic Hydrocarbons," Environ.
Scl. Technol., Vol. 17, pp. 183-186.
Olson, J. D., 1977: "Solubility of Nitrogen, Argon, Methane, and Ethane
in Ethylene Oxide," J. Chem. Eng. Data, Vol. 22, No. 3, pp. 326-329.
Phillips, L. F., 1978: Pressure Dependence of the Rate of Reaction of
OH with HCN," Chem. Phys. Lett., Vol. 57, pp. 538-539.
Pierotti, G., C. Deal and E. Derr, 1959: "Activity Coefficients and
Molecular Structures," Ind. Eng. Chem., Vol. 51, p. 95.
Pitts, J. N., Jr., A. M. Winer, G. J. Doyle and K. R. Darnall, 1978:
"Response to Correspondence," Environ. Scl. Technol., Vol. 12, pp. 100-
102.
Pitts, J. N., D. Grosjean, K. V. Cauwenberghe, et al., 1978:
"Photooxldation of Aliphatic Amines Under Simulated Atmospheric
Conditions: Formation of Nltrosamlnes, Nitramines, Amides and
Photochemical Oxidants," Environ. Scl. Technol., Vol. 12, pp. 946-953.
Pitts, J. N., J. P. Smith, D. R. Fritz, et al., 1977: "Enhancement of
Photochemical Smog by N,N'-Dlethylhydroxylamine in Polluted Ambient
Air", Science, Vol. 197, pp. 255-258.
Polak, J., and B. C. Y. Lu, 1973: "Mutual Solubilities of Hydrocarbons
and Water at 0 at 25#C," Can. J. Chem., Vol. 51, p. 4018.
58
-------
Reid, R. C., J. M. Prausnltz, and T. K. Sherwood, 1977: The Properties
of Gases and Liquids. McGraw-Hill Book Co., New York.
Schuck, E. A. and G. J. Doyle, 1959: "Photooxidatlon of Hydrocarbons in
Mixtures Containing Oxides of Nitrogen and Sulfur Dioxide," Air
Pollution Foundation Report No. 29, Stanford Research Institute, Irvine,
California.
Short, I., A. Sahgal, and W. Hayduk, 1983: "Solubility of Ammonia and
Hydrogen Sulfide in Several Solvents," J. Chem. Eng. Data. Vol. 28, No.
1, pp. 63-66.
Sickles, J. E. and R. S. Wright, 1979: "Atmospheric Chemistry of
Selected Sulfur-Containing Compounds-Outdoor Smog Chamber Study-Phase 1,
EPA-600/7-79-227.
Sickles, J. E., R. S. Wright, C. R. Sutcllffe, et al., 1980: "Smog
Chamber Studies of the Reactivity of Volatile Organic Compounds," 73rd
Annual APCA Meeting, Paper 80-50.1, Montreal, Canada.
Singh, H. B., 1976: "Phosgene In the Ambient Air," Nature. Vol. 264,
pp. 428-429.
Singh, H. B. and P. L. Hanst, 1981: "Peroxyacetyl Nitrate (PAN) in the
Unpolluted Atmosphere: An Important Reservoir for Nitrogen Oxides,"
Geophys. Res. Lett., Vol. 8, pp. 941-944.
Singh, H. B., J. R. Martinez, D. G. Hendry, et al., 1981: "Assessment
of the Oxidant-Forming Potential of Light Saturated Hydrocarbons in the
Atmosphere," Environ. Scl. Techno!., Vol. 15, pp. 113-119.
Singh, H. B., L. J. Salas, H. Shigeishi, et al., 1979: "Atmospheric
Distributions, Sources and Sinks of Selected Halocarbons, Hydrocarbons,
SF6 and N20," EPA-600/3-79-107.
Smith, J. H., D. C. Bomberger, and D. L. Haynes, 1980: "Prediction of
Volatilization Rates of High-Volatility Chemicals from Natural Water
Bodies," Environ. Sci. Technol., Vol. 14, pp. 1332-1337.
Smith, J. H., D. C. Bomberger, and D. L. Haynes, 1981: "Volatilization
Rates of Intermediate and Low Volatility Chemicals from Water,"
Chemosphere, Vol. 10, pp. 281-289.
Spicer, C. W., D. F. Miller and A. Levy, 1974: "Inhibition of
Photochemical Smog Reactions by Free Radical Scavengers," Environ. Scl.
Technol., Vol. 8, pp. 1028-1030.
Stief, L. J., D. F. Nara, W. A. Payne, and J. V. Michael, 1980: "Rate
Constant for the Reaction of Hydroxyl Radical with Formaldehyde Over the
Temperature Range 228-362K," J. Chem. Phys., Vol. 5, pp. 2254-2258.
59
-------
Stephen, H., and T. Stephen, 1963: Solubilities of Inorganic and
Organic Compounds, MacMillan Co., New York.
Stephens, E. R., and F. R. Burleson, 1967: "Analysis of the Atmosphere
for Light Hydrocarbons," J. Air Poll. Control Assoc., Vol. 17, pp. 147-
152.
Tewari, Y. B., M. M. Miller, S. P. Wasik and D. E. Martire, 1982:
"Aqueous Solubility and Octanol/Water Partition Coefficient of Organic
Compounds at 25.0#C," J. Chem. Eng. Data, Vol. 27, No. 4, pp. 451-454.
Verschueren, K., 1977: Handbook of Environmental Data on Organic
Chemicals,
Van Nostrand Reinhold Co., New York.
Waters, J. A. and G. A. Mortimer, 1972: "Some Solubility Data for
Ethane in n-Hexane," J. Chem. Eng. Data, Vol. 17, No. 2, pp. 156-157.
Weast, R. C. (Editor), 1973; Handbook of Chemistry and Physics, 54th
Edition, CRC Press, Cleveland, Ohio.
Wilhelm, E., and R. Battino, 1973: "Thermodynamic Functions of the
Solubilities of Gases in Liquids at 25aC," Chem. Rev., Vol. 73, No. 1,
pp. 1-9.
Wilson, K. W. and G. J. Doyle, 1970: "Investigation of Photochemical
Reactivities of Organic Solvents", SRI Project PSU-8029, Prepared for
the U.S. H.E.W. by Stanford Research Institute, Irvine, California.
Wine, P. H., W. L. Chameides and R. R. Ravishankara, 1981: "Potential
Roles of CS2 Photooxidations In Tropospherlc Sulfur Chemistry," Geophys.
Res. Lett., Vol. 8, pp. 543-546.
Winer, A. M., K. R. Darnall, R. Atkinson and J. N. Pits, 1979: "Smog
Chamber Study of the Correlation of Hydroxyl Radical Rate Constants with
Ozone Formation," Environ. Scl. Technol, Vol. 13, pp. 822-826.
WMO, 1982: "The Stratosphere 1981: Theory and Measurements," World
Meteorological Organization Report No. 11, Geneva, Switzerland.
Yanagihara, S., I. Shimada, E. Shinoyama, «c al., 1977: "Photochemical
Reactivities of Hydrocarbons," Proceedings of the 4th Int. Clean Air
Congress, Tokyo, Japan, pp. 472-477.
Yeung, C. K. and C. R. Phillips, 1974: "Estimation of NO Photooxidation
Reactivities of Olefins From Molecular Structure," Atmos. Environ., Vol.
8, pp. 493-506.
Zafonte, Z. and F. Bonamassa, 1977: "Relative Photochemical Reactivity
of Propane and n-Butane," Environ. Sci. Technol., Vol. 11, pp. 1015-
1017.
60
-------
Zetzsch, C., 1983: Unpublished race constant data.
Zwolinski, B. J. and R. C. Wilhoit, 1971: "Handbook of Vapor Pressures
and Heat9 of Vaporization of Hydrocarbons and Related Compounds," AP1-
44, TRC Publication No. 101: Texas A & M University, College Station,
TX.
61
-------
Appendix
REACTIVITY/VOLATILITY DATA SHEETS AND CLASSIFICATIONS
FOR 118 SELECTED SPECIES*
* — 13
The quantity in parenthesis is raised to the power of 10 7.3(-13)«7.3x10
All the properties are at room temperature (25°C) unless otherwise specified.
When necessary, OH rate constants and vapor pressure data were estimated
by methods of Hendry and Kenley (1979) and Lyman et al. (1982) as described
in the text. Henry's constants were estimated from vapor pressure and
solubility data as described in the test. Inf. (infinite) means the chemical
is miscible in the solvent in all proportions. To obtain Henry's coefficient
in dimensionles3 form (C /C-. ) multiply by 41.0.
gas liq
-------
Chemical Nam*: Acetic acid
Chemical Formula: CH^COOH (M.W.-60)
Chemical NO.: 1
CAS Registry NO.: 6A-19-7
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX. O]
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vhl
NO-FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OC)
NOx
IMOj/NO
CONC.
(PPM)
TIME
IK)
4.0
0.2
0.25
0.42
10-12
Sickles et al (1980)
4.0
0.07
0.25
0.94
10-12
Sickles et al (1980)
4.0
0.2
0.26
13.7
2.0
Dimitriades and Joshi (1977)
B. KINETIC DATA
REACTION
WITH
UNITS
RATI CONSTANT
VALUE rasti
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em' mot*"1 S'1
7.3 (-13)
Zetzsch (1983)
2.4
Unpublished
data
°3
Ctrl rTIOlfC 3
hv
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
rae'ci
REFERENCES
COMMENTS
VAPOR PRESSURE (mm.)
2.1 (-2)
Dreiabach (1961)
WATER SOLUBILITY fmol. m'3)
inf.
Dreisbach (1961)
HENRY'S CONSTANT Urn. m3 mol'1)
SOLVENT SOLUBILITY Imol. m'3)
PHYSICAL STATE
1.2 (-6)
miacible
liquid
Merck (1976)
calculated
alcohol, carbon tetra-
chloride, glycerol,
ether, carbon disulfide
0. CLASSIFICATIONS
REACTIVITY: XIX VOLATILITY: HI OVERALL: 111
E. GENERAL COMMENTS
Smog chamber data shows acetic acid reactivity to be consistent with an OH radical
concentration of 8xl06. This seems much too high. Acetic acid has been measured
in the ambient air in gas phase (Dawson et al., 1980).
A-l
-------
Chemical Name: Acetic anhydride
Chemical Formula: (CH^CO) ^ 0(M.W.«102)
Chemical NO.: 2
CAS Registry NO.: 108-24-7
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM»
MAX 03
total
IRRADIATION
TIME (ht
AVERAGE OC
DISAPPEARANCE
RATE (%/ht
NO-FORMA-
TION RATE
(PPS/Mint
REFERENCES
ORGANIC
CHEMICAL
(OCI
NOx
NOj/NO
CONC.
(PPM)
TIME
(M
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C>
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 mote*1 S'1
4.0 (-13)
Estimated
1.3
°3
cm^ moltc'1 S'1
hl>
S'1
C. VOLATILITY DATA
PROPERTY NAME {UNITS*
PROPERTY VALUE
<2«1C>
REFERENCES
COMMENTS
VAPOR PRESSURE Utm.)
6,7 (-3)
Jordan (1954)
WATER SOLUBILITY (mol. m*3)
1900
Estimated
HENRY'S CONSTANT («m. m3 mol*1)
3.5 (-6)
Calculated
SOLVENT SOLUBILITY (mof m'3)
soluble
Merck (1976)
Chloroform, ether
PHYSICAL STATE
liquid
~.CLASSIFICATIONS
REACTIVITY: 11 VOLATILITY: HI OVERALL: II
E. GENERAL COMMENTS
Acetic anhydride Is not likely to undergo gas phase hydrolysis and thus can participate
as an intact molecule in smog chemistry. In contact with water droplets rapid hydrolysis
to acetic acid occurs. Although SAR suggest an OH rate constant of 4xl0~13, It
suggests a relative rate at 2 times the acetic acid rate. Thus, a value of 1.4x10"
could also be Inferred leading to Reactivity Classification III.
A-2
-------
Chemical Name: Acetaldehyde
Chemical Formula: CHjCHO (M.W.-44)
Chemical NO.: 3
CAS Registry NO.: 75-07-0
A. SMOG CHAMBER DATA
INITIAL CONC.(PPM)
MAX. 03
TOTAL
IRRADIATION
TIME {hi
AVERAGE OC
OI3APPEARANCE
RATE (Vhl
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
2
O
X
NOj/NO
CONC.
(PPMI
TIME
(hi
1.0
0.4
0.25
0.94
10-12
Jefferies at al (1982)
0.5
0.5
0.37
0.60
10-12
8.0
Kamens et al (1981)
3.0
1.0
0.0
0.90
4.0
5
10.0
30.0
Kuntz et al (1973)
1.0
0.5
0.14
0.71
6
13.7
Dimitrades and Wesson (1972)
B. KINETIC OATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (28*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm® moUc"' S"'
1.5 (-11)
Atkinson et al (1979
48.4
°3
cm' mol«e"' S"'
hl>
s-1
1.0 (-5)
Hendry et al (1980)
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(25 *C)
REFERENCES
COMMENTS
VAPOR PRESSURE («m.l
1.2
Jordan (1954)
WATER SOLUBILITY (mot. m'3!
inf.
Verschueren (1977)
HENRY'S CONSTANT («tm. m3 mol')
SOLVENT SOLUBILITY (mol. m'3)
6 (-5)
inf.
Merclc (1976)
Calculated
alcohol
PHYSICAL STATE
gas
D. CLASSIFICATIONS
REACTIVITY: ni VOLATILITY: hi OVERALL: III
E. GENERAL COMMENTS
Acetaldehyde is nearly as effective in 0, formation as propylene (Cox et al, 1980).
Photochemical reaction products such as formaldehyde, carbon monoxide, peroxyacetyl
nitrate, methyl nitrate, and hydrogen peroxide have been identified.
A-3
-------
Chemical Name Acetone
Chemical Formula: (CH^CO (M.W.-58)
Chemical NO.: ^
CAS Reflittry NO.: 67-64-1
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.O3
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE IVh)
NO-FORMA-
TION RATE
(PPB/Minl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
(PPM)
TIME
(M
4.7
0.24
0.40
0.02
10-12
Jefferies et al (1982)
4.0
0.2
0.25
0.49
10-12
1.5 propane
Sickles et al (1980)
4.0
0.2
0.18
12.1
0.9
Dimitriades and Jashi (1977)
2.0
1.0
0.05
0.0
5
0.0
1.5
Yanagihara et al (1977)
1.5
0.6
0.05
0.1 x
5
= 2
0.2 x
Laity et al (1973)
toluei
e
toluene
4.0
2.0
0.0
6
0.0
Levy and Miller (1970)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (M'CI
REFERENCES
OH RATE CONST
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em3 moltc'1 S''
5.0 (-13)
Cox et al (1980)
1.6
°3
cm"* moitc'1 S"1
hv
s-'
5.0 (-6 )
Calvert and Pitts
(1966)
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(39 *C)
REFERENCES
COMMENTS
VAPOR PRESSURE latm.l
2.6 (-1)
Weast (1973)
WATER SOLUBILITY (mol. m'3)
inf.
Freier (1975)
HENRY'S CONSTANT (»tm. m3 mol'1)
1.6 (-5)
calculated
SOLVENT SOLUBILITY (mol. m"3)
inf.
Merck (1976)
alcohol, chloroform,
ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: I"
E. GENERAL COMMENTS
The very high OC/NOx ratios lead to significant O3 formation. Moderate or low
OC/NOx ratios show no O3 formation. Kinetic considerations show reactivity with
photolysis playing a dominant role.
A-4
-------
Chemical Nairn: Acetone Cyanohydrin
Chemical Formula: (CH^) 2C(0H) CN (M.W.-85)
Chemical NO.: 5
CAS Registry NO.: 75-86-5
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX. O3
total
IRRADIATION
TIME
AVERAGE OC
DISAPPEARANCE
RATE (%/ht
NO.FORMA-
TION RATE
(PPB/Mln)
REFERENCES
ORGANIC
CHEMICAL
(0C>
z
o
X
NOj/NO
CONC.
(PPM)
TIME
[hi
B. KINETIC DATA
R6 ACTION
WITH
UNITS
RATE CONSTANT
VALUE l»*C!
REFERENCES
OH RATE CONST.
RELATIVE TO
BTHANfi
comments on
RATE CONSTANT
ESTIMATION
I r»
O O
em3 mol*#"1
om3 molic1 S'1
6.0 (-13)
Estimated
1.9
Not strictly
amenable to
estimation
S"'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (ttm.l
1.2 (-3)
Estimated
WATER SOLUBILITY (mol. in'3)
3900
Estimated
HENRY'S CONSTANT (Mm. m3 moT'l
3.2 (-7)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
insoluble
Merck (1976)
Carbon disulfide, petro-
leum ether
PHYSICAL STATE
liquid
0. CLASSIFICATIONS
REACTIVITY: IX VOLATILITY: III OVERALL: II
E. GENERAL COMMENTS
No laboratory or smog chamber data are available.
A-5
-------
Chemical Nam#: Acetonicrile
Chemical Formula: CH^CN (M.W.-41)
Chemical NO.: 6
CAS Registry NO.: 75-05-8
A. SMOG CHAMBER DATA
INITIAL CONC. IPPMI
MAX.03
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE 1%/hl
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOCI
NOx
NOj/NO
CONC.
[PPMI
TIME
(hi
4.0
0.2
0.25
0.01
10-12
Sickles et al (1980)
4.0
1.07
0.25
0.01
10-12
Sickles et al (1980)
4.0
0.2
0.0
31
0.02
Dlmitr lades and Joshi (1977)
8. KINETIC DATA
REACTION
WITH
UNITS
RATI CONSTANT
VALUE (2S'C)
REFERENCES
OH RATE CONST
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
on' motoc'1 S''
4.9 (-14)
Harris et al (1981)
0.2
°3
cm' mortc'1 3"'
<1.5 (-19)
Harris et al (1981)
s-'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
(2S'C)
REFERENCES
COMMENTS
VAPOR PRESSURE l«m.)
1.1 (-1)
Drelsbach (1961)
WATER SOLUBILITY (mol. m'3)
inf.
Freier (1975)
HENRY'S CONSTANT l«m. m3mol'')
6.6 (-6)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
inf.
Merck (1976)
Methanol, acetone,
liquid
chloroform, ether
PHYSICAL STATE
~.CLASSIFICATIONS
REACTIVITY: i VOLATILITY: in OVERALL: I
E. GENERAL COMMENTS
Significantly less reactive than ethane.
A-6
-------
Chamicat Name: Acetylene
Chemical Formula: C.,H2 (M.W.-26)
Chemical NO.: 7
CAS Registry NO.: 74-86-2
A. SMOG CHAMBER DATA
INITIAL CONG.
PPMI
MAX. O3
TOTAL
IRRADIATION
TIME Ih)
AVERAGE OC
DISAPPEARANCE
RATE (Vhl
NO,FORMA-
TION RATE
IPPfl/MIn)
REFERENCES
ORGANIC
CHEMICAL
(OC)
z
0
X
NOj/NO
CONC.
(PPM)
TIME
(hi
4.0
3.2
0.2s
0.15
10-12
0.ftxpropane
Sickles et al (1980)
4.0
>.07
0.25
0.15
10-12
0.9xpropane
Sickles et al (1980)
4.0
3.2
0.10
5.3
6.3
Dlmitrlades and Jashi (1977)
2.0
L.O
0.05
0.0
5
3.4
2.8
Yanagihara et al (1977)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE <2S*CI
REFERENCES
OH RATE const.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em' motec'1 S1
1.7 (-13)
Atkinson et al (1979)
0.6
°3
cm3 mota'1 S"'
8.6 (-20)
NAS (1976)
I'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
<2S*C>
REFERENCES
COMMENTS
VAPOR PRESSURE (atm.l
48
Jordan (1954)
WATER SOLUBILITY Imol. m'3)
29
Stephen and Stephen (1963)
HENRY'S CONSTANT litm. m3 mot"1)
3.4 (-2)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
PHYSICAL STATE
1050
990
720
gas
Miyano and Hayduk (1981)
benzene
methanol
Hexane
0. CLASSIFICATIONS
REACTIVITY: 1 VOLATILITY: IH OVERALL: X
E. GENERAL COMMENTS
The high disappearance races cannot be reasonably explained. These would require
prevailing OH concentrations of approximately 10° molec cm~3 which are much too
high. The Sickles et al (1980) data may suffer from high background O3 levels.
These smog chamber data are Inconsistent with our current knowledge of photochemistry.
A-7
-------
Chemical Nam*: Acrylic acid
Chemical Formula: CH2CHCOOH (M.W.-72)
A. SMOG CHAMBER DATA
Chamical NO.:
CAS Registry NO.: 79-10-7
INITIAL CONC. (PPMI
MAX. 03
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (%/hl
NO.FORMA-
TION RATE
(PPB/Mini
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
(PPM)
TIME
IM
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALU6 (25*C>
REFERENCES
OH RATE CONST
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm^ S
2.8 (-11)
Estimated
90.3
°3
cm* mol«e'1 S"1
hU
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (atm.)
5.3 (-3)
Jordan (1954)
WATER SOLUBILITY (mol. m'3)
inf.
Freier (1975)
HENRY'S CONSTANT <«m. m3 mol'1)
3-2 (-7)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
inf.
Merck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: I" VOLATILITY: 111 OVERALL: 111
E. GENERAL COMMENTS
Expected to be significantly more reactive than acetic acid.
No smog chamber or Laboratory kinetic data are available.
A-8
-------
Chemical Nam*: Acrylonltrile
Chemical Formula: CHjCHCN (M.W.-53)
Chemical NO.: 9
CAS Resistry NO.: 107-13-1
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX
°3
TOTAL
IRRAOIATION
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE (K/hl
NO-FORMA-
TION RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
(PPM)
TIME
4.0
0.2
0.25
1.9
10-12
2xpropane
Sickles ec al (1980)
4.0
0.07
0.25
1.1
10-12
2xpropane
Sickles ec al (1980)
4.0
0.2
0.37
5.5
5.3
Dim!crlades and Joshl (1977)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (»*CI
REFERENCES
OH RATE CONST
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 melte'1 S'1
4.1 C-12)
Harris at al (1981)
13.2
°3
em3 rnol*"1 S"'
sl.O C—19)
Harris et al (1981)
IU>
s-1
,
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE Utm.l
1.5 C-l)
Jordan (1954)
WATER SOLUBILITY imel. m'3)
1500
Lyman at al (1982)
HENRY'S CONSTANT film, m3 mof')
9.8 C-5)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: III
E. GENERAL COMMENTS
A-9
-------
Chemical Nam*: Adipic acid
Chemical Formula: HOOC(CH2)4COOH (M.W.-146)
Chemical NO.: 10
CAS Raqittry NO.: 124-04-9
A. SMOG CHAMBER DATA
INITIAL CONC. IPPMI
MAX. Os
TOTAL
IRRADIATION
TIME
REFERENCES
COMMENTS
VAPOR PRESSURE (stmj
1.3 (-4)
Jordan (1954)
WATER SOLUBILITY (mol. m'3)
137
Morrison and Boyd (1973)
20°C
HENRY'S CONSTANT <«tm. m3 mo)*1)
9.5 (-7)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
soluble
Merck (1976)
acetone, methanol.
ethanol
PHYSICAL STATE
solid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: m OVERALL: hi
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
Should be significantly more reactive than acetic acid.
A-10
-------
Chemical Nam*: Aniline
Chemical Formula: (M.W.-93)
Chamical NO.: 11
CAS Ragittry NO.: 62-53-3
A. SMOG CHAMBER OATA
INITIAL CONC.(PPM)
MAX. 03
total
IRRADIATION
TIME
-------
Chemical Name: Benzene
Chemical Formula: (M.W.-78)
Chamical NO.: 12
CAS Registry NO.: 71-43-2
A. SMOG CHAMBER DATA
INITIAL CONC. IPPMI
MAX. O3
TOTAL
AVERAGE OC
NO-FORMA-
ORGANIC
CHEMICAL
(OCI
nox
NOj/NO
CONC.
IPPM)
TIMS
Ihl
IRRAOIATION
TIME III)
DISAPPEARANCE
RATE (Vhl
TION RATE
(PPB/Mlnl
REFERENCES
4.0
0.2
0.02
1.5
3.1
Dlmitriades and Joshi (1977)
2.0
1.0
0.05
0.0
5
3.3
1.9
Yanagihara et al (1977)
1.0
D.5
0.11
0.0
6
1.1-1.6
Dlmitriades et al (1975)
1.5
0.6
0.05
0.2x
toluei
e
5
K2.4
0.2xtoluen«
Laity et al (1973)
4.0
2.0
0.0
0.0
6
Levy and Miller (1970)
2.0
1.0
0.05
0.05
6
2.2
1.6
Heuss and Glasaon (1970)
8.0
2.0
0.0
0.0
6
Brunelle et al (1966)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (39*C1
REFERENCES
OH RATE CONST
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 molflc'1 5-'
1.2 (-12)
Atkinson et al (1979!
3.9
°3
cm3 mol»c 1 S'1
l\V
S'1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
K»*C)
REFERENCES
COMMENTS
VAPOR PRESSURE Utm.l
WATER SOLUBILITY tmol. m'3)
HENRY'S CONSTANT (ron. m3 mal'1!
SOLVENT SOLUBILITY Imol. m'3)
PHYSICAL STATE'
1.3 (-1)
22.8
5.4 (-3)
inf.
liquid
Zvolinski and Wilhoit (1971
McAuliffe (1966)
Mackay and Shiu (1981)
Merck (1976)
)
alcohol, acetone, ether
0. CLASSIFICATIONS
REACTIVITY: n VOLATILITY: III OVERALL: II
E. GENERAL COMMENTS
Although modarately reactive, It Is Inefficient In ozone formation. A large
fraction of products (sjIOOJ) i« phenol (Hendry, 1979). Thia radical scavenger
may be responsible for preventing significant 0^ formation.
A-12
-------
Chemical Nam#: Bisphenol-A
Chemical Formula: HOC6H4-C(CH3) j-CgH^OH (M.W.-228)
Chemical NO.: 13
CAS Registry NO.: 80-05-7
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.03
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE IVhl
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OC)
X
o
z
NOj/NO
CONC.
IPfM)
TIME
(hi
•
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S*C)
REFERENCES
OM HATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
HATE CONSTANT
ESTIMATION
OH
cm3 mot»e ' S 1
7.0 C-U)
Estimated
225.8
°3
em3 mol*"1 S"1
W
S-'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
os'ci
REFERENCES
COMMENTS
VAPOR PRESSURE (aim.)
WATER SOLUBILITY Imel. m"3)
HENRY'S CONSTANT («m. m3 mol-')
SOLVENT SOLUBILITY Imol. m'3)
PHYSICAL STATE
1.9 (-12)
1.5 (-1)
1.2 (-11)
soluble
slightly soluble
solid
Freier (1975)
Merck (1976)
Estimated
20°C
Calculated
alcohol, acetone
carbon tetrachloride
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: I OVERALL: 1
E. GENERAL COMMENTS
No laboratory or snog chamber data are available.
A-13
-------
Chemical Nam*: Butadiene-1,3
Chemical Formula: CHjCHCHCHj (M.W.«54)
Chemical NO.: 14
CAS Ragirtry NO.: 106-99-0
A. SMOG CHAMBER DATA
INITIAL CONC.
PPMI
MAX
•03
TOTAL
IRRADIATION
TIME (HI
AVERAGE OC
DISAPPEARANCE
RATE IVhl
NO,FORMA-
TION RATE
IPPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OC1
nox
NOj/NO
CONC.
(PPMl
TIME
(M
2.0
L.O
0.05
0.79
1.8
5
20.0
23.1
Yanaglhara et al (1977)
1.0
3.5
0.11
0.89
6
13.0
Dlmitriades et al (1975)
1.0
3.4
0.05
7
4.3
jlasson and Tuesday (1970)
2.0
L.O
0.05
0.43
6
15.0
25.0
tfeuas and Classon (1968)
3.3
).85
0.72
3
27.5
Utshuller et al (1966)
3.0
L.O
>20
0.65
0.75
6
49.0
Schuck and Doyle (1959)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S*CI
REFERENCES
OH RATE CONST
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 moWc"' 5'1
6.9 (-11)
Atkinson et al (1979)
222.5
cm3 mol«c'1 S'1
8.4 (-18)
Niki (1978)
HP
s-'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(JS'c)
REFERENCES
COMMENTS
VAPOR PRESSURE l»tm.l
2.77
Zwolinski and Wilholt(197i;
WATER SOLUBILITY (mol. m'3)
13.6
McAullffe (1966)
HENRY'S CONSTANT («m. m3 mol"')
7.4 (-2)
Mackay and Shiu (1981)
SOLVENT SOLUBILITY Intel, m'3)
PHYSICAL STATE
gas
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: m OVERALL: ni
E. GENERAL COMMENTS
Highly reactive. Several photochemical produces including formaldehyde, acrolein,
nicric acid, peroxyacetyl nitrate, ethyl nitrate, proplonaldehyde, acetone, and
propylene oxide have been identified.
A-14
-------
Chamical Nam*: n-Butane
Chemical Formula: CH3CH2CH2CH3 (M.W.-58)
Chamical NO.: 15
CAS Registry NO.: 106-97-8
A. SMOG CHAMBER DATA
INITIAL CONC.
PPMt
MAX
¦°3
TOTAL
IRRADIATION
TIME Ihl
AVERAGE OC
DISAPPEARANCE
RATE
1.1
McAuliffe (1966)
HENRY'S CONSTANT («tm. m3
9.5 (-1)
Mackay and Shiu (1981)
SOLVENT SOLUBILITY (mol. m'3)
1.9 (4)
Gerrard (1976)
Octanol
PHYSICAL STATE
gas
D. CLASSIFICATIONS
REACTIVITY: m VOLATILITY: m OVERALL: m
E. GENERAL COMMENTS
Ozone formation is highly sensitive to initial HC/N0X ratio. A ratio of 5 to 10 is
most efficient la 0, formation. A number of photochemical products such as acetal-
dehyde, carbon monoxide, carbon dioxide, methyl ethyl-ketone, formaldehyde, peroxyacetyl
nitrate, methyl nitrate, ethyl nitrate, propylnitrate, butylnitrates, and butyraldehyde
have been identified.
A-15
-------
Chemical Name: Iso-Butane
Chemical Formula: (C^CHCHj (M.W.-58)
Chemical NO.: 16
CAS Registry NO.: 75-28-5
A. SMOG CHAMBER DATA
INITIAL C0NC. (PPM)
MAX.O3
TOTAL
IRRAOIATION
TIME lh>
AVERAGE OC
disappearance
RATE 1%/h)
NO.FORMA-
TION RATS
(PPB/Min)
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NO^NO
CONC.
(PPMl
TIME
-------
Chemical Nam*: 1-Butene
Chemical Formula: CH^CH^CHCH^ (M.M.-56)
Chemical NO.: 17a
CAS Registry NO.: 106-98-9
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM1
MAX. O3
total
IRRAOIATION
TIME (h>
AVERAGE OC
DISAPPEARANCE
RATE IWN
NO,FORMA-
TION RATE
(PPS/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OC)
X
o
2
NOj/NO
CONC.
(PPM)
TIME
(hi
2.0
1.0
0.05
0.57
4.8
5
19.0
11.8
Kanagihara et al (1977)
1.0
0.5
0.11
0.67
6
7.0
Dimitriades et al (1975)
2.0
1.0
0.05
0.47
6
14.0
13.0
Heuss and Glasson (1968)
1.2
0.8
0.14
0.43
6
Brunelle et al (1966)
3.0
1.0
>20
0.58
0.75
3
55.0
Schuck and Doyle (1959)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (28*CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 -noltc"' s'1
2.9 (-11)
Atkinson et al (1979]
93.5
°3
em3 mo He'1 S'1
1.2 (-17)
Niki (1979)
he
S"'
C. VOLATILITY DATA
PROPERTY NAME (UNITSI
PROPERTY VALUE
(2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE latm.l
2.9
Zwolinalci and Wilhoit(1971)
WATER SOLUBILITY Imol. m'3!
4.0
McAuliffe (1966)
HENRY'S CONSTANT !«m. m3 mol 'l
2.6 (-1)
Mackay and Shiu (1981)
SOLVENT SOLUBILITY (mol. m-3)
PHYSICAL STATE
gas
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: 111
E. GENERAL COMMENTS
Highly reactive chesiical (Stephens and Burleson, 1967; AJLtshuller and Bufalinl, 1971).
Known products Include formaldehyde, aeetaldehyde, propionaldehyda, carbon monoxide,
peroxyacetyl nitrate, peroxypropionyl nitrate, nitric acid, butyraldehyde, butylene oxide,
methyl nitrate, ethyl nitrate, ethane and ethene.
A-17
-------
Chemical Nam*: cis-2-Butene
Chemical Formula: CH-jCHCHCHj (M.W.-56)
Chemical NO.: 17B
CAS Registry NO.: 590-18-1
A. SMOG CHAMBER DATA
INITIAL CONC. {PPM)
MAX. O3
TOTAL
AVERAGE OC
NO,FORMA-
ORGANIC
CONC.
TIME
IRRADIATION
DISAPPEARANCE
TION RATE
REFERENCES
CHEMICAL
(OC)
NOx
NOj/NO
IPPM)
(hi
TIME (hi
RATE (Vhl
(PPB/Mlnl
1.0
0.5
0.11
0.74
6
23.5
Dlmlcriadea et al (1975)
2.0
1.0
0.05
0.44
6
15.0
28.0
Heuss and Glasson (1968)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (78*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
*AT6 CONSTANT
estimation
OM
°3
cm3 mol«e°' S'1
cm' molM~' S'1
4.3 (-11)
1.4 (-16)
Atkinson ec al (1979)
Nlki (1979)
138.7
w
S"*
C. VOLATILITY OATA
PflOKftTY NAME (UNITS)
PROPERTY VALUE
(2S*C)
references
COMMENTS
VAPOR PRESSURE (sun.)
2.1
Zwolinaki and Wilhoit(1971)
WATER SOLUBILITY (mol. m'3)
1.4
Lyman ac al (1982)
HENRYS CONSTANT (Mm. m3 mol"1)
7.1 (-1)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
PHYSICAL STATE
gas
0. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: HI OVERALL: 111
E. GENERAL COMMENTS
A-18
-------
Chemical Nam*: trans-2-Butene
Chemical Formula: OUCHCHCH^ (M.W.-56)
Chemical NO.: 17C
CAS Registry NO.: 624-64-6
A. SMOG CHAMBER DATA
INITIAL CONC. IPPMI
max.Oj
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vhl
NO,FORMA-
TION RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
IPPMI
TIME
(hi
1.0
0.5
0.14
0.70
"6
34.1
Pi mlcriadea et al (1975)
4.0
2.0
0.0
0.67
0.8
6
82.6
Levy and Miller (1970)
2.0
1.0
0.05
0.44
6 '
7.1
38.0
Heusa and Glasson (1968)
3.0
1.0
> 20
0.73
0.5
3
50.0
Schuck and Doyle (1959)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (28*CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 mol«e'1 S'1
6.8 (-11)
Atkinson et al (1979]
219.4
°3
cm3 mol«e'' S '
2.6 (-16)
Niki (1979)
hi/
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
m'o
REFERENCES
COMMENTS
VAPOR PRESSURE latm.l
2.3
Zwolinakl and Hilhoit(1971)
WATER SOLUBILITY (mol. m'3)
1.4
Lyman et al (1982)
HENRY'S CONSTANT litm. m3 mol"')
7.1 C-l)
Calculated
SOLVENT SOLUBILITY (mol. m"3)
PHYSICAL STATE
gaa
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: III
E. GENERAL COMMENTS
Known reaction products include: acetaldehyde, peroxyacetyl nitrate, carbon
monoxide, formaldehyde, methyl ethyl ketone, methyl nitrate and nitric acid.
A-19
-------
Chemical Name: Isobutylene
Chamical Formula: (CH^J CM.W.-56)
Chemical NO.: J-8
CAS Ragistry NO.: "5-11-7
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.Oj
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE IH/hl
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OCI
nox
NOj/NO
CONC.
(PPM)
TIME
(hi
2.0
1.0
0.05
0.75
2.0
6
20.0
15.6
Yanaglhara ec al (1977)
1.0
0.4
0.05
3.5
Glaaaon and Tuesday (1970)
5.0
3.0
0.0
80.0
Altahuller and Cohen (1963)
3.0
1.0
>20
1.0
0.5
1.7
55.0
-20.0
Schuck and Doyle (1959)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (3S*CI
REFERENCES
OH RATE CONST
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em' -none'1 S''
4.7 (-11)
Atkinson et al (1979
151.6
°3
em' molte'1 S 1
6.0 (-18)
Niki (1979)
HV
S"'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(28'CI
REFERENCES
COMMENTS
VAPOR PRESSURE (ttm.l
3.0
Iwollnskl and Wllholt(1971)
WATER S0LU8ILITY (mol. m'J)
4.7
McAuliffe (1966)
HENRY S CONSTANT (Mm. m3 mol'1!
2.1 (-1)
Mackay and Shlu (1981)
SOLVENT SOLUBILITY (mol. m'3)
PHYSICAL STATE
gas
0. CLASSIFICATIONS
REACTIVITY: in VOLATILITY: m OVERALL: hi
E. GENERAL COMMENTS
Highly reactive. NO oxidation ability comparable to propene (Glaaaon and Tuesday* 1970).
A-20
-------
Chemical Nam*: n-Butanol
Chemical Formula: C^H^CHjOH (M.W.-74)
Chemical NO.: 19
CAS Ragiftry NO.: 71-36-3
A. SMOG CHAMBER DATA
INITIAL CONC.
PPM)
MAX. Ol
TOTAL
AVERAGE OC
NO,FORMA-
ORGANIC
CHEMICAL
IOCI
NOx
NOj/NO
CONC.
IPPM1
TIME
Ihi
IRRAOtATION
TIME (hi
DISAPPEARANCE
RATE IVhl
TION RATE
(PPB/Mlnl
REFERENCES
4.0
0.2
0.28
13.8
1.1
Oialtriades and Joshi (1977)
2.0
1.0
0.05
0.14
5
7.4
5.7
Yangihara et al (1977)
1.0
0.6
0.05
1.4x
:olueni
5
= 9.6
L.Oxtoluene
Laity et al (1973)
1.0
0.1
2.7
0.13
7
9.0
Wilson and Doyle (1970)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
value ro'ci
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 mol«c'' S'1
7.6 (-12)
Atkinson et al (1979)
°3
cm3 moUc'1 S'1
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY value
<2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE
8.4 (-3)
Jordan (1954)
WATER SOLUBILITY Imol. m"3)
1000
Verschueren (1977)
HENRY'S CONSTANT l«m. m3 mol"')
8.1 (-6)
Calculated
SOLVENT SOLUBILITY Imol. m'3)
inf.
Merck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: XXI VOLATILITY: III OVERALL: HI
E. GENERAL COMMENTS
These data are for t-Butanol which is less reactive than n-butanol (Laity et al, 1973)
A-21
-------
Chemical Nam*: 2-Butoxyethanol
Chemical Formula: (M.W.-119)
Chemical NO.: 20
CAS Registry NO.: 111-76-2
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.03
TOTAL
IRRADIATION
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE
X
O
z
NOj/NO
CONC.
(PPM)
TIME
(hi
2.0
1.0
0.05
0.38
5
4.5
9.3
Yanagihara et al (1977)
B. KINETIC DATA
REACTION
WITH
UNITS
HATE CONSTANT
VALUE (tt'c)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
an3 moltc*1 S'1
1.6 (-11)
Estimated
51.6
m
o
cm' S1
hv
$•'
C. VOLATILITY DATA
PROPERTY NAME IUNITS)
PROPERTY VALUE
125*0
REFERENCES
COMMENTS
VAPOR PRESSURE (inn.)
5.4 (-4)
Estimated
WATER SOLUBILITY (mol. m"3)
423
Merck (1976)
HENRY'S CONSTANT Ittm. m3mo('1)
1.9 (-6)
Calculated
SOLVENT SOLUBILITY (mot. m'3)
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: XIX VOLATILITY: III OVERALL: HI
E. GENERAL COMMENTS
A-22
-------
Chemical Name: n-Butyl acetate
Chemical Formula: CH3COOC4Hg (M.W.-116)
Chemical NO.: 21
CAS Registry NO.: 123-86-4
A. SMOG CHAMBER DATA
INITIAL CONC. IPPM)
MAX. O3
TOTAL
AVERAGE OC
NO,FORMA-
TION RATE
(PPS/Mlnl
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
(PPMI
TIMS
(hi
IRRAOIATION
TIME (hi
DISAPPEARANCE
RATE IW/h)
REFERENCES
2.0
1.0
0.05
0.02
5
5.3
3.5
Yanagihara et al (1977)
4.0
0.2
0.18
4.3
4.3
Dimitriades and Joshi (1977)*
1.0
0.6
0.05
0.8x
:oluem
1
5
4.4
0.7xtoluem
: Laity et al (1973)
4.0
2.0
0.0
>0.08
6
6.0
Levy and Miller (1970)*
1.0
0.2
5.3
0.11
7
5.0
Wilson and Doyle (1970)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S%!
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm' molac"' S'1
5.3 (-12)
Atkinson et al (1979)
16.1
Rate assumed
to be the same
°3
em' rot*1 S '
as that of
fW
s-'
s-Butyl acetate
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
(2S*CI
REFERENCES
COMMENTS
VAPOR PRESSURE ((tin.)
1.4 (-2)
Jordan (1954)
WATER SOLUBILITY (mot. m'3)
43
Verschueren (1977)
HENRY'S CONSTANT (Mm. m3 mol'1!
3.3 (-4)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
inf.
Merck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: IH OVERALL: 111
E. GENERAL COMMENTS
Ethyl acetate at high OC/NOX ratios (Sickles et al, 1980) shows significant 03
formation. Butyl acetate should be at least as much or more reactive than ethyl
acetate.
*
These data are for i-Butyl acetate
A-23
-------
Chemical Nam*: sec-Butyl alcohol
Chemical Formula: C2H5CHOHCH3 (M.W.-74)
Chemical NO.: 22
CAS Registry NO.: 78-92-2
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM|
max.Os
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE WW
NO-FORMA-
TION RATE
{PPB/Mln|
REFERENCES
ORGANIC
CHEMICAL
iOC)
z
O
X
NOj/NO
CONC.
(POMI
TIME
(hi
1.0
1-0
0.6
0.1
0.05
1.5
1.3x
:oluem
0.13
I
5
7
6.0
1. Oxtolueni
Laity et al (1973)
Wilson and Doyle (1970)*
B. KINETIC DATA
REACTION
WITH
UNITS
RATI CONSTANT
VALUE Q3*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RAT* CONSTANT
ESTIMATION
OH
on3 rnorte"' S 1
7.3 (-12)
Estimated
23.5
°3
cm' motoc'1 S1
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNIT3I
PROPERTY VALUE
(3S*CI
REFERENCES
COMMENTS
VAPOR PRESSURE
2.2 (-2)
Jordan (1954)
WATER SOLUBILITY Imol. m"3)
1700
Morrison and Boyd (1973)
HENRY'S CONSTANT l«m. m3 mol'1)
1.3 (-5)
Calculated
SOLVENT SOLUBILITY Imol. m'3)
inf.
Merck. (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: HI
E. GENERAL COMMENTS
*These data are for iso-Butyl alcohol.
A-24
-------
Chamical Nam*: t-Butyl alcohol
Chemical Formula: (CH^JjCOH (M.W.-74)
Chamical NO.: 23
CAS Registry NO.: 75-65-0
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. 03
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vh|
NO.FORMA-
TION RATH
(PPE/MIn)
REFERENCES
ORGANIC
CHEMICAL
(OC)
z
o
X
NOj/NO
CONC.
ippmi
TIME
Ihl
4.0
0.2
0.28
13.8
1.1
Dlmlcrlades and Joshl (1977)
1.0
0.6
0.05
0.3x
5
a 2
3.3x toluene
Laity et al (1973)
toluen
k
B. KINETIC DATA
REACTION
WITH
UNITS
RATI CONSTANT
VALUE <2#'C>
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
rate constant
estimation
OH
cm' moitc"1 S'1
6.0 <-13)
Estimated
1.9
°3
cm3 mot*"' S"'
hv
s-'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
I2S'C)
REFERENCES
COMMENTS
VAPOR PRESSURE Irnn.l
5.5 C-2)
Jordan (1954)
WATER SOLUBILITY (mat. m-3l
Inf.
Frier (1975)
20°C
HENRY'S CONSTANT lam. m3 moT')
3.3 (-6)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
Inf.
Merck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: 111 OVERALL: I"
E. GENERAL COMMENTS
A-25
-------
Chemical Nam#: Carbon disulfide
Chemical Formula: CS^ (M.W.-76)
Chemical NO.: 24
CAS Registry NO.: 75-15-0
A. SMOG CHAMBER DATA
INITIAL CONC. IPPMl
MAX. O3
TOTAL
IRRAOIATION
TIME (111
AVERAGE OC
DISAPPEARANCE
RATE IVItl
NO,forma-
tion RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
IOC)
nox
MOj/NO
CONC.
IPPM»
TIME
(HI
2.0
3.98
0.25
0.0
10
1.4
Sickles and Wright (1979)
2.0
3.49
0.25
0.01
8.6
10
2.2
2.0
3.20
0.25
0.05
8.1
10
2.8
2.0
3.10
0.25
0.33
9.3
10
3.8
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE 129*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
em3 S'1
on3 motae"' s '
<1.5 (-15)
Wine et al (1980);
WM0 (1982)
*0.0
hf
0
s-1
3.4 (-12)
WMO (1982)
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
(28 *C)
REFERENCES
COMMENTS
VAPOR PRESSURE (•on.)
4.8 (-1)
Dreisbach (1961)
WATER SOLUBILITY (mol. m'3)
22
Freier (1975)
HENRY'S CONSTANT («tm. n? mol"1)
2.2 C-2)
Calculated
SOLVENT SOLUSIUTY (mol.m'3!
inf.
Merck (1976)
methanol, ether, benzene
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: II VOLATILITY: III OVERALL: II
E. GENERAL COMMENTS
OH rate constant is negligible. However, there is enough evidence to suggest
that in the presence of oxygen it may be much faster. Assuming an 0(3p)
concentration of 4xl0'Si>olec. cm"-*, no significant reactivity occurs. Excited
state Cs2 oxidation (Wine et al., 1980) may lead to some SOj production but
the kinetics are not veil understood. Smog chamber data show considerable
reactivity, but cannot be considered firm. COS and SO2 are key secondary
products. A-26
-------
Chemical Name Carbon tetrachloride Chemical NO.: ^5
Chemical Formula: CCl^ (M.W.-154) CAS Registry NO.: 56-23-5
A. SMOG CHAMBER DATA
INITIAL CONC.
MAX.O]
TOTAL
IRRAOIATION
TIMC IK)
AVERAGE OC
DISAPPEARANCE
RATI IVAI
NO,FORMA-
TldN RATS
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OCJ
X
o
z
NOj/NO
CONC.
(PPMI
TIME
{hi
0.05
0.5
0.0
200
0.0
Lillian et al (1975)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE <2S%)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 mot*"' S'1
<1.0 C-16)
Hampson (1980)
55 0.0
°3
cm3 nwMc"' S'1
he
J"1
C. VOLATILITY DATA
PROPERTY NAME (UNITSI
PROPERTY VALUE
(28 *C)
REFERENCES
COMMENTS
VAPOR PRESSURE (nm.l
1.5 (-1)
Dreisbach (1959)
WATER SOLUBILITY (mol.m"3)
7.5
Verschueren (1977)
HENRY-S CONSTANT (ttm.m3 mol'')
2.0 C-2)
Mackay and Shiu (1981)
SOLVENT SOLUBILITY (mol. m"3)
inf.
(1976)
alcohol, benzene, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: X VOLATILITY: HI OVERALL: I
E. GENERAL COMMENTS
Completely unreactive in the troposphere. Decomposition by photolysis occurs
In the stratosphere (UMO, 1982).
A-27
-------
Chemical Nam*: chloroform
Chemical Formula: CHC13 (M.W.-119)
Chemical NO.: 26
CAS Registry NO.: 67-66-3
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O]
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vhl
NO,FORMA-
TION RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
IOC)
N0X
NOj/NO
CONC.
(PPM)
TIME
(hi
4.0
0.2
0.25
0.02
10-12
0.4xpropane
* Sickles et al (1980)
4.0
).07
0.25
0.2
10-12
0.8xpropane
* Sicklea et al (1980)
4.0
0.2
0.0
2.4
0.8
Dlmltriades and Joshi (1977)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE !2S*CI
REPERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
w
cm' mo(«c'1 s '
cm3 mol#e"' S'1
s"1
1.1 (-13)
Haopaon (1980)
0.33
C. VOLATILITY DATA
PROPERTY NAME IUNITSI
PROPERTY VALUE
I2S'C>
REFERENCES
COMMENTS
VAPOR PRESSURE (Mm.)
2.6 (-1)
Dreiabach (1959)
WATER SOLU8ILITY (mol. m"3!
78
Verschueren (1977)
HENRY'S CONSTANT («tm. m3 mol"')
3.8 (-3)
Mackay and Shiu (1981)
SOLVENT SOLUBILITY (mat. m'3)
inf.
Merck (1976)
alcohol, benzene, ether
PHYSICAL STATE
liquid
REACTIVITY: I
0. CLASSIFICATIONS
VOLATILITY: III
OVERALL: I
E. GENERAL COMMENTS
Reactivity expected to be significantly less than ethane. At vary high OC/NOX
ratioa («S0) 0.. production is seen (Sicklea et al, 1980). However, high background
O3 levels may Be responsible for this observation.
*
Maximum rate of NO oxidation.
A-28
-------
Chemical Nam*: Monochlorobanzena Chemical NO.: 27
Chamical Formula: cgH5Cl (M.W.-113) CAS Registry NO.: 108-90-7
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. 03
TOTAL
IRRAOIATION
TIME
AVERAGE OC
DISAPPEARANCE
RATE t%/h»
NO-FORMA-
TION RATE
(PPB/Min)
REFERENCES
ORGANIC
CHEMICAL
IOC)
z
O
X
NOj/NO
CONC.
(PfM)
TIM6
(hi
2.0
1.0
0.05
0.0
5
1.5
1.7
Yanaglhara et al (1977)
B. KINETIC DATA
REACTION
WITH
UNITS
BATS CONSTANT
value ra'ci
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em3 mot*'' S"1
5.0 C—13);
Suaten et al (1981);
1.6-2.9
9.0 C—13)
dill et al (.1982)
°3
om mot#c S
hv
S-'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
I2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (Mm.)
1.5 (-2)
Drelsbach (1955)
WATER SOLUBILITY (mot. m"3)
4. A
Drelsbach (1955)
HENRY'S CONSTANT faun. m3 mol"1)
3.8 (-3)
Mackay at al (1979)
SOLVENT SOLUaiLITY (mol. m'3)
freely soluble
Merck (1976)
alcohol, benzene, ether
PHYSICAL STATE
liquid
0. CLASSIFICATIONS
REACTIVITY: n VOLATILITY: III OVERALL: II
E. GENERAL COMMENTS
Only about half as reactive as benzene. Irradiations with high OC/NOX ratio
have not been performed. Should behave similarly Co benzene.
A-29
-------
Chemical Name: p-Dichlorobenzene
Chemical Formula: 1,4-C6H4C12 (M.W.-147)
Chemical NO.: 28
CAS Registry NO.: 106-46-7
A. SMOG CHAMBER DATA
INITIAL CONC. IPPMI
max. 03
TOTAL
IRRAOIATION
TIMC (hi
average oc
disappearance
RATE (Vh)
NO-FORMA-
TION RATE
-------
Chemical Nam*: 1,3-Dichloropropene Chemical NO.: 29A
Chemical Formula: CH2C1CHCHC1 gA5 Registry NO.: 542-75-6
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IRRADIATION
TIME
NO-FORMA-
TION RATE
(PPB/MlnJ
REFERENCES
ORGANIC
CHEMICAL
(OC)
NOx
NOj/NO
CONC.
IPPM>
TIME
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (tt'Cl
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm^ motte'1 S'1
1.3 C-U)
Estimated
41.9
°3
em^ motec'1 S*'
hp
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(28*C1
REFERENCES
COMMENTS
VAPOR PRESSURE
4.3 (-2)
Estimated
WATER SOLUBILITY (mol. m"3l
63
Estimated
HENRY'S CONSTANT (itm. m3 mol"1)
6.8 (-4)
Calculated
SOLVENT SOLUBILITY (mol. m'3!
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: HI OVERALL: 111
E. GENERAL COMMENTS
No snog chamber or laboratory kinetic data are available.
k- 31
-------
Chemical Name: 1,2-Dichloropropene
Chemical Formula: CH^CCICHCI (M.W.»111)
Chemical NO.:
CAS Registry NO.: 563-54-2
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.O3
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
disappearance
RATE (%/h|
NO-FORMA-
TION RATE
(PPB/Min)
REFERENCES
ORGANIC
CHEMICAL
(00)
X
o
z
NOj/NO
CONC.
(PPM)
TIME
{hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE <2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 mol*'1 S"1
1.3 (-11)
Estimated
41.9
°3
cm3 motac'1 S*'
hv
3-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE Itmvt
1.3 (-1)
Estimated
WATER SOLUBILITY I met. m'3)
16
Estimated
HENRY'S CONSTANT (itm. m3 mol*1)
7.9 (-3)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: hi VOLATILITY: III OVERALL: III
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
A-32
-------
Chemical Name: Cunene (Isopropylbenzene)
Chemical Formula: CgH5CH(CH3), (M.W.-120)
Chemical NO.: 30
CAS Registry NO.: 98-82-8
A. SMOG CHAMBER DATA
INITIAL CONC.IPPMI
MAX.Oj
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (*/hl
NO.FORMA-
TION RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
IOC)
nox
NOj/NO
CONC.
(PP**>
TIME
(hi
1.0
0.5
0.11
0.28
6
4.0
Dimitriades et al (1975)
4.0
2.0
0.0
0.41
5.3
6
6.5
Levy and Miller (1970)
2.0
1.0
0.05
0.19
6
5.5
6.6
Heuss and Glasson (1968)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (ZS'CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm* molte'1 S 1
7.8 (-12)
Atkinson et al (1979)
25.2
°3
cm* moloe'1 S"1
hv
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITSI
I2S*CI
REFERENCES
COMMENTS
VAPOR PRESSURE
6.1 (-3)
Drelsbach (1955)
WATER SOLUBILITY (mol. m'3)
4.2 (-1)
McAuliffe (1966)
HENRY'S CONSTANT l«m. m3 mol'1)
1.3 (-2)
Mackay and Shlu (1981)
SOLVENT SOLUBILITY (mol. m'3)
soluble
Merck (1976)
alcohol
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: HI VOLATILITY: III OVERALL: HI
E. GENERAL COMMENTS
A-33
-------
Chemical Name: C/ciohexane
Chemical Formula: C6H12
Chemical NO.: 31
CAS Registry NO.: 110-82-7
A. SMOG CHAMBER DATA
INITIAL CONC. [PPMI
max. 03
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (%/h)
NO,forma-
tion RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OC)
NOx
NOj/NO
CONC.
IPPVI
TIME
(HI
2.0
1.0
0.05
0.09
5
5.8
5.0
Yanagihara et al (1977)
4.0
2.0
0.0
0.27'
6.0
6
11.0
Levy and Miller (1970)
3.0
1.0
>20
0.20
1.4
3
45
Schuck and Doyle (1959)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S'C>
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 mol*c 1 S*1
6.2 (-12)
Atkinson et al (1979)
20.0
°3
cm3 mol*c 1 S 1
hv
S'1
C. VOLATILITY DATA
PROPERTY NAME IUNITSI
PROPERTY VALUE
(28 *CI
REFERENCES
COMMENTS
VAPOR PRESSURE (ran.)
WATER SOLUBILITY (mol. m'3)
HENRY'S CONSTANT t«m. m3 mol"')
SOLVENT SOLUBILITY (mol. m'3)
PHYSICAL STATE
1.3 (-1)
6.5 (-1)
1.8 (-1)
inf.
liquid
Zwolinski and Wilhoit (1971
McAuliffe (1966)
Mackay and Shiu (1981)
Merck (1976)
)
ethanol, acetone, benzem
D. CLASSIFICATIONS
REACTIVITY: HI VOLATILITY: HI OVERALL:
E. GENERAL COMMENTS
*
still Increasing at the end of the run.
A-34
-------
Chemical Name: Cyclohexanol
Chemical Formula: C,H..OH (M.W.-100)
0 11
Chemical NO.: 32
CAS Registry NO.: 108-93-0
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.O3
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (%/h)
NO.FORMA-
TION RATE
(PPfi/MIn)
REFERENCES
ORGANIC
CHEMICAL
fOC)
NOx
NOj/NO
CONC.
(PPM1
TIME
(h)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (28*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
estimation
OH
cm3 mol^c'1 S*1
6.6 (-12)
Estimated
21.3
°3
cm3 rrwttc'1 S*1
to
S'1
C. VOLATILITY OATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(25*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (atm.)
1.7 (-3)
Jordan (1954)
WATER SOLUBILITY (mol. m*3)
360
Verschueren (1977)
20°C
HENRY'S CONSTANT (aim. m3 mol*1)
4.7 (-6)
Calculated
SOLVENT SOLUBILITY (mol. m'2)
inf.
Merck (1976)
tthanol, aromatic hydro-
carbons
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: I11
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
A-35
-------
Chemical Name: Cyclohexanotie
Chemical Formula: C6Hiq° (M,w,"98)
Chemical NO.: 33
CAS Ragistry NO.: 108-94-1
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. Oj
TOTAL
AVERAGE OC
NO,FORMA-
ORGANIC
CONC.
TIME
IRRAOIATION
DISAPPEARANCE
TION RATE
REFERENCES
CHEMICAL
IOC)
nox
NOj/NO
(PPMI
(hi
TIME (hi
RATE IK/hl
(PPB/Mlnl
2.0
1.0
0.05
0.08
5.0
5
6.2
6.4
Yanagihara et al (1977)
1.0
0.6
0.05
0.6x
5
4.0
0.8xtoluene
Laity et al (1973)
toluen
e
4.0
2.0
0.0
0.10
4.8
6
8.5
Levy and Miller (1970)
1
0.2
1.2
0.08
7
7.0
Wilson and Doyle (1970)
B. KINETIC DATA
REACTION
WITH
UNITS
RATI CONSTANT
VALUE I2S"CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em3 malac'1 S'1
5.5 (-12)
Estimated
17.7
°3
em3 mol«c"' S '
hlf
S"'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2S*CI
REPERENCES
COMMENTS
VAPOR PRESSURE (aim.)
5.8 (-3)
Jordan (1954)
WATER SOLUBILITY (mol. m'3)
230
Verschueren (1977)
20°C
HENRY'S CONSTANT (itm. m3 mol'1)
2.5 (-5)
Calculated
SOLVENT SOLUBILITY (mol. m"3)
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: HI VOLATILITY: III OVERALL: HI
E. GENERAL COMMENTS
irradiation at high 0C/N0x ratios have not been performed.
A-36
-------
Chemical Nam*: Diethylene glycol
Chemical Formula: HOCH^CH^OCHjG^OH (M.W.-106)
Chemical NO.: 34
CAS Registry NO.: HJ--46-6
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM*
MAX.O3
TOTAL
IRRAOIATtON
TIME [hi
AVERAGE OC
DISAPPEARANCE
RATI {%/h|
NO- FORMA-
TION RATE
(PPB/Mint
REFERENCES
ORGANIC
CHEMICAL
(OC>
z
O
X
NOj/NO
CONC.
(PPM)
TIME
(h)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE t25*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
flATE CONSTANT
ESTIMATION
OH
cm3 mol®e'1 S"1
2.7 (-12)
Estimated
8.7
°3
em3 rnolw*1 S"1
hi/
S'1
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
<2fi*C)
REFERENCES
COMMENTS
VAPOR PRESSURE Utm.)
9.5 (-6)
. Estimated
WATEH SOLUBILITY (mol. m'3>
inf.
Merck (1976)
HENRY'S CONSTANT («m. m3 mol*1)
5.6 (-10)
Calculated
SOLVENT SOLUBILITY (met. m"3)
inf.
Merck (1976)
alcohol, acetone, ether
insoluble
benzene, carbon tet.
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: HI VOLATILITY: III OVERALL: HI
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
A-37
-------
Chemical Nam*: Di-(2-ethylhexyl)phthalate
Chemical Formula: C24H3g04 (M.W.-390)
Chamicai NO.: 35
CAS Regittry NO.: 117-81-7
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM1
MAX.O3
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (%/h|
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
§1
TIME
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATI CONSTANT
VALUE I29*C)
REFERENCES
OH RATE CONST
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
Ml
cm3 mol«e' S ''
on3 mot*"' S"'
S''
2.8 (-11)
Estimated
90.3
Not strictly
amenable to
estimation
C. VOLATILITY DATA
PROPERTY NAME IUNITSI
PROPERTY VALUE
(25*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (Mm.)
1.9 (-10)
Klopffer et al (1982)
WATER SOLUBILITY Imol, m'3)
1.0 (-4)
Klopffer et al (1982)
HENRY'S CONSTANT («tm. m3 mol'1!
1.9 (-6)
Calculated
SOLVENT SOLUBILITY (mol. m"3)
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY; ill VOLATILITY: X OVERALL: I
E. GENERAL COMMENTS
A-38
-------
Chemical Nam*: Dlisodecyl phthalate
Chemical Formula: C6H4(COOC1()Hn)2 (M.W.-447)
Chemical NO.: 36
CAS Registry NO.:
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IARAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vh)
NO-forma-
tion RATE
(PPB/Min)
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
(PPM)
TIME
(M
8. KINETIC DATA
reaction
WITH
UNITS
RATE CONSTANT
VALUE (2S*C!
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm' S
3.4 (-11)
Estimated
109.7
Wot strictly
amenable to
°3
em motae S
estimation
htf
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(28 "CI
REFERENCES
COMMENTS
VAPOR PRESSURE (aim.)
WATER SOLUBILITY (mol. m"3)
3.8 (-10)
Estimated from boiling
point data
HENRY'S CONSTANT l«tm. m3 mol"')
SOLVENT SOLUBILITY (mol. m"3!
PHYSICAL STATE
D. CLASSIFICATIONS
REACTIVITY: HI VOLATILITY: X OVERALL: I
E. GENERAL COMMENTS
A-39
-------
Chemical Name: Dimethyl terephthalate
Chemical Formula: p-CH-jOOCCgH^COOCH-j (M.W.»194)
Chemical NO.: 37
CAS Registry NO.: 120-61-6
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. 03
TOTAL
IRRADIATION
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE (VM
no2 forma-
tion RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
IOC>
z
o
X
no2/no
11
TIME
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
em3 moltc* S"1
cm3 mol#e"' S1
1.2 (-11)
Estimated
38.7
Not strictly
amenable to
estimation
hv
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(28*C)
REFERENCES
COMMENTS
VAPOR PRESSURE Utm.)
WATER SOLUBILITY (mot. m*3J
5.0 (-3)
Estimated from boiling
point data
HENRY'S CONSTANT («tm. m3 mol'1!
SOLVENT SOLUBILITY (mol. m'3}
PHYSICAL STATE
solid
D. CLASSIFICATIONS
REACTIVITY: m VOLATILITY: III OVERALL: III
E. GENERAL COMMENTS
A-40
-------
Chemical Nam*: Epichlorohydrin
o
Chemical Formula: Hjd-CHCHjCl (M.W.-92.5)
Chemical NO.: ^8
CAS Registry NO.: 106-89-8
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IflAAOIATtON
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE (%/hl
NO-FORMA-
TION RATE
(PPB/Min)
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
(PPM)
TIME
(hi
8. KINETIC DATA
reaction
WITH
UNITS
RATE CONSTANT
VALUE t»'C>
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
Th«a« data snow
OH
cm3 motac'1 S*1
2.4 (-11)
Dilllug ct al (1976)
77.4
that the r«latlv«
loat rtta of
03
cm3 S*1
•plehlorohydrla
and 1,1,2 eri-
chloro«ch«SM *r«
hl>
S'1
Rata
con»t«at viMd it
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
MOMRTY VALUE
(2S"C>
REFERENCES
COMMENTS
VAPOR PRESSURE (atrrU
2.1 (-2)
Jordan (1954)
WATER SOLUBILITY (mol. m'3)
650
Verschueren (1977)
20°C
HENRY'S CONSTANT Inm. m3 mol ')
3.2 (-5)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
inf.
Merck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: 111
E. GENERAL COMMENTS
A-41
-------
Chemical Name: Ethane
Chemical Formula: C,H, (M.W.»30)
L 0
Chemical NO.: 39
CAS Raoiitry NO.: 74-84-0
A. SMOG CHAMBER DATA
INITIAL CONC.
PPM)
MAX. 02
TOTAL
IRRADIATION
TIME Ihl
AVERAGE OC
DISAPPEARANCE
RATE 1%/ht
NO-FORMA-
TICjN RATE
(PPB/Minl
REFERENCES
ORGANIC
CHEMICAL
(OCI
nox
NO^NO
CONC.
IPPMI
TIME
IX)
4.0
0.2
0.03
3.0
0.5
Dlmltriades and Joshi (1977)
2.0
1.0
0.05
0.0
5
11.0
3.0
Yanagihara et al (1977)
2.0
1.0
0.05
0.0
6
0.0
Farley (1977)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (38*CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em' molae"1 S 1
3.1 (-13)
Hampson (1980)
1.0
°3
cm' mol«e'' S'1
w
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
ras'o
REFERENCES
COMMENTS
VAPOR PRESSURE (Km.)
38.5
Dreisbach (1959)
WATER SOLUBILITY (mol. m'3)
2.0
McAuliffe (1966)
HENRY'S CONSTANT («tm. m3 mol ')
5.0 (-1)
Mackay and Shlu (1981)
SOLVENT SOLUBILITY (mol. m'3)
825
Wilhelm and Battino (1973)
Benzene
535
Acetone
PHYSICAL STATE
215
Methanol
gas
0. CLASSIFICATIONS
REACTIVITY: I VOLATILITY: III OVERALL: I
E. GENERAL COMMENTS
The involvement of ethane In photochemical reactions la not In doubt (Singh and
Hanst, 1981) but it la considered too unreactlve to participate In smog formation
(Singh at al, 1981). Over a 24 hr period no reactivity is obaerved by Stephena
and Burleson (1967). High depletion rates measured by Yanagihara et al (1977)
can only be explained as a snog chamber artifact.
A-42
-------
Chemical Nam*: Ethanol amine
Chemical Formula: OHCH2CH2NH2 CM.W.-61)
Chemical NO.: 40A
CAS Regictry NO.: 141-43-5
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IRRADIATION
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE (Vh|
NO-FORMA-
TION RATE
(PP8/Min>
REFERENCES
ORGANIC
CHEMICAL
IOC)
X
0
2
no2/no
II
TIME
(h>
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (26*C)
references
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 moltc"1 S 1
1.3 (-11)
Estimated
41.9
Not strictly
amenable to
°3
em idoIk S"1
estimation
S'1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE Urm.)
9.2 (-4)
Estimated
WATER SOLUBILITY (mo), m"3)
inf.
Freier (1975)
20°C
HENRY'S CONSTANT |*tm. m3 mol*1)
4.2 (-5)
Calculated
SOLVENT SOLUBILITY (mol. m"3)
111
Merck (1976)
benzene
inf.
acetone
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: HI VOLATILITY: III OVERALL: 111
E. GENERAL COMMENTS
Somewhat more reactive than diethylamine. The latter has been irradiated in
smog chambers (0.5 pprn Oc/O.25 ppm NOx) and produced significant ozone con-
centrations (Pitts et al, 1978).
A-43
-------
Chemical Nam*: Diethanol amine Chemical NO.: 408
Chemical Formula: (OHCHjCHj)2^ (M.W.-105) CAS Registry NO.: 111-42-2
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
max. 0}
TOTAL
IRRADIATION
TIME th>
AVERAGE OC
DISAPPEARANCE
RATE IVh)
NO-FORMA-
TION RATE
(PPB/MInt
REFERENCES
organic
CHEMICAL
IOC)
X
O
z
NOj/NO
CONC.
IPPM)
TIME
IM
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C1
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 mol»c' ^ S1
4.3 (-11)
Estimated
138.7
Yot strictly
amenable £0
°3
cm molac S
estimation
tin
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
I3S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE Utm.l
2.1 (-9)
Estimated
WATER SOLUBILITY Imol. m"3)
9100
Verschueren (1977)
HENRY'S CONSTANT l«m. m3 mol"')
1.3 (-13)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
233
Merck (1976)
benzene
444
ether
PHYSICAL STATE
solid
O. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: I OVERALL: I
E. GENERAL COMMENTS
A-44
-------
ChttnicAl Nww Triethanol amine
Chemical Formula: (OHCH^CH^) (M.W.-1A9)
Chemical NO.: 400
CAS Registry NO.: 102-71-6
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IRRAOIATION
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE (%/h)
NO.FORMA-
TION RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
-------
Chemical Nam*: Ethyl acetate
Chemical Formula: CH3COOC2H5 (M.W.-88)
Chemical NO.: ^
CAS Registry NO.: 1*1-78-6
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX. O3
TOTAL
AVERAGE OC
NO.FORMA-
TION RATE
(PPtt/Mlol
ORGANIC
CHEMICAL
(OCI
NOx
NOj/NO
CONC.
IPFM)
TIME
(W
IRRADIATION
TIME (hi
disappearance
RATE (%/hl
REFERENCES
A .0
).2
0.25
0.80
10-12
1.8xpropane
Sickles et al (1980)
4.0
). 0 7
0.25
0.65
10-12
1.2xpropane
Sickles et al (1980)
2.0
L.O
0.05
0.01
5
1.9
2.6
Yanaglhara et al (1977)
1.0
).6
0.05
0.8x
toluen
3
5
2.4
0.5xtoluene
Laity et al (1973)
1.0
).2
0.7
0.08
7
4.0
Wilson and Doyle (1970)
B. KINETIC DATA
REACTION
WITH
UNITS
RATI CONSTANT
VALUE (28*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm^ mol«c*1 S*'
1.8 (-12)
Atkinson et al (1979)
5.8
°3
cm3 moltc1 S'1
hf
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(3S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (atm.l
1.2 (-1)
Jordan (1954)
WATER SOLUBILITY (mot. m"3)
843
Stephen and Stephen (1963)
HE N R Y*S CONSTANT («m. m3 mol"1)
1.4 (-4)
Calculated
SOLVENT SOLUBILITY (mol.m"3)
Inf.
Merck (1976)
alcohol, acetone, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: HI
E. GENERAL COMMENTS
Reactivity comparable to propane. High OC/NO^ ratios are required to produce
significant ozone formation.
A-46
-------
Chemical Name: Ethyl alcohol
Chemical Formula: c2h OH (M.W.-46)
Chemical NO.: **
CAS Registry NO.: 64-17-5
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAx.03
TOTAL
average oc
NO,FORMA-
ORGANIC
CONC.
TIME
IRRAOIATION
DISAPPEARANCE
TION RATE
REFERENCES
CHEMICAL
IOC)
N°X
NOj/NO
(PPM)
(hi
TIME (hi
RATE (*/ht
(PPB/Minl
4.0
0.2
0.25
0.64
10-12
Lx propane
Sickles et
al
(1980)
4.0
o.o;
0.25
0.73
10-12
Lx propane
Sickles ec
al
(1980)
2.0
1.0
0.05
0.0
5
2.2
Yanaglhara
et
al (1977)
1.0
0.6
0.05
lxtolu
>ne
5
as 2.a
2.6xtoluen
i Laity et
al
(1973)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S'CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em3 molte'1 s'1
2.5 (-12)
Atkinson et al (1979
1 8.1
°3
am3 moWe'1 s'
W
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2«*CI
REFERENCES
COMMENTS
VAPOR PRESSURE Utm.l
7.8 (-2)
Jordan (1954)
WATER SOLUBILITY Imol. m"3)
Inf.
Freier (1975)
20°C
HENRY'S CONSTANT lam. m3 mol"')
4.6 (-6)
Calculated
SOLVENT SOLUBILITY (mol. m-3)
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: 111 VOLATILITY: 111 OVERALL: 111
E. GENERAL COMMENTS
A-47
-------
Chemical Nam*: Ethyl benzene
Chemical Formula: C5H5CH3 (M.W.-106)
Chamieal NO.: 43
CAS Registry NO.: 100-41-4
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.03
TOTAL
AVERAGE OC
NO,FORMA-
TION RATE
(PPS/Mlnl
ORGANIC
CHEMICAL
IOCI
nox
NOj/NO
CONC.
(PPM)
TIME
(hi
IRRADIATION
TIME III)
DISAPPEARANCE
RATE 1%/hl
REFERENCES
2.0
1.0
0.05
0.24
5
6.5
5.4
Yanagihara ec al (1977)
1.0
0.5
0.11
0.32
6
4.2
Dimicriades ec al (1975)
1.0
0.6
0.05
lxtolu
ma
5
6.4
3.3xtoluene
Laity et al (1973)
4.0
2.0
0.0
0.42
6
10.9
Levy and Miller (1970)
2.0
1.0
0.05
0.21
6
4.8
7.2
Heuss and Glasaon (1968)
8. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S*C)
REFERENCES
OH RATE CONST
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 motoc'1 S'1
8.0 (-12)
Atkinson et al (1979)
25.8
°3
mol«e"' s '
w
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
ITS'C)
REFERENCES
COMMENTS
VAPOR PRESSURE litm.l
1.2 (-2)
Zwolinski and Wilhoit (1971
WATER SOLUBILITY (mol. m"3)
1.4
McAuliffe (1966)
HENRY'S CONSTANT (Mm. m3 mof1)
7.9 (-3)
Mackay and Shiu (1981)
SOLVENT SOLUilLITY (mol. m'3)
PHYSICAL STATE
liquid
REACTIVITY: HI
D. CLASSIFICATIONS
VOLATILITY: HI
E. GENERAL COMMENTS
OVERALL: 111
A-43
-------
Chemical Nam*: Ethyl chloride
Chemical Formula: €2^01 (M.W.- 64.5)
Chemical NO.: 44
CAS Registry NO.: 75"°°-3
A. SMOG CHAMBER DATA
INITIALCONC. tPPM*
MAX.O3
TOTAL
IRRADIATION
TIME (M
AVERAGE OC
DISAPPEARANCE
RATE <%/M
NO-FORMA-
TION RATE
(PPB/Min)
REFERENCES
ORGANIC
CHEMICAL
fOCl
NOx
NOj/NO
CONC.
(PPMI
TIME
Ih)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I29'C]
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 mol**1 S*1
3.9 (-13)
Hampson (1980)
1.3
°3
cm^ motvc"'
h*»
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(3S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE tatm.)
1.58
Dxeisbach (1959)
WATER SOLUBILITY (mot. m'3l
89
Verschueren (1977)
20°C
HENRY'S CONSTANT (ttm. m3 mol*')
1.1 (-2)
Calculated
SOLVENT SOLUBILITY Imot. m"3>
8500
Merck (1976)
alcohol
PHYSICAL STATE
gas
0. CLASSIFICATIONS
REACTIVITY: I VOLATILITY: HI OVERALL: 1
E. GENERAL COMMENTS
A-49
-------
Chsmical Nam*: 2- Ethoxy hexanol Chemical NO.: ^
Chamical Formula: C2HJOCH2CH2OC2HJ (M.H.-118) CAS Registry NO.:
A. SMOG CHAMBER OATA
INITIAL CONC. (PPM)
MAX. 03
TOTAL
IRRAOIATION
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE IVM
NO.FORMA-
TION RATE
-------
Chemical Name: E thy Lane
Chemical Formula: CjH4 (M.W.-28)
Chemical NO.: 46
CAS Roflittry NO.: 74-85-1
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
max. o3
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vhl
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OCI
nox
NOj/NO
CONC.
IPPMI
TIME
Iht
2.0
3.6
0.50
1.1
10-12
Jefferiea et al (1982)
2.0
1.0
0.05
0.44
5.0
5
11.3
9.6
Yanagihara et al (1977)
1.8
3.8
>20
1.2
4.0
4
21.0
Gay et al (1976)
2.1
1.0
0.0
0.9
5.0
6
14.0
Gay et al (1976)
1.0
3.5
0.11
0.56
6
4.1
Dimicriades et al (1975)
4.0
2.0
0.0
0.59
4.0
6
24.0
Levy and Miller (1970)
2.0
L.O
0.05
0.28
6
7.5
5.8
Heuss and Glaaaon (1968)
6.0
2.0
>20
1.0
2.3
3
35.0
Schuck and Doyle (1959)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S'C)
REFERENCES
OH BATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 malte"' S'1
7.9 (-12)
Atkinson et al (1979)
25.4
°3
cm' mote"1 S''
1.8 (-18)
Niki (1979)
hp
S'1
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
(2B*C)
REFERENCES
COMMENTS
VAPOR PRESSURE («m.|
WATER SOLUBILITY (mot. m'3l
HENRYS CONSTANT (mm. m3 mol'1)
SOLVENT SOLUBILITY
-------
Chamical Nam*: Ethylene dibromide
Chamical Formula: CH^BrCH^Br (M.W."188)
Chamical NO.: 47
CAS Ragistry NO.: 106-93-4
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX. O3
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATI IVhl
NO, FORMA—
T1WI RATE
(PPS/MIn)
references
ORGANIC
CHEMICAL
IOC)
«x
NOj/NO
CONC.
(PPMI
TIME
IM
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
value as'a
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
M>
cm3 motes'1 S"'
cm3 melt"1 S"1
s-'
2.5 {-13)
Haapaoa (1980)
0.81
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
~fl'C)
REFERENCES
COMMENTS
VAPOR PRESSURE («m.)
1.5 C-2)
Drelsbach C1959)
WATER SOLUBILITY (mat. m"3)
27
EaClMtad
HENRY'S CONSTANT (Km. m3 mol"1!
5.7 (-4)
Calculated
SOLVENT SOLUBILITY (mol. m"3)
Inf.
Marck (1976)
alcohol
PHYSICAL STATE
liquid
0. CLASSIFICATIONS
REACTIVITY: I VOLATILITY: III OVERALL: I
E. GENERAL COMMENTS
A-52
-------
Chemical Nam*: Ethylene dichloride
Chemical Formula: CH2C1CH2C1 (M.W.-99)
Chemical NO.: 48
CAS Raqirtry NO.: 107-06-2
A. SMOG CHAMBER DATA
INITIAL C0NC. (PPMI
MAX. O3
TOTAL
IRRADIATION
TIME (h)
average oc
DISAPPEARANCE
RATE (Vh>
NO-FORMA-
TION RATE
IPPBflWnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
IPPM)
TIME
-------
Chemical Name: Ethyl ether
Chemical Formula: C2HJOC2H2 (M.W.-74)
Chemical NO.: 49
CAS Registry NO.: 60-29-7
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX. 03
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vhl
NO,FORMA-
TION RATE
(PPS/Mfnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
N0„
NOj/NO
CONC.
(PPMI
TIME
(hi
1.0
0.6
0.05
2.5xtc
luene
5
12.0
1.7xtoluene
Laity et al (1973)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (»tl
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
wn3 motac'1 S'1
8.9 (-12)
Atkinson et al (1979)
28.7
°3
cm3 molte*' S"'
he
s'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(28*C)
REFERENCES
COMMENTS
VAPOR PRESSURE l«m.l
7.1 (-1)
Jordan (1954)
WATER SOLUBILITY (mol. m"3)
816
Verschueren (1977)
HENRY'S CONSTANT <«m. m3mol'1)
8.7 (-4)
Calculated
SOLVENT SOLUBILITY (mot. m"3)
Inf.
Merck (1976)
benzene, pet. ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: HI VOLATILITY: HI OVERALL: I"
E. GENERAL COMMENTS
Ethyl ether Is about 50Z more reactive than toluene baaed an OH reactivity alone.
A-54
-------
Chemical Nam#: Ethylene glycol
Chemical Formula: CHjOHCHjOH (M.W.-62)
Chemical NO.: 50
CAS Registry NO.: 107-21-1
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IRRAOIATION
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE (X/hl
NO,FORMA-
TION RATE
(PPS/Mlnl
REFERENCES
organic
CHEMICAL
IOC)
X
o
z
NOj/NO
CONC.
(PPM)
TIME
(hi
B. KINETIC OATA
REACTION
WITH
UNITS
RATS CONSTANT
VALUE I2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
on" molae'* s '
4.4 (-12)
Estimated
14.2
°3
cm3 mol*"' S''
hv
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(28'CI
REFERENCES
COMMENTS
VAPOR PRESSURE l»m.)
1.7 (-4)
Short et al (1983)
WATER SOLUBILITY (mol. m'3)
lni.
Merck (1976)
HENRY S CONSTANT (nm. m3 mol'1)
1.0 (-8)
Calculated
SOLVENT SOLUBILITY (mol. m"3)
Inf.
Merck (1976)
acetone
Insoluble
benzene, petr. ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: lit VOLATILITY: III OVERALL: lit
E. GENERAL COMMENTS
Should be about 502 more reactive than ethanol.
A-55
-------
Chemical Nam*: Ethylene ox±de Chemical NO.: 51
Chemical Formula: (M.W.-44) CAS Regittry NO.: 75-21-8
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX. O3
TOTAL
IRRADIATION
TIME (M
AVERAGE OC
DISAPPEARANCE
RATE (%/hl
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NoyNo
CONC.
-------
Chemical Name: 2-Ethyl hexanol Chemical NO.:
Chemical Formula: C^HgCHCH,011 (M.W.-130) caS Registry NO.: 104-76-7
C2H5
A. SMOG CHAMBER DATA
INITIAL CONC.(PPM)
max. 03
TOTAL
IRRAOIATION
time m»
AVERAGE OC
DISAPPEARANCE
RATE 1%/hl
NO.FORMA-
TION RATE
(PPB/Minl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOyNO
CONC.
(PPM)
TIME
(M
B. KINETIC DATA
REACTION
WITH
UNITS
SATE CONSTANT
VALUE (2S*CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em^ mode*' S*'
1.0 (-11)
Estimated
32.2
°3
3 .1 .1
em mouc S
hi'
s-'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
<26 *C)
REFERENCES
COMMENTS
VAPOR PRESSURE (atm.)
2.8 (-4)
Estimated
WATER SOLUBILITY (mol. m'3)
67.6
Lyman et al (1983)
HENRY'S CONSTANT (»tm. m3 mol'1)
4.1 (-6)
Calculated
SOLVENT SOLUBILITY (mol. m"3l
PHYSICAL STATE
liquid
O. CLASSIFICATIONS
REACTIVITY: HI VOLATILITY: HI OVERALL: 111
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
A-57
-------
Chemical Nam*: Fluorocarboa-U
Chemical Formula: CTCl^ (M.W.-137)
ChemicaJ NO.: 53
CAS Registry NO.: 75-69-4
A. SMOG CHAMBER DATA
INITIAL CONC. IPPMI
MAX. O3
TOTAL
IRRAOIATION
TIME (W
AVERAGE OC
DISAPPEARANCE
RATE <«/h|
NO, FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
(PPM)
TIME
(HI
0.012
0.5
0.0
400
0.0
Ml Han et al (1975)
0.025*
1.0
7
0.0
Heater et al (1974)
0.025+
1400
0.0
Hester et al (1974)
B. KINETIC DATA
REACTION
WITH
UNITS
RATS CONSTANT
VALUE 139%)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em3 iiiulw"1 S'1
<1.0 C-17)
Uampsoa (1980)
0.0
°3
Mr
an3 iimIbc"* S"'
S"1
C. VOLATILITY OATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
oa'a
REFERENCES
COMMENTS
VAPOR PRESSURE (m.i
1.08
DuPont (1969)
WATER SOLUBILITY Imol. m'3)
8.0
DuPont (1969)
HENRY'S CONSTANT (dm. m3 mot'')
1.2 (-1)
Calculated
SOLVENT SOLUBILITY Imol. in'3)
soluble
Merck (1976)
alcohol, ether
PHYSICAL STATE
gas
0. CLASSIFICATIONS
REACTIVITY: I VOLATILITY: III OVERALL: I
E. GENERAL COMMENTS
Uareactive in Che troposphere (HMO, 1982)
*
plus I ppm C^Hg
+1d ambient air
A-58
-------
Chemical Nam*: Fluorocarbon-12
Chemical Formula: ccl^ (M.W.-121)
Chemical NO.:
CAS Registry NO.: 75-71-8
A. SMOG CHAMBER DATA
INITIAL CONC.
PPMI
MAX
03
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (%/hl
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
(PPMI
TIME
(hi
0.02
0.5
400
0.0
Lillian et al (1975)
0.008
1.0
7
0.0
Hester et al (1974)
0.025f
1440
0.0
Hester et al (1974)
8. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
an3 molte'' S'1
<1.0 (-16)
Hampson (19S0)
0.0
°3
em3 molae"1 S1
hp
S'1
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
(3S"C)
REFERENCES
COMMENTS
VAPOR PRESSURE Utm.)
6.53
DuPont (1969)
WATER SOLUBILITY (mol. m'3)
2.3
DuPont (1969)
HENRY'S CONSTANT (itm. m3 mol"1)
4.3 (-1)
Calculated
SOLVENT SOLUBILITY Imol. m"3!
soluble
Merck (1976)
alcohol, ether
PHYSICAL STATE
gas
0. CLASSIFICATIONS
REACTIVITY: 1 VOLATILITY: 111 OVERALL: 1
E. GENERAL COMMENTS
Unreaccive in the troposphere
it
plus 1 ppm C^Hg
In the ambient air
A-59
-------
Chemical Name: Fluorocarbcra-Z2
Chemical Formula: CHC1F2 (M.W.-86.5)
Chemical NO.:
CAS Registry NO.: 75-45-6
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX.O3
TOTAL
IRRADIATION
TIME (HI
average oc
DISAPPEARANCE
RATE (Vh)
NO-FORMA-
TION RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
(OC)
NOx
NOj/NO
CONC.
(PPM)
TIMS
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (3S*C)
REFERENCES
OH HATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 melee"1 S*1
4.8 (-15)
Hampson (1980)
0.02
°3
cm3 mote'1 S'1
h«»
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
(»*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (91111.)
10.5
DuPont (1969)
WATER SOLUBILITY (mol. m"3)
34.7
DuPont (1969)
HENRY'S CONSTANT (ttm. m3 mol'1)
2.9 (-2)
Calculated
SOLVENT SOLUBILITY Imol m'3)
PHYSICAL STATE
gas
D. CLASSIFICATIONS
REACTIVITY: i VOLATILITY: m OVERALL: i
E. GENERAL COMMENTS
A-60
-------
Chemical Name: Fluorocarbon-113
Chemical Formula: CCl^FCClFj (M.W.-187.5)
Chemical NO.: 56
CAS Registry NO.: 75-13-1
A. SMOG CHAMBER DATA
INITIAL CONC. IPPMI
MAX. O3
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vhl
NO-FORMA-
TION RATE
(PPB/Minl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
IPPMI
TIME
(W
0.015
3.50
0.0
400
0.0
Lillian et al (1975)
1.0
5.11
2.7
0.06
7
3.0
Wilson and Doyle (1970)
1.0
3.20
1.1
0.06
7
4.0
Wilson and Doyle (1970)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
on3 mol«e"' S"1
<3.0 (-16)
Hampson (1980)
0
°3
em3 T*oi#c'1 S"'
ho
J"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2B*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (Mm.)
4.4 (-1)
DuPont (1969)
WATER SOLUBILITY (mol. m'3)
9.1 (-1)
DuPont (1969)
HENRY'S CONSTANT l«tn. m3 mol"')
4.9 (-1)
Calculated
SOLVENT SOLUBILITY |m«l. m'3)
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: I VOLATILITY: HI OVERALL: 1
E. GENERAL COMMENTS
Unreactive in the troposphere. The loss rate measured by Wilson and Doyle (1970)
is comparable to the inadvertant dilution rate in their smog chamber.
A-61
-------
Chemical Nam*: Fluorocarbon-114
Chemical Formula: (M.W.-171)
ChamicaJ NO.: 5?
CAS Raflirtry NO.: 75-14-2
A. SMOG CHAMBER DATA
INITIAL CONC.
8. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
value a%'o
REFERENCES
OH RATE CONST.
RELATIVE TO
ethane
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
on3 motoc*' S*'
<1.0 (-16)
Hampson (1980)
a 0.0
°3
on3 motac'1 S"1
S'1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
<2s*a
REFERENCES
COMMENTS
VAPOR PRESSURE
2.18
DuPont (1969)
WATER SOLUBILITY tmoi. m*3)
7.6 (-1)
DuPont (1969)
HENRY'S CONSTANT (aim. m3 moT1)
1.3
Calculated
SOLVENT SOLUBILITY (mol. m'3)
soluble
Merck (1976)
Alcohol, ether
PHYSICAL STATE
gas
D. CLASSIFICATIONS
REACTIVITY: I VOLATILITY: XII OVERALL: 1
E. GENERAL COMMENTS
Unreacclve In Che troposphere.
A-62
-------
Chemical Name: Formaldehyde
Chemical Formula: HCHO (M.W.-30)
Chemical NO.: 58
CAS Regiitry NO.: 50-00-0
A. SMOG CHAMBER DATA
INITIAL CONC. IPPMI
MAX. 0]
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE l*/hl
NO-FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOCI
nox
NOj/NO
CONC.
(PPM)
TIME
(hi
1.2
0.5
0.44
0.59
10-12
Jefferies et al (1982)
1.0
0.5
0.14
0.14
6
8.0
Dimitriades and Wesson (1972)
3.6
0.2
0.43
3
Altshuller ec al (1966)
5.6
0.0
0.44
3
Altshuller et al (1966)
6.1
0.9
1.05
3
Altshuller eC al (1966)
5.0
3.0
0.0
3.3
20.0
Altshuller and Cohen (1963)
B. KINETIC DATA
REACTION
WITH
UNITS
RATI CONSTANT
VALUE <2S'CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em' moMc"1 S 1
1.1 (-11)
Stief et al (1980)
35.4
°3
cm' moUe"1 S 1
htf
S°
5.0 (-5)
Calvert (1980)
C. VOLATILITY DATA
PROPERTY NAME IUNITSI
PROPERTY VALUE
(2S*CI
REFERENCES
COMMENTS
VAPOR PRESSURE (Mm.)
4.56
Jordan (1954)
WATER SOLUBILITY (mol. m"3l
18.3
Merck (1976)
HENRY'S CONSTANT (atm. m3 mol'1)
5.5 (-2)
Calculated
SOLVENT SOLUBILITY (mol. m"3!
soluble
Merck (1976)
alcohol, ether
PHYSICAL STATE
gas
0. CLASSIFICATIONS
REACTIVITY. Ill VOLATILITY: III OVERALL: III
E. GENERAL COMMENTS
An intermediate product of hydrocarbon oxidation in virtually all photochemical
systems (Altshuller and Bufalinl, 1971; Calvert, 1980). Typical products are
CO, H2 and HjOj.
A-63
-------
Chemical Nam*: Glycerine
Chemical Formula: HOCHjCHOHCHjOH (M.W.-91)
Chemical NO.: 59
CAS Registry NO.: 56-81-5
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. 0]
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (*fhl
NO.FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
N0X
NOj/NO
CONC.
(PPMI
TIME
Ihl
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C)
REFERENCES
OH RATI CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATI CONSTANT
ESTIMATION
OH
em' mo**"1 S"1
1.6 (-12)
Estimated
5.2
°3
cm' mot*"' S*'
nv
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
OS'C)
REFERENCES
COMMENTS
VAPOR PRESSURE (Km.)
2.5 (-7)
Cammenga et al (1977)
WATER SOLUBILITY Imol. m"3)
inf.
Freier (1975)
20°C
HENRY'S CONSTANT («m. m3 mol"')
1.5 (-H)
Calculated
SOLVENT SOLUBILITY Imol. m'3)
inf.
Merck (1976)
alcohol
PHYSICAL STATE
liquid
0. CLASSIFICATIONS
REACTIVITY: IX VOLATILITY: II OVERALL: "
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are avllable.
A-64
-------
Chemical Nam*: Hexamethylenetetramlne (Formln)
Chemical Formula: C-H.-N. (M.W.-140)
O 1/ 4
Chemical NO.: 60
CAS Registry NO.: 100-97-0
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.O]
TOTAL
IRRADIATION
TIME (It)
AVERAGE OC
DISAPPEARANCE
RATE (%/hl
no2 forma-
tion RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
-------
Chemical Nam#: Heptenes Chemical NO.: 61
. , _ , r u (M.W.«98) — - — 592-76-7 (1-Heptene)
Chemical Formula: 7 14 wl"w* *o; CAS Registry NO.:
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX
03
TOTAL
AVERAGE OC
NO,FORMA-
TION RATE
(PPB/MIn)
ORGANIC
CHEMICAL
IOC)
nox
NOj/NO
CONC.
(PPMI
TIME
|h>
IRRADIATION
TIME (hi
DISAPPEARANCE
RATE (Vhl
REFERENCES
5.0
1.5
0.05
0.68
1.5
6
40
Miller
and
Joseph (1976)
3.0
1.0
>20
0.72
1.0
3
43
Scbuclc
and
Doyle (1959)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
an' rrxMe'^ s'1
3.5 (-11)
Atldnson et al (1979)
113.0
rate constants
°3
cm' mol«c"* S'1
8.5 (-18)
NAS (1976)
for 1-Heptene
hi/
3"'
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
(3S'CI
REFERENCES
COMMENTS
VAPOR PRESSURE latin.)
6.0 (-2)to7.4(-2'
Drelsbach (1959)
WATER SOLUBILITY (md. m'3l
1.9 (-1)
Tevarl et al (1982)
1-hepcene
HENRY'S CONSTANT («m.m3 mot'1)
3.9 (-1)
1-heptene, calculated
SOLVENT SOLUBILITY Imoi. m'3)
PHYSICAL STATE
liquid
0. CLASSIFICATIONS
REACTIVITY: In VOLATILITY: m OVERALL: III
E. GENERAL COMMENTS
Other HepCenes (such ae 2-Heptene, 3-Heptene) are roughly Cwlce as reactive as
1-Heptene. Based on OH and 0^ reactivity depletion rates larger than 25Z/h are
possible for all Heptenes.
A-66
-------
Chemical Name: 1,6-Hexanedianine
Chemical Formula:
Chemical NO.: 62
CAS Registry NO.: 124-09-4
A. SMOG CHAMBER DATA
INITIAL CONC. IPPM1
MAX.O3
TOTAL
IRRADIATION
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE iVh)
NO- FORMA-
TION RATE
(PPB/Min)
REFERENCES
ORGANIC
CHEMICAL
IOC)
X
O
z
NOj/NO
CONC.
TIME
860
Merck (1976)
HENRY'S CONSTANT («m. m3 mol*1)
<1.9 (-7)
Calculated
SOLVENT SOLUBILITY fmol. m*3)
slightly soluble
Merck (1976)
alcohol, benzene
PHYSICAL STATE
solid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: I11
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
A-67
-------
Chemical Nam*: Hydrogen Cyanide Chemical NO.: 63
Chemical Formula: HCN (M.W.-27) CAS Registry NO.: 74-90-8
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.O3
TOTAL
IRRA0IAT10N
TIME (W
AVERAGE OC
OISAPPEARANCE
RATE (Vhl
NO-FORMA-
TION RAT*
(PPS/MIn)
REFERENCES
ORGANIC
CHEMICAL
iOC)
NOx
NOj/NO
CONC.
(PPM)
TIME
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (26*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm"® moMe ' 3"'
<1.0 (-15)
Phillips (1978)
» 0.0
°3
cm3 motoc'1 S*1
a'1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
REFERENCES
COMMENTS
VAPOR PRESSURE (am.)
9.7 (-1)
Drelabach (1961)
WATER SOLUBILITY (mot. m'3)
Inf.
Merck (1976)
HENRY'S CONSTANT (atm. m3 mot'1)
5.7 (-5)
calculated
SOLVENT SOLUBILITY (md. m"3]
Inf.
Merck (1976)
alcohol
PHYSICAL STATE
liquid
0. CLASSIFICATIONS
REACTIVITY: X VOLATILITY: III OVERALL: I
E. GENERAL COMMENTS
No snog chamber or laboratory kinetic data are available. The molecule appears
to be virtually unreactive in the troposphere.
A 68
-------
Chemical Nam*: Isodecyl alcohol
Chamical Formula: (CH3)2CH(CH2)6CH2OH (M.W.-158)
Chamical NO.: 64
CAS Registry NO.:
A. SMOG CHAMBER DATA
INITIAL CONC.tPPMl
MAX.03
TOTAL
IRRADIATION
TIMS (h)
AVERAGE OC
DISAPPEARANCE
RATE (Vh>
NO-FORMA-
TION RATE
(PPB/Mln»
REFERENCES
ORGANIC
CHEMICAL
(OC1
z
o
X
NO^NO
CONC.
(FPMI
TIME
(h»
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE IZfl'C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 molK'1 S 1
1.0 (-11)
Estimated
32.2
°3
cm3 moltc'1 S1
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2St)
REFERENCES
COMMENTS
VAPOR PRESSURE f«m.)
8.0 (-7)
Estimate
WATER SOLUBILITY (mal. m*3)
Insoluble
Merck (1976)
HENRY'S CONSTANT (»tm. m3 mol"1)
SOLVENT SOLUBILITY (met. m"3>
soluble
Merck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: Ttl VOLATILITY: II OVERALL: 11
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
A-69
-------
Chemical Nam*: Isoprene
Chemical Formula: HjCCHCCHj
(M.W.-68)
Chamical NO.: 65
CAS Ragistry NO.: 78-79-5
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.03
TOTAL
AVERAGE OC
NO,FORMA-
ORGANIC
CONC.
TIMS
1ARAOIATION
DISAPPEARANCE
TION RATE
REFERENCES
CHEMICAL
<0C)
nox
NO^/NO
|PPM»
(hi
TIME 1h>
RATE (Vhl
(PPB/MIn)
0.8
0.2
0.3
0.66
10-12
Jcfferlea ec al (1982)
0.2-13
>.33
0.0
0.06tc
6
50-100
Arnts eC al (1981)
0.6
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em3 molae'* S"1
9.3 (-11)
Kleindienat ec al
300.0
°3
em3 mofee'1 S'1
1.5 (-17)
(1982)
Arnts et al (1981)
fw
S*1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
FROMRTY VALUE
os'ci
REFERENCES
COMMENTS
VAPOR PRESSURE
7.5 C-l)
Jordan (1954)
WATER SOLUBILITY (mol. m'3)
9.2
Estimated
HENRY'S CONSTANT (nut. m3 mal 'l
8.1 (-2)
Calculated
SOLVENT SOLUBILITY (mol. m'3!
inf.
Merck (1976)
alcohol, ether
PHYSICAL STATE
liquid
0. CLASSIFICATIONS
REACTIVITY: 111 VOLATILITY: "I OVERALL: 111
E. GENERAL COMMENTS
Highly reactive and can produce significant ozone. Optimum OC/NO^ ratio la about
2. Identified products are formaldehyde, carbon monoxide, formic acid, methacrolein,
methyl vinyl ketone, carbon dioxide, peroxyacetyl nitrate and nitric add.
A-70
-------
Chemical Name: Isopropyl alcohol
Chemical Formula: (CH^CHOH (M.W.-60)
Chamical NO.: 66
67-63-0
CAS Registry NO.:
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
max.Oj
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vhl
NO.FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OCI
NOx
NO^NO
CONC.
IPPMI
TIME
(HI
4.0
0.2
0.32
8.6
3.3
Dimitrlades and Joehi (1977)
2.0
1.0
0.05
0.01
5
4.0
3.2
Yauagihara et al (1977)
1.0
0.6
0.05
lxtolu
sne
5
6.8
0.5xtoluene
Laity et al (1973)
4.0
2.0
0.0
0.09
6
6.3
Levy and Miller (1970)
1.0
>.13
0.17
0.11
7
5.0
Wilson and Doyle (1970)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
hp
em3 molae"1 S1
em3 moltc*' S"1
S"1
5.5 (-12)
Atkinson et al (1979
) 17.7
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
property VALUE
ras'ci
REFERENCES
COMMENTS
VAPOR PRESSURE («tm.)
5.8 (-2)
Jordan (1954)
WATER SOLUBILITY (mol. m"3)
inf.
Freier (1975)
20°C
HENRY'S CONSTANT («tm. m3 mol"')
3.5 (-6)
Calculated
SOLVENT SOLUBILITY (mol. m"3)
inf.
Merck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: HI OVERALL:
E. GENERAL COMMENTS
A-71
-------
Chemical Name: a-Propyl alcohol
Chemicd Formula: C3H7OH
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
I28*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (Mm.)
2.6 (-2)
Jordan (1954)
WATER SOLUBILITY (mol. m'3)
Inf.
Freler (1975)
20°C
HENRY'S CONSTANT (ran. m3 mol"')
1.6 (-6)
calculated
SOLVENT SOLUBILITY Imol. m'3!
Inf.
Merck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: VOLATILITY: "I OVERALL: 111
E. GENERAL COMMENTS
Considered reactive by analogy with lsopropyl alcohol.
A-72
-------
Chemical Nam*: Maleic anhydride Chemical NO.: 68
Chemical Formula: H£ ~ co^0 CAS Regiitry NO.: 108-31-6
" /
hc - ccr
A. SMOG CHAMBER DATA
INITIAL CONC.
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 rno(»c 1 S*1
6.0 (-11)
Estimated
193.6
°3
cm3 mol*'1 S"1
W
s-'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(58'C)
REFERENCES
COMMENTS
VAPOR PRESSURE (ttm.l
1.4(-4)
Jordan (1954)
WATER SOLUBILITY (mol. m'3)
inf.
Merck (1976)
reacts to maleic acid
HENRY'S CONSTANT («m. m3mor')
8.2 (-9)
calculated
SOLVENT SOLUBILITY (mol. «T3)
5100
5400
Merck (1976)
benzene
chloroform
PHYSICAL STATE
2400
solid
toluene
0. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: 111
E. GENERAL COMMENTS
So smog chamber or laboratory kinetic data are available.
A-73
-------
Chemical Nam*: Methanol
Chemical Formula: CH^OH (M.W.-32)
Chemical NO.: 69
CAS Registry NO.: 67-56-1
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX
03
TOTAL
IRRADIATION
TIME Ih)
AVERAGE OC
DISAPPEARANCE
RATE (VXt
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC!
z
o
X
NOj/NO
CONC.
(PPM)
TIME
IM
4.0
0.2
o.ii
0.20
10.8
Joshl et al (1982)
4.0
0.2
0.25
0.33
10-12
1.8xpropane
Sickles ec al (1980)
4.0
o.o;
0.75
0.75
10-12
1.3xpropane
Sickles ec al (1980)
4.0
0.2
0.25
i.2.3
1.3
Dlmitrlades and Joshl (1977)
2.0
1.0
0.05
0.0
5
0.0
1.4
Yanagihara ec al (1977)
5.0
3.0
0.0
5-10
Altshuller and Cohen (1963)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE 138%)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em' molac"1 S"'
1.1 (-12)
Atkinson et al.
3.5
°3
am' malce'1 S*1
(1979)
W
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
I2S*C>
REFERENCES
COMMENTS
VAPOR PRESSURE (Mm.)
1.6 (-1)
Jordan (1954)
WATER SOLUBILITY Imol. m'3!
inf.
Freler (1975)
20°C
HENRYS CONSTANT «tm. m3 mot')
9.5 (-6)
Atkinson ec al (1979)
calculated
SOLVENT SOLUBILITY Imol. m"3)
Inf.
Merck (1976)
ethanol, ether, benzene
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: in OVERALL: hi
E. GENERAL COMMENTS
A-74
-------
Chemical Nam*: Methyl chloride
Chemical Formula: CHjCl (M.W.-50.5)
Chemical NO.: 70
CAS Ragiftry NO.: 74-87"3
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
max.o3
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE
NO-FORMA-
TION RATE
(PPS/MIn)
REFERENCES
ORGANIC
CHEMICAL
(OC)
NOx
no2/no
CONC.
(PPM)
TIME
(h»
•
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2Sfc>
REFERENCES
OH rate const.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm^ mote*' 8*'
4.4 (-14)
Hajnpsoa (1980)
0.14
°3
cm3 moltc** S"1
S*1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
<2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (atm.)
5-7
Drelsbach (1959
WATER SOLUBILITY {mol. m*3}
107
Dllling (1977)
HENRY'S CONSTANT («tm. m3 mol*1)
9.4 (-3)
Maclcay and Shiu (1981)
SOLVENT SOLUBILITY (mol. m"3)
PHYSICAL STATE
gas
D. CLASSIFICATIONS
REACTIVITY: I VOLATILITY: III OVERALL: 1
E. GENERAL COMMENTS
Significantly less reactive than ethane.
A-75
-------
Chemical Name: Methylene chloride
Chemical Formula: CH^Clj (M.W.-85)
Chemical NO.: 71
CAS Registry NO.: 75-09-2
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX. Oj
TOTAL
IRRADIATION
TIMS (hi
AVERAGE OC
DISAPPEARANCE
RATE (VKI
NO.FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOj/NO
CONC.
(PPMI
TIME
(hi
4.0
D.07
0.25
0.1
10-12
0.6xpropane
Sickles et al (1980)
4.0
0.2
0.03
1.8
5.7
Dimitriades and Joshi (1977,
2.0
L.O
0.05
0.0
5
1.9
1.4
Yanagihara et al (1977)
1.0
3.1
2.0
0.06
7
5.5
Uilaon and Doyle (1970)
B. KINETIC DATA
REACTION
WITH
UNITS
RATS CONSTANT
VALUE os'ci
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANe
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em3 mone"' S'1
1.6 (-13)
Hanspson (1980)
0.5
°3
on3 n»He"' S'1
hl>
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
rb'ci
REFERENCES
COMMENTS
VAPOR PRESSURE latm.l
5.7 (-1)
Dreisbach (1959)
WATER SOLUBILITY M. m"3)
200
Verschueren (1977)
HENRY'S CONSTANT («tm. m3 mol"1)
2.9 (-3)
Mackay and Shiu (1981)
SOLVENT SOLUBILITY (mol. m'3)
inf.
Merck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: I VOLATILITY: HI OVERALL: 1
E. GENERAL COMMENTS
the reactivity of Methylene chloride is leas than ethane. Billing et al (19761 show
loss of 5Z In 21 h irradiation. The high loa» rata in the results of Wilson and
Doyle (1970) is explicable as an uncontrolled dilution rate. However, the data of
Dimitriades and Joshi (1977) cannot be explained. Sickles et al (1980) Oj levels are
indistinguishable from background.
A-76
-------
Chemical Nam*: Methyl ethyl ketone
Chemical Formula: Cn^COC^^ (M.V.-72)
Chemical NO.: 72
CAS Registry NO.: 78-93-3
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX
•°3
TOTAL
IRRADIATION
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE (Vhl
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OC)
nox
NOj/NO
If
TIME
(hi
1.5
3.18
0.38
0.55
10-12
Jefferies et al (1982)
4.0
3.2
0.3
8.3
1.5
D1m1triade3 and Joshi (1977)
2.0
L.O
0.05
0.01
5
2.2
2.1
Yanaglhara et al (1977)
1.0
3.6
0.05
0.9xtc
Luene
5
2.4
0.6xtoluene
Laity et al (1973)
4.0
2.0
0.0
0.28
6
9.4
Levy and Miller (1970)
1.0
3.15
3.7
0.12
7
5.5
Wilson and Doyle (1970)
4.0
L.O
0.1
0.32
4.0
6
11.4
Brunelle et al (1966)
8.0
2.0
0.1
0.23
6.0
6
9.4
Brunelle et al (1966)
3.0
L.O
>20
0.0
3
Schuck and Doyle (1959)
8. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S'C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em' moiac*' S1
3.4 C—12)
Atkinson et al (1979)
10.9
°3
em'moUe"1 S"'
w
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
I3S*C>
REFERENCES
COMMENTS
VAPOR PRESSURE <«on.l
WATER SOLUBILITY (mol.
HENRY'S CONSTANT l«tm. m3 moT1)
SOLVENT SOLUBILITY {mol. m3)
PHYSICAL STATE
1.2 (-1)
3600
3.5 (-5)
inf.
liquid
Jordan (1954)
Morrison and Boyd (1973)
Merck (1976)
Calculated
alcohol, echer, benzene
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: "I
E. GENERAL COMMENTS
Highly effective in NO-^NOj conversion (Cox et al, 1980).
A-77
-------
Chemical Nam*: Methyl isobutyl ketone
Chemical Formula: (CH3)3CCOCH3 (M.W.-100)
Chemical NO.: 73
CAS Registry NO.: 103-10-1
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. Oj
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATH (Vhl
NO,FORMA-
TION RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
IOC)
X
o
z
NOj/NO
CONC.
IPPMI
TIME
(hi
2.0
1.0
0.05
0.26
5
5.0
7.2
Yaoaglhara et al (1977)
1.0
0.6
0.05
1.4xto
Luene
5
4.8
1.7xtoluene
Laity et al (1973)
4.0
2.0
0.0
0.45
6
17.2
Levy and Millar (1970)
1.0
0.2
2.4
0.15
7
8.0
Wllaon and Doyle (1970)
3.0
2.0
0.02
0.5
6
8.3
Brunelle at al (1966)
B. KINETIC DATA
REACTION
WITH
UNITS
RATI CONSTANT
VALUE (28"CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
HP
cm^ S ^
3 -t -1
cm motac S
s-'
1.4 (-11)
Atkinson et al (1979
) 45.2
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
(25 *C)
REFERENCES
COMMENTS
VAPOR PRESSURE latm.l
3.9 (-2)
Weast (1973)
WATER SOLUBILITY M. m'3)
190
Morrison and Boyd (1973)
HENRY'S CONSTANT («m. m3 mol"')
2.0 (-4)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
Inf.
Merck (1976)
alcohol, benzene, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: HI VOLATILITY: HI OVERALL: 111
E. GENERAL COMMENTS
A-73
-------
Chtmical Nam*: Methyl methacrylate
Chwnicai NO.:
74
Chemical Formula: CH^C-COOCH^ CM.W.-100)
CAS Registry NO.:
80-62-6
CH-
A. SMOG CHAMBER DATA
INITIAL CONC.IPPMI
MAX. O3
total
IRRAOIATION
TIME Iht
AVERAGE OC
OISAPPEARANCE
RATE (*/h)
NO,FORMA-
TION RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
(PPMI
TIME
(hi
4.0
4.0
2.0
0.2
0.11
0.11
0.73
0.20
4.4
1.4
Joshi et al (1982)
Joshi et al (1982)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE IJS'CI
INFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em' md»e"1 S'1
5.0 C-ll)
Estimated
161.2
°3
an® moke1 S"1
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITSI
PROPERTY VALUE
(26 °C)
REFERENCES
COMMENTS
VAPOR PRESSURE (mm.)
5.1 (-2)
Jordan (1954)
WATER SOLUBILITY (mol. m"3!
18.9
Estimated
HENRY'S CONSTANT l«m. m3 mol'')
2.7 (-3)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: "I VOLATILITY: 111 OVERALL: 111
E. GENERAL COMMENTS
A-79
-------
Chemical Nam*: Solvent naphtha Chemical NO.: 75
Chemical Formula: Mixture of C^-Cjg aliphatics CAS Registry NO.: 8030-30-6
A. SMOG CHAMBER DATA
INITIAL CONC-
PPM)
MAX. Oj
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (VM
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
organic
CHEMICAL
(OC)
2
O
X
NOj/NO
CONC.
(PPM)
TIME
IK)
4.0*
2.0
0.0
0.53
9.0
16.5
3.6
Brunelle et al (1966)
4.0**
2.0
0.0
0.58
7.0
16.5
7.9
Brunelle et al (1966)
4.0*
2.0
0.0
0.53
9.0
16.5
4.3
Brunelle et al (1966)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE iji'd
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
hv
cm^ molac"' S"1
cm^ S"1
s"1
H
1
O
H
Estimated
» 32
Reactivity as-
sumed to be In
the C8-C1Q
alkane range
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
I39*C)
REFERENCES
COMMENTS
VAPOR PRESSURE latin.)
4.6 (-2)
Estiaaced
WATER SOLUSILITV {mot. m'3)
HENRVS CONSTANT latm. m3 mol ')
SOLVENT SOLUBILITY imol. m'3!
PHYSICAL STATE
liquid
O. CLASSIFICATIONS
REACTIVITY: m VOLATILITY: m OVERALL: in
E. GENERAL COMMENTS
Reactive aliphatic solvent mixture
it &A V
VM and P Naptha; Mineral Spirits; Eastern Stoddard solvent
A-80
-------
Chemical Nairn: Naphthalene
Chemical Formula: ciqH3 (M.W.-128)
Chemical NO.: 76
CAS Registry NO.: 91-20-3
A. SMOG CHAMBER OATA
INITIAL CONC. (PPMI
MAX. O3
TOTAL
IRRADIATION
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE (W/M
NO„FORMA-
TION RATE
(PP8/Min)
REFERENCES
ORGANIC
CHEMICAL
(OC)
NOx
NOj/NO
CONC.
(PPMI
TIME
(hi
0.4
0.97
0.0
4
Splcer et al (1974)
B. KINETIC OATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE <29*C>
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 mol^e'1 S"1
1.6 (-11)
Estimated
51.6
°3
«m3 motoe'1 s"1
M>
s-'
d. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
128 *C)
REFERENCES
COMMENTS
VAPOR PRESSURE <«m.)
2.8 (-4)
Dreisbach (1955)
WATER SOLUBILITY Imol. m'3)
3.1 (-1)
Dreisbach (1955)
HENRY'S CONSTANT («m. m3 mol'1l
SOLVENT SOLUBILITY Imol. m"1)
PHYSICAL STATE
4.3 (-4)
5400
5130
940
solid
Maclcay and Shiu (1981)
Dreisbach (1955)
acetone
benzene
ethanol
D. CLASSIFICATIONS
REACTIVITY: II VOLATILITY: III OVERALL: "
E. GENERAL COMMENTS
A free radical scavenger. Although highly reactive, It Is unable to form significant
ozone. High OC/NOjj irradiations have not been performed. Leads to significant
aerosol formation (Splcer et al, 1974).
A-81
-------
Ctofnicsl Nimi: Nitrobenzene
Chemical Formula: C^HjNOj (M.W.-123)
Chemical NO.: 77
CAS Registry NO.: 98-95-3
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM!
MAX. O3
TOTAL
AVERAGE OC
NO,FORMA-
ORGANIC
CONC.
TIME
IRRADIATION
DISAPPEARANCE
TION RATE
REFERENCES
CHEMICAL
IOC)
nox
NOj/NO
(PPMI
(hi
TIME (hi
RATE (%/hl
(PPB/Mlnl
4.0
0.2
0.25
0.01
10-12
Sickles et al (1980)
4.0
1.067
0.25
0.02
10-12
Sickles et al (1980)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
IU>
am3 S"1
cm3 moke1 S"'
2.1 (-13)
Zeczsch (1983)
0.7
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2S*CI
REFERENCES
COMMENTS
VAPOR PRESSURE lim.l
3.7 (-4)
Dreisbach (1955)
WATER SOLUBILITY (mol m'3)
16
Merck (1976)
HENRY'S CONSTANT Inm. m3 mol'1)
2.3 (-5)
Calculated
SOLVENT SOLUBILITY (mat. m"3)
PHYSICAL STATE
liquid
0. CLASSIFICATIONS
REACTIVITY: I VOLATILITY: III OVERALL: I
E. GENERAL COMMENTS
Also a snog inhibitor (Gitchell et al, 1974a).
A-82
-------
Chemical Nam*: n-Octyl-n-decyl phthalate Chemical NO.: 78
Chemical Formula: COCKCH^gCH^ (M.W.-418) CAS Registry NO.: 1-323-73-5
COO(CH2)7CH3
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IRRAOIATION
TIME (h)
AVERAGE OC
DISAPPEARANCE
RATE |*/hl
NO.forma-
tion RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NCyNO
CONC.
(PPM)
TIME
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (3S'C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 motoc'1 S'1
1.7 C-ID
Estimated
54.8
Not strictly
amenable to
cm3 mo**"1 S'1
estimate
hf
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2S*C)
REFERENCES
COMMENTS
i
.
VAPOR PRESSURE (atm.)
WATER SOLUBILITY Imol. m'3)
9.1 (-9)
Estimated from boiling
point data
HENRY'S CONSTANT (Mm. m3 moi'1)
SOLVENT SOLUBILITY (mot. m*3)
PHYSICAL STATE
D. CLASSIFICATIONS
REACTIVITY: HI VOLATILITY: I OVERALL: 1
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
A-83
-------
Chemical Nam: Nonyl phenol (ethoxylated) Chemical NO.:
79
Chemical Formula: (M.W.-248) CAS Registry NO.:
9H19
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM1
MAX.O3
TOTAL
IRRAOIATION
TIME
AVERAGE OC
DISAPPEARANCE
RATE IVh)
NO-FORMA-
TION RATE
IPPB/Mln)
REFERENCES
ORGANIC
CHEMICAL
(OCJ
NOx
NOj/NO
CONC.
(PPM1
T1MC
(W
B. KINETIC DATA
REACTION
WITH
UNITS
RATI CONSTANT
VALUE I2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em' S"1
4.7 C-U)
Estimated
151.6
O
u
em' motoe'1 S'1
S-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
(28'C)
REFERENCES
COMMENTS
VAPOR PRESSURE (ran.)
WATER SOLUBILITY (mol. m"3)
No estimate* possible
HENRY'S CONSTANT Utm. m3 mol'1)
SOLVENT SOLUBILITY (mol. m'3)
PHYSICAL STATE
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: II OVERALL: II
E. GENERAL COMMENTS
A-84
-------
Chemical Nam*: Perchloroethylene
Chemical Formula: c2Cl4 (M.W.-166)
Chemical NO.: 80
CAS Registry NO.: 127-18-4
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IRRADIATION
TIME (HI
AVERAGE OC
DISAPPEARANCE
RATE (%/h)
NO,FORMA-
Tlbnl RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
(OC)
NOx
NOj/NO
CONC.
ippmi
TIME
Ihl
4.0
0.2
0.25
0.54
10-12
L.2xpropane
Sickles et al (1980)
4.0
0.07
0.25
1.19
10-12
L. 6xpropane
Sickles et al (1980)
4.0
0.2
0.49
1.8
12.8
Dlmltrlades and Joshl (1977)
2.0
1.0
0.05
0.0
5
0.2
1.9
Yanagihara et al (1977)
5.0
1.77
0.07
4.5
2.0
Gay et al (1976)
0.85
0.48
0.5
7.0
9
12.5
Lillian et al (1975)
6.4
2.0
0.02
0.0
7
6.0
Brunelle et al (1966)
3.0
1.0
0.05
6
Schuck and Doyle (1959)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 motac'' S"'
1.7 C-13)
Bampson (1980)
0.5
°3
cm3 mot*"1 S'1
s"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
I3S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (*1111.)
2.4 (-2)
Dralsbach (1959)
WATER SOLUBILITY Imol. m"3)
9.0 (-1)
Verschueren (1977)
HENRY'S CONSTANT (Mm. m3 md'1)
2.7 (-2)
Calculated
SOLVENT SOLUBILITY Imol. m'3)
inf.
Kerck (1976)
alcohol, ether, benzene
PHYSICAL STATE
liquid
0. CLASSIFICATIONS
REACTIVITY: H VOLATILITY: III OVERALL: II
E. GENERAL COMMENTS
Because of CI atom initiated oxidation of C^Cl^; somg chambers do not simulate the
atmosphere. In the absence of CI radicals, OH reactivity is dominant but too slow.
These findings have recently been reviewed by Dlmltrlades et al (1983). Smog
chamber reaction products are trichloroacetyl chloride, phosgene, hydrochloric acid,
carbon monoxide, and formic acid.
A-85
-------
Chemical Nam*: Phenol
Chamiol Formula: CgHjOH (M.tf."94)
Chemical NO.: 81
CAS Ragistiy NO.: 10&"95_2
A. SMOG CHAMBER DATA
INITIAL CONC.(PPM)
MAX. 03
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
OISAPPCARANCE
RATE IVW
NO, forma-
tion RATS
im/Mini
rcfercnces
ORGANIC
CHEMICAL
IOC)
nox
no7n*o
CONC.
Ml
TIME
(hi
4.0
4.0
0.2
0.07
0.25
0.25
0.03
0.05
10-12
10-12
).3zpropane
Sickles et al (1980)
Sickles et al (1980)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE Qg'C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
an3 motac"^ S ^
2.8 (-U)
Gusten et al (1981)
90.3
*°3
aw3 molt'1 S"'
2.0 (-12)
Carter et al (1981)
h*
s'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
as'o
REFERENCES
COMMENTS
VAPOR PRESSURE Inn.)
7.0 (-4)
Dreisbach (1955)
WATER SOLUBILITY (mat. m'3)
870
Drelsbach (1955)
HENRY'S CONSTANT (Mm. m3 mol"')
8.0 (-7)
Calculated
SOLVENT SOLUBILITY (mol. m"3)
very soluble
Merck (1976)
alcohol, ether
PHYSICAL STATE
solid
0. CLASSIFICATIONS
REACTIVITY: " VOLATILITY: HI OVERALL: 11
E. GENERAL COMMENTS
Although highly reactive, no evidence of 0. formation Is seen. Phenol Is a
known smog Inhibitor and provides an efficient sink for N0X (Gltchell et ml, 1974).
At night rapid removal could occur by reaction with NO3 radicals (Carter et al, 1981).
A-86
-------
Chemical Nam*: Phosgene
Chemical Formula: COCl^ (M.W.-99)
A. SMOG CHAMBER DATA
Chemical NO.: 82
CAS Registry NO.: 75-44-5
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vh»
NO-FORMA-
TION RATE
IPPB/Min)
REFERENCES
ORGANIC
CHEMICAL
(OC)
NOx
SOj/NO
CONC.
IWMI
TIME
fh)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
en*3 motac'1 S'1
<1.0 c-w
Estimated
<0.03
°3
cm3 molte*1 S'1
htf
S*1
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
<2S*C>
REFERENCES
COMMENTS
VAPOR PRESSURE Utm.)
WATER SOLUBILITY (mol. m"3)
1.9
. decomposes
Drelsbach (1961)
Verschueren (1977)
HENRY'S CONSTANT («tfn. m3 mol'1)
SOLVENT SOLUBILITY (mot. m*3)
PHYSICAL STATE
gas
D. CLASSIFICATIONS
REACTIVITY: I VOLATILITY: III OVERALL: I
E. GENERAL COMMENTS
Formed aa a by-product of chloroethylene oxidation (Gay et al, 1976). Shows no
perceptible reactivity in smog chambers over a 24 h period (Singh, 1976).
Most likely removal process is slow liquid phase hydrolysis. No laboratory
kinetic or smog chamber data are available.
A-87
-------
Chamical Formula: /\3 ^ (M.H.-148) CAS Ra«i«try NO.: 85-44-9
Chamical Nama: Phthalic anhydride Chamical NO.: 83
o
o
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX. O3
TOTAL
irradiation
TIME (hi
average oc
DISAPPEARANCE
RATE IVhl
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NO„
NOj/NO
CONC.
(PPMI
TIME
(n»
B. KINETIC OATA
reaction
WITH
UNITS
RATE CONSTANT
VALUE as'ci
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 S '
1.2 (-11)
Estimated
38.7
°3
on' motae"1 S"'
M>
S"'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
I3S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE lam.l
6.8 (-7)
Jordan (1954)
WATER SOLUBILITY (mol. m"3)
42
Freier (1975)
Hydrolyzes to acid
HENRY'S CONSTANT <«tm, m3 mol"')
1.6 C-8)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
PHYSICAL STATE
solid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: IX OVERALL: II
E. GENERAL COMMENTS
No laboratory of smog chamber data are available*
A-88
-------
Chemical Nam*: propane Chemical NO.: 84
Chemical Formula: C^Hg (M.W.-44) CAS Registry NO.: 74-98-6
A. SMOG CHAMBER DATA
INITIAL CONC. IPPMI
MAX. Os
TOTAL
IRRAOIATION
TIME
AVERAGE OC
DISAPPEARANCE
RATE (%/hl
NO,FORMA-
TION RATE
(PPS/Mlnl
REFERENCES
ORGANIC
CHEMICAL.
IOC)
NOx
NOj/NO
CONC.
(PPM)
TIMS
th>
4.0
0.2
11
3.17
9.8
Joshi et al (1982)
4.0
2.0
0.25
J-0.48
10-12
Sickles et al (1980)*
to
0.0
4.0
0.2
0.08
3.6
2.0
Disnitrlades and Joshi (1977)
2.0
1.0
0.05
0.03
5.0
5
4.1
3.3
Yanagihara et al (1977)
7.8
0.2
0.0
0.15
10
0.9
Zfonte and Bonamassa (1977)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
value ast)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 mol«c'1 J"1
1.9 (-12)
Atkinson at al (1979
1 6.2
°3
cm' mol«c"1 s"'
hv
S"'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(»*C)
REFERENCES
COMMENTS
VAPOR PRESSURE Urn.)
9.3
Drelsbach (1959)
WATER SOLUBILITY (mol. n"3)
1.4
McAuliffe (1966)
HENRY'S CONSTANT (Mm. m3 mol"1)
7.1 (-1)
Mackay and Shiu (1981)
SOLVENT SOLUBILITY (mol. m"3)
6400
Hayduk (1972)
hexane
PHYSICAL STATE
gas
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: HI OVERALL: 111
E. GENERAL COMMENTS
Like other alkanes, propane/NOx ratio ia critical towarda efficient oxidant formation.
OC/NOx ratio of 40-80 appears to be optimal. The stoichiometry for NO -*N02 conversion
is comparable to that of propene after OH attack (Cox et al, 1980; Singh et al, 1981).
A-89
-------
Chemical Nam*: Propylene
Chemical Formula: C^Hg (M.W.-42)
Chemical NO.:
CAS Ragtrtry NO.:
1X5-07-1
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
max. a3
TOTAL
AVERAGE OC
NO. FORMA-
TION RATE
(PPS/Mlnl
ORGANIC
CHEMICAL
(OCI
nox
HOj/UO
CONC.
IPPMI
TIMS
(hi
IRRADIATION
TIME 20
0.68
1.3
3
43.0
Schuck and Doyle (1959)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (29*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 motoc"' S*1
2.5 C-ll)
Atkinson et al (1979
80.6
°3
em' motpo"1 S"'
1.0 (-17)
Niki (1979)
ho
«r»
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
(2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (ran.!
11.4
Zwolinskl and Wilhoit(1971
WATER SOLUBILITY (mot. m'3!
4.8
McAuliffe (1966)
HENRY'S CONSTANT («m. m3 W1)
2.1 (-1)
Mackay and Shiu (1981)
SOLVENT SOLUBILITY Imol. m"3)
PHYSICAL STATE
gas
0. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: III
E. GENERAL COMMENTS
One of the most extensively studied and modeled OC/NO system (Altahuller and Bufalini,
1971; Finlayson and Pitta, 1976; Nilci, 1979; Akiaoto et al, 1979). Products include
formaldehyde, acetaldehyde, formic acid, PAN, nitric acid, propylene oxide, propional-
dehyde, methyl, ethyl and i-propyl nitrates; propeneglycol dinitrate and diacetyl acetone.
A-90
-------
Chemical Nam*: Propylene glycol
Chemical Formula: CH^CHOHCI^OH (M.W.-76)
Chemical NO.: 86
CAS R«gi»try NO.: 57"55-6
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE
-------
Chemical Nam*:
Chemical Formula:
Propylene oxide
H3CHC -CH2 (M.W.-58)
Chemical NO.: 87
CAS Registry NO.: 75-56-9
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. 03
TOTAL
IRRADIATION
T1MC (hi
AVERAGE OC
0I8APPCARANCE
RATE (%/h)
NO-FORMA-
TION RATE
(PPB/MIn)
REFERENCES
ORGANIC
CHEMICAL
IOC>
NOx
NO^/NO
CONC.
(PPM)
TIME
(M
B. KINETIC DATA
REACTION
WITH
UNITS
RATH CONSTANT
VALUE I2S*CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
zoo
* w I
cm3 melK^ 51
on' molK ' S"'
s-'
1.3 (-12)
Atlcinson ec al (1979
i 4.2
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
aa'a
REFERENCES
COMMENTS
VAPOR PRESSURE Iran.)
6.7 (-1)
Jordan (1954)
WATER SOLUBILITY (moi. m'3)
9100
Verschueren (1977)
HENRY'S CONSTANT (tun. m3 mo)'1)
7.4 (-5)
Calculated
SOLVENT SOLUBILITY (mol. m"3)
Inf.
Merck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: II VOLATILITY: III OVERALL: II
E. GENERAL COMMENTS
A-92
-------
Chemical Nam*: Styrene
Chemical Formula: CgH^CH-CHj (M.W.-104)
A. SMOG CHAMBER DATA
Chemical NO.: 88
CAS Registry NO.: 100-42-5
INITIAL CONC. (PPM)
MAx.03
TOTAL
AVERAGE OC
NO,FORMA-
TION RATE
(PPS/Mlnl
ORGANIC
CHEMICAL
IOC)
nox
NOjJNO
CONC.
(PPM)
TIME
(hi
IRRADIATION
TIME (h)
DISAPPEARANCE
RATE (%/hl
REFERENCES
2.0
1.0
0.05
0.18
5.0
5
18.0
6.1
Yanagihara at al (1977)
4.0
2.0
0.0
0.31
5.6
6
10.5
Levy and Miller (1970)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 moW1 S'1
3.2 (-11)
Estimated
103.2
em' mol*'1 S1
3.0 (-17)
NAS (1976)
hf
s-'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
iw'ci
REFERENCES
COMMENTS
VAPOR PRESSURE Htm.]
8.0 (-3)
Orelsbach (1955)
WATER SOLUBILITY (mol. m'3)
1.5
Banerjee et al (1980)
HENRY'S CONSTANT («tm. m3 mol ')
5.2 (-3)
Calculated
SOLVENT SOLUBILITY (mol. m"3)
PHYSICAL STATE
liquid
O. CLASSIFICATIONS
REACTIVITY: HI VOLATILITY: III OVERALL: III
E. GENERAL COMMENTS
Reacts Co form products with high-eye Irritation index. Major product likely to be
PBzN.
A-93
-------
Chemical Name: Terephthallc acid Chemical NO.: 89
Chemical Formula: COOH CAS Registry NO.: ioo-21-O
f > (M.W.-166)
^»/(X)OH
A. SMOG CHAMBER DATA
INITIAL CONC. IWII
MAX.03
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE fVh)
NO,forma-
tion RATI
(FTB/MW
REFERENCES
ORGANIC
CHEMICAL
(OC)
NOx
NOj/NO
CONC.
TIME
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
HATE CONSTANT
VALUE QS%)
REFERENCES
OH RAT* CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
cm3 nNho'1 S*'
3 * *1 *'1
iTWC )
8.0 C-12)
Estimated
25.8
Not strictly
amenable to
estimation
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALue
aCa
REFERENCES
COMMENTS
VAPOR PRESSURE linnj
8.8 (-«)
Jordan (1954)
WATER SOLUBILITY (mot. m"3)
9.6 (-2)
Verschueren (1977)
HENRY'S CONSTANT {Km. m3 mol'1)
9.1 (-5)
Calculated
SOLVENT SOLUBILITY M.m<3|
PHYSICAL STATE
solid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: in OVERALL: III
E. GENERAL COMMENTS
Ho smog chamber or laboratory kinetic data are available.
A-94
-------
Chemical Nam*: Terephthalic acid (dimethyl ester) Chemical NO.: 90
Chemical Formula: ^C00CH3 CAS Registry NO.: 120-6I-6
(M.W.-194)
COOCH,
A. SMOG CHAMBER DATA
coo
Q
coo
INITIAL CONC. (PPMI
MAX. O3
TOTAL
IRRADIATION
TIME m»
AVERAGE OC
disappearance
RATE (Vh|
no2 forma-
tion RATE
(PP8/Mln|
REFERENCES
ORGANIC
CHEMICAL
(OCl
N0X
NOj/NO
CONC.
(PPM)
TIME
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (39%)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
hC
cm3 molae'1 S'1
cm^ motac'1 S*1
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(28*C)
REFERENCES
COMMENTS
VAPOR PRESSURE
WATER SOLUBILITY (mo*, m'3)
HENRY'S CONSTANT («tm. m3 mol*1)
SOLVENT SOLUBILITY (mol. m*3)
PHYSICAL STATE
0. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: "X
E. GENERAL COMMENTS
This Is just another name of chemical No. 37 (Dimethyl terephthalate). It Is,
therefore, omitted from our list of chemicals.
A-95
-------
Chemical Nan*: Tetrapropylene
OMmkai Formula: C12H2/, (M.W.-168)
Chemical NO.: 91
CAS Registry NO.:
A. SMOG CHAMBER DATA
INITIAL CONC. (WMI
MAX. 03
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE WW
NO, FORMA-
TION RATE
(PPWMM
REFERENCES
ORGANIC
CHEMICAL
(OC)
"°x
NOyNO
CONC.
(PPM)
TIMS
(M
a KINETIC DATA
REACTION
WITH
UNITS
RATS CONSTANT
VALUE I29*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
-3
cm nwwc •
3.7 C-ll)
Estimated
19.4
°3
em3 moUe'1 s'1
SV
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2«"C)
REFERENCES
COMMENTS
VAPOR PRESSURE
WATER SOLUBILITY Imol. m"3)
HENRY'S CONSTANT (ion. in3 mof'l
SOLVENT SOLUBILITY M. m"3)
PHYSICAL STATE
4.6 C-4)
liquid
Estimated from boiling
point data
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: m OVERALL: m
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
A-96
-------
Chemical Name: Toluene
Chemical Formula: CgHjCH^ (M.W.-92)
Chemical NO.: ^2
CAS Registry NO.: 108-88-3
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.O3
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vhl
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOCI
NO*
NOj/NO
CONC.
IPWI
TIMS
(hi
2.2
0.34
0.25
0.40
10-12
Jefferies et al (1982)
1.1
0.49
0.3
6.0
6
8.3
2.4
Hendry (1979)
2.0
1.0
0.05
0.25
5.0
5
8.0
5.0
Yanaglhara et al (1977)
1.0
0.5
0.11
0.36
6
4.4
Pfmttriadea et al (1975)
4.0
2.0
0.0
0.44
3.3
6
L0.4
Levy and Miller (1970)
1.0
0.16
0.6
0.10
7
6.0
Wilson and Doyle (1970)
8.0
2.0
0.05
0.27
4.0
6
Bruaelle et al (1966)
5.0
3.0
0.0
0.56
3.0
3
L5.0
Altshuller and Cohen (1963)
1.9
0.1
0.0
0.36
3.0
3
12.3
Altshuller and Cohen (1963)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C>
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em' matec"' S"'
5.8 (-12)
Atkinson et al (1979
18.7
°3
cm3 metoc'1 S"1
1.5 (-22)
HAS (1976)
hi>
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE 1 Mm.)
3.7 (-2)
Zwollnakl and Wllholt(197i;
WATER SOLUBILITY (mol.m'3)
5.6
McAuliffe (1966)
HENRY'S CONSTANT («tm. m3 moT1)
6.7 (-3)
Maclcay and Shlu (1981)
SOLVENT SOLUBILITY M. m"3)
inf.
Merck (1976)
alcohol, acetone, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: III
E. GENERAL COMMENTS
Kinetics of che photoxidacion of Coluena have been studied extensively (Hendry, 1979;
O'Brien et al, 1979). A number of smog chamber runs summarized by O'Brien ec al (1979)
clearly show significant ozone and FAN formation for all toluene initial concentrations
exceeding 1 ppm. Identified products are carbon monoxide, formaldehyde, acetaldehyde,
peroxyacetyl nitrate, benzaldehyde, cresols, unsat. bl-functlonal aliphatic prouducts,
dlcarbonyls and nltrotoluenea.
A-97
-------
ChamM Nana: Toluene Dllsocyanate Chemicad NO.: 93
CH,
Qmial Formula: /\ J „ . ,,, CAS Registry NO.:
(M.W.-174)
^S-OO
A. SMOG CHAMBER DATA
INITIAL CONC. imm
MAX
•03
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (S/N
HO. FORMA—
TICM RATE
IPPe/MW
REFERENCES
ORGANIC
CHEMICAL
(OC1
NOx
NOj/MO
CONC.
(mm
TIME
(IU
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE a*t\
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
IM>
on3 mote*' S'1
em1 iimIbi* s"'
s'
1.0 C-ll)
Estimated
32.2
Not strictly
•¦•liable to
estimation
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
as'o
REFERENCES
COMMENTS
VAPOR PRESSURE (nmj
5.1 (-5)
Estimated (2,4 Isomer)
WATER SOLUBILITY (mot. m"3)
reacts
Merck (1976)
2,4 - isomer
HENRY'S CONSTANT (am. m3 moT1)
SOLVENT SOLUBILITY (mol. m-3)
inf.
Merck (1976)
•ther, acetone, benzene
PHYSICAL STATE
liquid
0. CLASSIFICATIONS
REACTIVITY: m VOLATILITY: m OVERALL: hi
E. GENERAL COMMENTS
This chemical may play a chain terminating role, typical of smog Inhibitors.
A-98
-------
Chemical Nam: 1,1,1 Trlchloroethane
Chemical Formula: CH-jCCl^ (M.W.-133.5)
Chamical NO.: 94
CAS Registry NO.: 71-55-6
A. SMOG CHAMBER DATA
INITIAL CONC. IPPMI
max. Oa
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATS (*/h|
NO,FORMA-
TION SATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OC>
NOx
NOy'NO
CONC.
(PPMI
T1MC
(hi
4.0
0.02
0.2
0.5
0.0
0.0
4.6
19
0.1
0.0
Dimltriadea and Joshi (1977)
Lillian et al (1975)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (3S'C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em® S"1
1.2 (-14)
Hanpson (1980)
0.04
°3
era® motae' S"'
hi>
S'1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(28*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (nm.l
1.6 (-1)
Drelsbach (1959)
WATER SOLUBILITY (mol. m"3)
5.4
Dilllng (1977)
HENRY'S CONSTANT Iran, m3 mot'1)
3.0 C-2)
Mackay and Shlu (1981)
SOLVENT SOLUBILITY (mol. m"3)
soluble
Merck (.1976)
acetone, benzene, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: I VOLATILITY: HI OVERALL: I
E. GENERAL COMMENTS
Signltlcantly less reactive than ethane.
A-99
-------
Chemical Nam*: Trichloroethylene
Chemical Fonnuia: CjHCl-j (M.W.-131.5)
Chemical NO.: 95
CAS Registry NO.: 79-01-6
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IRRAOIATION
TIME (HI
AVERAGE OC
DISAPPEARANCE
RATE
NO,FORMA-
TlON RATE
(PPO/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
nox
NOj/NO
CONC.
(PPM)
TIME
(M
2.0
1.0
0.05
0.11
5.0
5
9.4
5.4
Yanaglhara et al (1977)
3.4
1.3
>20
0.24
l.S
3.3
29.0
Gay et al (1976)
1.0
0.7
>20
0.70
3.0
24
7.0
-70.0
Appleby (1976)
4.0
1.0
0.02
0.51
6.0
16.5
10. J
Brunelle et al (1966)
4.0
2.0
0.02
0.50
11.5
16.5
14.0
Brunelle et al (1966)
3.0
1.0
>20
0.0
6
-
Schuck and Doule (1959)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE QS'C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
mote*1 S"1
2.2 (-12)
Atkinson et al (1979)
7.1
°3
—3 ¦ - e't
vn nmns 9
s"'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
o»*c>
REFERENCES
COMMENTS
VAPOR PRESSURE (MmJ
9.8 (-2)
Dreisbach (1959)
WATER SOLUBILITY (mol. m"3)
8.4
Verschueren (1977)
HENRY'S CONSTANT turn. m3 mof')
1.2 (-2)
Calculated
SOLVENT SOLUBILITY (mol.m-3)
inf.
Merck (1976)
ether, alcohol
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: m VOLATILITY: m OVERALL: m
E. GENERAL COMMENTS
Some CI atom Interactions may occur In snog chamber data. However, this chemical is
sufficiently reactive with OH radicals to lead to ozone formation. Measured products
in snog chambers are dichloroacetyl chloride, phosgene, hydrogenchlorlde, nitric acid,
formic acid and carbon monoxide.
A-100
-------
Chemical Name: methylene glycol.
Chemical Formula: (CH20HCH20CH2)2 (M.W.-150)
Chemical NO.: 96
CAS Registry NO.: 112-27-6
A. SMOG CHAMBER DATA
INITIAL CONC. IPPM)
MAX.O3
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATS (*/hl
NO,FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
IMOj/NO
CONC.
ippmi
TIME
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (2S*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
. RATI CONSTANT
ESTIMATION
OH
am' morte'1 S'1
2.7 C-U)
Estimated
87.0
°3
am3 mo Ik"1 S'1
hf
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
ta'ci
REFERENCES
COMMENTS
VAPOR PRESSURE IrmJ
1.7 (-6)
Jordan (1954)
WATER SOLUBILITY (mol. m'3)
Inf.
Freler (1975)
20°C
HENRY'S CONSTANT («m. m3 mol"1)
1.0 (-10)
Calculated
SOLVENT SOLUBILITY (mol. m'3)
Inf.
Merck (1976)
alcohol, benzene
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: hi VOLATILITY: m OVERALL: m
E. GENERAL COMMENTS
Ho smog chamber or laboratory kinetic data are available.
A-101
-------
Chauiicai Mama: Vinyl acetate oononer
Chamicad Formula: CH^COOCH-CH^ (M.W.-86)
Ch«nica< NO.: 97
CAS Ragttiry NO.: 108~05"*
A. SMOG CHAMBER DATA
INITIAL CONC. Mil
max.o3
TOTAL
IRRAOIATION
TIME (M
AVERAGE OC
DISAPPEARANCE
RATEfB/W
NO. FORMA-
TION RATE
mAiw
REFERENCES
ORGANIC
CHEMICAL
IOC)
*>x
HOyNO
CONC.
(PPM>
TIME
<«
4.0
4.0
2.0
0.2
o o
• •
0.40
0.34
17.4
3.6
Joshi ec al (1982)
Joahi et *1 (1982)
B. KINETIC DATA
REACTION
WITH
UNITS
NATE CONSTANT
VALUE (39%)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
crn'moMa' S"'
3.0 (-11)
Estimated
96.8
Not strictly
amenable to
°3
cm31 wit' s '
estimation
r'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
as'ci
REFERENCES
COMMENTS
VAPOR PRESSURE lim.1
1.5 (-1)
Jordan (1954)
WATER SOLUBILITY Imol. m'3)
290
Verschueren (1977)
HENRY'S CONSTANT lam. m3 mot"1)
5.2 (-4)
Calculated
SOLVENT SOLUBILITY lire*, m'3)
Inf.
Marck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: I" VOLATILITY: HI OVERALL: 111
E. GENERAL COMMENTS
A-102
-------
Chemical Nam*: Vinyl chloride monomer
Chemical Formula: CH2»CHC1 (M.W.-62.5)
Chemical NO.: 98
CAS Registry NO.: 75-01-4
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX.O3
TOTAL
IRRAOIATION
TIME (M
AVERAGE OC
DISAPPEARANCE
RATE (%/hl
NO,FORMA-
TION RATE
(PPS/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OCt
NOx
NOj/NO
CONC.
(PPM)
TIME
(hi
4.6
1.5
>20
1.3*
3.0
3
14.0
Gay et al (1976)
1.7
1.0
0.0
0.45*
5.5
6
6.0
Gay et al (1976)
10.0
4.5
>20
2.0
5.0
9.5
9.0
Appleby (1976)
B. KINETIC OATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE <28'C1
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 molw"1 S1
6.6 (-12)
Atkinson et al(1979)
21.3
°3
cm' rrKJt^c"1 s'1
1.9 C-19)
Gay et al (1976)
W
S'1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2S*C)
REFERENCES
COMMENTS
VAPOR PRESSURE (Mm.)
WATER SOLUBILITY Imol. m-3)
HENRY'S CONSTANT (mm. m3 mol"')
SOLVENT SOLUBILITY (mol. m"3)
PHYSICAL STATE
3.5
1.8 (-2)
57
gas
Dreisbach (1959)
Varschueren (1977)
Calculated
0. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: III
E. GENERAL COMMENTS
Known products are formaldehyde, formic acid, hydrogen chloride and CO.
*ozone still increasing
A-103
-------
CfcamkJ Nam: m-and nixed Xylenes Chemical NO.: 99
CtNmiari Formula: l,3-C6H4(CH3)2 (M.W.-106) CAS Registry NO.: 108-38-3 (a-xylene)
1330-20-7 (alxed)
A. SMOG CHAMBER DATA
INITIAL CONC.
MAX.03
TOTAL
AVERAOS OC
NO, FORMA-
TION RAT*
20
0.18
0.9
3
Schuck and Doyle (1959)
B. KINETIC OATA
RCACTION
WITH
UNITS
RATI CONSTANT
VALUC ost)
MPIRfNCCS
ON RATI CONST.
RtLATIVSTO
ethane
COMMMTOON
RATI CONSTANT
ESTIMATION
ON
cm3 mo**'1 S'1
2.1 (-11)
Atkinson eC al (1979
67.7
°3
em3 motac'' 8'1
*0
S"'
C. VOLATILITY DATA
PROPIRTY NAME (UNITS)
PROPIRTY VALUS
os%>
RIPERSNCU
COMMNTS
VAPOR PRESSURE (mm.)
1.1 (—2)
ZwoLlsakl and Wilhoit(1971
a-Xylene only
WATER SOLUSILITY (mol. in3)
1.5
Polak and Lu (1973)
¦-Xylene only
HENRY'S CONSTANT lam. m3 mot"1)
7.0 t-3)
Mackay and Shlu (1981)
aHCylene only
SOLVENT SOLUSILITY (mal. m"3)
inf.
Merck (1976)
alcohol, ether
PHYSICAL STATI
liquid
D. CLASSIFICATIONS
REACTIVITY: hi VOLATILITY: m OVERALL: III
E. GENERAL COMMENTS
Product of o-Xylene photooxidation are peroxyacetyl nltrace, carbon monoxide,
foraaldehyda, methyl glyoxal, nitric acid, aliphatic dicarbonyla(ac«taldahyde, end
a-tolualdehyde
*
mixed Xylenes
A-104
-------
Chemical Nam*: o-Xylene Chemical NO.: 100
Chemical Formula: l,2-C6HA(CH.j)2 CM.W.-106) CAS Registry NO.: 95-47-6
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
ORGANIC
CHEMICAL
IOC)
nox
NOj/NO
0.6
0.32
0.33
2.0
1.0
0.05
1.0
0.5
0.11
1.0
0.6
0.05
2.0
1.0
0.05
4.0
1.0
0.02
5.0
3.0
0.0
MAX. O3
CONC.
(PPM)
TIME
(hi
TOTAL
IRRAOIATION
TIMS (hi
AVERAGE OC
DISAPPEARANCE
RATE (WD)
NO-FORMA-
TION RATE
(PPS/Mlnl
REFERENCES
0.51
0.51
0.53
1.8x
Coluei^i
0.32
0.32
0.7
2.5
e
6.0
2.0
10-12
5
6
5
6
6
2
11.1
5.4
12.8
8.7
Jefferies e£ al (1982)
13.1 Yanagihara et al (1977)
Dimitriades at al (1975)
1.5xtoluen4 Laity ec al (1973)
13.6
40.0
Heuss and Glasson (1968)
Brunelle et al (1966)
Altahuller and Cohen (1963)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (28'C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em'melee'1 S"'
1.2 (-11)
Atkinson et al (1979)
38.7
°3
em3 mo lee'1 S'1
hl>
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
property VALUE
I2S*CI
REFERENCES
COMMENTS
VAPOR PRESSURE (etm.l
8.7 t-3)
Zwolinski and Wilhoit(1971)
WATER SOLUBILITY Intel, m"3)
2.0
Polak and Lu (1973)
HENRY'S CONSTANT letm. m3 mol"1)
4.4 C-3)
Maclcay and Shiu (1981)
SOLVENT SOLUBILITY Imd. m'3)
inf.
Merck C1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: m VOLATILITY: m OVERALL: m
E. GENERAL COMMENTS
Xylenes are abouc half as efficient In ozone formation aa propene (Cox et al, 1980).
Known photodegradatlon products are formaldehyde, peroxyacecyl nitrate, biacetyl,
glyoxal methyl, glyoxal o-tolualdehyde, 3,4-dimethyl nitro—benzene, 2,3-dimethyl-
nitro benzene, and o-methylbenzyl nitrate.
A-105
-------
Chemical Nww: p—Xylene
Chemical Formula: 1,4-C6H4(CHj)2 (M.W.-106)
Chemical NO.: 101
CAS Registry NO.: 106-42-3
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX
03
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vhl
NO.FORMA-
TION RATE
(PPS/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
nox
NOj/NO
CONC.
IPPMI
TIME
(hi
2.0
1.0
0.05
0.39
4.5
5
10.7
7.8
Yanaglhara et al (1977)
1.0
0.5
0.11
0.49
6
5.4
Dioltrlades et al (1975)
2.0
1.0
0.05
0.26
6.0
6
7.0
7.7
Heuss and Glasson (1968)
5.0
3.0
0.0
0.65
2.5
30.0
Alcshuller and Cohen (1963)
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S*CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OM
om^ motoc'* 3*'
1.1 (-11)
Atkinson et al (1979
35.4
°3
hv
on3 moUe"' S 1
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITSI
PROPERTY VALUE
(3B*CI
REFERENCES
COMMENTS
VAPOR PRESSURE (lira.)
1.2 (-2)
Zvolinskl and Wllhoit(1971
WATER SOLUBILITY (md. m'3)
1.7
Polak and Lu (1973)
HENRY'S CONSTANT (Mm. m3 mot'1!
6.7 (-3)
Mackay and Shlu (1981)
SOLVENT SOLUBILITY (mol. m'3)
soluble
M«rck (1976)
alcohol, ether
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: HI
E. GENERAL COMMENTS
Products similar Co o- and n-Xylenes.
A-106
-------
Chemical Name: Dimethyl succinate
Chemical Formula: CH3OOC(CH2)2COOCH3 (M.W.-146)
Chemical NO.: 102
CAS Registry NO.: 106-65-0
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (*/hl
NO,FORMA-
TION RATE
(PPE/MIn)
REFERENCES
ORGANIC
CHEMICAL
(OCI
NOx
NOj/NO
CONC.
(PPMI
TIME
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
value ash
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
°3
W>
em® melee'1 S"'
an® motoe'1 S"'
S"1
3.0 (-12)
Estimated
10.0
dot strictly
amenable to
estimation
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2S°C)
REFERENCES
COMMENTS
VAPOR PRESSURE lim.1
6.4 (-4)
Estimated
WATER SOLUBILITY (mol. m'3)
57
Merck (1976)
HENRY'S CONSTANT l«m. m3 mo)'1)
1.1 (-5)
Calculated
SOLVENT SOLUSILITY (mol. m-3)
200
Merck (1976)
alcohol
PHYSICAL STATE
liquid
0. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: HI
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
A-107
-------
Chemical Nam*: Dimethyl glutarate
Chemical Formula: CH3OOC(CH2) 3COOCH3 (M.W.-160)
Chemical NO.: 103
CAS Registry NO.: 1H9-40-0
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX O3
TOTAL
IRRAOIATION
TIME
-------
Chemical Name: Dlmethyl
adipate
Chemical Formula: CHjOOCCCHj) 4COOCH3 (M.W.-174)
Chemical NO.: 104
CAS Registry NO.: 627-93-0
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. 03
TOTAL
IRRADIATION
TIME (III
AVERAGE OC
DISAPPEARANCE
RATE <%/hl
NO.FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
X
o
X
NOj/NO
CONC.
(PPM)
TIME
(W
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (23*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
on3 fr*o4»c'* S"'
4.8 C-12)
Estimated
15.4
Not strictly
amenable to
°3
om3 mol*®"1 S"'
estimation
hv
S'1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
I2»*C)
REFERENCES
COMMENTS
VAPOR PRESSURE latm.)
9.9 (-5)
Estimated
WATER SOLUBILITY (mol. m'3)
l.a
Estimated
HENRY'S CONSTANT Iran, m3 mol'')
5.5 (-5)
Calculated
SOLVENT SOLUBILITY (mol. m"3)
liquid
PHYSICAL STATE
D. CLASSIFICATIONS
REACTIVITY: m VOLATILITY: m OVERALL: III
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
A-109
-------
Chemical Name: 2-Mechoxy ethanol
Chemical Formula: CH^CHjCHjOH (M.W.-76)
Chemical NO.: LQ5
CAS Rafliitry NO.: 109-86-4
A. SMOG CHAMBER OATA
INITIAL CONC. (PPM)
MAx.03
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE (Vh)
NO-FORMA-
TION RATE
(PPB/MIM
references
ORGANIC
CHEMICAL
(OCI
NOx
NoyNO
CONC.
IPPM)
TIME
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE I2S^1
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm"* motoe'1 S"1
7.1 C-12)
Estimated
22.9
°3
cm3 mote'1 S"1
W
s*1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(39 *C)
REFERENCES
COMMENTS
VAPOR PRESSURE (atm.)
1.9 (-2)
Estimated
WATER SOLUBILITY (mol. m"3]
HENRY'S CONSTANT («tm. m3 moi'S
SOLVENT SOLUBILITY {mol. m'3)
PHYSICAL STATE
liquid
~.CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: III
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available.
A-110
-------
Chemical Nam*: Ethylene glycol monomethyl echer
Chemical Formula: HOCH2CH2OCH3 (M.W.-76)
Chemical NO.: 106
CAS Registry NO.: 109-36-4
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX.O3
TOTAL
mNAOIATION
TIME IM
AVER ACS OC
DISAPPEARANCE
NATE <%/hl
NO-FORMA-
TION RATE
(PPB/Minl
REFERENCES
ORGANIC
CHEMICAL
-------
Chemical Nam*: Ethylene glycol monoethyl ether
Chemical Formula: HOCH2CH2OC2H5 (M.W.-90)
Chemical NO.: 107
CAS Registry NO.: 110-80-5
A. SMOG CHAMBER DATA
INITIAL CONC. (PfMI
MAX. 03
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE IK/ht
NO,FORMA-
TION RATE
(PPS/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOyNO
CONC.
ippmi
TIME
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE 0»fc>
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
am' mono'1 S'1
1.4 C-ll)
Estimated
45.2
°3
cm5 molt'1 S"1
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
OS'CI
REFERENCES
COMMENTS
VAPOR PRESSURE (ran.)
7.0 C-3)
Mellan Qa77)
WATER SOLUBILITY (md. m"°)
lni.
Mellan C1977)
HENRY'S CONSTANT (atm. m3 mo*'1)
4.2 C-7)
Calculated
SOLVENT SOLUBILITY In*. m'3)
inf.
Mellon (1977)
acetone, benzene
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: III
6. GENERAL COMMENTS
No snog chamber or laboratory kinetic data are available.
A-112
-------
Chemical Nam*: Diisoamyl ketone Chemical NO.: 108
Chamical Formula: ^^3 > CHCHj^ CO (M.W.-142) CAS Registry NO.:
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
MAX. O3
TOTAL
IRRAOIATION
TIMS (hi
AVERAGE OC
DISAPPEARANCE
RATE (%/hl
NO,FORMA-
TION RATE
(PPS/Mlnl
REFERENCES
ORGANIC
CHEMICAL
(OC)
z
o
X
NOj/NO
CONC.
(PPMI
TIMC
IM
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE ISS'CI
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 mol«e ' S'1
8.0 C-12)
Estimated
25.8
°3
em3 moWe"1 S"'
hp
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(2B*C)
REFERENCES
COMMENTS
VAPOR PRESSURE litm.1
No eatimaclon is possible
WATER SOLUBILITY (mal. m"3)
HENRY'S CONSTANT (urn. m3 msl"1!
SOLVENT SOLUEILITY (mol. m"3)
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: m VOLATILITY: II OVERALL: 11
E. GENERAL COMMENTS
No smog chamber or laboratory kinetic data are available. No vapor
pressure estimation was possible.
A-113
-------
Chemical Name: Propylene glycol methyl ether Chemical NO.: 109
Chamical Formula: CH^CHCHjOCHj (M.W.-90) CAS Registry NO.: 107-98-2
OH
A. SMOG CHAMBER DATA
initial conc. ipvmi
MAX.
TOTAL
IRRADIATION
TIME (hi
AVERAGE OC
disappearance
RATE (Vh|
NO-FORMA-
TION RATE
(PPS/Mtal
REFERENCES
ORGANIC
CHEMICAL
-------
Chemical Nam*: Dipropylene glycol methyl ether
Chemical Formula: CH3(CHOH)2CH2CBOHCH2OCH3 (M.W.-164)
ChamicaJ NO.: 110
CAS Registry NO.: 34590-94-8
A. SMOG CHAMBER DATA
INITIAL CONC. (PPM)
max.o3
TOTAL
IRRAOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATE
NO,FORMA-
TION RATE
(WS/Mlnl
REFERENCES
Organic
CHEMICAL
IOC)
NO*
NOj/NO
CONC.
(PPMI
TIMS
(M
B. KINETIC DATA
REACTION
WITH
UNITS
NATE CONSTANT
VALUE (29t)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
moll*1 S"'
1.2 C-ll)
Estimated
38.7
°3
an® mote'1 S"1
hv
s-'
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
(21%)
REFERENCES
COMMENTS
VAPOR PRESSURE (mm.)
5.3 (-4)
Mellaa (1977)
WATER SOLUBILITY [mot. m"3)
inf.
Mallan (1977)
HENRY'S CONSTANT latin, m3 moC1)
3.2 C-8)
Calculated
SOLVENT SOLUIIUTY (mot. m"3)
PHYSICAL STATS
liquid
O. CLASSIFICATIONS
REACTIVITY: III VOLATILITY: III OVERALL: III
E. GENERAL COMMENTS
No amog chamber or laboratory kinetic data are available.
A-115
-------
Chemical Nam*: o-cresol
Chemical Formula: CH3C6H40H (M-w>"108)
Chamicai NO.: 111A
CAS Registry NO.: 95-48-7
A. SMOG CHAMBER DATA
INITIAL CONC. (PPMI
MAX.O3
TOTAL
IRRAOIATION
TIME IN
AVERAGE OC
DISAPPEARANCE
RATE IVhl
NO, FORMA-
T1WI RATE
IPPS/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NO„
NOj/NO
CONC.
IPPMI
TIMS
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATI CONSTANT
VALUE I2S'C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
cm3 motaa*' 3"'
4.7 C-ll)
Atkinson ec al (1979
151.6
NO3
on3 n»ol«c"' 31
1.2 (-11)
Carter et al (1981)
S"1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
as'ci
REFERENCES
COMMENTS
VAPOR PRESSURE (ran.)
5.6 (-4)
Drelsbach (1955)
WATER SOLUBILITY (mol. m'3)
242
Freler (1975)
HENRY'S CONSTANT (aim. m3 mol'1)
2.3 (-6)
Calculated
SOLVENT SOLUSILITY (mot. m'3!
inf.
Merck (1976)
alcohol, ether, chloro-
PHYSICAL STATE
solid
form
D. CLASSIFICATIONS
REACTIVITY: m VOLATILITY: m OVERALL: ni
E. GENERAL COMMENTS
The major produce of OH attack should be dlhydroxytoluenes. In tha preaenca of N0X
hydroxynitrotoluenes have bean observed (Hendry, 1979). During nighttime affective ronoval
via NO- radical attack could occur (Carter et al., 1981). Cresols (especially o and p),
because of their aromatic ring and quinoidal resonance possibilities, may act as chain
terminators. However, available evidence suggests that even chain terminators can
produce ozone (Pitts et al., 1977; Cupltt and Corse, 1979).
A-116
-------
Chemical Nsm«:
Chemical Formula: CHjCgl^OH (M.W.-108)
Chwnicai NO.: 111B
CAS Registry NO.: 108-39-4
A. SMOG CHAMBER DATA
INITIAL CQNC. (PPMI
MAX.O]
TOTAL
IR8AOIATION
TIME (hi
AVERAGE OC
DISAPPEARANCE
RATI (*/h)
NO- FORMA-
TION RATE
(PPB/Mlnl
REFERENCES
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
(PPMI
TIMe
(hi
B. KINETIC DATA
REACTION
WITH
UNITS
RATE CONSTANT
VALUE (28*C)
REFERENCES
OH RATE CONST.
RELATIVE TO
ETHANE
COMMENTS ON
RATE CONSTANT
ESTIMATION
OH
em3 molae'1 S'1
6.7 C-U)
Atkinson at al (1979)
216.1
i»3
cm3 moke'' S'1
7.0 C-12)
Carter et al (1981)
s-1
C. VOLATILITY DATA
PROPERTY NAME (UNITS)
PROPERTY VALUE
Q8*C>
REFERENCES
COMMENTS
VAPOR PRESSURE Iran.)
2.5 C-4)
Crelsbach (1955)
WATER SOLUBILITY (mol. m"3)
26
Tevarl «c al (1982)
HENRY'S CONSTANT («tm. m3 moT1)
9.6 C-6)
Calculated
SOLVENT SOLUBILITY (mol. m"3!
Inf.
Merck C1976)
alcohol, ether, chloro-
form
PHYSICAL STATE
liquid
D. CLASSIFICATIONS
REACTIVITY: m VOLATILITY: m OVERALL: III
E. GENERAL COMMENTS
Same as o~cresol•
A-117
-------
Chemical Name: p-cresol
Chemical Formula: CH^CgH^OH (M.W.-103)
Chemical NO.: 111C
CAS Registry NO.: 106-44-5
A. SMOG CHAMBER DATA
INITIAL CONC. IfWI
MAX. 03
TOTAL
IRftAOIATION
TIMC (h)
AVBRAGI OC
DISAPfCARANCS
RATE OUhl
MO.FORMA-
TION RATI
(PfB/Minl
MFEREMCU
ORGANIC
CHEMICAL
IOC)
NOx
NOj/NO
CONC.
mil
TIMC
(HI
B. KINETIC DATA
REACTION
WITH
UNITS
NATE CONSTANT
value as'a
REFERENCES
OH rate const.
RELATIVE TO
ETHANE
COMMENTS ON
HATH CONSTANT
ESTIMATION
OH
om3 ^ s*'
5.2 C-U)
Atkinson sC al(1979)
167.7
NO,
an' matme' s1
1.3 (-11)
Career at al (1981)
s-'
C. VOLATILITY DATA
PROPERTY NAME (UNITS!
PROPERTY VALUE
(2S'C)
REFERENCES
COMMENTS
VAPOR PRESSURE (Mm.)
2.6 (-4)
Dreiabach (1955)
WATER SOLUBILITY tmol. m'3)
213
Morrison and Boyd (1973)
HENRY'S CONSTANT («tm. m3 mol 'l
1.2 (-6)
Calculated
SOLVENT SOLUBILITY (mat. m'3!
PHYSICAL STATE
•olid
D. CLASSIFICATIONS
REACTIVITY: in VOLATILITY: m OVERALL: III
E. GENERAL COMMENTS
Same as o-cresol.
A-118
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing/
1. REPORT NO.
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE ANO SUBTITLE
REACTIVITY/VOLATILITY CLASSIFICATION OF SELECTED
ORGANIC CHEMICALS: EXISTING DATA
S. REPORT DATE
S. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Hanwant B, Singh, Helen M. Jaber, John E. Davenport
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME ANO ADORESS
SRI International
Menlo Park, California 94025
10. PROGRAM ELEMENT NO.
C0WA1A/01 - 2297 (FY-84)
11. CONTRACT/GRANT NO.
CR810346-01
12. SPONSORING AGENCY NAME ANO AOORESS
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 ANO PERIOD COVERED
Interim
14. SPONSORING AGENCY CODE
EPA/600/09
IS. SUPPLEMENTARY NOTES
IS. ABSTRACT
This study deals with the reactivity/volatility classification of some 118
organic chemicals specified by the U. S. Environmental Protection Agency (EPA).
The classification system has been developed based on existing and available infor-
mation. It was clear at the outset that little or no experimental data were avail-
able for a significant fraction of these chemicals. In such cases we relied heavily
on our ability to make valid predictions, based on sound physico-chemical principles.
As requested by EPA, a three-tiered Individual, as well as composite, classification
scheme of the reactivity and volatility of these 118 chemicals was developed. The
three-tiered classification system was conceived as follows: Class I (26 chemicals):
These chemicals are sufficiently nonvolatile or unreactive so that they may not par-
ticipate in photochemical smog formation; Class II (17 chemicals): Chemicals that
are borderline cases, or for which available data are inadequate to draw definitive
conclusions; Class III (75 chemicals): These chemicals are both reactive and vola-
tile, and can participate 1n processes of smog formation.
Because of extensive shortcomings 1n existing information a number of recommendations
were made to bridge current Information gaps.
17. KBY WORDS ANO OOCUMCNT ANALYSIS
a. DESCRIPTORS
b.lOENTIPIERS/OPEN ENDED TERMS
c. COSATI Field/Gioup
1B. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
IS. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
20. SECURITY CLASS
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