INVESTIGATION OF ATMOSPHERIC OZONE IMPACTS 

OF TRANS 1-CHLORO-3,3,3-TRIFLUOROPROPENE

Final Report 

By 

William P. L. Carter 

June 8, 2009 

Center for Environmental Research and Technology 

College of Engineering 

University of California 

Riverside, California 92521 
ii 

ABSTRACT 

An experimental and modeling study was carried out to assess the impacts of trans 1-chloro3,3,3-trifluoropropene on ground-level ozone formation compared to other chemicals that are emitted into 

the atmosphere. The experiments consisted of incremental reactivity environmental chamber experiments 

to determine the effect of adding the halopropene compound to irradiations of reactive organic gas (ROG) 

surrogate - NOx mixtures representing ambient conditions. The results were modeled using the SAPRC07 mechanism with the reactions of the halopropene added. The data were reasonably well simulated after 

adjusting, to within its level of uncertainty, the overall nitrate yield in the reactions of NO with the peroxy 

radical intermediates. This mechanism was then used to calculate the atmospheric ozone impact of this 

compound in the box model scenarios to derive the Maximum Incremental Reactivity (MIR) and other 

ozone reactivity scales. Trans 1-chloro-3,3,3-trifluoropropene was calculated to have an ozone impact on 

a mass basis that is the that was less than ethane under all the conditions simulated. The average ratio of 

mass-based incremental reactivities relative to ethane for all the box model scenarios was 0.19±0.03 and 

the MIR ratio was 0.16±0.02. It is concluded that if ethane is used as the standard to define “negligible” 

ozone impact for the purpose of determining VOC exemptions for ozone precursors, then trans 1-chloro3,3,3-trifluoropropene will meet this standard. The yields of halogen-containing products formed in the 

oxidation of this compound under various atmospheric conditions were also calculated. Trans 1-chloro3,3,3-trifluoropropenewas also found to have no significant effect on particle formation in the incremental 

reactivity chamber experiments. 
iii 

ACKNOWLEDGEMENTS AND DISCLAIMERS 

The environmental chamber experiments for this project were carried out at the College of 

Engineering Center for Environmental Research and Technology (CE-CERT) primarily by Qi Li, Kurt 

Bumiller, and Quentin Malloy. Mr. Dennis Fitz also provided assistance in administering this project, and 

Ms. Kathy Cocker provided assistance in conducting the experiments and processing the data. 

The contents of this report reflect only the opinions and conclusions of the author. Mention of 

trade names and commercial products does not constitute endorsement or recommendation for use. 
iv 

TABLE OF CONTENTS 

INTRODUCTION ........................................................................................................................................ 1

EXPERIMENTAL METHODS.................................................................................................................... 2

Chamber Description.............................................................................................................................. 2

Analytical Instrumentation ..................................................................................................................... 4

Sampling methods .................................................................................................................................. 7

Characterization Methods....................................................................................................................... 7

Experimental Procedures........................................................................................................................ 8

Materials................................................................................................................................................. 9

MECHANISM AND MODELING METHODS........................................................................................ 10

Base Mechanism................................................................................................................................... 10

Mechanism for Trans 1-Chloro-3,3,3-Trofluoropropene ..................................................................... 11

Representation of Chamber Conditions................................................................................................ 14

Atmospheric Reactivity Simulations.................................................................................................... 18

RESULTS AND DISCUSSION ................................................................................................................. 19

Characterization Results....................................................................................................................... 19

Incremental Reactivity and Mechanism Evaluation Results ................................................................ 22

Atmospheric Reactivity Calculation..................................................................................................... 26

Ozone Impacts ............................................................................................................................... 26

Product Yield Calculations ............................................................................................................ 28

CONCLUSIONS......................................................................................................................................... 31

REFERENCES ........................................................................................................................................... 33

APPENDIX A. BASE MECHANISM LISTING....................................................................................... 37
v 

LIST OF TABLES 

Table 1. List of analytical and characterization instrumentation for the UCR EPA chamber................. 5

Table 2. List of model species added to the base mechanism to represent the atmospheric 

reactions of trans-1-chloro-3,3,3-trifluoropropene and its oxidation products ...................... 14

Table 3. List of reactions and rate constants used to represent the atmospheric reactions of 

trans-1-chloro-3,3,3-trifluoropropene and its oxidation products.......................................... 15

Table 4. Summary of experiments carried out for this project.............................................................. 20

Table 5. Summary of initial concentrations and selected gas-phase results of the incremental 

reactivity experiments. ........................................................................................................... 23

Table 6. Summary of conditions of scenarios used for reactivity assessment....................................... 27

Table 7. Calculated atmospheric incremental reactivities for trans-1-chloro-3,3,3-

trifluoropropene and ethane. .................................................................................................. 29

Table A-1. List of model species used in the base SAPRC-07 mechanism, including the VOC 

species used in the chamber and atmospheric reactivity simulations. ................................... 37

Table A-2. Reactions and rate constants in the SAPRC-07 mechanism used in this work. See 

Carter (2009a) for documentation.......................................................................................... 41

Table A-3. Summary of photolysis rates used in chamber and ambient simulations............................... 57

LIST OF FIGURES 

Figure 1. Schematic of the UCR EPA environmental chamber reactors and enclosure........................... 3

Figure 2. Spectrum of the light sources used in the UCR EPA chamber, with intensities 

normalized to give the same NO2 photolysis rates. A representative solar spectrum is 

also shown................................................................................................................................ 3

Figure 3. Plots of best fit HONO offgasing parameters against UCR EPA run number. ....................... 21

Figure 4. Experimental and calculated results of the incremental reactivity experiments with 

added trans-1-chloro-3,3,3-trifluoropropene.......................................................................... 25

Figure 5. Plots of relative yields of fluorine-containing products in the oxidation of trans 

1,3,3,3-tetrafluoropropene against relative NOx levels and days of irradiation in the 

"averaged conditions" scenarios, and number of days in the MOIR scenario extended 

on for 9 additional days.......................................................................................................... 30
1 

INTRODUCTION 

Ozone in photochemical smog is formed from the gas-phase reactions of volatile organic 

compounds (VOCs) and oxides of nitrogen (NOx) in sunlight, and control of both VOCs and NOx is 

required to attain air quality standards for ozone. Many different types of VOCs are emitted into the 

atmosphere, each reacting at different rates and having different mechanisms for their reactions. Because 

of this, they can differ significantly in their effects on ozone formation, or their “reactivity”. In 

recognition of this, the U.S. EPA has exempted volatile organic certain compounds with ozone impacts 

expected to be less than ethane from regulations as VOC ozone precursors (Dimitriades, 1999; RRWG, 

1999a, EPA, 2005), and the California Air Resources Board (CARB) has adopted regulations with 

reactivity-based adjustments for several types of VOC sources (CARB 1993, 2000) and is investigating 

their use for other sources (CARB, 2008). 

Halogenated propenes such as trans 1,3,3,3-tetrafluoropropene (CF3CH=CHF), 2,3,3,3-

tetrafluoropropene (CF3CF=CH2), and 1-chloro-3,3,3-trifluoropropene (CF3CH=CHCl) are compounds of 

interest whose use and manufacture may result in their being emitted into the atmosphere. This will result 

in these compounds being subject to VOC regulations aimed at reducing ozone formation, which may 

adversely impact their production costs and marketability. If these compounds can be shown to have 

ozone impacts less than or equal to ethane on a mass basis, a case might be made to the U.S. EPA to 

exempt them from regulations as VOC ozone precursors (EPA, 2005). Because the ozone impacts of 

these compounds had not been studied previously, predictions of the ozone impacts of these compounds 

would need to be verified experimentally. 

In view of this, the College of Engineering, Center for Environmental Research and Technology 

(CE-CERT) at the University of California at Riverside (UCR) was funded to carry out a project to reduce 

uncertainties in estimates of the atmospheric ozone impacts of 1-chloro-3,3,3-trifluoropropene, using the 

procedures previously employed for trans 1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene 

(Carter, 2009b,c). This included developing atmospheric reaction mechanisms for the compounds suitable 

for predicting their impacts on ozone formation in the atmosphere, conducting environmental chamber 

experiments suitable for testing the ability of these mechanisms to predict their impacts on ozone 

formation, evaluating and if necessary revising the mechanisms based on their ability to simulate these 

data, and calculating the atmospheric ozone impacts of these compounds in various reactivity scales 

(Carter, 2009a), where they can be compared with those for ethane and other compounds. The approach 

used is similar to that used many other VOCs that have been studied previously (Carter, 2009a, and 

references therein). The methods, results, and conclusions of our study of the atmospheric ozone impacts 

of the third compound, trans 1-chloro-3,3,3-trifluoropropene, are documented in this report. 
2 

EXPERIMENTAL METHODS 

Chamber Description 

All of the environmental chamber experiments for this project were carried out using the UCR 

EPA environmental chamber at CE-CERT. This is the same as the chamber used in our recently 

completed studies of trans 1,3,3,3-tetrafluoropropene (Carter, 2009b) and 2,3,3,3-tetrafluoropropene 

(Carter, 2009c). This chamber was constructed under EPA funding to address the needs for an improved 

environmental chamber database for mechanism evaluation (Carter et al, 1999, Carter, 2002). The 

objectives, design, construction, and results of the initial evaluation of this chamber facility are described 

in more detail elsewhere (Carter et al, 1999, Carter, 2002; Carter, 2004, Carter et al, 2005a). A brief 

description of the chamber is also given below. 

The UCR EPA chamber consists of two ~85,000-liter Teflon® reactors located inside a 16,000 

cubic ft temperature-controlled “clean room” that is continuously flushed with purified air. The clean 

room design is employed in order to minimize background contaminants into the reactor due to 

permeation or leaks. Two alternative light sources can be used. The first consists of a 200 KW argon arc 

lamp with specially designed UV filters that give a UV and visible spectrum similar to sunlight. Banks of 

blacklights are also present to serve as an alternative lower cost light source when blacklight irradiation is 

sufficient. Blacklights have a good representation of sunlight in the UV portion of the spectrum that 

affects most photolysis reactions of interest, and their use is sufficient for test compounds whose 

mechanisms involve do not involve photoreactive compounds, or only photoreactive compounds with 

known action spectra (Carter et al, 1995b). Since this is the case for the halopropenes studied here and by 

Carter (2009b), they were used for all experiments for this project. The interior of the enclosure is 

covered with reflective aluminum panels in order to maximize the available light intensity and to attain 

sufficient light uniformity, which is estimated to be ±10% or better in the portion of the enclosure where 

the reactors are located (Carter, 2002). A diagram of the enclosure and reactors is shown in Figure 1, and 

spectra of the light sources are shown in Figure 2. 

The dual reactors are constructed of flexible 2 mil Teflon® film, which is the same material used 

in the other UCR Teflon chambers used for mechanism evaluation (e.g., Carter et al, 1995a; Carter, 

2000a, and references therein). A semi-flexible framework design was developed to minimize leakage 

and simplify the management of large volume reactors. The Teflon film is heat-sealed into separate sheets 

for the top, bottom, and sides (the latter sealed into a cylindrical shape) that are held together and in place 

using bottom frames attached to the floor and moveable top frames. The moveable top frame is held to the 

ceiling by cables that are controlled by motors that raise the top to allow the reactors to expand when 

filled or lower the top to allow the volume to contract when the reactors are being emptied or flushed. 

These motors in turn are controlled by pressure sensors that raise or lower the reactors as needed to 

maintain slight positive pressure. During experiments the top frames are slowly lowered to maintain 

continuous positive pressure as the reactor volumes decrease due to sampling or leaks. The experiment is 

terminated once the volume of one of the reactor reaches about 1/3 the maximum value, where the time 

this took varied depending on the amount of leaks in the reactor, but was greater than the duration of most 

of the experiments discussed in this report. Since at least some leaks are unavoidable in large Teflon film 

reactors, the constant positive pressure is important to minimize the introduction of enclosure air into the 

reactor that may otherwise result. 
3 

20 ft. 20 ft.

20 

 ft. 

This volume kept clear 

to maintain light 

uniformity 

Temperature controlled room flushed 

with purified air and with reflective 

material on all inner surfaces 

Dual Teflon 

Reactors 

Two air Handlers 

are located in the 

corners on each 

side of the light 

(not shown). 

Gas sample lines to 

laboratory below Access 

Door 

200 KW 

Arc Light 

2 Banks of 

Blacklights 

SEMS (PM) 

Instrument 

Floor Frame 

Movable top 

frame allows 

reactors to 

collapse 

under 

pressure 

control 

Mixing System

Under floor 

of reactors 

Figure 1. Schematic of the UCR EPA environmental chamber reactors and enclosure. 

0.0

0.2

0.4

0.6

0.8

0.300 0.350 0.400 0.450 0.500 0.550 0.600

Wavelength (microns)

Arc Light

Blacklights

Solar Z=0

0.00

0.02

0.04

0.06

0.08

0.10

0.12

Relative Intensity (Normalized to give

0.290 0.300 0.310 0.320

same NO2 photolysis rate)

Figure 2. Spectrum of the light sources used in the UCR EPA chamber, with intensities normalized 

to give the same NO2 photolysis rates. A representative solar spectrum is also shown. 
4 

As indicated in Figure 1, the floor of the reactors has openings for a high volume mixing system 

for mixing reactants within a reactor and also for exchanging reactants between the reactors to achieve 

equal concentrations in each. This utilizes four 10” Teflon pipes with Teflon-coated blowers and flanges 

to either blow air from one side of a reactor to the other, or to move air between each of the two reactors. 

Teflon-coated air-driven metal valves are used to close off the openings to the mixing system when not in 

use, and during the irradiation experiments. 

An AADCO air purification system that provides dry purified air at flow rates up to 1500 liters 

min-1 is used to supply the air to flush the enclosure and to flush and fill the reactors between 

experiments. The air is further purified by passing it through cartridges filled with Purafil® and heated 

Carulite 300® which is a Hopcalite® type catalyst and also through a filter to remove particulate matter. 

The measured NOx, CO, and non-methane organic concentrations in the purified air were found to be less 

than the detection limits of the instrumentation employed (see Analytical Equipment, below). 

The chamber enclosure is located on the second floor of a two-floor laboratory building that was 

designed and constructed specifically to house this facility (Carter et al, 2002). Most of the analytical 

instrumentation is located on the ground floor beneath the chamber, with sampling lines leading down as 

indicated in Figure 1. 

Analytical Instrumentation 

Table 1 gives a listing of the analytical and characterization instrumentation whose data were 

utilized for this project. Other instrumentation was available and used for some of these experiments, as 

discussed by Carter 2002a and Carter et al, 2005a, but the data obtained were not characterized for 

modeling and thus not used in the mechanism evaluations for this project. The table includes a brief 

description of the equipment, species monitored, and their approximate sensitivities, where applicable. 

These are discussed further in the following sections. 

Ozone, CO, NO, and NOy were monitored using commercially available instruments as indicated 

in Table 1. The instruments were spanned for NO, NO2, and CO and zeroed prior to all experiments using 

the gas calibration system indicated in Table 1, and a prepared calibration gas cylinder with known 

amounts of NO and CO. O3 and NO2 spans were conducted by gas phase titration using the calibrator 

during this period. Span and zero corrections were made to the NO, NO2, and CO data as appropriate 

based on the results of these span measurements, and the O3 spans indicated that the UV absorption 

instrument was performing within its specifications. 

Organic reactants were measured by gas chromatography with FID detection as described 

elsewhere (Carter et al, 1995a); see also Table 1. The surrogate gaseous compounds ethylene, propylene, 

n-butane and trans-2-butene were monitored by using 30 m megabore GS-Alumina column and the loop 

sampling system. The second signal of the same GC outfitted with FID, loop sampling system and 30 m 

megabore DB-5 column was used to analyze surrogate liquid components toluene, n-octane and mxylene. The sampling methods employed for injecting the sample with the test compounds on the GC 

column depended on the volatility or “stickiness” of the compounds. For analyses of more volatile species 

such as trans-1-chloro-3,3,3-trifluoropropene the same loop method was suitable. 

Both the GC instruments were controlled and their data were analyzed using Agilent 

ChemStation software installed on a dedicated PC. The GC's were spanned using the prepared calibration 

cylinder with known amounts of ethylene, propane, propylene, n-butane, n-hexane, toluene, n-octane and 
5 

Table 1. List of analytical and characterization instrumentation for the UCR EPA chamber. 

Type Model or Description Species Sensitivity Comments 

 

Ozone 

Analyzer 

Dasibi Model 1003-AH. UV 

absorption analysis. 

O3 2 ppb Standard monitoring instrument. 

NO - NOy NO 1 ppb 

Analyzer 

Teco Model 42 C with external 

converter. Chemiluminescent 

analysis for NO, NOy by 

catalytic conversion. 

NOy 1 ppb 

Useful for NO and initial NO2

monitoring. Converter close-coupled to 

the reactors so the “NOy” channel should 

include HNO3 as well as NO2, PANs, 

organic nitrates, and other species 

converted to NO by the catalyst. 

CO Analyzer Thermo Environmental 

Instruments Inc. Model 48 C 

CO 50 ppb Standard monitoring instrument 

GC-FID 

Instruments 

Dual Agilent 6890 Series II 

GC with dual columns, loop 

injectors and FID detectors. 

Controlled by computer 

interfaced to network. 

VOCs ~10 ppbC 30 m x 0.53 mm GS-Alumina column 

used for the analysis of light 

hydrocarbons such as ethylene, 

propylene, n-butane and trans-2-butene 

and 30 m x 0.53 mm DB-5 column used 

for the analysis of C5+ alkanes and 

aromatics, such as toluene and m-xylene. 

Loop injection is suitable for low to 

medium volatility VOCs that are not too 

“sticky” to pass through valves. Two 30 

m x 0.32 mm DB-5 column measure C5+

alkanes and aromatics, such as toluene 

and m-xylene. 

Gas 

Calibrator 

Model 146C Thermo 

Environmental Dynamic Gas 

Calibrator 

N/A N/A Used for calibration of NOx and other 

analyzers. Instrument acquired early in 

project and under continuous use. 

Data 

Acquisition 

Sytem 

Windows PC with custom 

LabView software, 16 analog 

input, 40 I/O, 16 thermocouple, and 8 RS-232 channels. 

N/A N/A Used to collect data from most 

monitoring instruments and control 

sampling solenoids. In-house LabView 

software was developed using software 

developed by Sonoma Technology for 

ARB for the Central California Air 

Quality Study as the starting point. 

Temperature 

sensors 

Various thermocouples, 

radiation shielded 

thermocouple housing 

Tempera

-ture 

~0.1 o

C Primary measurement is thermocouples 

inside reactor. However, comparison with 

temperature measurements in the sample 

line suggest that irradiative heating may 

bias these data high by ~2.5o

C (Carter, 

2004). 

Humidity 

Monitor 

General Eastern HYGRO-M1 

Dew Point Monitor 

Humidity Dew point 

range: -40 - 

50o

C 

Instrument performs as expected, but dew 

point below the performance range for 

most of the experiments discussed in this 

report, except for those with added 

humidity. 
Table 1 (continued) 

6 

Type Model or Description Species Sensitivity Comments 

 

Spectroradiometer LiCor LI-1800 

Spectroradiometer 

300-850 

nm Light 

Spectrum 

Adequate Resolution relatively low but adequate 

for this project. Used to obtain relative 

spectrum. Also gives an absolute 

intensity measurement on surface useful 

for assessing relative trends. 

QSL 

Spherical 

Irradiance 

Sensor 

Biospherical QSL-2100 PAR 

Irradiance Sensor. Responds to 

400-700 nm light. 

Spherical 

Broadband 

Light 

Intensity

Adequate Provides a measure of absolute intensity 

and light uniformity that is more directly 

related to photolysis rates than light 

intensity on surface. Gives more precise 

measurement of light intensity trends 

than NO2 actinometry, but is relatively 

sensitive to small changes in position. 

Scanning 

Mobility 

Particle Sizer 

(SMPS) 

TSI 3080L column, TSI 3077 

85Kr neutralizer, and TSI 3771 

CPC. Instrument design, 

control, and operation Similar 

to that described in Cocker et 

al. (2001) 

Aerosol 

number 

and size 

distributions 

Adequate Provides information on size distribution 

of aerosols in the 28-735 nm size range, 

which accounts for most of the aerosol 

mass formed in our experiments. Data 

can be used to assess effects of VOCs on 

secondary PM formation. 

m-xylene in ultrapure nitrogen. Analyses of the span mixture were conducted approximately every day an 

experiment was run, and the results were tracked for consistency. 

The surrogate components analyzed by the above system were calibrated by repeated analysis of 

a standard mixture containing these compounds, and verified by injecting and sampling known amounts 

of the compound in calibration chamber of known volume. The amounts of gaseous compounds injected 

were determined by vacuum methods, using an MKS Baratron precision pressure gauge, and bulbs of 

known volume, determined by weighing when filled with water. The amounts of liquid compounds 

injected were determined by measuring amounts injected using microliter syringes. The volumes of the 

calibration chambers were determined by injecting and analyzing compounds whose analyses have been 

calibrated previously. 

The GC analysis of trans-1-chloro-3,3,3-trifluoropropene was calibrated by injecting a 

quantitative amount of the compound in the chamber reactors. The chamber reactors have a known 

volume and therefore contain a known concentration of the injected compound. The calibration factor was 

then determined as a result of the GC analyses conducted prior to the start of the irradiations. 

 As indicated in Table 1, aerosol number and size distributions were also measured in conjunction 

with our experiments. The instrumentation employed is similar to that described by Cocker et al. (2001), 

and is the same as employed in our previous studies of coatings VOCs (Carter et al, 2005b). Particle size 

distributions are obtained using a scanning mobility particle sizer (SMPS) equipped with a 3077 85Kr 

charger, a 3081L cylindrical long column, and a 3771 condensation particle counter (CPC). Flow rates of 

2.5 LPM and 0.25 LPM for sheath and aerosol flow, respectively, are maintained using Labview 6.0-

assisted PID control of MKS proportional solenoid control valves. Both the sheath and aerosol flow are 

obtained from the reactor enclosure. The data inversion algorithm described by Collins et al (2002) 

converts CPC counts versus time to particle size distribution. 
7 

Most of the instruments other than the GCs and aerosol instrument were interfaced to a PC-based 

computer data acquisition system under the control of a LabView program written for this purpose. These 

data, and the GC data from the Agilent ChemStation computer, were collected over the CE-CERT 

computer network and merged into Excel files that are used for applying span, zero, and other corrections, 

and preparation of the data for modeling. 

Sampling methods 

Samples for analysis by the continuous monitoring instruments were withdrawn alternately from 

the two reactors and zero air, under the control of solenoid valves that were in turn controlled by the data 

acquisition system discussed above. For most experiments the sampling cycle was 5 minutes for each 

reactor, the zero air, or (for control purposes) the chamber enclosure. The program controlling the 

sampling sent data to the data acquisition program to indicate which state was being sampled, so the data 

could be appropriately apportioned when being processed. Data taken less than 3-4 minutes after the 

sample switched were not used for subsequent data processing. The sampling system employed is 

described in more detail by Carter (2002). 

Samples for GC analysis of surrogate compounds were taken at approximately every 20-minute 

directly from each of the reactors through the separate sample lines attached to the bottom of the reactors. 

The GC sample loops were flushed for a desired time with the air from the reactor being sampled. 

Characterization Methods 

Use of chamber data for mechanism evaluation requires that the conditions of the experiments be 

adequately characterized. This includes measurements of temperature, humidity, light and wall effects 

characterization. Wall effects characterization is discussed in detail by Carter (2004) and updated by 

Carter and Malkina (2005) and Carter (2007) and most of that discussion is applicable to the experiments 

for this project. The instrumentation used for the other characterization measurements is summarized in 

Table 1, above, and these measurements are discussed further below. 

Temperature was monitored during chamber experiments using calibrated thermocouples 

attached to thermocouple boards on our computer data acquisition system. The temperature in each of the 

reactors was continuously measured using relatively fine gauge thermocouples that were located ~1 foot 

above the floor of the reactors. These thermocouples were not shielded from the light, though it was 

hoped that irradiative heating would be minimized because of their small size. Experiments where the 

thermocouple for one of the reactors was relocated to inside the sample line indicated that radiative 

heating is probably non-negligible, and that a correction needs to be made for this by subtracting ~2.5o

C 

from the readings of the thermocouples in the reactors. This is discussed by Carter (2004). 

Light Spectrum and Intensity. The spectrum of the light source in the 300-850 nm region was 

measured using a LiCor LI-1800 spectroradiometer, which is periodically calibrated at the factory. 

Spectroradiometer readings were taken periodically, though the relative spectra were found to have very 

little variation during the course of these experiments. The absolute light intensity is measured by 

carrying out NO2 actinometry experiments periodically using the quartz tube method of Zafonte et al 

(1977) modified as discussed by Carter et al (1995a). In most cases the quartz tube was located in front of 

the reactors. Since this location is closer to the light than the centers of the reactors, the measurement at 

this location is expected to be biased high, so the primary utility of these data are to assess potential 

variation of intensity over time. However, several special actinometry experiments were conducted prior 

to the experiments carried out for this project where the quartz tube was located inside the reactors, to 

provide a direct measurement of the NO2 photolysis rates inside the reactors. The photolysis rates used 
8 

when modeling these experiments were the same as used by Carter (2009b) when modeling the recently 

completed experiments for trans 1,3,3,3-and 2,3,3,3-tetrafluoropropenes. 

Experimental Procedures 

The reaction bags were collapsed to the minimum volume by lowering the top frames, then 

cleaned by emptying and refilling them at least six times after each experiment, and then filled with dry 

purified air on the nights before experiments. Span measurements were generally made on the continuous 

instruments prior to injecting the reactants for the experiments. The reactants were then injected through 

Teflon injection lines (that are separate from the sampling lines) leading from the laboratory below to the 

reactors. The common reactants were injected in both reactors simultaneously, and were mixed by using 

the reactor-to-reactor exchange blowers and pipes for 10 minutes. The valves to the exchange system 

were then closed and the other reactants were injected to their respective sides and mixed using the inreactor mixing blowers and pipes for 1 minute. The contents of the chamber were then monitored for at 

least 30 minutes prior to irradiation, and samples were taken from each reactor for GC analysis. 

 Once the initial reactants are injected, stabilized, and sampled, the light or lights employed 

(blacklights in the case of this project) are turned on to begin the irradiation. During the irradiation the 

contents of the reactors are kept at a constant positive pressure by lowering the top frames as needed, 

under positive pressure control. The reactor volumes therefore decrease during the course of the 

experiments, in part due to sample withdrawal and in part due to small leaks in the reactor. A typical 

irradiation experiment ended after about 6 hours, by which time the reactors are typically down to about 

half their fully filled volume. Larger leaks are manifested by more rapid decline of reactor volumes, and 

the run is aborted early if the volume declines to about 1/3 the maximum. This was the case for a few of 

the experiments discussed in this report. After the irradiation the reactors were emptied and filled six 

times as indicated above. 

The procedures for injecting the various types of reactants were as follows. The NO, and NO2

were prepared for injection using a vacuum rack. Known pressures of NO, measured with MKS Baratron 

capacitance manometers, were expanded into Pyrex bulbs with known volumes, which were then filled 

with nitrogen (for NO) or purified air (for NO2). In order to maintain constant NO/NO2 ratios the same 

two bulbs of specified volume were utilized in most of experiments. The contents of the bulbs were then 

flushed into the reactor(s) with nitrogen. Some of the gaseous reactants such as propylene (other than for 

surrogate experiments) and trans-1-chloro-3,3,3-trifluoropropene were prepared for injection using a high 

vacuum rack as well. For experiments with added CO, the CO was purified by passing it through an inline activated charcoal trap and flushing it into the reactor at a known rate for the amount of time required 

to obtain the desired concentration. Measured volumes of volatile liquid reactants were injected, using a 

micro syringe, into a 2 ft long Pyrex injection tube surrounded with heat tape and equipped with one port 

for the injection of the liquid and other ports to attach bulbs with gas reactants. For injections into both 

reactors (e.g, the NOx and base ROG surrogate components in incremental reactivity experiments), one 

end of the injection tube was attached to the “Y”-shape glass tube (equipped with stopcocks) that was 

connected to reactors and the other end of injection tube was connected to a nitrogen source. The 

injections into a single reactor (e.g., for trans-1-chloro-3,3,3-trifluoropropene in the reactivity 

experiments) was similar except the “Y” tube was not used. 

The procedures for injection of the hydrocarbon surrogate components were as follows. A 

cylinder containing n-butane, trans-2-butene, propylene and ethylene in nitrogen, was used for injecting 

the gaseous components of the surrogate. The cylinder was attached to the injection system and a gas 

stream was introduced into reactors at controlled flow for certain time to obtain desired concentrations. A 

prepared liquid mixture with the appropriate ratios of toluene, n-octane and m-xylene was utilized for 

injection of these surrogate components, using the procedures as discussed above for pure liquid 
9 

reactants. All the gas and liquid reactants intended to be the same in both reactors were injected at the 

same time. The injection consisted of opening the stopcocks and flushing the contents of the bulbs and the 

liquid reactants with nitrogen, with the liquid reactants being heated slightly using heat that surrounded 

the injection tube. The flushing continued for approximately 10 minutes. 

The trans-1-chloro-3,3,3-trifluoropropene used in these experiments was provided as a gas in a 

lecture bottle, and was injected into the chamber using vacuum injection methods similar to that discussed 

above for NO and other gaseous reactants. 

Materials 

The sources of the NO, CO and the various base case surrogate compounds came from various 

commercial vendors as employed in previous projects at our laboratory. The trans-1-chloro-3,3,3-

trifluoropropene, with a stated purity of ≥ 99.98%, was provided by Honeywell International Inc. No 

significant impurities were detected in any of the GC analyses of these samples. 
10 

MECHANISM AND MODELING METHODS 

Base Mechanism 

The starting point for the chemical mechanism evaluated in this work is the SAPRC-07 

mechanism as documented by Carter (2009a). This is a complete update of the SAPRC-99 mechanism of 

Carter (2000a), but it is very similar to it in its major features. The reactions and rate constants in this 

mechanism are given in tables in Appendix A to this report, and complete documentation of this 

mechanism is given by Carter (2009a). Files and software implementing this chemical mechanism are 

available at the SAPRC mechanism web site1

, with the chemical mechanism simulation computer 

programs available there being essentially the same as those employed in this work. 

As discussed previously (Carter, 2000a,b, 2009a), the current SAPRC mechanisms consists of a 

“base mechanism” that represents the reactions of the inorganic species and common organic products 

and lumped organic radical model species and “operators”, and separate mechanisms for the initial 

reactions of the many types other organic compounds that are not in the base mechanism. The 

compounds, or groups of compounds, that are not included in the base mechanism but for which 

mechanism assignments have been made, are referred to as detailed model species. The latter include all 

the base ROG surrogate constituents and compounds whose reactivities are being assessed (trans-1-

chloro-3,3,3-trifluoropropene in this case). These compounds can either be represented explicitly, with 

separate model species with individual reactions or sets of reactions for each, or using lumped model 

species similar to those employed in the “fixed parameter” version of SAPRC (Carter, 2000b, 2009a). The 

latter approach is used when modeling complex mixtures in ambient simulations or simulations of 

experiments with complex mixtures, but the other approach, representing each compound explicitly, is 

more appropriate when evaluating mechanisms for individual compounds or simple mixtures. This is 

because the purpose of mechanism evaluations against chamber data is to assess the performance of the 

mechanism itself, not to assess the performance lumping approaches. The latter is most appropriately 

assessed by comparing simulations of explicit and condensed versions of the same mechanism in ambient 

simulations. 

In this work, all of the organic constituents in the environmental chamber experiments were 

represented explicitly using separate model species for each compound, while complex mixture of emitted 

species in the atmospheric reactivity simulations were represented using the appropriate lumped model 

species for the fixed parameter mechanism, as indicted in Table A-1 in Appendix A. The reactions and 

rate constants in the base mechanism are given in Table A-2, and the photolysis rates used are given in 

Table A-3. These photolysis rates were calculated from applicable actinic flux or light source 

characterization data and absorption cross-sections and quantum yields given by Carter (2009a). 

The version of the SAPRC-07 mechanism used in this work is the same as that employed in our 

recent study of 2,3,3,3-tetrafluoropropene, but incorporated several corrections relative to the version 

used in our study of trans 1,3,3,3-tetrafluoropropene (Carter, 2009b). These corrections are discussed in 

Appendix E of Carter (2009a), and primarily concern hydroperoxide reactions that are not important in 

affecting ozone formation and have no significant affect calculations of ozone impacts of these 

halopropenes. 

 

1

 Reports and files concerning the latest version of the SAPRC chemical mechanisms and their associated 

reactivity scales are available at http://www.cert.ucr.edu/ ~carter/SAPRC. 
11 

Mechanism for Trans 1-Chloro-3,3,3-Trofluoropropene 

Alkenes can react in the atmosphere with OH radicals, O3 or NO3 radicals, and in general all three 

need to be taken into account when developing mechanisms for their O3 formation potential. The rate 

constants for the reactions of trans-1-chloro-3,3,3-trifluoropropene with OH radicals and O3 have been 

measured to be 4.40±0.38 x 10-12 and 1.46±0.12 x 10-21 cm3

 molec-1 s-1, respectively (Sulbaek Andersen et 

al, 2008). The rate constant for the reaction with O3 is too low for this reaction to be an important sink 

compared to reaction with OH radicals, so it can be ignored. The rate constant for reaction with NO3

radicals have not been measured, but can be estimated by correlation between measured OH and NO3

radical rate constants for other alkenes (e.g., see Atkinson, 1991; Calvert et al, 2003; Carter, 2000). Based 

on this correlation, the rate constant for the reactions of trans-1-chloro-3,3,3-trifluoropropene is estimated 

to be negligible under atmospheric conditions. Sulbaek Andersen et al (2008) obtained a relatively high 

rate constant of 5.22±0.72 x 10-11 cm3

 molec-1 s-1 for the reactions of this compound with chlorine atoms, 

but chlorine atom reactions are not expected to be important sinks for VOCs under most atmospheric 

conditions, including those used for ozone reactivity assessment in this work. 

Therefore, the only loss process for trans-1-chloro-3,3,3-trifluoropropene that needs to be 

considered in estimating its ozone impact is reaction with OH radicals. Although no product or 

mechanistic data are available for this compound, the products and mechanism are expected to be similar 

to those for trans-1,3,3,3-tetrafluoropropene (Javadi et al, 2008; Carter, 2009a). In particular, Javadi et al 

(2008) studied the reactions of trans 1,3,3,3-tetrafluoropropene with OH and found that the major 

products were CF3CHO and FCHO with yields that were “indistinguishable from 100%”. This suggests 

that the major products from trans-1-chloro-3,3,3-trifluoropropene would be CF3CHO and ClCHO 

 This is consistent with the following mechanism for the OH reaction, and is also 

consistent with mechanisms for OH reactions with most other alkenes (Calvert et al, 2003; Carter, 2000a, 

2008a): 

 OH + CF3CH=CHCl → CF3CH(OH)CHCl· 

 OH + CF3CH=CHCl → CF3CH(·)CHClOH 

 CF3CH(OH)CHCl·+ O2 → CF3CH(OH)CHClOO· 

 CF3CH(·)CHClOH + O2 → CF3CH(OO·)CHClOH 

 CF3CH(OH)CHClOO· + NO → NO2 + CF3CH(OH)CHClO· 

 CF3CH(OO·)CHClOH + NO → NO2 + CF3CH(O·)CHClOH 

 CF3CH(OH)CHClO· → CF3CH(OH)· + ClCHO 

 CF3CH(O·)CHClOH → CF3CHO + ·CHClOH 

 CF3CH(OH)· + O2 → HO2 + CF3CHO 

 ·CHClOH + O2 → HO2 + ClCHO 

or overall: 

 OH + CF3CH=CHCl → CF3CHO + ClCHO + HO2 - NO + NO2

An additional reaction that needs to be considered is the formation of organic nitrates as a minor 

route in the reaction of peroxy radicals with NO, e.g., 

 CF3CH(OH)CHFOO· + NO → CF3CH(OH)CHFONO2

This reaction is assumed to occur ~1.5% of the time in the propene system (Carter, 2008a), but Carter 

(2009b) found that the best fit to the chamber data for trans 1,3,3,3-tetrafluoropropene was obtained if the 

analogous reactions in that system are assumed to occur ~5% of the time. On the other hand, Carter 

(2009c) found that the best fit to the chamber data for 2,3,3,3-tetrafluoropropene was obtained if the 

analogous reactions are assumed to be negligible. Because the branching ratio of this reaction is uncertain 

and can significantly affect model predictions, this was treated as an adjustable parameter when 
12 

evaluating this mechanism against the chamber experiments. As discussed in the Results section, the best 

fits to the data are obtained using an overall organic nitrate yield of 2.5%, which is well within the 

uncertainty for this parameter, and within the range observed for the other tetrahalopropenes we studied 

(Carter, 2009b,c). This is used in most of the model simulations in this work unless indicated otherwise. 

The secondary reactions of the products formed also need to be considered when estimating the 

ozone impacts of a VOC. ClCHO reacts only very slowly with OH radicals (IUPAC, 2007). It does 

absorb light to a small extent under conditions of the lower atmosphere (IUPAC, 2000), but the photolytic 

half life calculated using the recommended absorption cross sections (IUPAC, 2000) for direct overhead 

sun is over 35 days, if unit quantum yields are assumed. This is too slow for the photolysis to be a nonnegligible process affecting ozone reactivity. Therefore, the reactions of ClCHO can be neglected in 

models for O3 formation. 

However, the secondary reactions of trifluoroacetaldehyde need to be taken into account. This is 

discussed below. Note that this product is also formed in the oxidation of trans 1,3,3,3-tetrafluoropropene, 

and the mechanism used for this product is the same as used in our previous study of that compound 

(Carter, 2009b). 

As with acetaldehyde, trifluoroacetaldehyde can react either with OH radicals or by photolysis. 

The absorption cross section data for trifluoroacetaldehyde, given by IUPAC (2004), is similar to that for 

acetaldehyde, which means that its photolysis could be non-negligible under lower atmospheric 

conditions if the quantum yields for photodecomposition were sufficiently high. However, this compound 

was observed to loss by photolysis in sunlight irradiation at a rate consistent with an overall 

photodecomposition quantum yield of less than 2% (Sellevåg et al, 2004), indicating that its photolysis is 

negligible under atmospheric conditions. Therefore, reaction with OH radicals is probably the only 

process that needs to be considered when assessing its ozone impact. 

Available data concerning the rate constant for the reaction of OH radicals with 

trifluoroacetaldehyde have been evaluated by IUPAC (2005), and a value of 5.7 x 10-13 cm3

 molec-1 s-1 is 

recommended. This is considerably lower than the rate constant of 1.5 x 10-11 cm3

 molec-1 s-1 for 

acetaldehyde (IUPAC, 2006). The mechanism is expected to be similar to the reaction of OH with 

acetaldehyde, i.e., 

 CF3CHO + OH → CF3C(O)· + H2O 

 CF3C(O)· + O2 → CF3C(O)OO· 

 CF3C(O)OO· + NO2 → CF3C(O)OONO2

 CF3C(O)OONO2 → CF3C(O)OO· + NO2

 CF3C(O)OO· + NO → NO2 + CF3C(O)O· 

 CF3C(O)O· → CF3· + CO2

 CF3· + O2 → CF3OO· 

 CF3OO· + NO → NO2 + CF3O· 

The subsequent reactions of CF3O· are unknown, but it probably reacts primarily with VOCs in a 

manner similar to OH radicals, forming CF3OH (which is relatively unreactive) and similar VOC 

oxidation radicals and products as formed in their OH radical reactions. For simplicity, the net effect of 

CF3O· is represented in the mechanism by assuming it is converted immediately to CF3OH and OH 

radicals, where the OH then reacts to form similar products and radicals as would CF3O·. Given the 

uncertainty of CF3O· reactions, using a more complex and explicit mechanism is probably not justified. 

The impact of this uncertainty on O3 predictions should be minor since reactions forming CF3O· are 

predicted to be relatively minor under conditions where O3 formation occurs (see predictions of CF3OH in 

Figure 5a in the "Product Yield Calculations" in the "Results" section of this report). This assumption was 
13 

also made in our modeling study of the reactions of trans 1,3,3,3-tetrafluoropropene, where CF3CHO is 

also formed (Carter, 2009b). 

The above discussion focuses on the reactions of the tetrahalopropene and its oxidation products 

in the presence of NOx, which are the major reactions of significance in affecting their ozone impacts. 

However, to estimate the ultimate environmental fate of this compound and its halogen-containing 

products, one needs to also consider the reactions in the absence of NOx, and the reactions of products 

formed under such conditions. The most important reactions in the absence of NOx are reactions of the 

peroxy radicals with HO2. For the initially formed peroxy radicals, these include the following: 

 CF3CH(OH)CHClOO· + HO2 → O2 + CF3CH(OH)CHClOOH 

 CF3CH(OO·)CHClOH + HO2 → O2 + CF3CH(OOH)CHClOH 

 CF3CH(OH)CHClOOH + OH → H2O + CF3CH(OH)CHClOO· 

 CF3CH(OO·)CHClOH + OH → H2O + CF3CH(OO·)CHClOH 

 CF3CH(OH)CHClOOH + hν → CF3CH(OH)CHClO· + OH 

 CF3CH(OO·)CHClOH + hν → CF3CH(O·)CHClOH + OH 

The subsequent reactions of the alkoxy radicals formed in the photolyses are as shown above, and the rate 

constants and photolysis rates are estimated based on those for methyl hydroperoxide. The OH reactions 

may also occur by abstraction from the C-H bonds in the hydroperoxides but these pathways are 

estimated to be less important than reaction at the hydroperoxide group and are ignored. 

In the absence of NOx the major additional reactions in the trifluoroacetaldehyde oxidation would 

be the following: 

 CF3C(O)OO· + HO2 → CF3C(O)OOH + O2

 CF3C(O)OO· + HO2 → CF3C(O)OH + O3

with rate constants and branching ratios estimated by analogy with the analogous reactions of acetyl 

peroxy radicals. The trifluoroacetic acid is assumed to be relatively unreactive, and the 

trifluoroperoxyacetic acid is assumed to react as follows: 

 CF3C(O)OOH + OH → H2O + CF3C(O)OO· 

 CF3C(O)OOH + hν → CF3C(O)O· + OH 

with the rate constant for the OH reaction estimated based on that used in SAPRC-07 for methyl 

hydroperoxide, and the photolysis rate estimated using the absorption cross sections of peroxyacetic acid 

(Orlando and Tyndall, 2003), assuming unit quantum yield. 

Reactions of the peroxy and acetyl peroxy radicals with other peroxy and acetyl peroxy radicals 

also need to be considered under low NOx conditions, though they are less important than the reactions 

with HO2 discussed above. These are estimated using the general procedures associated with the 

SAPRC07 mechanism, as discussed by Carter (2008a) and shown in Table 3 below. 

The representation of these reactions in SAPRC-07 mechanism is given in Table 2 and Table 3, 

which list the model species and reactions, respectively. Table 2 gives a description of the model species 

used and footnotes to Table 3 indicate the source of the rate constants or parameters used and give 

additional discussion about how the mechanism was estimated or represented. Carter (2009a) should be 

consulted for a more complete discussion of the chemical operators and other species used in the SAPRC07 mechanism. A complete listing of the other reactions used in the SAPRC-07 mechanism for the model 

simulations for this study is given in Appendix A. 
14 

Table 2. List of model species added to the base mechanism to represent the atmospheric reactions 

of trans-1-chloro-3,3,3-trifluoropropene and its oxidation products 

Name Description 

 

Active Species

 R1233ZDE trans 1-chloro-3,3,3-Trifluoropropene 

 CLCHO Formyl chloride. Assumed to be relatively unreactive. 

 TFACET Trifluoroacetaldehyde 

 CF3CO3 Trifluoro acetyl peroxy radicals. Assumed to react analogously to CH3C(O)OO·. 

 CF3PAN Trifluoroperoxyacetyl nitrate. Assumed to react analogously to PAN. 

RF4OOH CF3CH(OOH)CHClOH or CF3CH(OH)CHClOOH formed following the reactions of OH 

with the tetrahalopropene and reaction of the subsequently formed peroxy radical with HO2. 

Assumed to react analogously to methyl hydroperoxide, with reactions at the C-H bonds 

neglected. 

RF4OH CF3CH(OH)CHClOH, CF3C(O)CHClOH or isomers formed when peroxy radicals formed 

following OH + trans 1-chloro-3,3,3-trifluoropropene reaction reacts by disproportionation 

with other peroxy radicals. Assumed to be relatively unreactive. 

 CF3OOH Trifluoromethylhydroperoxide. Assumed to react analogously to methyl hydroperoxide. 

CF3CO3H Trifluoroperoxyacetic acid. OH reaction assumed to be analogous to methyl hydroperoxide 

and photolysis estimated using absorption cross sections for peroxyacetic acid. 

 CF3CO2H Trifluoroacetic acid. Assumed to be relatively reactive. 

 CF3OH Trifluoromethanol. Assumed to be relatively unreactive 

Steady State Species

CF3O Trifluoromethoxy radicals. Assumed to react with VOCs present with the net effect being 

formation of CF3OH and formation of products formed in OH reactions. 

xTFACET Formation of trifluoroacetone from alkoxy radicals formed in peroxy radical reactions with 

NO and NO3 (100% yields) and RO2 (50% yields) 

 xCLCHO As above, except for formyl chloride. 

 xCF3O As above, except for trifluoromethoxy radicals 

yRF4OOH Formation of CF3CH(OOH)CHClOH or CF3CH(OH)CHClOOH following RO2 + HO2

reactions, or formation of H-shift disproportionation products in the RO2 + RC(O)OO· and 

RO2 + RO2 reactions. 

yCF3OOH As above, but for CF3OOH 

Representation of Chamber Conditions 

The procedures used in the model simulations of the environmental chamber experiments for this 

project are the same as those used for the experiments with trans 1,3,3,3-tetrafluoropropene (Carter, 

2009b) and 2,3,3,3-tetrafluoropropene (Carter, 2009c) and are based on those discussed in detail by Carter 

(2004) and employed in the studies of Carter and Malkina (2005) and Carter et al (2005b), updated for 

SAPRC-07 as discussed by Carter (2009a). Carter (2004) should be consulted for details of the 

characterization model and chamber effects parameters employed. The temperatures used when modeling 

were the averages of the temperatures measured in the reactors, corrected as discussed by Carter (2004). 

The light intensity for the blacklight experiments declines slowly with time when the lights are 

new, though the rate of decline decreases as the lights age (Carter et al, 1995a; Carter, 2004, 2007). The 

characterization of the light intensity for the previous set of reported experiments is discussed by Carter 
15 

Table 3. List of reactions and rate constants used to represent the atmospheric reactions of trans-1-

chloro-3,3,3-trifluoropropene and its oxidation products 

Rate Parameters [b] Reaction and Products [a] k(298) A Ea 

Refs & 

Notes [c]

OH + R1233ZDE = #.975 {xHO2 + RO2C + xTFACET + 

xCLCHO} + #.025 {RO2XC + zRNO3} + yRF4OOH 

+ #-0.075 XC 

4.40e-13 1 

xTFACET = TFACET k is variable parameter: RO2RO 2 

xTFACET = #2 XC k is variable parameter: RO2XRO 2 

xCLCHO = CLCHO k is variable parameter: RO2RO 2 

xCLCHO = XC k is variable parameter: RO2XRO 2 

yRF4OOH = RF4OOH + #-3 XC k is variable parameter: RO2HO2 2 

yRF4OOH = RF4OH + #-3 XC k is variable parameter: RO2RO2M 2 

yRF4OOH = k is variable parameter: RO2RO 2 

OH + TFACET = CF3CO3 5.70e-13 3 

CF3CO3 + NO2 = CF3PAN Same k as rxn BR28 4 

CF3PAN = CF3CO3 + NO2 4.79e-4 1.60e+16 26.80 4 

CF3PAN + HV = #.6 {CF3CO3 + NO2} + #.4 {RO2C + 

yCF3OOH + xCF3O + CO2 + NO3} 

Phot Set= PAN 4,5 

CF3CO3 + NO = NO2 + CO2 + RO2C + xCF3O + 

yCF3OOH 

Same k as rxn BR31 4,5 

CF3CO3 + HO2 = #.75 {CF3CO3H + O2} + #.25 

{CF3CO2H + O3} 

Same k as rxn BR22 4 

CF3CO3 + NO3 = NO2 + O2 + CO2 + RO2C + xCF3O + 

yCF3OOH 

Same k as rxn BR09 4,5 

CF3CO3 + MEO2 = CF3CO2H + HCHO + O2 Same k as rxn BR24 4 

CF3CO3 + RO2C = CF3CO2H + O2 Same k as rxn BR25 4 

CF3CO3 + RO2XC = CF3CO2H + O2 Same k as rxn BR25 4 

CF3CO3 + MECO3 = #2 CO2 + MEO2 + RO2C + 

xCF3O + yCF3OOH 

Same k as rxn BR27 4,5 

CF3CO3 + RCO3 = #2 {CO2 + RO2C} + xCF3O + 

yCF3OOH + xHO2 + yROOH + xCCHO 

Same k as rxn BR27 4,5 

CF3CO3 + BZCO3 = #2 {CO2 + RO2C} + xCF3O + 

yCF3OOH + BZO 

Same k as rxn BR27 4,5 

CF3CO3 + MACO3 = #2 CO2 + HCHO + MECO3 + 

RO2C + xCF3O + yCF3OOH 

Same k as rxn BR27 4,5 

CF3CO3 + CF3CO3 = #2 {RO2C + xCF3O + yCF3OOH 

+ CO2} 

Same k as rxn BR27 4,5 

RF4OOH + OH = H2O + TFACET + CLCHO + HO2 3.55e-12 6,7 

RF4OOH + HV = OH + TFACET + CLCHO + HO2 Phot Set= COOH 7,8 

CF3OOH + OH = H2O + CF3O 3.55e-12 6 
Table 3 (continued) 

16 

Rate Parameters [b] Reaction and Products [a] k(298) A Ea 

Refs & 

Notes [c]

CF3OOH + HV = OH + CF3O Phot Set= COOH 8 

CF3O = OH + CF3OH 1.00e-3 9 

CF3CO3H + OH = H2O + CF3CO3 Same k as rxn Ze24 10 

CF3CO3H + HV = xCF3O + CO2 + OH Phot Set= PAA 11 

xCF3O = CF3O k is variable parameter: RO2RO 2 

xCF3O = XC k is variable parameter: RO2XRO 2 

yCF3OOH = CF3OOH + #-1 XC k is variable parameter: RO2HO2 2 

yCF3OOH = CF3OH + #-1 XC k is variable parameter: RO2RO2M 2 

yCF3OOH = k is variable parameter: RO2RO 2 

[a] Format of reaction listing: “=“ separates reactants from products; “#number” indicates stoichiometric 

coefficient, “#coefficient {product list}” means that the stoichiometric coefficient is applied to all the 

products listed. 

[b] Except as indicated, the rate constants are given by k(T) = A · e-Ea/RT, where the units of k and A are 

cm3

 molec-1 s-1, Ea are kcal mol-1, T is oK, and R=0.0019872 kcal mol-1 deg-1. If A and Ea are not 

given then the rate constant is assumed to be temperature independent. The following special rate 

constant expressions are used: 

Phot Set = name: The absorption cross sections and (if applicable) quantum yields for the photolysis 

reaction are given by Carter (2008a), except for "PAA", which are given below. Here, “name” 

indicates the photolysis set used. Photolysis rates used in chamber and ambient simulations are 

given in Table A-3. 

Same K as Rxn xx: Uses the same rate constant as the reaction in the base mechanism with the same 

label. The base mechanism is given in Table A-2 in Appendix A. 

k is variable parameter name: The rate constant is calculated using variable parameters that are 

calculated using concentrations of various species. See Footnotes [c] and [e] to Table A-2 in 

Appendix A for a discussion of the parameters and how they are calculated. 

[c] Footnotes discussing reactions or rate constants used are as follows: 

 1 See text for a discussion of the mechanism. The rate constant is from Sulbaek Andersen et al, 

(2008). The overall nitrate yield was adjusted to fit chamber data as discussed in the Results 

section. 

 2 See Carter (2008a) and footnotes to Table A-2 for a discussion of the reactions of peroxy radical 

operator species. xTFACET is the operator that represents the formation of trifluoroacetaldehyde 

from peroxy radical reactions. yRF4OOH is the operator that represents the formation of 

tetrafluorohyderoperoxides formed when the peroxy radicals from the OH + tetrahalopropene 

reactions react with HO2. 

 3 Rate constant from IUPAC (2006). The reaction is assumed to be analogous to OH + 

acetaldehyde. 

 4 Rate constants and mechanisms assumed to be the same as or analogous to those used for lumped 

acyl peroxy radicals (RCO3) or lumped higher PANs (PAN2), except as indicated otherwise. See 

Table A-2. 

 5 CF3· radicals are assumed to react analogously to alkyl centered radicals except that CF3O· 

radicals are treated as the end product in this representation. Using the general SAPRC07 

mechanism peroxy radical operator approach, the net effects of its reactions are represented by 
Table 3 (continued) 

17 

RO2C + xCF3O + yCF3OOH, where the RO2C represents the NO to NO2 conversions when the 

peroxy radical reacts with NO, the xCF3O represents the formation of CF3O as a product, and 

yCF3OOH represents the formation of CF3OOH when the peroxy radical reacts with HO2. 

 6 The reaction is assumed to occur primarily with OH abstracting from the OOH group, with a rate 

constant assumed to be the same as used for that process in the reaction of OH with 

methylhydroperoxide (COOH). See Table A-2. 

 7 The alkoxy radicals formed should be the same as those formed in the OH + tetrahalopropene 

reaction, so the same overall products are assumed to be formed, i.e., HO2 + ClCHO + 

trifluoroacetaldeyde. 

 8 The photolysis is assumed to occur at the same rate as used for methyl hydroperoxide, and the 

products are assumed to be OH + the alkoxy radical. See Carter (2008a). 

 9 The atmospheric fate of CF3O· radicals is uncertain. It is assumed to react relatively rapidly with 

other VOCs present in a manner analogous to OH radicals or halogen atoms, forming CF3OH and 

peroxy radicals. For simplicity, these are represented as forming the same products as the 

corresponding OH reactions, so the net effect is approximately the same as rapid formation of 

CF3OH and OH radicals from CF3O·. The rate constant is set at an arbitrary value that is 

sufficiently high that the conversion is fast and independent of the rate constant. Note that this is a 

better approximation than representing CF3O· as unreactive, since this would be a radical sink 

process which is probably not the case. 

 10 For lack of other data, we assume that the rate of abstraction from OOH is the same as used for 

methyl hydroperoxide and CF3OOH. 

 11 Perfluoroperoxyacetic acid is assumed to have the same absorption cross sections as peroxyacetic 

acid, and to photolyze with a unit quantum yield. This is probably an upper limit photolysis rate. 

The absorption cross sections used for peroxyacetic acid (PAA) are from Orlando and Tyndall 

(2003) and the values used in the applicable range are as follows, where wavelengths (Wl) are in 

nm and the absorption cross sections (Abs) are 10-21 cm2

 molec-1. The values for 342 and 344 nm 

are extrapolated. 

 Wl Abs Wl Abs Wl Abs Wl Abs Wl Abs 

 280 5.06 294 1.93 308 0.69 322 0.20 336 0.09 

 282 4.44 296 1.70 310 0.62 324 0.20 338 0.09 

 284 3.86 298 1.41 312 0.45 326 0.17 340 0.06 

 286 3.34 300 1.23 314 0.44 328 0.14 342 0.03 

 288 2.97 302 1.07 316 0.40 330 0.09 344 0 

 290 2.56 304 0.94 318 0.35 332 0.11 

 292 2.26 306 0.78 320 0.25 334 0.11 

(2007), and based on extrapolating the light intensity assignments for the experiments carried out then to 

the current experiments we assign a light intensity corresponding to an NO2 photolysis rate of 0.115 min-1

for the experiments modeled in this report. Model simulations of the control experiments for this and the 

trans 1,3,3,3-tetrafluoropropene (Carter, 2009b) and 2,3,3,3-tetrafluoropropene (Carter, 2009c) projects 

indicate that this is an appropriate assignment. The blacklight spectral distribution given by Carter et al 

(1995a) was found to be appropriate for the blacklights in this chamber and is used when modeling the 

runs in this chamber using the blacklight light source. 

The chamber effects parameters used when modeling the experiments in this chamber were the 

same as those given by Carter (2004) except for the HONO offgasing parameters, which were derived 

based on results of characterization runs carried out in conjunction with these experiments as discussed 
18 

below. As discussed by Carter (2004), the chamber effects model currently used for this chamber 

represents both the chamber radical source and background NOx offgasing by HONO offgasing, whose 

magnitude is determined by the chamber effects parameter RN-I, which is the ratio of the HONO 

offgasing rate to the NO2 photolysis rate. The RN-I parameter that best fits the characterization data tends 

to vary over time depending on the conditions of the chamber, and the results of the characterization 

experiments applicable to modeling the experiments discussed in this report, and the assignment of the 

RN-I values used, are given in the Characterization Results section, below. 

The initial reactant concentrations used in the model simulations were based on the 

experimentally measured values. However, the calibration of the trans-1-chloro-3,3,3-trifluoropropene 

measurements were based on calculated amounts of compound injected and the volume of the reactors, 

which were measured by injecting known quantities of CO or NOx, and measuring the CO or NOx using 

instruments that were independently calibrated. 

Atmospheric Reactivity Simulations 

Atmospheric reactivity model simulations were carried out to derive MIR and other atmospheric 

reactivity values for trans-1-chloro-3,3,3-trifluoropropene. The base mechanism, scenarios, and methods 

used were the same as those used when calculating the MIR and other atmospheric ozone reactivity scales 

for the SAPRC-07 mechanism by Carter (2009a), so the atmospheric reactivities calculated for trans-1-

chloro-3,3,3-trifluoropropene reactivities in this work are directly comparable with those given by Carter 

(2009a) for the ~1100 other types of VOCs represented using the SAPRC-07 mechanism. The mechanism 

used for trans-1-chloro-3,3,3-trifluoropropene is the same as gave the best fits to the results of the 

chamber simulations, as discussed in the Results section below, and is given in Table 3, above. The inputs 

used in the reactivity scenarios are described by Carter (1994a,b). 

In order to more systematically assess how the products formed from trans 1-clhoro-3,3,3-

trifluoropropene varied with NOx conditions, a series of reactivity simulations were carried out using the 

"Averaged Conditions" scenario with NOx inputs systematically varied. The inputs of those scenarios, 

other than the total NOx emissions that were varied, were derived by averaging the conditions of the base 

case reactivity assessment scenarios. These inputs are also given by Carter et al (1994a,b). In addition, to 

determine how relative products yields change in multi-day episodes, an "Averaged Conditions" scenario 

calculations with NOx inputs adjusted for maximum 1-day ozone yields (MOIR) was conducted for an 

additional 9 days. No emissions or dilution was assumed to occur on the subsequent days of the 

simulations. 
19 

RESULTS AND DISCUSSION 

A chronological listing of the environmental chamber experiments carried out for this project is 

given in Table 4. These include experiments with trans-1-chloro-3,3,3-trifluoropropene and appropriate 

characterization and control experiments needed for the data to be useful for mechanism evaluation. The 

results of the characterization experiments will be discussed first, followed by a discussion of the results 

of the mechanism evaluation experiments and of the model simulations of these experiments. 

Characterization Results 

The individual characterization experiments that are relevant to this project are summarized in 

Table 4. Except as discussed below, the characterization results are consistent with those discussed by 

Carter et al (2005b), Carter and Malkina (2005, 2007), Carter (2007) and Carter (2009b,c), and the same 

characterization parameters were used for modeling. The only chamber effect parameter that was changed 

when modeling the experiments for this project relative to some of the others concerns the apparent 

HONO offgasing, which is believed to be responsible for both the chamber radical source and NOx

offgasing effects (Carter, 2004). This is represented in the chamber effects model by the parameter RN-I, 

which is the HONO offgasing rate used in the simulations divided by the light intensity as measured by 

the NO2 photolysis rate. Figure 3 shows the HONO offgasing parameters that best fit the radical or NOx - 

sensitive characterization experiments carried out in the UCR EPA during the period of the last three sets 

of reactors. Note that the best-fit parameters depend on the mechanism used (particularly the OH + NO2

rate constant), and all these were calculated for SAPRC-07, the mechanism used in this work. 

 The experiments carried out for this project start at run EPA982, so the applicable 

characterization data is for the last set of reactors shown on the figure. The average RN-I parameter that 

fit the results of the experiments with this reactor was approximately 10 ppt, and this was used when 

modeling the experiments carried out for this project. This is the same as used when modeling the 

experiments with 2,3,3,3-tetrafluoropropene (Carter, 2009c), though it is slightly higher than the 9 ppt 

value used when modeling the earlier experiments with trans 1,3,3,3-tetrafluoropropene. Although there is 

a large amount of scatter in the RN-I parameter that gave the best fit to the data in these characterization 

experiments, it should be noted that the simulation of the surrogate - NOx incremental reactivity 

experiments, which are the experiments used for mechanism evaluation, are not very sensitive to this 

parameter. Test calculations showed that variation of this parameter within the range shown on Figure 4 

has only a minor effect on the simulations of these experiments, and does not affect conclusions 

concerning the tetrahalopropene mechanism that gives the best fits to the data. 

For modeling purposes, we use the same chamber effects parameters as used by Carter (2004), 

Carter and Malkina (2005), Carter et al (2005b), and Carter (2007) for all the other chamber effect 

parameters. Simulations of the incremental reactivity experiments are also not very sensitive to these 

parameters. 

Other control experiments carried out during this period was a side equivalency test (with the 

same reactive organic gas surrogate - NOx mixture simultaneously irradiated in both reactors). In addition, 

a propene - NOx control experiment and several pure air runs were carried out, and the results were as 

expected. The results of the side equivalency test carried out with this project, as with the recent projects 

with the other two tetrahalopropenes (Carter, 2009b,c) indicated acceptable side equivalency. The results 

of the most recent side equivalency test are given in Table 5, in conjunction with the results of the 

reactivity experiments with trans-1-chloro-3,3,3-trifluoropropene, discussed below. 
20 

Table 4. Summary of experiments carried out for this project. 

Run 

[a] Date Type [b] Purpose and Applicable Conditions Results 

982 3/20/09 CO - Air 

Irradiation 

Chamber NOx offgasing 

characterization. 36 ppm 

CO injected into both 

reactors. 

Results were consistent with chamber 

wall model used for these experiments. 

See Figure 3. 

991 4/9/09 MIR Surrogate 

- NOx side 

equivalency 

and perfluorohexane test 

Irradiation 

Control for incremental 

reactivity experiments to 

test side equivalency and to 

verify that the addition of 

the perfluoro n-hexane 

dilution tracer does not 

affect reactivity results. 3.5 

ppm pefluorohexane added 

to Side A. 

Initial concentrations in the appropriate 

range. Relevant results are summarized 

on Table 5. Good side equivalency 

obtained. As expected, the presence of 

perfluorohexane did not affect the gasphase results. No useable PM data. 

997 4/17/09 MOIR/2 

Incremental 

reactivity 

experiment 

Incremental reactivity 

experiment to test 

mechanism for test 

compound at ROG and 

NOx levels representative 

of lower NOx than MOIR 

conditions. 

Initial concentrations in the appropriate 

range. Relevant results are summarized 

on Table 5 and shown on Figure 4. 

1000 4/23/09 CO - air 

irradiation and 

halopropene 

light decay test. 

~65 ppm of CO and ~ 1 

ppm each of 2,3,3,3-tetrafluoropropene, trans 

1,3,3,3-tetrafluoropropene, 

trans-1-chloro-3,3,3-trifluoropropene, perfluorohexane and n-butane were 

injected into both reactors 

and irradiated. [c] 

The ozone formation in this experiment 

was consistent with that expected using 

the standard chamber characterization 

model. See Figure 3. See text for a 

discussion of the results of the 

measurements of the organic reactants 

and their implications. 

1004 5/3/09 CO - NOx

Irradiation 

40 ppb of CO and 20 ppb 

of NOx and ~50 ppb 

perfluorohexane injected 

into both reactors. 

The NO oxidation rate in this 

experiment was in the range expected 

using the standard chamber 

characterization model. See Figure 3. 

1007 5/6/09 MIR 

Incremental 

reactivity 

experiment 

Incremental reactivity 

experiment to test 

mechanism for test 

compound at low 

ROG/NOx ratios 

Initial concentrations in the appropriate 

range. Relevant results are summarized 

on Table 5 and shown on Figure 4. 

1010 5/12/09 MOIR/2 

Incremental 

reactivity 

experiment 

Repeat of run EPA997 

except with higher added 

test compound 

Initial concentrations in the appropriate 

range. Relevant results are summarized 

on Table 5 and shown on Figure 4. 
Table 4 (continued) 

21 

Run 

[a] Date Type [b] Purpose and Applicable Conditions Results 

1012 5/14/09 MIR 

Incremental 

reactivity 

experiment 

Repeat of run EPA1007 

except with higher added 

test compound 

Initial concentrations in the appropriate 

range. Relevant results are summarized 

on Table 5 and shown on Figure 4. 

1013 5/16/09 CO - air 

irradiation 

Chamber NOx offgasing 

characterization. 46 ppm 

CO injected into both 

reactors. 

Results were consistent with chamber 

wall model used for these experiments. 

See Figure 3. 

1021 6/2/09 Propene - NOx

irradiation 

Standard control run to test 

experimental and modeling 

conditions. 20 ppb NOx and 

0.26 ppm propene injected 

into both reactors. 

Results were as expected and 

reasonably consistent with model 

predictions. 

[a] Gaps in run number indicate experiments whose data were not useful for this project. 

[b] All experiments are ~6-hour irradiations using blacklights. "Surrogate" indicates a ROG surrogate - 

NOx mixture irradiated; "MIR" and "MOIR/2" mean the target initial NOx and base ROG surrogate 

were 30 ppb and 0.55 ppmC and 25 ppb and 1.1 ppmC, respectively. "Incremental Reactivity" 

indicates that a reactant was added to one of the two reactors. 

[c] See text for a discussion of the purpose of injecting the n-butane and halopropenes, whose gas-phase 

reactions are expected to be negligible under the conditions of the experiment. The experiment can be 

treated as a simple CO - air irradiation for the purpose of chamber characterization. 

0

5

10

15

20

500 550 600 650 700 750 800 850 900 950 1000

EPA Run Number

HONO Input Parameter (RN-I) (ppt)

Radical sensitive (Side A)

Radical sensitive (Side B)

NOx sensitive (Side A)

NOx sensitive (Side B)

Humidified

Used in Model

Replaced Reactors

Figure 3. Plots of best fit HONO offgasing parameters against UCR EPA run number. 
22 

The side equivalency experiment EPA991 also had ~4 ppm of perfluoro n-hexane added to one of 

the reactors, to verify that the presence of this compound as a dilution tracer does not affect reactivity 

results. The results indicated that presence of this compound at this level did not affect the results, as 

expected since this compound should be inert. For most of the other experiments for this project, 

approximately 70 ppb of the perfluorohexane was added as a dilution tracer. The prefluorohexane data 

was used to derive the dilution value to use when modeling these experiments, which ranged from 

approximately zero to 5 x 10-5 min-1 (0 to 0.3%/hour). 

An additional control experiment listed in Table 4 was EPA1000, where n-butane, 

perfluorohexane, and several tetrahalopropenes were added to a CO - air irradiation. The purpose of 

injecting the n-butane and halopropenes was to test whether the measured consumptions of the 

halopropenes occur at faster rates in this reactor than can be accounted for by gas-phase processes, as was 

indicated from the results of some of the incremental reactivity experiments. Loss of these compounds by 

reaction with OH radicals is calculated to be negligible under the conditions of these experiments. The nbutane was injected as a control and dilution tracer because it is known not to have unknown loss 

processes and can be analyzed with precision. The perfluorohexane was also added as a dilution tracer, 

but its data turned out not to be useful in this experiment because of GC interferences. However, useable 

data were obtained for the other added compounds. The results indicated that concentrations of 2,3,3,3-

tetrafluoropropene decline at the same rates as CO and n-butane, which is attributable to dilution. 

However, the trans 1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoro-propene declined in the 

reactor slightly faster than can be accounted for gas-phase processes. This is consistent with the results of 

the trans-1-chloro-3,3,3-trifluoro-propene measurements during the incremental reactivity experiments 

with this compound, which are discussed in the following section. 

Incremental Reactivity and Mechanism Evaluation Results 

The conditions and selected results of the incremental reactivity experiments used to evaluate the 

trans-1-chloro-3,3,3-trifluoropropene mechanism are summarized on Table 5. These experiments consist 

of irradiations of a reactive organic gas (ROG) - NOx mixture serving as a simplified model of the 

chemical system involved on O3 formation in urban atmospheres, together in irradiations of the same 

mixture with trans-1-chloro-3,3,3-trifluoropropene (the test compound) added. The experiment without 

the added test compound is referred to as the "base case" experiment, and the experiment where the test 

compound is added is the "test" experiment. The differences in O3 formation and other measures of 

reactivity in these experiments provide a measure of the effects of the test compound in a system more 

closely representing atmospheric conditions than the simpler experiments discussed above, and provide a 

more realistic test of the mechanism's ability to predict its atmospheric reactivity. 

As in previous incremental reactivity experiments carried out in this chamber (Carter and 

Malkina, 2005, 2007; Carter et al, 2005b), two types of base case experiments were employed. The first is 

a lower ROG/NOx experiment designed to approximate conditions where O3 formation is most sensitive 

to VOC emissions, which serve as the basis for the MIR reactivity scale, and are referred to as "MIR" 

experiments. The second is at higher ROG/NOx ratios with NOx levels at approximately half that yielding 

maximum ozone concentrations, and are referred to as "MOIR/2" experiments. For the MIR experiments 

the target initial NOx was approximately 30 ppb and the target initial base case ROG was approximately 

0.6 ppmC, while for the MOIR/2 experiments the target initial levels were approximately 25 ppb and 2.3 

ppmC, respectively. In both cases, the base ROG surrogate mixture representing reactive organic gases 

from all sources consists of n-butane, n-octane, ethene, propene, trans-2-butene, toluene and m-xylene, 

and is based on a mixture derived previously (Carter et al, 1995b) as a simplification of ambient mixtures 

used in the atmospheric reactivity calculations. Earlier versions of this mixture also contained 

formaldehyde, but this was not included in the current experiments for experimental reasons. As 
23 

Table 5. Summary of initial concentrations and selected gas-phase results of the incremental 

reactivity experiments. 

Base Run Initial 

Concentrations 5 Hr O3 (ppb) D([O3]-[NO]) 

Change (ppb) 

IntOH 

change 

5 Hr PM 

(μg/m3

) EPA 

Run 

No. 

Test 

Side 

Test 

Cmpd 

Added 

(ppm) 

NOx

(ppb) 

ROG 

(ppmC) Base Test 2 Hr 5 Hr (pptmin) Base Test 

Side Equivalency and added Perfluorohexane Experiment 

991 A 3.49 [a] 33 0.54 37 37 1 0 1 [b] [b] 

Added trans-1-chloro-3,3,3-trifluoropropene Experiments (MIR Conditions) 

1007 B 2.71 33 0.53 36 78 13 41 [b] [b] [b] 

1012 A 4.26 28 0.57 43 103 22 58 0.02 0.07 

Added trans-1-chloro-3,3,3-trifluoropropene Experiments (MOIR/2 Conditions) 

997 B 2.70 24 1.13 84 100 13 15 -4 [b] [b] 

1010 A 4.57 23 1.05 84 117 29 33 -7 0.43 0.16 

[a] Run carried out with added prefluorohexane to verify that this compound is unreactive and its 

presence would not affect reactivity results. 

[b] No useable data obtained for the time indicated. 

discussed by Carter and Malkina (2005), this does not significantly affect the utility of the experiments 

for mechanism evaluation. 

The measures of gas-phase reactivity used to evaluate the mechanisms in the incremental 

reactivity experiments are the effects of the test compound on ∆([O3]-[NO]), or ([O3]t-[NO]t)-([O3]0-

[NO]0), and IntOH, the integrated OH radical levels. As discussed elsewhere (e.g., Johnson, 1983; Carter 

and Atkinson, 1987; Carter and Lurmann, 1991, Carter et al, 1993), ∆([O3]-[NO]) gives a direct measure 

of the amount of conversion of NO to NO2 by peroxy radicals formed in the photooxidation reactions, 

which is the process that is directly responsible for ozone formation in the atmosphere. This gives a useful 

measure of factors affecting O3 reactivity even early in the experiments where O3 formation is suppressed 

by the unreacted NO. Although this is the primary measure of the effect of the VOC on O3 formation, the 

effect on radical levels is also a useful measure for mechanism evaluation, because radical levels affect 

how rapidly all VOCs present, including the base ROG components, react to form ozone. 

The integrated OH radical levels are not measured directly, but can be derived from the amounts 

of consumption of reactive VOCs that react only with OH radical levels. In particular, 

tracer

0 t

t kOH

ln([tracer] [tracer] ) Dt IntOH − = (I) 

where [tracer]0 and [tracer]t are the initial and time t concentrations of the compound used as the OH 

tracer, kOHtracer its OH rate constant, and D is the dilution rate in the experiments. The latter is neglected 

in our IntOH analysis. The base ROG surrogate component m-xylene was used as the tracer to derive the 

IntOH levels in these experiments. The OH + m-xylene rate constant used was 2.36 x 10-11 cm3

 molec-1 s-1

(Atkinson, 1989). 

Plots of experimental ∆([O3]-[NO]) in the base case and test experiments, changes in 

∆([O3]-[NO]) and IntOH caused by adding the trans-1-chloro-3,3,3-trifluoropropene, are shown on 
24 

Figure 4 and changes in these quantities are also summarized on Table 5. It can be seen that the addition 

of the trans-1-chloro-3,3,3-trifluoropropene caused a measurable increase in NO oxidation and O3

formation in all the experiments, increasing with the amount of test compound added. The effect of 

adding a given amount of the tetrahalopropene on ∆([O3]-[NO]) was larger in the MIR experiment than 

the lower NOx MOIR/2 runs, which is expected since MIR conditions are generally more sensitive to 

most VOCs. 

The effects of the added tetrahalopropene on the integrated OH levels in the experiments were 

relatively low, though generally negative. This indicates that this compound has a tendency to inhibit 

radical levels in the experiments, though the effect is small. Many VOCs have a tendency to inhibit 

overall radical levels in experiments to varying degrees. This was seen for trans 1,3,3,3-

tetrafluoropropene (Carter, 2009b) and 2,3,3,3-tetrafluoropropene (Carter, 2009c) as well. 

Results of model simulations of the incremental reactivity experiments are also shown on Figure 

4. For all experiments the model simulated the ∆([O3]-[NO]) results of the base case experiment quite 

well. The best fits to the ∆([O3]-[NO]) incremental reactivity data were obtained if it is assumed that 2.5% 

nitrate formation occurs in the overall reaction, as shown with the solid line ("model used") curves on 

Figure 4. It is assumed that overall nitrate formation occurs with a ~5% yield, which gives best fits to the 

data for trans 1,3,3,3-tetrafluoropropene (Carter, 2009b), then the model has a small but consistent bias 

towards underpredicting ∆([O3]-[NO]) reactivities, as shown by the dashed lines on Figure 4. Note that 

the reactivity data for 2,3,3,3-tetrafluoropropene are best fit assuming no nitrate formation in the overall 

reaction, so these results for trans 1-chloro-3,3,3-trifluoropropene are within the range of the results for 

the other two tetrahalopropenes studied. Changing the overall nitrate yield has no significant effect on 

calculations of IntOH reactivity or the rates of tetrahalopropene consumption. 

Figure 4 also shows the experimental and model calculated data for the consumption of the trans1-chloro-3,3,3-trifluoropropene during the experiment. In all cases the consumption of this compound 

was relatively slow and the fractions reacted were low. Because even relatively low levels of reactor 

dilution would affect consumption data for such slowly reacting compounds, in most experiments we 

added perfluoro n-hexane as a tracer to determine dilution rates to use when modeling these experiments. 

The results indicated that some dilution was occurring in some experiments but not in others, though the 

dilution rates were never greater than 0.3% per hour. Although small, this level of dilution did have an 

effect on the model simulations of the tetrahalopropene consumption rate, so dilution rates adjusted to fit 

the perfluorohexane data were used when modeling runs where perfluorohexane data were available. 

Figure 4 shows that even after correcting for dilution the model still had a slight tendency to 

underpredict the consumption rates of trans-1-chloro-3,3,3-trifluoropropene to a slight extent for most of 

the experiments. However, this underprediction was also seen for n-butane, which is present in all 

experiments as a base ROG surrogate, and which also reacts relatively slowly (though with a rate constant 

that is about 2.3 times higher than the tetrahalopropene. The consumption rate of the tetrahalopropene 

relative to n-butane, after correction for dilution in most cases, was found to be about twice that predicted 

using the rate constant ratios for these two compounds, indicating that there is some unknown loss 

process (or analytical bias) for gas-phase trans 1-chloro-3,3,3-trifluoropropene in these experiments. This 

is consistent with the results of the control experiment EPA1000 discussed above, where the measured 

decay rate for this compound under conditions where gas-phase loss processes should be negligible was 

found to be higher than dilution. Similar results were seen for trans 1,3,3,3-tetrafluoropropene but not for 

2,3,3,3-tetrafluoropropene in that experiment. The reason for this slightly higher apparent gas-phase loss 

for these compounds is unknown, but it is considered unlikely to have implications on the gas-phase 

reactivity of these compounds. This is indicated by the relatively good performance of the model in 

simulating the overall reactivity of these compounds, as indicated in Figure 4 for trans 1-chloro-3,3,3-

trifluoropropene and by a similar figure in Carter (2009a) for trans 1,3,3,3-tetrafluoropropene. 
25 

EPA1007B EPA1012A EPA997B EPA1010A

MIR (3.0 ppm added) MIR (4.7 ppm added) MOIR/2 (3.0 ppm added) MOIR/2 (5.1 ppm added)

∆(O3-NO) (ppm) vs Hour

IR ∆(O3-NO) (mole basis) vs Hour

IR IntOH (ppt-min/ppm) vs Hour

n-C6F14 (ppm) vs Hour

1-Chloro-3,3,3-Trifluoropropene (ppm) vs Hour

0.00

0.03

0.06

0.09

0123456

0.000

0.005

0.010

0.015

0123456

-1.0

-0.5

0.0

0.5

1.0

1.5

0123456

0.00

0.04

0.08

0.12

012345

0.000

0.005

0.010

0.015

012345

-1.0

-0.5

0.0

0.5

012345

0.00

0.04

0.08

0.12

0123456

0.000

0.002

0.004

0.006

0123456

-2

-1

0

1

0123456

0.00

0.04

0.08

0.12

01234

0.000

0.002

0.004

0.006

01234

-1.5

-1.0

-0.5

0.0

0.5

01234

Base Experiment Test Experiment Base Calc

Model Used 5% Nitrate calc

0.060

0.062

0.064

0.066

0.068

0.070

0123456

0.056

0.060

0.064

0.068

012345

0.058

0.060

0.062

0.064

0.066

0123456

0.063

0.064

0.065

0.066

0.067

01234

2.60

2.64

2.68

2.72

0123456

0

1

2

3

4

5

012345

2.4

2.5

2.6

2.7

2.8

0123456

4.48

4.50

4.52

4.54

4.56

4.58

01234

Figure 4. Experimental and calculated results of the incremental reactivity experiments with added 

trans-1-chloro-3,3,3-trifluoropropene. 
26 

Measurements of particle formation were also made during the course of the experiments, using 

the procedures discussed above and by Carter et al (2005b), and representative results are summarized on 

Table 5. The addition of the trans-1-chloro-3,3,3-trifluoropropene was found not to significantly change 

the amounts of PM formed in the experiments, indicating that this compound is not a significant source of 

secondary organic aerosol (SOA). This is not unexpected, since the mechanism derived for this compound 

does not involve formation of low volatility products, and similar results are seen for the other two 

tetrahalopropenes studied (Carter, 2009a,b). 

Atmospheric Reactivity Calculation 

Ozone Impacts 

Conditions and maximum O3 concentrations of the ambient scenarios used for reactivity 

assessment are summarized on Table 6. These are the same scenarios as used to calculate the atmospheric 

reactivities of the ~1100 types of VOCs using the SAPRC-07 mechanism by Carter (2009a), and are also 

the same as used in previous reactivity scales calculated using the SAPRC-99 (Carter, 2000a), and 

SAPRC-90 (Carter, 1994a) mechanisms. All of these are 1-day box model scenarios with varying 

inversion heights, initially present and emitted NOx and reactive organics, and O3 and background VOCs 

entrained from aloft as the inversion heights increase during the day (Carter, 1994a,b), with inputs 

designed to represent various urban areas around the United States (Baugues, 1990). As discussed 

previously, four types of scenarios are employed. 

• Base. The base case scenarios have the NOx and other inputs as originally specified by Baugues 

(1990) to represent the various urban areas around the United States. Note that these are not good 

representations of current conditions, since generally these scenarios predict much higher O3

levels than currently occur, and these box model incorporate significant simplifications of 

transport, mixing, and emissions, and multi-day effects, which can be important. However, they 

do represent a variety of chemical conditions, which are the main factors reflecting relative

atmospheric reactivities of VOCs. These scenarios represent a variety of relative NOx levels, 

which is a major factor affecting absolute and relative reactivities of VOCs (Carter and Atkinson, 

1989; Carter, 1994a). For this reason, other types of scenarios, discussed below, are derived to 

represent standard conditions of NOx availability. 

• MIR. The Maximum Incremental Reactivity (MIR) scenarios have the NOx inputs adjusted so 

that the base ROG mixture used to represent all the anthropogenic VOC emissions has the 

maximum incremental reactivity relative to ozone formation. All the other inputs are the same as 

in the base case scenarios. Although the base ROG reactivity is used to define the MIR NOx level, 

most other types of VOCs also have their maximum incremental reactivity at this same NOx level. 

These scenarios represent the relatively high NOx conditions where O3 formation is the most 

sensitive to VOC emissions. The averages incremental reactivities in all these scenarios are used 

to derive the MIR scale that is used in regulatory applications in California (CARB 1993, 2000). 

• MOIR. The Maximum Ozone Incremental Reactivity (MOIR) scenarios have the NOx inputs 

adjusted to give the maximum daily maximum ozone concentration. All other inputs are the same 

as in the base and MIR scenarios. These scenarios represent NOx conditions that are optimum for 

O3 formation, which is always lower than those for MIR. The averages incremental reactivities in 

all these scenarios are used to derive the MOIR scale, which can be considered as an alternative 

to MIR (Carter, 1994a). 

• EBIR. The Equal Benefit Incremental Reactivity (EBIR) scenarios have the NOx inputs adjusted 

so that O3 formation is equally sensitive to changes in total ROG or NOx inputs. All the other 

inputs are the same as in the base, MIR, and MOIR scenarios. The NOx inputs are always lower 
27 

Table 6. Summary of conditions of scenarios used for reactivity assessment 

Max O3 (ppb) ROG / NOx 

Scenario 

Base MIR MOIR EBIR Base MIR MOIR EBIR

Max 

Height 

(kM) 

ROG 

input 

(m.mol 

m-2) 

O3 aloft 

(ppb) 

Final H 

(m) 

Averaged 

Conditions 178 225 211 3.9 5.9 9.1 1.8 15 70 1823 

Atlanta, GA 171 144 176 168 7.3 3.7 5.6 7.9 2.1 12 63 2146 

Austin, TX 170 153 185 175 9.3 3.5 5.4 8.2 2.1 11 85 2108 

Baltimore, MD 310 243 318 293 5.2 4.0 6.2 10.1 1.2 17 84 1169 

Baton Rouge, LA 234 185 234 224 6.8 4.5 6.6 8.7 1.0 11 62 968 

Birmingham, AL 238 203 257 242 6.9 2.8 4.3 6.4 1.8 13 81 1770 

Boston, MA 191 164 199 189 6.5 2.9 4.4 6.8 2.6 14 105 2598 

Charlotte, NC 139 137 162 158 7.8 1.9 3.0 4.1 3.0 7 92 3046 

Chicago, IL 284 241 320 299 11.6 4.4 6.6 9.9 1.4 25 40 1392 

Cincinnati, OH 195 158 197 182 6.4 3.5 5.3 9.1 2.8 17 70 2816 

Cleveland, OH 241 194 241 228 6.6 4.4 6.9 10.3 1.7 16 89 1650 

Dallas, TX 184 160 202 192 4.7 4.2 6.4 9.2 2.3 18 75 2250 

Denver, CO 193 161 199 187 6.3 5.0 7.6 11.6 3.4 29 57 3358 

Detroit, MI 235 183 238 218 6.8 3.8 5.8 10.0 1.8 17 68 1844 

El Paso, TX 175 144 175 168 6.6 4.6 7.2 10.0 2.0 12 65 2000 

Hartford, CT 167 145 184 173 8.4 2.9 4.5 7.3 2.3 11 78 2318 

Houston, TX 298 226 298 277 6.1 4.1 6.2 9.5 1.7 25 65 1748 

Indianapolis, IN 202 156 203 191 6.6 4.0 6.5 9.8 1.7 12 52 1675 

Jacksonville, FL 149 126 156 149 7.6 3.7 5.5 7.6 1.5 8 40 1485 

Kansas City, MO 151 126 158 146 7.1 3.1 4.9 8.5 2.2 9 65 2200 

Lake Charles, LA 288 229 305 291 7.4 3.6 5.3 7.2 0.5 7 40 457 

Los Angeles, CA 558 403 559 528 7.6 5.2 8.0 11.2 0.5 23 100 503 

Louisville, KY 201 162 202 192 5.5 3.3 5.1 7.4 2.5 14 75 2518 

Memphis, TN 223 178 231 216 6.8 3.4 5.1 7.8 1.8 15 58 1750 

Miami, FL 129 120 149 143 9.6 2.9 4.5 6.4 2.7 9 57 2720 

Nashville, TN 161 146 186 175 8.0 2.6 4.0 6.0 1.6 7 50 1608 

New York, NY 372 302 378 357 8.1 4.8 6.7 9.8 1.5 39 103 1512 

Philadelphia, PA 234 178 234 218 6.2 4.1 6.3 9.7 1.8 19 53 1800 

Phoenix, AZ 267 208 267 244 7.6 5.0 7.8 13.0 3.3 40 60 3250 

Portland, OR 159 131 163 156 6.5 3.1 4.9 7.0 1.6 6 66 1575 

Richmond, VA 231 181 233 214 6.2 3.6 5.5 9.4 1.9 16 64 1932 

Sacramento, CA 195 150 196 183 6.6 3.9 6.0 9.1 1.1 7 60 1103 

St Louis, MO 304 237 311 288 6.1 4.7 7.2 11.6 1.6 26 82 1625 

Salt Lake City, UT 180 156 189 177 8.5 3.5 5.5 9.1 2.2 11 85 2150 

San Antonio, TX 119 101 122 118 3.9 3.0 4.7 6.5 2.3 6 60 2308 

San Diego, CA 185 146 185 177 7.1 4.7 7.2 10.1 0.9 8 90 850 

San Francisco, CA 225 345 455 434 4.8 6.1 9.0 12.0 0.7 25 70 650 

Tampa, FL 212 172 218 209 4.4 3.5 5.2 7.0 1.0 8 68 991 

Tulsa, OK 219 171 219 202 5.3 3.5 5.4 8.8 1.8 15 70 1830 

Washington, DC 272 209 273 256 5.3 3.2 4.8 7.4 1.4 13 99 1421 
28 

than those yielding maximum O3 (MOIR), and represent the lowest NOx levels where VOC 

control is at least as effective as NOx control. The averages incremental reactivities in all these 

scenarios are used to derive the EBIR scale, which is a useful complement to the MIR scale in 

assessing how NOx levels affect relative reactivities. 

• Averaged Conditions. The averaged conditions scenarios have all inputs other than total NOx

derived to represent the average for the base case scenarios. The NOx inputs are varied to assess 

how measures of reactivity depend on NOx with other inputs held constant. Incremental 

reactivities in the MIR, MOIR, and EBIR averaged conditions scenarios (i.e., whose NOx inputs 

are adjusted to represent those respective conditions) usually give good approximations to 

reactivities in those respective scales, though they are not used in deriving these scales. 

Table 7 gives the calculated incremental reactivities for trans-1-chloro-3,3,3-trifluoropropene in 

these various scenarios. These were calculated using the mechanism that gave the best fit to the chamber 

data, i.e. with the nitrate yield set at 2.5% (see Table 3). The calculated incremental reactivities for 

ethane, the compound that has been used by the U.S. EPA as the informal standard to define "negligible" 

ozone impact for the purpose of exempting VOCs from regulation as ozone precursors (Dimitriades, 

1999), are also shown on the table. It can be seen that although its incremental reactivities of trans 1-

chloro-3,3,3-trifluoropropene are always positive, they are relatively low, and consistently lower, on a 

mass basis, than those for ethane. The reactivity relative to ethane shows relatively little variability from 

scenario to scenario, with the mass-based reactivity ratio being 19±3%. The MIR ratio is 16±2%, which is 

within the variability for all the types of scenarios. 

Product Yield Calculations 

Although the major objective of this project is assessing ozone impacts, the mechanism derived in 

this work can also be used to assess the distribution of the products formed in the oxidation of trans 1-

chloro-3,3,3-trifluoropropene in the atmosphere. This could be a consideration when assessing the 

environmental impact because fluorine-containing products are not ultimately oxidized to CO or CO2, as 

is the case for hydrocarbons. The products expected to be formed are listed in Table 2, above, which also 

indicates which of these products are assumed to be relatively unreactive, at least on the time scale 

relevant to regional ozone formation. 

Figure 5a gives plots of relative yields of the fluorine-containing products from the oxidation of 

trans 1-chloro-3,3,3-trifluoropropene against relative NOx levels in the "averaged conditions" scenarios. 

As expected, the major products are the ClCHO and trifluoroacetaldehyde formed in the initial reaction, 

though under sufficiently low NOx conditions the initially formed C3F4 hydroperoxides also become 

important, with yields approaching 50%. The maximum yields of CF3OH, which results from the 

formation of CF3O· radicals, is about 4.5%, and occurs under maximum O3, or MOIR, conditions. This 

indicates that uncertainties concerning the reactions of CF3O· are probably not major factors in the ozone 

simulations. These are very similar to the results obtained for trans 1,3,3,3-tetrafluoropropene (Carter, 

2009b), except that FCHO is formed instead of ClCHO. 

The averaged conditions scenarios used to produce the data on Figure 5a are all one-day 

simulations, and greater yields of secondary products are expected to be formed in long range transport 

conditions. To assess that, the averaged conditions MOIR scenario simulation was carried out for an 

additional 9 days, with no emissions or dilution on the subsequent days. The relative yields of the 

products at midday are plotted against number of days of irradiation on Figure 5b. In long term irradiation 

conditions the yields of these hydroperoxides decline because of their reactions, and yields of 

trifluoromethanol and trifluoroacetic acid become more important, becoming ~25% and ~13% after 10 

days. These are also very similar to the results obtained for trans 1,3,3,3-tetrafluoropropene (Carter, 
29 

Table 7. Calculated atmospheric incremental reactivities for trans-1-chloro-3,3,3-trifluoropropene 

and ethane. 

trans-1-chloro-3,3,3-trifluoropropene 

Incremental Reactivity 

(gm O3 / gm VOC) 

 Ethane Incremental Reactivity 

Scenario (gm O3 / gm VOC) 

Base MIR MOIR EBIR Base MIR MOIR EBIR 

Averaged Conditions 0.040 0.032 0.023 0.268 0.184 0.130 

Reactivity Scale Value 

(Scenario averages)

0.030 

±0.006 

0.042 

±0.008 

0.034 

±0.006 

0.026 

±0.005 

0.162 

±0.043 

0.264 

±0.065 

0.184 

±0.051 

0.133 

±0.038 

Atlanta, GA 0.027 0.041 0.033 0.026 0.140 0.252 0.179 0.129 

Austin, TX 0.026 0.044 0.037 0.028 0.132 0.276 0.208 0.146 

Baltimore, MD 0.036 0.040 0.033 0.025 0.208 0.254 0.178 0.128 

Baton Rouge, LA 0.026 0.034 0.027 0.022 0.123 0.196 0.129 0.090 

Birmingham, AL 0.029 0.053 0.039 0.030 0.173 0.351 0.245 0.183 

Boston, MA 0.030 0.046 0.037 0.029 0.155 0.276 0.201 0.149 

Charlotte, NC 0.024 0.048 0.041 0.035 0.124 0.306 0.242 0.199 

Chicago, IL 0.020 0.039 0.030 0.023 0.089 0.239 0.149 0.104 

Cincinnati, OH 0.035 0.047 0.039 0.029 0.206 0.306 0.229 0.165 

Cleveland, OH 0.032 0.036 0.031 0.024 0.164 0.217 0.158 0.115 

Dallas, TX 0.037 0.036 0.028 0.022 0.236 0.232 0.165 0.116 

Denver, CO 0.032 0.033 0.029 0.022 0.156 0.184 0.123 0.086 

Detroit, MI 0.033 0.045 0.035 0.026 0.188 0.288 0.206 0.148 

El Paso, TX 0.027 0.031 0.026 0.021 0.145 0.186 0.132 0.094 

Hartford, CT 0.029 0.050 0.042 0.032 0.166 0.322 0.247 0.183 

Houston, TX 0.034 0.043 0.033 0.025 0.188 0.277 0.185 0.128 

Indianapolis, IN 0.035 0.043 0.036 0.027 0.191 0.280 0.194 0.138 

Jacksonville, FL 0.026 0.043 0.034 0.027 0.122 0.270 0.174 0.123 

Kansas City, MO 0.035 0.051 0.042 0.031 0.206 0.345 0.256 0.183 

Lake Charles, LA 0.026 0.049 0.035 0.027 0.109 0.296 0.166 0.112 

Los Angeles, CA 0.019 0.024 0.017 0.014 0.088 0.139 0.082 0.061 

Louisville, KY 0.040 0.052 0.042 0.032 0.228 0.338 0.245 0.176 

Memphis, TN 0.032 0.052 0.039 0.029 0.165 0.329 0.209 0.148 

Miami, FL 0.023 0.046 0.037 0.030 0.108 0.289 0.202 0.153 

Nashville, TN 0.029 0.061 0.048 0.036 0.172 0.450 0.310 0.222 

New York, NY 0.025 0.033 0.027 0.022 0.075 0.158 0.091 0.065 

Philadelphia, PA 0.034 0.044 0.034 0.025 0.177 0.265 0.175 0.124 

Phoenix, AZ 0.030 0.035 0.029 0.022 0.194 0.261 0.190 0.131 

Portland, OR 0.032 0.047 0.039 0.030 0.172 0.295 0.215 0.161 

Richmond, VA 0.034 0.044 0.036 0.027 0.188 0.278 0.201 0.146 

Sacramento, CA 0.029 0.041 0.032 0.024 0.191 0.307 0.208 0.146 

St Louis, MO 0.031 0.034 0.028 0.021 0.171 0.211 0.144 0.103 

Salt Lake City, UT 0.028 0.040 0.035 0.027 0.168 0.285 0.222 0.159 

San Antonio, TX 0.035 0.038 0.030 0.025 0.223 0.247 0.186 0.140 

San Diego, CA 0.023 0.029 0.023 0.018 0.099 0.143 0.097 0.070 

San Francisco, CA 0.014 0.021 0.018 0.015 0.085 0.113 0.071 0.051 

Tampa, FL 0.040 0.049 0.034 0.027 0.209 0.263 0.160 0.113 

Tulsa, OK 0.040 0.051 0.040 0.030 0.209 0.307 0.208 0.146 

Washington, DC 0.033 0.045 0.035 0.027 0.186 0.279 0.199 0.148 
30 

(a) Yield vs NOx Input (One day) (b) Yield vs day for Multi-Day (NOx = MOIR)

0.001

0.01

0.1

1

0.01 0.1 1 10

NOx / MOIR NOx

Yield Relative to Amount Reacted

0.001

0.01

0.1

1

0 2 4 6 8 10

Days

CLCHO

TFACET

RF4OOH

RF4OH

CF3OH

CF3PAN

CF3CO2H

CF3OOH

CF3CO3H

Figure 5. Plots of relative yields of fluorine-containing products in the oxidation of trans 1,3,3,3-

tetrafluoropropene against (a) relative NOx levels and days of irradiation in the "averaged 

conditions" scenarios, and (b) number of days in the MOIR scenario extended on for 9 

additional days. Yields are given relative to the amount of tetrahalopropene reacted. 

2009b). Note that these calculations do not consider deposition of the primary products, so they may be 

overestimating the yields of these secondary products. More detailed calculations that give better 

representations of actual scenarios, and that include deposition processes, are needed to for more realistic 

assessments of atmospheric fates. 
31 

CONCLUSIONS 

This project has been successful in obtaining information needed to reduce uncertainties in 

estimating atmospheric ozone impacts of trans-1-chloro-3,3,3-trifluoropropene. The available kinetic data 

are sufficient to determine the atmospheric reaction rates of this compound, and although mechanistic 

data are not available, mechanisms can be estimated based on mechanisms derived trans 1,3,3,3-

tetrafluoropropene and other alkenes. These are sufficient to derive an atmospheric reaction mechanism 

for this compound that can be used to estimate its atmospheric ozone impacts. However, the mechanism 

had uncertainties and estimates that needed to be tested, and experimental data were needed to establish 

the predictive capability of the mechanism before its predictions can be used as a basis for VOC 

exemption decisions. The experiments carried out for this project were successful in establishing the 

predictive capability of the mechanism developed for this compound, though some adjustments had to be 

made in order for the mechanism to simulate the data. These adjustments were well within the uncertainty 

of the estimates, so the mechanism can now be considered to be reasonably well established. 

The evaluated mechanism predicted that the ozone impacts of trans-1-chloro-3,3,3-

trifluoropropene, on a mass basis averaged 19±3% that of ethane for all the scenarios considered, with the 

ratio being 16±2% in the MIR scale. There were no scenarios where the ozone impact of trans 1-chloro3,3,3-trifluoropropene was calculated to be higher than that of ethane on a mass basis. Note that all the 

scenarios considered are one-day simulations, and compounds that react in the atmosphere more slowly 

than ethane might have higher relatively higher ozone impacts in multi-day simulations. However, trans 

1-chloro-3,3,3-trifluoropropene reacts somewhat more rapidly than ethane in the atmosphere, so if 

anything its ozone impacts relative to ethane are more likely to decrease in multi-day simulations. 

Therefore, if ethane is used as the standard to define “negligible” ozone impact for the purpose of 

determining VOC exemptions for ozone precursors, then trans 1-chloro-3,3,3-trifluoropropene will meet 

this standard. 

The uncertain portion of the trans 1-chloro-3,3,3-trifluoropropene mechanism that had to be 

adjusted to yield satisfactory simulations of the chamber data concerned the nitrate yields in the reaction 

of NO with the initially formed HOC3F3ClH2OO· peroxy radicals. The overall nitrate yield might be 

expected to be somewhere between ~0% and ~5%, based on the values that gave the best fits to the 

environmental chamber reactivity data for 2,3,3,3-tetrafluoropropene (Carter, 2009c) and trans-1,3,3,3-

tetrafluoropropene (Carter, 2009b), respectively. The data for trans 1-chloro-3,3,3-trifluoropropene are 

best fit if an overall nitrate yield of ~2.5% is assumed, which is between the values derived for the two 

tetrafluoropropenes. The fact that the best fit mechanisms suggest different nitrate yields for these 

tetrahalopropenes suggest that the nature and position of the halogen atoms on the molecule has an effect 

on the overall nitrate yields in the photooxidation mechanism. Note, however, that these yields are 

derived indirectly based on modeling ozone reactivity, and not direct measurements of nitrate formation. 

The near-explicit mechanism developed for this compound also permitted predictions of the gasphase products formed in the atmospheric oxidations of trans 1-chloro-3,3,3-trifluoropropene. The major 

products are the formyl chloride and trifluoroacetaldehyde formed in high yields in the initial reactions in 

the presence of NOx, though if NOx is sufficiently low then significant yields of C3F3Cl hydroperoxides 

will also be formed. In longer term irradiations the trifluoroacetaldehyde and the C3F3Cl hydroperoxides 

will undergo secondary reactions, with the major secondary products ultimately formed being 

trifluoromethanol and trifluoroacetic acid, with yields approaching 10-20% after many days of photolysis. 

However, if deposition of the primary products is significant, then the yields of these secondary products 

would be less. If this is of interest, then modeling using more comprehensive and realistic representations 
32 

of ambient simulations are needed. The mechanism developed in this work could be used for such 

modeling, and the results presented here are indicative of the types of information that can be obtained. 

Although this was outside the stated scope of this project, data were also obtained in this project 

concerning the effects of trans-1-chloro-3,3,3-trifluoropropene on atmospheric particle formation. The 

results indicated that the addition of this compound to atmospheric reactive organic gas surrogate - NOx

irradiations either had no significant effect on the mass or particles formed. This indicates that this 

compound does not form measurable amounts of secondary organic aerosol. This is as expected, since it 

is not predicted to form low volatility products. Furthermore, the products that it forms apparently do not 

also undergo significant heterogeneous reactions to form condensable compounds, at least under the 

relatively clean and dry conditions of these experiments. 
33 

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37 

APPENDIX A. BASE MECHANISM LISTING 

Table A-1. List of model species used in the base SAPRC-07 mechanism, including the VOC species 

used in the chamber and atmospheric reactivity simulations. The model species used for 

trans-1-chloro-3,3,3-trifluoropropene and its reaction products and intermediates are 

given in Table 2, above. 

Name Description 

 

Constant Species.

 O2 Oxygen 

 M Air 

 H2O Water 

 H2 Hydrogen Molecules 

 HV Light 

Active Inorganic Species.

 O3 Ozone 

 NO Nitric Oxide 

 NO2 Nitrogen Dioxide 

 NO3 Nitrate Radical 

 N2O5 Nitrogen Pentoxide 

 HONO Nitrous Acid 

 HNO3 Nitric Acid 

 HNO4 Peroxynitric Acid 

 HO2H Hydrogen Peroxide 

 CO Carbon Monoxide 

 SO2 Sulfur Dioxide 

 H2 Hydrogen 

Active Radical Species and Operators.

 OH Hydroxyl Radicals 

 HO2 Hydroperoxide Radicals 

 MEO2 Methyl Peroxy Radicals 

RO2C Peroxy Radical Operator representing NO to NO2 and NO3 to NO2 conversions, and the 

effects of peroxy radical reactions on acyl peroxy and other peroxy radicals. 

RO2XC Peroxy Radical Operator representing NO consumption (used in conjunction with organic 

nitrate formation), and the effects of peroxy radical reactions on NO3, acyl peroxy radicals, 

and other peroxy radicals. 

 MECO3 Acetyl Peroxy Radicals 

 RCO3 Peroxy Propionyl and higher peroxy acyl Radicals 

 BZCO3 Peroxyacyl radical formed from Aromatic Aldehydes 

 MACO3 Peroxyacyl radicals formed from methacrolein and other acroleins. 

Steady State Radical Species

 O3P Ground State Oxygen Atoms 

 O1D Excited Oxygen Atoms 

 TBUO t-Butoxy Radicals 

 BZO Phenoxy Radicals 
Table A-1 (continued) 

38 

Name Description 

 

PAN and PAN Analogues

 PAN Peroxy Acetyl Nitrate 

 PAN2 PPN and other higher alkyl PAN analogues 

 PBZN PAN analogues formed from Aromatic Aldehydes 

 MAPAN PAN analogue formed from Methacrolein 

Explicit and Lumped Molecule Reactive Organic Product Species

 HCHO Formaldehyde 

 CCHO Acetaldehyde 

 RCHO Lumped C3+ Aldehydes. Mechanism based on propionaldehyde 

 ACET Acetone 

MEK Ketones and other non-aldehyde oxygenated products that react with OH radicals faster 

than 5 x 10-13 but slower than 5 x 10-12 cm3

 molec-2 sec-1. Mechanism based on methyl ethyl 

ketone. 

 MEOH Methanol 

 HCOOH Formic Acid 

 CCOOH Acetic Acid. Also used for peroxyacetic acid. 

 RCOOH Higher organic acids and peroxy acids. Mechanism based on propionic acid. 

 COOH Methyl Hydroperoxide 

ROOH Lumped organic hydroperoxides with 2-4 carbons. Mechanism based n-propyl 

hydroperoxide. 

R6OOH Lumped organic hydroperoxides with 5 or more carbons (other than those formed following 

OH addition to aromatic rings, which are represented separately). Mechanism based on 3-

hexyl hydroperoxide. 

RAOOH Organic hydroperoxides formed following OH addition to aromatic rings, which is 

represented separately because of their probable role in SOA formation. Mechanism based 

on two isomers expected to be formed in the m-xylene system. 

 GLY Glyoxal 

 MGLY Methyl Glyoxal 

 BACL Biacetyl 

 CRES Phenols and Cresols. Mechanism based on o-cresol. 

 NPHE Nitrophenols 

 BALD Aromatic aldehydes. Mechanism based on benzaldehyde 

 MACR Methacrolein 

 MVK Methyl Vinyl Ketone 

 IPRD Lumped isoprene product species. Mechanism based on that of Carter and Atkinson (1996).

Aromatic unsaturated ring fragmentation products (see discussion of aromatic mechanisms) 

AFG1 Lumped photoreactive monounsaturated dicarbonyl aromatic fragmentation products that 

photolyze to form radicals. 

AFG2 Lumped photoreactive monounsaturated dicarbonyl aromatic fragmentation products that 

photolyze to form non-radical products 

 AFG3 Lumped diunsaturatred dicarbonyl aromatic fragmentation product. 
Table A-1 (continued) 

39 

Name Description 

 

Lumped Parameter Products

PROD2 Ketones and other non-aldehyde oxygenated products that react with OH radicals faster 

than 5 x 10-12 cm3

 molec-2 sec-1. Mechanism based on CH3C(O)CH2CH2CH2OH, CH3C(O)-

CH2CH(CH3)CH2OH, CH3CH2C(O)CH2CH2CH(CH3)OH, CH3CH2C(O)CH2CH2CH(OH)-

CH2CH3, and CH3CH2CH2CH(OH)CH2-CH2C(O)CH2CH3 (PROD2-1 through 5), each 

weighed equally. 

RNO3 Lumped Organic Nitrates. Mechanism based on CH3CH2CH(CH3)ONO2, CH3CH(OH)CH2-

CH2CH2ONO2, CH3CH2CH(CH3)CH(CH3)ONO2, CH3CH2CH2CH2CH2CH(ONO2)CH2OH, 

CH3CH2C(CH3)(ONO2)CH2CH(CH3)CH3, and CH3CH2CH2CH2CH2CH2CH2CH(ONO2)-

CH2CH3 (RNO3-1 through 6), each weighed equally. 

Steady state operators used to represent radical or product formation in peroxy radical reactions.

xHO2 Formation of HO2 from alkoxy radicals formed in peroxy radical reactions with NO and 

NO3 (100% yields) and RO2 (50% yields) 

 xOH As above, but for OH 

 xNO2 As above, but for NO2

 xMEO2 As above, but for MEO2 

 xMECO3 As above, but for MECO3 

 xRCO3 As above, but for RCO3 

 xMACO3 As above, but for MACO3 

 xTBUO As above, but for TBUO 

 xCO As above, but for CO 

 xHNO3 As above, but for HNO3 

 xHCHO As above, but for HCHO 

 xCCHO As above, but for CCHO 

 xRCHO As above, but for RCHO 

 xACET As above, but for ACET 

 xMEK As above, but for MEK 

 xPROD2 As above, but for PROD2 

 xGLY As above, but for GLY 

 xMGLY As above, but for MGLY 

 xBACL As above, but for BACL 

 xBALD As above, but for BALD 

 xAFG1 As above, but for AFG1 

 xAFG2 As above, but for AFG2 

 xAFG3 As above, but for AFG3 

 xMACR As above, but for MACR 

 xMVK As above, but for MVK 

 xIPRD As above, but for IPRD 

 xRNO3 As above, but for RNO3 

 xHCOOH As above, but for HCOOH 

 xCCOOH As above, but for CCOOH 

 xRCOOH As above, but for RCOOH 

zRNO3 Formation of RNO3 in the RO2 + NO, reaction, or formation of corresponding non-nitrate 

products (represented by PROD2) formed from alkoxy radicals formed in RO2 + NO3 and 

(in 50% yields) RO2 + RO2 reactions. 
Table A-1 (continued) 

40 

Name Description 

 

yROOH Formation of ROOH following RO2 + HO2 reactions, or formation of H-shift 

disproportionation products (represented by MEK) in the RO2 + RCO3 and (in 50% yields) 

RO2 + RO2 reactions. 

yR6OOH As above, but with the RO2 + HO2 product represented by R6OOH and the H-shift products 

are represented by PROD2. 

 yRAOOH As above, but with the RO2 + HO2 product represented by R6OOH 

Non-Reacting Species

 CO2 Carbon Dioxide 

 SULF Sulfates (SO3 or H2SO4) 

 XC Lost Carbon or carbon in unreactive products 

 XN Lost Nitrogen or nitrogen in unreactive products 

Primary Organics Represented explicitly

 CH4 Methane 

 ETHENE Ethene 

 ISOPRENE Isoprene 

 ACETYLEN Acetylene 

 BENZENE Benzene 

 ETHANE Ethane (not part of the base mechanism, but used in atmospheric reactivity simulations) 

Organics represented explicitly in the chamber simulations (not used in the atmospheric simulations)

 N-C4 n-Butane 

 N-C8 n-Octane 

 PROPENE Propene 

 T-2-BUTE trans-2-Butene 

 TOLUENE Toluene 

 M-XYLENE m-Xylene 

Lumped model species used in the atmospheric reactivity simulations (not used in chamber simulations) 

ALK1 Alkanes and other non-aromatic compounds that react only with OH, and have kOH (OH 

radical rate constant) between 2 and 5 x 102

 ppm-1 min-1. (Primarily ethane) 

ALK2 Alkanes and other non-aromatic compounds that react only with OH, and have kOH 

between 5 x 102

 and 2.5 x 103 ppm-1 min-1. (Primarily propane) 

ALK3 Alkanes and other non-aromatic compounds that react only with OH, and have kOH 

between 2.5 x 103

 and 5 x 103 ppm-1 min-1. 

ALK4 Alkanes and other non-aromatic compounds that react only with OH, and have kOH 

between 5 x 103

 and 1 x 104 ppm-1 min-1. 

ALK5 Alkanes and other non-aromatic compounds that react only with OH, and have kOH greater 

than 1 x 104

 ppm-1 min-1. 

 ARO1 Aromatics with kOH < 2x104

 ppm-1 min-1. 

 ARO2 Aromatics with kOH > 2x104

 ppm-1 min-1. 

 OLE1 Alkenes (other than ethene) with kOH < 7x104

 ppm-1 min-1. 

 OLE2 Alkenes with kOH > 7x104

 ppm-1 min-1. 

 TERP Terpenes 
41 

Table A-2. Reactions and rate constants in the SAPRC-07 mechanism used in this work. See Carter 

(2009a) for documentation. The reactions used for trans-1-chloro-3,3,3-trifluoropropene 

are given in Table 3, above. 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

Inorganic Reactions 

 1 NO2 + HV = NO + O3P Phot Set= NO2-06 

 2 O3P + O2 + M = O3 + M 5.68e-34 5.68e-34 0.00 -2.60

 3 O3P + O3 = #2 O2 8.34e-15 8.00e-12 4.09 

 4 O3P + NO = NO2 1.64e-12 Falloff, F=0.60, N=1.00

 0: 9.00e-32 0.00 -1.50

 inf: 3.00e-11 0.00 0.00

 5 O3P + NO2 = NO + O2 1.03e-11 5.50e-12 -0.37 

 6 O3P + NO2 = NO3 3.24e-12 Falloff, F=0.60, N=1.00

 0: 2.50e-31 0.00 -1.80

 inf: 2.20e-11 0.00 -0.70

 7 O3 + NO = NO2 + O2 2.02e-14 3.00e-12 2.98 

 8 O3 + NO2 = O2 + NO3 3.72e-17 1.40e-13 4.91 

 9 NO + NO3 = #2 NO2 2.60e-11 1.80e-11 -0.22 

 10 NO + NO + O2 = #2 NO2 1.93e-38 3.30e-39 -1.05 

 11 NO2 + NO3 = N2O5 1.24e-12 Falloff, F=0.35, N=1.33

 0: 3.60e-30 0.00 -4.10

 inf: 1.90e-12 0.00 0.20

 12 N2O5 = NO2 + NO3 5.69e-2 Falloff, F=0.35, N=1.33

 0: 1.30e-3 21.86 -3.50

 inf: 9.70e+14 22.02 0.10

 13 N2O5 + H2O = #2 HNO3 2.50e-22 

 14 N2O5 + H2O + H2O = #2 HNO3 + H2O 1.80e-39 

 N2O5 + HV = NO3 + NO + O3P (Slow) 

 N2O5 + HV = NO3 + NO2 (Slow) 

 15 NO2 + NO3 = NO + NO2 + O2 6.75e-16 4.50e-14 2.50 

 16 NO3 + HV = NO + O2 Phot Set= NO3NO-06 

 17 NO3 + HV = NO2 + O3P Phot Set= NO3NO2-6 

 18 O3 + HV = O1D + O2 Phot Set= O3O1D-06 

 19 O3 + HV = O3P + O2 Phot Set= O3O3P-06 

 20 O1D + H2O = #2 OH 1.99e-10 

 21 O1D + M = O3P + M 3.28e-11 2.38e-11 -0.19 

 22 OH + NO = HONO 7.31e-12 Falloff, F=0.60, N=1.00

 0: 7.00e-31 0.00 -2.60

 inf: 3.60e-11 0.00 -0.10

 23 HONO + HV = OH + NO Phot Set= HONO-06 

 24 OH + HONO = H2O + NO2 5.95e-12 2.50e-12 -0.52 

 25 OH + NO2 = HNO3 1.05e-11 Falloff, F=0.60, N=1.00

 0: 1.80e-30 0.00 -3.00

 inf: 2.80e-11 0.00 0.00

 26 OH + NO3 = HO2 + NO2 2.00e-11 
Table A-2 (continued) 

42 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

27 OH + HNO3 = H2O + NO3 1.51e-13 k = 

k0+k3M/(1+k3M/k2) 

 k0: 2.40e-14 -0.91 0.00

 k2: 2.70e-17 -4.37 0.00

 k3: 6.50e-34 -2.65 0.00

 28 HNO3 + HV = OH + NO2 Phot Set= HNO3 

 29 OH + CO = HO2 + CO2 2.28e-13 k = k1 + k2 [M] 

 k1: 1.44e-13 0.00 0.00

 k2: 3.43e-33 0.00 0.00

 30 OH + O3 = HO2 + O2 7.41e-14 1.70e-12 1.87 

 31 HO2 + NO = OH + NO2 8.85e-12 3.60e-12 -0.54 

 32 HO2 + NO2 = HNO4 1.12e-12 Falloff, F=0.60, N=1.00

 0: 2.00e-31 0.00 -3.40

 inf: 2.90e-12 0.00 -1.10

 33 HNO4 = HO2 + NO2 1.07e-1 Falloff, F=0.60, N=1.00

 0: 3.72e-5 21.16 -2.40

 inf: 5.42e+15 22.20 -2.30

 34 HNO4 + HV = #.61 {HO2 + NO2} + #.39 {OH + NO3} Phot Set= HNO4-06 

 35 HNO4 + OH = H2O + NO2 + O2 4.61e-12 1.30e-12 -0.76 

 36 HO2 + O3 = OH + #2 O2 2.05e-15 2.03e-16 -1.38 4.57

 37 HO2 + HO2 = HO2H + O2 2.84e-12 k = k1 + k2 [M] 

 k1: 2.20e-13 -1.19 0.00

 k2: 1.90e-33 -1.95 0.00

 38 HO2 + HO2 + H2O = HO2H + O2 + H2O 6.09e-30 k = k1 + k2 [M] 

 k1: 3.08e-34 -5.56 0.00

 k2: 2.66e-54 -6.32 0.00

39 NO3 + HO2 = #.8 {OH + NO2 + O2} + #.2 {HNO3 + 

O2} 

4.00e-12 

 40 NO3 + NO3 = #2 NO2 + O2 2.41e-16 8.50e-13 4.87 

 41 HO2H + HV = #2 OH Phot Set= H2O2 

 42 HO2H + OH = HO2 + H2O 1.80e-12 1.80e-12 0.00 

 43 OH + HO2 = H2O + O2 1.10e-10 4.80e-11 -0.50 

 44 OH + SO2 = HO2 + SULF 9.49e-13 Falloff, F=0.60, N=1.00

 0: 3.30e-31 0.00 -4.30

 inf: 1.60e-12 0.00 0.00

 45 OH + H2 = HO2 + H2O 7.02e-15 7.70e-12 4.17 

Methyl peroxy and methoxy reactions 

 BR01 MEO2 + NO = NO2 + HCHO + HO2 7.64e-12 2.30e-12 -0.72 

 BR02 MEO2 + HO2 = COOH + O2 4.65e-12 3.46e-13 -1.55 0.36

 BR03 MEO2 + HO2 = HCHO + O2 + H2O 4.50e-13 3.34e-14 -1.55 -3.53

 BR04 MEO2 + NO3 = HCHO + HO2 + NO2 1.30e-12 

 BR05 MEO2 + MEO2 = MEOH + HCHO + O2 2.16e-13 6.39e-14 -0.73 -1.80

 BR06 MEO2 + MEO2 = #2 {HCHO + HO2} 1.31e-13 7.40e-13 1.03 

Active Peroxy Radical Operators 

 BR07 RO2C + NO = NO2 9.23e-12 2.60e-12 -0.76 

 BR08 RO2C + HO2 = HO2 7.63e-12 3.80e-13 -1.79 
Table A-2 (continued) 

43 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

 BR09 RO2C + NO3 = NO2 2.30e-12 

BR10 RO2C + MEO2 = #.5 {RO2C + xHO2 + xHCHO + O2} 

+ #.25 {HCHO + MEOH} 

2.00e-13 

 BR11 RO2C + RO2C = 3.50e-14 

 

 BR12 RO2XC + NO = XN Same k as rxn BR07 

 BR13 RO2XC + HO2 = HO2 Same k as rxn BR08 

 BR14 RO2XC + NO3 = NO2 Same k as rxn BR09 

BR15 RO2XC + MEO2 = #.5 {RO2C + xHO2 + xHCHO + 

O2} + #.25 {HCHO + MEOH} 

Same k as rxn BR10 

 BR16 RO2XC + RO2C = Same k as rxn BR11 

 BR17 RO2XC + RO2XC = Same k as rxn BR11 

Reactions of Acyl Peroxy Radicals, PAN, and PAN analogues 

 BR18 MECO3 + NO2 = PAN 9.37e-12 Falloff, F=0.30, N=1.41

 0: 2.70e-28 0.00 -7.10

 inf: 1.21e-11 0.00 -0.90

 BR19 PAN = MECO3 + NO2 6.27e-4 Falloff, F=0.30, N=1.41

 0: 4.90e-3 24.05 0.00

 inf: 4.00e+16 27.03 0.00

BR20 PAN + HV = #.6 {MECO3 + NO2} + #.4 {MEO2 + 

CO2 + NO3} 

Phot Set= PAN 

 BR21 MECO3 + NO = MEO2 + CO2 + NO2 1.97e-11 7.50e-12 -0.58 

 BR22 MECO3 + HO2 = CCOOH + #.7 O2 + #.3 O3 1.36e-11 5.20e-13 -1.95 

 BR23 MECO3 + NO3 = MEO2 + CO2 + NO2 + O2 Same k as rxn BR09 

BR24 MECO3 + MEO2 = #.9 {CCOOH + HCHO + O2} + #.1 

{HCHO + HO2 + MEO2 + CO2} 

1.06e-11 2.00e-12 -0.99 

 BR25 MECO3 + RO2C = CCOOH 1.56e-11 4.40e-13 -2.13 

 BR26 MECO3 + RO2XC = CCOOH Same k as rxn BR25 

 BR27 MECO3 + MECO3 = #2 {MEO2 + CO2} + O2 1.54e-11 2.90e-12 -0.99 

 

 BR28 RCO3 + NO2 = PAN2 1.21e-11 1.21e-11 0.00 -1.07

 BR29 PAN2 = RCO3 + NO2 5.48e-4 8.30e+16 27.70 

BR30 RCO3 + NO = NO2 + RO2C + xHO2 + yROOH + 

xCCHO + CO2 

2.08e-11 6.70e-12 -0.68 

 BR31 RCO3 + HO2 = RCOOH + #.75 O2 + #.25 O3 Same k as rxn BR22 

BR32 RCO3 + NO3 = NO2 + RO2C + xHO2 + yROOH + 

xCCHO + CO2 + O2 

Same k as rxn BR09 

 BR33 RCO3 + MEO2 = RCOOH + HCHO + O2 Same k as rxn BR24 

 BR34 RCO3 + RO2C = RCOOH + O2 Same k as rxn BR25 

 BR35 RCO3 + RO2XC = RCOOH + O2 Same k as rxn BR25 

BR36 RCO3 + MECO3 = #2 CO2 + MEO2 + RO2C + xHO2 

+ yROOH + xCCHO + O2 

Same k as rxn BR27 

BR37 RCO3 + RCO3 = #2 {RO2C + xHO2 + xCCHO + 

yROOH + CO2} 

Same k as rxn BR27 

 

 BR38 BZCO3 + NO2 = PBZN 1.37e-11 

 BR39 PBZN = BZCO3 + NO2 4.27e-4 7.90e+16 27.82 

 BR40 BZCO3 + NO = NO2 + CO2 + BZO + RO2C Same k as rxn BR30 
Table A-2 (continued) 

44 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

BR41 BZCO3 + HO2 = RCOOH + #.75 O2 + #.25 O3 + #4 

XC 

Same k as rxn BR22 

 BR42 BZCO3 + NO3 = NO2 + CO2 + BZO + RO2C + O2 Same k as rxn BR09 

 BR43 BZCO3 + MEO2 = RCOOH + HCHO + O2 + #4 XC Same k as rxn BR24 

 BR44 BZCO3 + RO2C = RCOOH + O2 + #4 XC Same k as rxn BR25 

 BR45 BZCO3 + RO2XC = RCOOH + O2 + #4 XC Same k as rxn BR25 

 BR46 BZCO3 + MECO3 = #2 CO2 + MEO2 + BZO + RO2C Same k as rxn BR27 

BR47 BZCO3 + RCO3 = #2 CO2 + RO2C + xHO2 + yROOH 

+ xCCHO + BZO + RO2C 

Same k as rxn BR27 

 BR48 BZCO3 + BZCO3 = #2 {BZO + RO2C + CO2} Same k as rxn BR27 

 BR49 MACO3 + NO2 = MAPAN Same k as rxn BR28 

 BR50 MAPAN = MACO3 + NO2 4.79e-4 1.60e+16 26.80 

 BR51 MACO3 + NO = NO2 + CO2 + HCHO + MECO3 Same k as rxn BR30 

 BR52 MACO3 + HO2 = RCOOH + #.75 O2 + #.25 O3 + XC Same k as rxn BR22 

BR53 MACO3 + NO3 = NO2 + CO2 + HCHO + MECO3 + 

O2 

Same k as rxn BR09 

 BR54 MACO3 + MEO2 = RCOOH + HCHO + XC + O2 Same k as rxn BR24 

 BR55 MACO3 + RO2C = RCOOH + XC Same k as rxn BR25 

 BR56 MACO3 + RO2XC = RCOOH + O2 + XC Same k as rxn BR25 

BR57 MACO3 + MECO3 = #2 CO2 + MEO2 + HCHO + 

MECO3 + O2 

Same k as rxn BR27 

BR58 MACO3 + RCO3 = HCHO + MECO3 + RO2C + xHO2 

+ yROOH + xCCHO + #2 CO2 

Same k as rxn BR27 

BR59 MACO3 + BZCO3 = HCHO + MECO3 + BZO + 

RO2C + #2 CO2 

Same k as rxn BR27 

 BR60 MACO3 + MACO3 = #2 {HCHO + MECO3 + CO2} Same k as rxn BR27 

Other Organic Radical Species 

 BR61 TBUO + NO2 = RNO3 + #-2 XC 2.40e-11 

 BR62 TBUO = ACET + MEO2 1.18e+3 7.50e+14 16.20 

 

 BR63 BZO + NO2 = NPHE 3.79e-11 2.30e-11 -0.30 

 BR64 BZO + HO2 = CRES + #-1 XC Same k as rxn BR08 

 BR65 BZO = CRES + RO2C + xHO2 + #-1 XC 1.00e-3 

Steady-State Peroxy Radical operators (for formation of inorganic and radical products) [c]

 RO01 xHO2 = HO2 k is variable parameter: RO2RO 

 RO02 xHO2 = k is variable parameter: RO2XRO 

 RO03 xOH = OH k is variable parameter: RO2RO 

 RO04 xOH = k is variable parameter: RO2XRO 

 RO05 xNO2 = NO2 k is variable parameter: RO2RO 

 RO06 xNO2 = XN k is variable parameter: RO2XRO 

 RO07 xMEO2 = MEO2 k is variable parameter: RO2RO 

 RO08 xMEO2 = XC k is variable parameter: RO2XRO 

 RO09 xMECO3 = MECO3 k is variable parameter: RO2RO 

 RO10 xMECO3 = #2 XC k is variable parameter: RO2XRO 

 RO11 xRCO3 = RCO3 k is variable parameter: RO2RO 

 RO12 xRCO3 = #3 XC k is variable parameter: RO2XRO 

 RO13 xMACO3 = MACO3 k is variable parameter: RO2RO 
Table A-2 (continued) 

45 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

 RO14 xMACO3 = #4 XC k is variable parameter: RO2XRO 

 RO15 xTBUO = TBUO k is variable parameter: RO2RO 

 RO16 xTBUO = #4 XC k is variable parameter: RO2XRO 

 RO17 xCO = CO k is variable parameter: RO2RO 

 RO18 xCO = XC k is variable parameter: RO2XRO 

 RO19 xHNO3 = HNO3 k is variable parameter: RO2RO 

 RO20 xHNO3 = XN k is variable parameter: RO2XRO 

Explicit and Lumped Molecule Organic Products 

 BP01 HCHO + HV = #2 HO2 + CO Phot Set= HCHOR-06 

 BP02 HCHO + HV = H2 + CO Phot Set= HCHOM-06 

 BP03 HCHO + OH = HO2 + CO + H2O 8.47e-12 5.40e-12 -0.27 

 BP07 HCHO + NO3 = HNO3 + HO2 + CO 6.06e-16 2.00e-12 4.83 

 

 BP08 CCHO + OH = MECO3 + H2O 1.49e-11 4.40e-12 -0.73 

 BP09 CCHO + HV = CO + HO2 + MEO2 Phot Set= CCHO_R 

 BP10 CCHO + NO3 = HNO3 + MECO3 2.84e-15 1.40e-12 3.70 

 

BP11 RCHO + OH = #.965 RCO3 + #.035 {RO2C + xHO2 + 

xCO + xCCHO + yROOH} 

1.97e-11 5.10e-12 -0.80 

BP12 RCHO + HV = RO2C + xHO2 + yROOH + xCCHO + 

CO + HO2 

Phot Set= C2CHO 

 BP13 RCHO + NO3 = HNO3 + RCO3 6.74e-15 1.40e-12 3.18 

 

 BP14 ACET + OH = RO2C + xMECO3 + xHCHO + yROOH 1.91e-13 4.56e-14 -0.85 3.65

 BP15 ACET + HV = #.62 MECO3 + #1.38 MEO2 + #.38 CO Phot Set= ACET-06, qy= 0.5 

 

BP16 MEK + OH = #.967 RO2C + #.039 {RO2XC + 

zRNO3} + #.376 xHO2 + #.51 xMECO3 + #.074 

xRCO3 + #.088 xHCHO + #.504 xCCHO + #.376 

xRCHO + yROOH + #.3 XC 

1.20e-12 1.30e-12 0.05 2.00

BP17 MEK + HV = MECO3 + RO2C + xHO2 + xCCHO + 

yROOH 

Phot Set= MEK-06, qy= 0.175 

 

 BP18 MEOH + OH = HCHO + HO2 9.02e-13 2.85e-12 0.69 

 BP19 HCOOH + OH = HO2 + CO2 4.50e-13 

BP20 CCOOH + OH = #.509 MEO2 + #.491 RO2C + #.509 

CO2 + #.491 xHO2 + #.491 xMGLY + #.491 yROOH + 

#-0.491 XC 

7.26e-13 4.20e-14 -1.70 

BP21 RCOOH + OH = RO2C + #.08 CO2 + xHO2 + #.063 

CO2 + #.142 xCCHO + #.4 xRCHO + #.457 xBACL + 

yROOH + #-0.455 XC 

1.20e-12 

 

 BP22 COOH + OH = H2O + #.3 {HCHO + OH} + #.7 MEO2 7.40e-12 3.80e-12 -0.40 

 BP23 COOH + HV = HCHO + HO2 + OH Phot Set= COOH 

 

BP24 ROOH + OH = #.744 OH + #.251 RO2C + #.004 

RO2XC + #.004 zRNO3 + #.744 RCHO + #.239 xHO2 

+ #.012 xOH + #.012 xHCHO + #.012 xCCHO + #.205 

xRCHO + #.034 xPROD2 + #.256 yROOH + #-0.115 

XC 

2.50e-11 

 BP25 ROOH + HV = RCHO + HO2 + OH Phot Set= COOH 

 
Table A-2 (continued) 

46 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

BP26 R6OOH + OH = #.84 OH + #.222 RO2C + #.029 

RO2XC + #.029 zRNO3 + #.84 PROD2 + #.09 xHO2 + 

#.041 xOH + #.02 xCCHO + #.075 xRCHO + #.084 

xPROD2 + #.16 yROOH + #.02 XC 

5.60e-11 

BP27 R6OOH + HV = OH + #.142 HO2 + #.782 RO2C + 

#.077 RO2XC + #.077 zRNO3 + #.085 RCHO + #.142 

PROD2 + #.782 xHO2 + #.026 xCCHO + #.058 

xRCHO + #.698 xPROD2 + #.858 yR6OOH + #.017 

XC 

Phot Set= COOH 

 

BP28 RAOOH + OH = #.139 OH + #.148 HO2 + #.589 RO2C 

+ #.124 RO2XC + #.124 zRNO3 + #.074 PROD2 + 

#.147 MGLY + #.139 IPRD + #.565 xHO2 + #.024 

xOH + #.448 xRCHO + #.026 xGLY + #.030 xMEK + 

#.252 xMGLY + #.073 xAFG1 + #.073 xAFG2 + #.713 

yR6OOH + #2.674 XC 

1.41e-10 

BP29 RAOOH + HV = OH + HO2 + #.5 {GLY + MGLY + 

AFG1 + AFG2} + #.5 XC 

Phot Set= COOH 

 

 BP30 GLY + HV = #2 {CO + HO2} Phot Set= GLY-07R 

 BP31 GLY + HV = HCHO + CO Phot Set= GLY-07M 

BP32 GLY + OH = #.63 HO2 + #1.26 CO + #.37 RCO3 + #-

.37 XC 

1.10e-11 

BP33 GLY + NO3 = HNO3 + #.63 HO2 + #1.26 CO + #.37 

RCO3 + #-.37 XC 

1.02e-15 2.80e-12 4.72 

 

 BP34 MGLY + HV = HO2 + CO + MECO3 Phot Set= MGLY-06 

 BP35 MGLY + OH = CO + MECO3 1.50e-11 

 BP36 MGLY + NO3 = HNO3 + CO + MECO3 2.53e-15 1.40e-12 3.77 

 

 BP37 BACL + HV = #2 MECO3 Phot Set= BACL-07 

 

BP38 CRES + OH = #.2 BZO + #.8 {RO2C + xHO2 + 

yR6OOH} + #.25 xMGLY + #5.05 XC 

4.03e-11 1.70e-12 -1.89 

 BP39 CRES + NO3 = HNO3 + BZO + XC 1.40e-11 

 

 BP40 NPHE + OH = BZO + XN 3.50e-12 

 BP41 NPHE + HV = HONO + #6 XC Phot Set= NO2-06, qy= 1.5e-3 

 BP42 NPHE + HV = #6 XC + XN Phot Set= NO2-06, qy= 1.5e-2 

 

 BP43 BALD + OH = BZCO3 1.20e-11 

 BP44 BALD + HV = #7 XC Phot Set= BALD-06, qy= 0.06 

 BP45 BALD + NO3 = HNO3 + BZCO3 2.73e-15 1.34e-12 3.70 

 
Table A-2 (continued) 

47 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

Lumped Unsaturated Aromatic Ring-Opening Products 

BP46 AFG1 + OH = #.217 MACO3 + #.723 RO2C + #.060 

{RO2XC + zRNO3} + #.060 zRNO3 + #.521 xHO2 + 

#.201 xMECO3 + #.334 xCO + #.407 xRCHO + #.129 

xMEK + #.107 xGLY + #.267 xMGLY + #.783 

yR6OOH + #-.076 XC 

7.40e-11 

BP47 AFG1 + O3 = #.826 OH + #.522 HO2 + #.652 RO2C + 

#.522 CO + #.174 CO2 + #.432 GLY + #.568 MGLY + 

#.652 xRCO3 + #.652 xHCHO + #.652 yR6OOH + #-

.872 XC 

9.66e-18 

BP48 AFG1 + HV = #1.023 HO2 + #.173 MEO2 + #.305 

MECO3 + #.500 MACO3 + #.695 CO + #.195 GLY + 

#.305 MGLY + #.217 XC 

Phot Set= AFG1 

 

BP49 AFG2 + OH = #.217 MACO3 + #.723 RO2C + #.060 

{RO2XC + zRNO3} + #.060 zRNO3 + #.521 xHO2 + 

#.201 xMECO3 + #.334 xCO + #.407 xRCHO + #.129 

xMEK + #.107 xGLY + #.267 xMGLY + #.783 

yR6OOH + #-.076 XC 

7.40e-11 

BP50 AFG2 + O3 = #.826 OH + #.522 HO2 + #.652 RO2C + 

#.522 CO + #.174 CO2 + #.432 GLY + #.568 MGLY + 

#.652 xRCO3 + #.652 xHCHO + #.652 yR6OOH + #-

.872 XC 

9.66e-18 

 BP51 AFG2 + HV = PROD2 + #-1 XC Phot Set= AFG1 

 

BP52 AFG3 + OH = #.206 MACO3 + #.733 RO2C + #.117 

{RO2XC + zRNO3} + #.117 zRNO3 + #.561 xHO2 + 

#.117 xMECO3 + #.114 xCO + #.274 xGLY + #.153 

xMGLY + #.019 xBACL + #.195 xAFG1 + #.195 

xAFG2 + #.231 xIPRD + #.794 yR6OOH + #.236 XC 

9.35e-11 

BP53 AFG3 + O3 = #.471 OH + #.554 HO2 + #.013 MECO3 

+ #.258 RO2C + #.007 {RO2XC + zRNO3} + #.007 

zRNO3 + #.580 CO + #.190 CO2 + #.366 GLY + #.184 

MGLY + #.350 AFG1 + #.350 AFG2 + #.139 AFG3 + 

#.003 MACR + #.004 MVK + #.003 IPRD + #.095 

xHO2 + #.163 xRCO3 + #.163 xHCHO + #.095 

xMGLY + #.264 yR6OOH + #-.617 XC 

1.43e-17 

BP54 MACR + OH = #.5 MACO3 + #.5 {RO2C + xHO2} + 

#.416 xCO + #.084 xHCHO + #.416 xMEK + #.084 

xMGLY + #.5 yROOH + #-0.416 XC 

2.84e-11 8.00e-12 -0.76 

BP55 MACR + O3 = #.208 OH + #.108 HO2 + #.1 RO2C + 

#.45 CO + #.117 CO2 + #.1 HCHO + #.9 MGLY + 

#.333 HCOOH + #.1 xRCO3 + #.1 xHCHO + #.1 

yROOH + #-0.1 XC 

1.28e-18 1.40e-15 4.17 

BP56 MACR + NO3 = #.5 {MACO3 + RO2C + HNO3 + 

xHO2 + xCO} + #.5 yROOH + #1.5 XC + #.5 XN 

3.54e-15 1.50e-12 3.61 

 BP57 MACR + O3P = RCHO + XC 6.34e-12 
Table A-2 (continued) 

48 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

BP58 MACR + HV = #.33 OH + #.67 HO2 + #.34 MECO3 + 

#.33 MACO3 + #.33 RO2C + #.67 CO + #.34 HCHO + 

#.33 xMECO3 + #.33 xHCHO + #.33 yROOH 

Phot Set= MACR-06 

 

BP59 MVK + OH = #.975 RO2C + #.025 {RO2XC + 

zRNO3} + #.3 xHO2 + #.675 xMECO3 + #.3 xHCHO + 

#.675 xRCHO + #.3 xMGLY + yROOH + #-0.725 XC 

1.99e-11 2.60e-12 -1.21 

BP60 MVK + O3 = #.164 OH + #.064 HO2 + #.05 {RO2C + 

xHO2} + #.475 CO + #.124 CO2 + #.05 HCHO + #.95 

MGLY + #.351 HCOOH + #.05 xRCO3 + #.05 xHCHO 

+ #.05 yROOH + #-0.05 XC 

5.36e-18 8.50e-16 3.02 

 BP61 MVK + NO3 = #4 XC + XN (Slow) 

 BP62 MVK + O3P = #.45 RCHO + #.55 MEK + #.45 XC 4.32e-12 

BP63 MVK + HV = #.4 MEO2 + #.6 CO + #.6 PROD2 + #.4 

MACO3 + #-2.2 XC 

Phot Set= MVK-06 

 

BP64 IPRD + OH = #.289 MACO3 + #.67 {RO2C + xHO2} 

+ #.041 {RO2XC + zRNO3} + #.336 xCO + #.055 

xHCHO + #.129 xCCHO + #.013 xRCHO + #.15 

xMEK + #.332 xPROD2 + #.15 xGLY + #.174 xMGLY 

+ #-0.504 XC + #.711 yR6OOH 

6.19e-11 

BP65 IPRD + O3 = #.285 OH + #.4 HO2 + #.048 {RO2C + 

xRCO3} + #.498 CO + #.14 CO2 + #.124 HCHO + #.21 

MEK + #.023 GLY + #.742 MGLY + #.1 HCOOH + 

#.372 RCOOH + #.047 xCCHO + #.001 xHCHO + 

#.048 yR6OOH + #-.329 XC 

4.18e-18 

BP66 IPRD + NO3 = #.15 {MACO3 + HNO3} + #.799 

{RO2C + xHO2} + #.051 {RO2XC + zRNO3} + #.572 

xCO + #.227 xHCHO + #.218 xRCHO + #.008 xMGLY 

+ #.572 xRNO3 + #.85 yR6OOH + #.278 XN + #-.815 

XC 

1.00e-13 

BP67 IPRD + HV = #1.233 HO2 + #.467 MECO3 + #.3 

RCO3 + #1.233 CO + #.3 HCHO + #.467 CCHO + 

#.233 MEK + #-.233 XC 

Phot Set= MACR-06 

Lumped Parameter Organic Products 

BP68 PROD2 + OH = #.472 HO2 + #.473 RO2C + #.070 

RO2XC + #.070 zRNO3 + #.002 HCHO + #.001 CCHO 

+ #.143 RCHO + #.329 PROD2 + #.379 xHO2 + #.029 

xMECO3 + #.049 xRCO3 + #.211 xHCHO + #.083 

xCCHO + #.402 xRCHO + #.115 xMEK + #.007 

xPROD2 + #.528 yR6OOH + #.883 XC 

1.55e-11 

BP69 PROD2 + HV = #.400 MECO3 + #.600 RCO3 + #1.590 

RO2C + #.086 RO2XC + #.086 zRNO3 + #.914 xHO2 

+ #.303 xHCHO + #.163 xCCHO + #.780 xRCHO + 

yR6OOH + #-.085 XC 

Phot Set= MEK-06, qy= 4.86e-3 

 
Table A-2 (continued) 

49 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

BP70 RNO3 + OH = #.019 NO2 + #.189 HO2 + #.976 RO2C 

+ #.175 RO2XC + #.175 zRNO3 + #.001 RCHO + 

#.010 MEK + #.007 PROD2 + #.189 RNO3 + #.312 

xNO2 + #.305 xHO2 + #.011 xHCHO + #.428 xCCHO 

+ #.036 xRCHO + #.004 xACET + #.170 xMEK + 

#.030 xPROD2 + #.305 xRNO3 + #.792 yR6OOH + 

#.175 XN + #.054 XC 

7.20e-12 

BP71 RNO3 + HV = NO2 + #.344 HO2 + #.721 RO2C + 

#.102 RO2XC + #.102 zRNO3 + #.074 HCHO + #.214 

CCHO + #.074 RCHO + #.124 MEK + #.190 PROD2 + 

#.554 xHO2 + #.061 xHCHO + #.230 xCCHO + #.063 

xRCHO + #.008 xACET + #.083 xMEK + #.261 

xPROD2 + #.656 yR6OOH + #.396 XC 

Phot Set= IC3ONO2 

Steady-State Peroxy Radical operators (for formation of organic product species formed in 

peroxy + NO reactions) [c]

 

 PO01 xHCHO = HCHO k is variable parameter: RO2RO 

 PO02 xHCHO = XC k is variable parameter: RO2XRO 

 PO03 xCCHO = CCHO k is variable parameter: RO2RO 

 PO04 xCCHO = #2 XC k is variable parameter: RO2XRO 

 PO05 xRCHO = RCHO k is variable parameter: RO2RO 

 PO06 xRCHO = #3 XC k is variable parameter: RO2XRO 

 PO07 xACET = ACET k is variable parameter: RO2RO 

 PO08 xACET = #3 XC k is variable parameter: RO2XRO 

 PO09 xMEK = MEK k is variable parameter: RO2RO 

 PO10 xMEK = #4 XC k is variable parameter: RO2XRO 

 PO11 xPROD2 = PROD2 k is variable parameter: RO2RO 

 PO12 xPROD2 = #6 XC k is variable parameter: RO2XRO 

 PO13 xGLY = GLY k is variable parameter: RO2RO 

 PO14 xGLY = #2 XC k is variable parameter: RO2XRO 

 PO15 xMGLY = MGLY k is variable parameter: RO2RO 

 PO16 xMGLY = #3 XC k is variable parameter: RO2XRO 

 PO17 xBACL = BACL k is variable parameter: RO2RO 

 PO18 xBACL = #4 XC k is variable parameter: RO2XRO 

 PO19 xBALD = BALD k is variable parameter: RO2RO 

 PO20 xBALD = #7 XC k is variable parameter: RO2XRO 

 PO21 xAFG1 = AFG1 k is variable parameter: RO2RO 

 PO22 xAFG1 = #5 XC k is variable parameter: RO2XRO 

 PO23 xAFG2 = AFG2 k is variable parameter: RO2RO 

 PO24 xAFG2 = #5 XC k is variable parameter: RO2XRO 

 PO25 xAFG3 = AFG3 k is variable parameter: RO2RO 

 PO26 xAFG3 = #7 XC k is variable parameter: RO2XRO 

 PO27 xMACR = MACR k is variable parameter: RO2RO 

 PO28 xMACR = #4 XC k is variable parameter: RO2XRO 

 PO29 xMVK = MVK k is variable parameter: RO2RO 

 PO30 xMVK = #4 XC k is variable parameter: RO2XRO 

 PO31 xIPRD = IPRD k is variable parameter: RO2RO 

 PO32 xIPRD = #5 XC k is variable parameter: RO2XRO 
Table A-2 (continued) 

50 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

 PO33 xRNO3 = RNO3 k is variable parameter: RO2RO 

 PO34 xRNO3 = #6 XC + XN k is variable parameter: RO2XRO 

 PO35 xHCOOH = HCOOH k is variable parameter: RO2RO 

 PO36 xHCOOH = XC k is variable parameter: RO2XRO 

 PO37 xCCOOH = CCOOH k is variable parameter: RO2RO 

 PO38 xCCOOH = #2 XC k is variable parameter: RO2XRO 

 PO39 xRCOOH = RCOOH k is variable parameter: RO2RO 

 PO40 xRCOOH = #3 XC k is variable parameter: RO2XRO 

Steady-State Peroxy Radical operators (for formation of organic nitrates formed in peroxy + NO 

reactions) [d]

 PO41 zRNO3 = RNO3 + #-1 XN k is variable parameter: RO2NO 

 PO42 zRNO3 = PROD2 + HO2 k is variable parameter: RO22NN 

 PO43 zRNO3 = #6 XC k is variable parameter: RO2XRO 

Steady-State Peroxy Radical operators (for formation of hydroperoxides formed in peroxy + HO2

reactions) [e]

 PO44 yROOH = ROOH + #-3 XC k is variable parameter: RO2HO2 

 PO45 yROOH = MEK + #-4 XC k is variable parameter: RO2RO2M

 PO46 yROOH = k is variable parameter: RO2RO 

 PO47 yR6OOH = R6OOH + #-6 XC k is variable parameter: RO2HO2 

 PO48 yR6OOH = PROD2 + #-6 XC k is variable parameter: RO2RO2M

 PO49 yR6OOH = k is variable parameter: RO2RO 

 PO50 yRAOOH = RAOOH + #-8 XC k is variable parameter: RO2HO2 

 PO51 yRAOOH = PROD2 + #-6 XC k is variable parameter: RO2RO2M

 PO52 yRAOOH = k is variable parameter: RO2RO 

Explicitly Represented Primary Organics 

 BE01 CH4 + OH = H2O + MEO2 6.62e-15 1.85e-12 3.36 

 

 BE02 8.15e-12 Falloff, F=0.60, N=1.00

 0: 1.00e-28 0.00 -4.50

 

ETHENE + OH = RO2C + xHO2 + #1.61 xHCHO + 

#.195 xCCHO + yROOH 

inf: 8.80e-12 0.00 -0.85

BE03 ETHENE + O3 = #.16 OH + #.16 HO2 + #.51 CO + 

#.12 CO2 + HCHO + #.37 HCOOH 

1.68e-18 9.14e-15 5.13 

BE04 ETHENE + NO3 = RO2C + xHO2 + xRCHO + 

yROOH + #-1 XC + XN 

2.24e-16 3.30e-12 5.72 2.00

BE05 ETHENE + O3P = #.8 HO2 + #.51 MEO2 + #.29 RO2C 

+ #.51 CO + #.1 CCHO + #.29 xHO2 + #.278 xCO + 

#.278 xHCHO + #.012 xGLY + #.29 yROOH + #.2 XC

7.43e-13 1.07e-11 1.59 

 

BE06 ISOPRENE + OH = #.986 RO2C + #.093 {RO2XC + 

zRNO3} + #.907 xHO2 + #.624 xHCHO + #.23 

xMACR + #.32 xMVK + #.357 xIPRD + yR6OOH + #-

0.167 XC 

9.96e-11 2.54e-11 -0.81 

BE07 ISOPRENE + O3 = #.266 OH + #.066 HO2 + #.192 

RO2C + #.008 {RO2XC + zRNO3} + #.275 CO + #.122 

CO2 + #.4 HCHO + #.1 PROD2 + #.39 MACR + #.16 

MVK + #.15 IPRD + #.204 HCOOH + #.192 

{xMACO3 + xHCHO} + #.2 yR6OOH + #-0.559 XC 

1.34e-17 7.86e-15 3.80 
Table A-2 (continued) 

51 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

BE08 ISOPRENE + NO3 = #.936 RO2C + #.064 {RO2XC + 

zRNO3} + #.749 xHO2 + #.187 xNO2 + #.936 xIPRD + 

yR6OOH + #-0.064 XC + #.813 XN 

6.81e-13 3.03e-12 0.89 

BE09 ISOPRENE + O3P = #.25 MEO2 + #.24 RO2C + #.01 

{RO2XC + zRNO3} + #.75 PROD2 + #.24 xMACO3 + 

#.24 xHCHO + #.25 yR6OOH + #-1.01 XC 

3.50e-11 

 

BE10 ACETYLEN + OH = #.7 OH + #.3 HO2 + #.3 CO + #.7 

GLY + #.3 HCOOH 

7.56e-13 Falloff, F=0.60, N=1.00

BE11 ACETYLEN + O3 = #.5 OH + #1.5 HO2 + #1.5 CO + 

#.5 CO2 

1.16e-20 1.00e-14 8.15 

 

BE12 BENZENE + OH = #.116 OH + #.29 {RO2C + xHO2} 

+ #.024 {RO2XC + zRNO3} + #.57 {HO2 + CRES} + 

#.116 AFG3 + #.290 xGLY + #.029 xAFG1 + #.261 

xAFG2 + #.314 yRAOOH + #-.976 XC 

1.22e-12 2.33e-12 0.38 

Reactions of Compounds represented explicitly in the chamber simulations

CH05 N-C4 + OH = #1.334 RO2C + #.079 RO2XC + #.079 

zRNO3 + #.921 xHO2 + #.632 xCCHO + #.120 xRCHO 

+ #.485 xMEK + yROOH + #-.038 XC 

2.38e-12 1.63e-12 -0.23 

CH09 N-C8 + OH = #1.432 RO2C + #.354 RO2XC + #.354 

zRNO3 + #.646 xHO2 + #.024 xRCHO + #.622 

xPROD2 + yR6OOH + #2.072 XC 

8.16e-12 2.45e-12 -0.72 

CH11 PROPENE + OH = #.984 RO2C + #.016 RO2XC + 

#.016 zRNO3 + #.984 xHO2 + #.984 xHCHO + #.984 

xCCHO + yROOH + #-.048 XC 

2.60e-11 4.85e-12 -1.00 

CH12 PROPENE + O3 = #.350 OH + #.165 HO2 + #.355 

MEO2 + #.525 CO + #.215 CO2 + #.500 HCHO + #.500 

CCHO + #.185 HCOOH + #.075 CCOOH + #.070 XC 

1.05e-17 5.51e-15 3.73 

CH13 PROPENE + NO3 = #.949 RO2C + #.051 RO2XC + 

#.051 zRNO3 + #.949 xHO2 + yROOH + #2.694 XC + 

XN 

9.73e-15 4.59e-13 2.30 

CH14 PROPENE + O3P = #.450 RCHO + #.550 MEK + #-

.550 XC 

4.01e-12 1.02e-11 0.56 

CH16 T-2-BUTE + OH = #.965 RO2C + #.035 RO2XC + 

#.035 zRNO3 + #.965 xHO2 + #1.930 xCCHO + 

yROOH + #-.070 XC 

6.32e-11 1.01e-11 -1.09 

CH17 T-2-BUTE + O3 = #.540 OH + #.170 HO2 + #.710 

MEO2 + #.540 CO + #.310 CO2 + CCHO + #.150 

CCOOH + #.140 XC 

1.95e-16 6.64e-15 2.10 

CH18 T-2-BUTE + NO3 = #.920 RO2C + #.080 RO2XC + 

#.080 zRNO3 + #.705 xNO2 + #.215 xHO2 + #1.410 

xCCHO + #.215 xRNO3 + yROOH + #-.590 XC + 

#.080 XN 

3.93e-13 1.10e-13 -0.76 

 CH19 T-2-BUTE + O3P = MEK 1.99e-11 1.09e-11 -0.36 
Table A-2 (continued) 

52 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

CH21 TOLUENE + OH = #.312 {OH + AFG3} + #.181 {HO2 

+ CRES} + #.454 {RO2C + xHO2} + #.054 {RO2XC 

+zRNO3} + #.238 xGLY + #.151 xMGLY + #.065 

xBALD + #.195 xAFG1 + #.195 xAFG2 + #.073 

yR6OOH + #.435 yRAOOH + #-.109 XC 

5.58e-12 1.81e-12 -0.67 

CH23 M-XYLENE + OH = #.239 {OH + AFG3} + #.159 

{HO2 + CRES} + #.52 {RO2C +xHO2} + #.082 

{RO2XC + zRNO3} + #.100 xGLY + #.380 xMGLY + 

#.041 xBALD + #.336 xAFG1 + #.144 xAFG2 + #.047 

yR6OOH + #.555 yRAOOH+ #.695 XC 

2.31e-11 

Reactions of Ethane used in its Atmospheric Reactivity Simulations

 C201 ETHANE + OH = RO2C + xHO2 + xCCHO + yROOH 2.54E-13 1.34E-12 0.992 2.0 

Reactions of Lumped Species used in Atmospheric Reactivity Simulations

 BL01 ALK1 + OH = RO2C + xHO2 + xCCHO + yROOH 2.54e-13 1.34e-12 0.99 

BL02 ALK2 + OH = #.965 RO2C + #.035 {RO2XC + 

zRNO3} + #.965 xHO2 + #.261 xRCHO + #.704 

xACET + yROOH + #-.105 XC 

1.11e-12 1.49e-12 0.17 

BL03 ALK3 + OH = #1.253 RO2C + #.07 {RO2XC + 

zRNO3} + #.694 xHO2 + #.236 xTBUO + #.026 

xHCHO + #.445 xCCHO + #.122 xRCHO + #.024 

xACET + #.332 xMEK + yROOH + #-.046 XC 

2.31e-12 1.51e-12 -0.25 

BL04 ALK4 + OH = #1.773 RO2C + #.144 {RO2XC + 

zRNO3} + #.834 xHO2 + #.011 xMEO2 + #.011 

xMECO3 + #.002 xCO + #.030 xHCHO + #.454 

xCCHO + #.242 xRCHO + #.442 xACET + #.110 

xMEK + #.128 xPROD2 + yR6OOH + #-.097 XC 

4.26e-12 3.67e-12 -0.09 

BL05 ALK5 + OH = #1.597 RO2C + #.348 {RO2XC + 

zRNO3} + #.652 xHO2 + #.037 xHCHO + #.099 

xCCHO + #.199 xRCHO + #.066 xACET + #.080 

xMEK + #.425 xPROD2 + yR6OOH + #2.012 XC 

9.22e-12 2.65e-12 -0.74 

 

BL06 OLE1 + OH = #1.138 RO2C + #.095 {RO2XC + 

zRNO3} + #.904 xHO2 + #.001 xMEO2 + #.700 

xHCHO + #.301 xCCHO + #.470 xRCHO + #.005 

xACET + #.119 xPROD2 + #.026 xMACR + #.008 

xMVK + #.006 xIPRD + yROOH + #.822 XC 

3.29e-11 6.18e-12 -1.00 

BL07 OLE1 + O3 = #.193 OH + #.116 HO2 + #.104 MEO2 + 

#.063 RO2C + #.004 {RO2XC + zRNO3} + #.368 CO + 

#.125 CO2 + #.500 HCHO + #.147 CCHO + #.353 

RCHO + #.006 MEK + #.189 PROD2 + #.185 HCOOH 

+ #.022 CCOOH + #.112 RCOOH + #.040 xHO2 + 

#.007 xCCHO + #.031 xRCHO + #.002 xACET + #.044 

yR6OOH + #.69 XC 

1.09e-17 3.15e-15 3.38 

BL08 OLE1 + NO3 = #1.312 RO2C + #.176 {RO2XC + 

zRNO3} + #.824 xHO2 + #.009 xCCHO + #.002 

xRCHO + #.024 xACET + #.546 xRNO3 + yR6OOH + 

#.454 XN + #.572 XC 

1.44e-14 4.73e-13 2.08 
Table A-2 (continued) 

53 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

BL09 OLE1 + O3P = #.450 RCHO + #.437 MEK + #.113 

PROD2 + #1.224 XC 

5.02e-12 1.49e-11 0.65 

 

BL10 OLE2 + OH = #.966 RO2C + #.086 {RO2XC + 

zRNO3} + #.914 xHO2 + #.209 xHCHO + #.787 

xCCHO + #.483 xRCHO + #.136 xACET + #.076 

xMEK + #.021 xPROD2 + #.027 xMACR + #.002 

xMVK + #.037 xIPRD + yR6OOH + #.113 XC 

6.41e-11 1.26e-11 -0.97 

BL11 OLE2 + O3 = #.421 OH + #.093 HO2 + #.290 MEO2 + 

#.199 RO2C + #.003 {RO2XC + zRNO3} + #.296 CO + 

#.162 CO2 + #.152 HCHO + #.426 CCHO + #.316 

RCHO + #.048 ACET + #.031 MEK + #.042 PROD2 + 

#.028 MACR + #.021 MVK + #.033 HCOOH + #.061 

CCOOH + #.222 RCOOH + #.039 xHO2 + #.147 

xMECO3 + #.007 xRCO3 + #.108 xHCHO + #.066 

xCCHO + #.019 xRCHO + #.196 yR6OOH + #.133 XC

1.24e-16 8.15e-15 2.49 

BL12 OLE2 + NO3 = #1.185 RO2C + #.136 {RO2XC + 

zRNO3} + #.409 xNO2 + #.423 xHO2 + #.033 xMEO2 

+ #.074 xHCHO + #.546 xCCHO + #.153 xRCHO + 

#.110 xACET + #.002 xMEK + #.026 xMVK + #.007 

xIPRD + #.322 xRNO3 + yR6OOH + #.270 XN + #.117 

XC 

7.70e-13 2.15e-13 -0.76 

BL13 OLE2 + O3P = #.014 HO2 + #.013 RO2C + #.074 

RCHO + #.709 MEK + #.203 PROD2 + #.007 xHO2 + 

#.007 xMACO3 + #.006 xCO + #.006 xMACR + #.014 

yR6OOH + #.666 XC 

2.06e-11 1.43e-11 -0.22 

 

BL14 ARO1 + OH = #.283 OH + #.166 HO2 + #.483 RO2C + 

#.068 {RO2XC + zRNO3} + #.166 CRES + #.283 

AFG3 + #.483 xHO2 + #.217 xGLY + #.138 xMGLY + 

#.049 xBALD + #.079 xPROD2 + #.164 xAFG1 + #.192 

xAFG2 + #.150 yR6OOH + #.402 yRAOOH+ #.004 XC

6.18e-12 

BL15 ARO2 + OH = #.199 OH + #.108 HO2 + #.582 RO2C + 

#.111 RO2XC + #.111 zRNO3 + #.108 CRES + #.199 

AFG3 + #.582 xHO2 + #.111 xGLY + #.291 xMGLY + 

#.104 xBACL + #.033 xBALD + #.042 xPROD2 + 

#.223 xAFG1 + #.211 xAFG2 + #.074 xAFG3 + #.090 

yR6OOH + #.603 yRAOOH+ #1.503 XC 

2.20e-11 

 

BL16 TERP + OH = #1.147 RO2C + #.2 {RO2XC + zRNO3} 

+ #.759 xHO2 + #.042 xRCO3 + #.002 xCO + #.264 

xHCHO + #.533 xRCHO + #.036 xACET + #.005 

xMEK + #.255 xPROD2 + #.009 xMGLY + #.014 

xBACL + #.002 xMVK + #.001 xIPRD + yR6OOH + 

#5.055 XC 

7.98e-11 1.87e-11 -0.86 
Table A-2 (continued) 

54 

 Rate Parameters [b] 

 Label Reaction and Products [a] k(300) A Ea B 

BL17 TERP + O3 = #.585 OH + #.052 HO2 + #.875 RO2C + 

#.203 RO2XC + #.203 zRNO3 + #.166 CO + #.045 CO2 

+ #.079 HCHO + #.004 MEK + #.409 PROD2 + #.107 

HCOOH + #.043 RCOOH + #.067 xHO2 + #.126 

xMECO3 + #.149 xRCO3 + #.019 xCO + #.150 xHCHO 

+ #.220 xRCHO + #.165 xACET + #.001 xGLY + #.002 

xMGLY + #.055 xBACL + #.001 xMACR + #.001 

xIPRD + #.545 yR6OOH + #3.526 XC 

6.99e-17 1.02e-15 1.60 

BL18 TERP + NO3 = #1.508 RO2C + #.397 RO2XC + #.397 

zRNO3 + #.422 xNO2 + #.162 xHO2 + #.019 xRCO3 + 

#.010 xCO + #.017 xHCHO + #.001 xCCHO + #.509 

xRCHO + #.174 xACET + #.001 xMGLY + #.003 

xMACR + #.001 xMVK + #.002 xIPRD + #.163 xRNO3 

+ yR6OOH + #4.476 XC + #.415 XN 

6.53e-12 1.28e-12 -0.97 

BL19 TERP + O3P = #.147 RCHO + #.853 PROD2 + #4.441 

XC 

3.71e-11 

[a] Format of reaction listing: “=“ separates reactants from products; “#number” indicates stoichiometric 

coefficient, “#coefficient {product list}” means that the stoichiometric coefficient is applied to all the 

products listed. 

[b] Except as indicated, the rate constants are given by k(T) = A · (T/300)B

 · e-Ea/RT, where the units of k 

and A are cm3

 molec-1 s-1, Ea are kcal mol-1, T is oK, and R=0.0019872 kcal mol-1 deg-1. If A, Ea, and 

B are not given the rate constants are assumed to be temperature independent. The following special 

rate constant expressions are used: 

Phot Set = name: The absorption cross sections and (if applicable) quantum yields for the photolysis 

reaction are given by Carter (2009). Here, “name” indicates the photolysis set used. If a 

“qy=number” notation is given, the number given is the overall quantum yield, which is assumed to 

be wavelength independent. Photolysis rates used in chamber and ambient simulations are given in 

Table A-3. 

Falloff: The rate constant as a function of temperature and pressure is calculated using k(T,M) = 

{k0(T)·[M]/[1 + k0(T)·[M]/kinf(T)]}· FZ

, where Z = {1 + [log10{k0(T)·[M])/kinf(T)}/N]2 }-1, [M] 

is the total pressure in molecules cm-3, F and N are as indicated on the table, and the temperature 

dependences of k0 and kinf are as indicated on the table. 

k = k0+k3M(1+k3M/k2): The rate constant as a function of temperature and pressure is calculated 

using k(T,M) = k0(T) + k3(T)·[M] ·(1 + k3(T)·[M]/k2(T)), where [M] is the total bath gas (air) 

concentration in molecules cm-3, and the temperature dependences for k0, k2 and k3 are as 

indicated on the table. 

k = k1 + k2 [M]: The rate constant as a function of temperature and pressure is calculated using 

k(T,M) = k1(T) + k2(T)·[M], where [M] is the total bath gas (air) concentration in molecules cm-3, 

and the temperature dependences for k1, and k2 are as indicated on the table. 

Same K as Rxn xx: Uses the same rate constant as the reaction with the same label. 

k is variable parameter name: The rate constant is calculated using variable parameters that are 

calculated using concentrations of various species. See Footnotes [c], [d], and [e], below. 

 [c] The xPROD chemical operator species are used to represent the formation of radicals and products 

from alkoxy radicals formed in the reactions of peroxy radicals with NO, NO3, and other peroxy 

radicals. These products are not formed when peroxy radicals react with HO2 and acyl peroxy 
Table A-2 (continued) 

55 

radicals, since those reactions are assumed not form alkoxy radicals, but instead form 

hydroperoxides or H-shift disproportion products that are represented by separate yROOH chemical 

operator species, discussed in a separate footnote. The reactions of peroxy radicals with other peroxy 

radicals are assumed to form alkoxy radicals 50% of the time, so the products from alkoxy radical 

reactions are represented as being formed in 50% yields in these reactions. The consumption and 

products formed from these species can be represented in several ways. The most straightforward 

method is to include a reaction for each of the types of peroxy radical reactions, as follows: 

 xPROD + NO → NO + PROD 

 xPROD + HO2 → HO2 

 xPROD + NO3 → NO3 + PROD 

 xPROD + MECO3 → MECO3 (& similar reactions for RCO3, BZCO3, and MACO3) 

 xPROD + RO2C → RO2C + 1/2 PROD (& a similar reaction for RO2XC) 

 where "PROD" represents the product species for the operator (e.g, HO2 for xHO2). The rate 

constants for these reactions should be the same as those for the corresponding reactions of RO2C or 

RO2XC. This is a somewhat cumbersome method because it requires 9 reactions for each of the 

many xPROD species. An alternative method, implemented in this table, uses the coefficient 

"RO2RO" to determine the rate of formation of the product species and "RO2XRO" to represent 

processes where the product is not formed. These are calculated as follows, where the k(RO2+..)'s 

refer to the rate constants for the reactions of RO2C or RO2XC with the indicated reactant. 

 RO2RO = k(RO2+NO)[NO] + k(RO2+NO3)[NO3] + 0.5 k(RO2+MEO2)[MEO2] + 

 0.5 k(RO2+RO2){[RO2C]+[RO2XC]) 

 RO2XRO = k(RO2+HO2)[HO2] + k(RO2+MECO3){[MECO3]+[RCO3]+[BZCO3]+ 

 [MACO3]) + 0.5 k(RO2+MEO2)[MEO2] + 0.5 k(RO2+RO2){[RO2C]+ [RO2XC]) 

 The steady state approximation must be used for these operators when this representation is used, 

and the operators must not be allowed to be diluted or transported. 

[d] The zRNO3 chemical operator species is used to represent the formation organic nitrates formed 

when peroxy radicals react with NO, or formation of radicals and products from alkoxy radicals 

formed in the reactions of peroxy radicals with NO3 and other peroxy radicals. These products are 

not formed when peroxy radicals react with HO2 and acyl peroxy radicals, since those reactions are 

assumed not form organic nitrates or alkoxy radicals, but instead form hydroperoxides or H-shift 

disproportion products that are represented by separate yROOH chemical operator species, discussed 

in a separate footnote. The zRNO3 operator corresponds to the single lumped organic nitrate model 

species in the present mechanism, but other such operators an operatorscan be added if it is desired 

to have separate organic nitrate model species. In the case of zRNO3, the products resulting if alkoxy 

radicals are formed in the RCO3 or RO2 reactions would depend on reactant and individual radicals, 

and are approximated by PROD2 and HO2 (as might occur following the reaction of a peroxy radical 

with O2 to form HO2 and a ketone species). As with the xPROD species, the consumption and 

products formed from these species can be represented in several ways, with the most 

straightforward method being to include a reaction for each of the types of peroxy radical reactions, 

as follows: 

 zRNO3 + NO → NO + RNO3 

 zRNO3 + HO2 → HO2 

 zRNO3 + NO3 → NO3 + PROD2 + HO2 

 zRNO3 + MECO3 → MECO3 (& similar reactions for RCO3, BZCO3, and MACO3) 

 zRNO3 + RO2C → RO2C + 1/2 {PROD2 + HO2} (& a similar reaction for RO2XC) 

 The rate constants for these reactions should be the same as the rate constant for the corresponding 

reactions of RO2C or RO2XC. As with xPROD, an alternative method, requiring fewer reactions, is 

implemented in this table. In this case, the coefficient "RO2NO" is used to determine the rate of 
Table A-2 (continued) 

56 

formation of organic nitrates, "RO22NN" is used to determine the rate of formation of the alkoxy 

radical products, and "RO2XRO" is used to represent processes where these products are is not 

formed, and is the same as used for xPROD. These are calculated as follows, where the k(RO2+..)'s 

refer to the rate constants for the reactions of RO2C or RO2XC with the indicated reactant. 

 RO2NO = k(RO2+NO)[NO] 

 RO22NN = k(RO2+NO3)[NO3] + 0.5 k(RO2+MEO2)[MEO2] + 

 0.5 k(RO2+RO2){[RO2C]+ [RO2XC]) 

 RO2XRO = k(RO2+HO2)[HO2] + k(RO2+MECO3){[MECO3]+[RCO3]+[BZCO3]+ 

 [MACO3]) + 0.5 k(RO2+MEO2)[MEO2] + 0.5 k(RO2+RO2){[RO2C]+ [RO2XC]) 

 (same as used for xPROD) 

 The steady state approximation must be used for these operators when this representation is used, 

and the operators must not be allowed to be diluted or transported. 

[e] The yROOH chemical operator species is used to represent the formation of organic hydroperoxides 

formed with peroxy radicals react with HO2, or of H-shift disproportionation products formed when 

peroxy radicals react with acyl peroxy radicals or (in 50% yields) with other peroxy radicals. Note 

that the products formed when peroxy radicals react to form alkoxy radicals or organic nitrates (in 

the NO reaction) are represented using separate xPROD or zRNO3 species, and together these three 

types of operators represent all the products and radicals formed. Separate such yROOH species are 

used to represent formation of hydroperoxides or H-shift disproportion products in different 

molecular weight ranges or volatilities, and more can be added as needed for appropriate predictions 

of SOA formation. The hydroperoxide formed in the HO2 reaction is represented by either ROOH, 

R6OOH, or RAOOH, and the H-shift disproportion products are represented by either MEK (for 

yROOH) or PROD2 (for the others). As with the xPROD and zRNO3 species, the consumption and 

products formed from these species can be represented in several ways, with the most 

straightforward method being to include a reaction for each of the types of peroxy radical reactions, 

as follows for yROOH (the reactions for the other two are analogous). 

 yROOH + NO → NO 

 yROOH + HO2 → HO2 + ROOH 

 yROOH + NO3 → NO3 

 yROOH + MECO3 → MECO3 + MEK (& similar reactions for RCO3, BZCO3, and 

 MACO3) 

 yROOH + RO2C → RO2C + 1/2 MEK (& a similar reaction for RO2XC) 

 The rate constants for these reactions should be the same as the rate constant for the corresponding 

reactions of RO2C or RO2XC. As with the other operators, an alternative method, requiring fewer 

reactions, is implemented in this table. In this case, the coefficient "RO2HO2" is used to determine 

the rate of formation of organic hydroperoxides, "RO2RO2M" to determine the rate of formation of 

H-shift disproportion products, and "RO2RO" is used to represent processes where these products 

are is not formed. Note that the latter is the same as the coefficient that is used to represent the 

formation products from the xPROD species. These are calculated as follows, where the k(RO2+..)'s 

refer to the rate constants for the reactions of RO2C or RO2XC with the indicated reactant. 

 RO2HO2 = k(RO2+HO2)[HO2] 

 RO2RO2M = k(RO2+MECO3){[MECO3]+[RCO3]+[BZCO3]+ [MACO3]) + 0.5 

 k(RO2+MEO2)[MEO2] + 0.5 k(RO2+RO2){[RO2C]+ [RO2XC]) 

 RO2RO = k(RO2+NO)[NO] + k(RO2+NO3)[NO3] + 0.5 k(RO2+MEO2)[MEO2] + 

 0.5 k(RO2+RO2){[RO2C]+[RO2XC]) 

 The steady state approximation must be used for these operators when this representation is used, 

and the operators must not be allowed to be diluted or transported. 
57 

Table A-3. Summary of photolysis rates used in chamber and ambient simulations. 

Photolysis rates (min-1) 

Phot File Chamber Ambient simulations (as function of solar zenith angle) [b] 

[a] Z=0 Z=10 Z=20 Z=30 Z=40 Z=50 Z=60 Z=70 Z=78 Z=86 

Base Mechanism [c] 

NO2-06 0.115 0.723 0.718 0.702 0.676 0.631 0.560 0.430 0.253 0.093 0.005 

NO3NO-06 2.44e-4 1.91e+0 1.91e+0 1.90e+0 1.89e+0 1.87e+0 1.82e+0 1.65e+0 1.37e+0 9.15e-1 4.85e-1

NO3NO2-6 4.83e-2 1.54e+1 1.54e+1 1.53e+1 1.52e+1 1.49e+1 1.44e+1 1.29e+1 1.03e+1 6.50e+0 2.80e+0

O3O1D-06 1.83e-4 3.06e-3 2.96e-3 2.68e-3 2.24e-3 1.67e-3 1.06e-3 4.91e-4 1.33e-4 2.01e-5 3.66e-7

O3O3P-06 4.84e-4 3.66e-2 3.66e-2 3.62e-2 3.57e-2 3.48e-2 3.32e-2 2.95e-2 2.37e-2 1.57e-2 8.36e-3

HONO-06 2.81e-2 1.14e-1 1.13e-1 1.10e-1 1.06e-1 9.78e-2 8.54e-2 6.38e-2 3.55e-2 1.18e-2 4.32e-4

HNO3 4.42e-6 5.40e-5 5.28e-5 4.91e-5 4.31e-5 3.49e-5 2.50e-5 1.40e-5 4.99e-6 9.91e-7 2.29e-8

HNO4-06 6.66e-5 5.42e-4 5.32e-4 5.01e-4 4.52e-4 3.81e-4 2.90e-4 1.77e-4 7.28e-5 1.70e-5 4.56e-7

H2O2 9.00e-5 5.64e-4 5.56e-4 5.29e-4 4.86e-4 4.21e-4 3.33e-4 2.14e-4 9.43e-5 2.35e-5 6.64e-7

PAN 7.17e-6 6.12e-5 6.00e-5 5.65e-5 5.08e-5 4.26e-5 3.22e-5 1.95e-5 7.90e-6 1.81e-6 4.80e-8

HCHOR-06 2.53e-4 2.76e-3 2.72e-3 2.59e-3 2.36e-3 2.03e-3 1.58e-3 9.85e-4 4.05e-4 9.08e-5 2.35e-6

HCHOM-06 6.12e-4 3.12e-3 3.08e-3 2.97e-3 2.77e-3 2.47e-3 2.02e-3 1.37e-3 6.41e-4 1.69e-4 5.00e-6

CCHO_R 2.53e-5 4.16e-4 4.06e-4 3.75e-4 3.27e-4 2.60e-4 1.81e-4 9.50e-5 2.99e-5 4.86e-6 8.30e-8

C2CHO 1.05e-4 1.40e-3 1.37e-3 1.28e-3 1.14e-3 9.29e-4 6.74e-4 3.80e-4 1.36e-4 2.62e-5 5.79e-7

ACET-06 3.85e-6 6.47e-5 6.28e-5 5.69e-5 4.78e-5 3.60e-5 2.32e-5 1.10e-5 3.05e-6 4.50e-7 7.35e-9

MEK-06 6.96e-5 9.66e-4 9.45e-4 8.80e-4 7.78e-4 6.33e-4 4.56e-4 2.54e-4 8.86e-5 1.66e-5 3.53e-7

COOH 7.11e-5 3.94e-4 3.89e-4 3.71e-4 3.42e-4 2.99e-4 2.40e-4 1.58e-4 7.21e-5 1.89e-5 5.51e-7

GLY-07R 9.60e-4 9.06e-3 9.00e-3 8.78e-3 8.44e-3 7.86e-3 6.97e-3 5.39e-3 3.29e-3 1.35e-3 1.31e-4

GLY-07M 4.40e-4 3.18e-3 3.14e-3 3.00e-3 2.78e-3 2.44e-3 1.98e-3 1.33e-3 6.41e-4 1.91e-4 8.80e-6

MGLY-06 1.02e-3 1.56e-2 1.56e-2 1.52e-2 1.47e-2 1.38e-2 1.24e-2 9.83e-3 6.27e-3 2.72e-3 2.87e-4

BACL-07 2.06e-3 2.67e-2 2.66e-2 2.61e-2 2.54e-2 2.40e-2 2.18e-2 1.75e-2 1.12e-2 4.81e-3 4.67e-4

BALD-06 1.32e-2 5.10e-2 5.05e-2 4.88e-2 4.61e-2 4.17e-2 3.52e-2 2.49e-2 1.26e-2 3.71e-3 1.17e-4

AFG1 6.82e-2 3.87e-1 3.83e-1 3.70e-1 3.50e-1 3.17e-1 2.69e-1 1.94e-1 1.04e-1 3.51e-2 1.99e-3

MACR-06 3.43e-5 1.97e-4 1.94e-4 1.86e-4 1.72e-4 1.51e-4 1.21e-4 7.98e-5 3.64e-5 9.42e-6 2.74e-7

MVK-06 1.32e-5 7.50e-5 7.40e-5 7.07e-5 6.54e-5 5.73e-5 4.60e-5 3.02e-5 1.37e-5 3.51e-6 1.01e-7

IC3ONO2 1.82e-5 2.35e-4 2.30e-4 2.15e-4 1.91e-4 1.57e-4 1.15e-4 6.57e-5 2.41e-5 4.80e-6 1.11e-7

 

[a] Photolysis rates for a chamber experiment with blacklight light source. The chamber photolysis rates 

are for the experiments carried out for this project. 

[b] See Carter (1994) for documentation of solar actinic fluxes used in the atmospheric reactivity 

calculations. 

[c] Calculated using absorption coefficients and cross sections given by Carter (2009)