DEVELOPMENT OF REVISED SAPRC AROMATICS MECHANISMS

More documents

Recommendations

Info

Table 9. ID Summary of environmental chambers whose data were used for aromatics mechanism evaluation. Brief description and references for additional information EC ITC DTC XTC CTC (≤82) CTC (≥83) EPA Chambers at the Statewide Air Pollution Research Center (SAPRC) or the College of Engineering Center for Environmental Research and Technology (CE-CERT) at the University of California at Riverside (UCR) A 5774-liter evacuable chamber constructed of Teflon-coated aluminum with Quartz end windows. Located at SAPRC. Xenon arc solar simulator light source (see Figure 4 for a representative spectrum). Most experiments at ~50% RH and around 300 o K. Experiments were carried out 1975 - 1984. See Carter et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This chamber is now primarily being used for mechanistic studies. One semi-collapsible ~6400-liter reactor constructed of 2 mil FTP Teflon film held in a framework. Blacklight light source (see Figure 4 for spectrum, which was used for all chambers using blacklights). Located at SAPRC. Most experiments at ~50% RH and around 300 o K. Experiments were carried out 1982 - 1986. See Carter et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This chamber is now primarily being used for mechanistic studies. Two semi-collapsible ~5000-liter reactors constructed of 2 mil FTP Teflon film held in a framework. Initially located at the outdoor laboratory building at SAPRC, but subsequently relocated to CE-CERT. Two irradiations carried out simultaneously, one in Side “A” and the other in Side “B”. Blacklight light source. Most experiments used dry air at around 300 o K. Experiments carried out 1993 - 1999. See Carter et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This chamber no longer exists. One semi-collapsible ~5000-liter reactor constructed of 2 mil FTP Teflon film held in a framework. Xenon arc light source (see Figure 4 for a representative spectrum). Located the outdoor laboratory building at SAPRC. Experiments used dry air at around 300 o K. Experiments carried out in 1993. See Carter et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This chamber no longer exists. Semi-collapsible ~5000-liter reactor constructed of 2 mil FTP Teflon film held in a framework. The same Xenon arc light source was used as the XTC. Located at CE-CERT. Experiments used dry air at around 300 o K. Experiments carried out in 1994 - 1995. See Carter et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This configuration is applicable to runs from 11 through 82. Two semi-collapsible ~2500-liter reactors constructed of 2 mil FTP Teflon film held in a framework. The same Xenon arc light source was sued. Located at CE-CERT. Experiments used dry air at around 300 o K. Experiments carried out in 1995 - 1999. This configuration is applicable to runs 83 and higher. See Carter et al (1995a) for description of chamber and experimental methods and Carter (2000a) for a discussion of the modeling methods used. This chamber no longer exists. (Also referred to as the UCR EPA chamber.) Two ~90% collapsible ~100,000-liter reactors constructed of 2 mil FEP Teflon film held on a framework with a moveable top for positive pressure control. Located in a temperature-controlled “clean room” clean room enclosure flushed 34
Table 9 (continued) ID TVA CSI Brief description and references for additional information with purified air. Located at CE-CERT. Can use either an argon arc solar simulator light source (see Figure 4 for a representative spectrum) or blacklights. Two irradiations can be carried out simultaneously, one in Side “A” and the other in Side “B”. Although the temperature and humidity can be varied, all experiments in this evaluation were carried out with dry air at around 300 o K. Experiments were carried out from 2003 through present, with the latest run in this evaluation being carried out in mid-2011. See Carter (2004) and Carter et al (2005) for a description of the chamber and experimental methods and Carter (2004) for a discussion of the modeling methods used. Note that mechanism evaluation experiments in this chamber can be carried out under lower NO x conditions than the other chambers at UCR or the UNC outdoor chamber. This chamber is still in operation and was employed for most of the new experiments modeled in this study. Chamber at the Tennessee Valley Authority (TVA). One 28,300-liter reactor constructed of 0.13 mm FEP Teflon film on a rigid frame located inside an enclosure flushed with purified air. Special procedures used to clean between experiments to permit experiments at lower concentrations. The light source consisted of blacklights and sunlamps (see Figure 4 for the spectrum). Experiments carried out at about 15% RH and the temperature varied from ~300-315 o K. Experiments carried out in 1993 - 1995. See Simonaitis and Bailey (1995) and Bailey et al (1996) for a description of the chamber and experimental methods and Carter (2004) for a discussion of the modeling methods used. Note that mechanism evaluation experiments in this chamber were carried out under lower NO x conditions than in the other chambers except for UCR EPA, but the chamber experience high background formaldehyde levels that needed to be taken into account when modeling the experiments (Carter, 2004). This chamber no longer exists. Chamber at the Commonwealth Scientific and Industrial Research Organisation in Australia (CSIRO) (Not used for SAPRC-07 mechanism development) Single 18,000-liter reactor lined with FEP Teflon film. It is fitted with two UV-A lighting modules, each containing 40 black-light tubes (36W Sylvania Blacklight Blue 350). These lamps emit radiation over the range 350–390 nm, with peak intensity at 366 nm (see Figure 4 for the spectrum). See Hynes et al (2005) and White et al (2010) for a description of the chamber and Azzi et al (2010) for a discussion of the use of data from this chamber for evaluating the SAPRC- 07 mechanism. The CSIRO experiments modeled in this work were carried out at around 300 K with a relative humidity of ~3%. The characterization assignments used when modeling the CSIRO experiments for this project were provided by White (2010). Although use of arc light spectra that better represent sunlight is obviously preferred for mechanism evaluation, it is important to recognize that the spectrum of the light source is taken into account when calculating the photolysis rates. Therefore experiments with light sources with unrepresentative spectra can still be useful for mechanism evaluation as long as the differences in light source spectra are properly taken into account. In fact, the use of experiments with a variety of light sources and spectra provide a more comprehensive evaluation of how well the model can simulate effects of changes in light spectrum that may occur in ambient simulations. The uncertainty arises if the action spectrum of important photolysis reactions are uncertain, as may be the case for photoreactive aromatic products that are not well characterized. The existence of this type of problem would be indicated by the 35
Page 1 and 2: DEVELOPMENT OF REVISED SAPRC AROMAT
Page 3 and 4: ACKNOWLEDGEMENTS AND DISCLAIMERS Th
Page 5 and 6: TABLE OF CONTENTS (continued) APPEN
Page 7 and 8: LIST OF FIGURES (continued) Figure
Page 9 and 10: EXECUTIVE SUMMARY Background and Pr
Page 11 and 12: However, this issue is probably not
Page 13 and 14: significant uncertainties in their
Page 15 and 16: New UCR EPA Experiments New CSIRO E
Page 17 and 18: Table 1. List of model species in t
Page 19 and 20: Table 2. Reactions that were modifi
Page 21 and 22: Table 2 (continued) Phot Set = name
Page 23 and 24: mechanism using the generic lumped
Page 25 and 26: Table 3 (continued) 4 Average of 5.
Page 27 and 28: Hydroperoxides (R6OOH) Phenolic Pro
Page 29 and 30: Table 5 (continued) 3 Yields of pro
Page 31 and 32: Table 6. Summary of yields of lumpe
Page 33 and 34: thus the model species AFG3 used to
Page 35 and 36: simulations of the chamber data usi
Page 37 and 38: separately primarily because they a
Page 39 and 40: the photoreactive α-dicarbonyls an
Page 41: MECHANISM EVALUATION Methods Chambe
Page 45 and 46: Modeling Methods The procedures use
Page 47 and 48: irradiation time would not yield a
Page 49 and 50: Adjustments to Mechanisms to Fit Da
Page 51 and 52: Compound ∆([O 3 ]-[NO]) Formation
Page 53 and 54: Benzene Number of Runs 14 Average M
Page 55 and 56: Toluene Plots and tables of selecte
Page 57 and 58: CTC108B ETC101 ETC103 CTC127B IR Su
Page 59 and 60: Ethyl Benzene (Model "A") Number of
Page 61 and 62: n-Propyl Benzene Number of Runs 4 5
Page 63 and 64: m-Xylene Number of Runs 128 Average
Page 65 and 66: m-Xylene (continued) o-Xylene p-Xyl
Page 67 and 68: IntOH Model Error 100% 50% 0% -50%
Page 69 and 70: p-Ethyl toluene Number of Runs 7 Av
Page 71 and 72: 1,3,5-trimethylbenzene Model Error
Page 73 and 74: Phenol Number of Runs 5 50% Model E
Page 75 and 76: Although there is somewhat greater
Page 77 and 78: ∆([O3]-[NO]) Model Error Full Sur
Page 79 and 80: constants and product yield paramet
Page 81 and 82: 25 20 10 SAPRC-11 Reactivity 15 10
Page 83 and 84: there is an inconsistency between t
Page 85 and 86: e obtained from the AFG1 / (AFG1+AF
Page 87 and 88: higher NO x experiment. Note that t
Page 89 and 90: in this evaluation, as well as the
Page 91 and 92: develop chemically detailed or expl
Page 93 and 94:
laboratory data and theories of atm
Page 95 and 96:
REFERENCES Anderson, R.S., Czuba, E
Page 97 and 98:
Carter, W. P. L. (2000a): “Docume
Page 99 and 100:
IUPAC (2008e): http://www.iupac-kin
Page 101 and 102:
White, S.J., M. Azzi, D. E. Angove,
Page 103 and 104:
Table A-1 (continued) Type and Name
Page 105 and 106:
Table A-1 (continued) Type and Name
Page 107 and 108:
Table A-2. Listing of reactions and
Page 109 and 110:
Table A-2 (continued) Label Reactio
Page 111 and 112:
Page 113 and 114:
Page 115 and 116:
Page 117 and 118:
Page 119 and 120:
Page 121 and 122:
Page 123 and 124:
Table A-2 (continued) Phot Set = na
Page 125 and 126:
Table B-1 (continued) Run New [a] C
Page 127 and 128:
Page 129 and 130:
Page 131 and 132:
Page 133 and 134:
Table B-2. Summary of incremental r
Page 135 and 136:
Table B-3 (continued) Run ID Surrog
Page 137 and 138:
Table B-3 (continued) Run ID Surrog
Page 139 and 140:
Table B-4. (continued) Cham. Set(s)
Page 141:
Table B-4. (continued) Cham. Set(s)
show all

DEVELOPMENT OF REVISED SAPRC AROMATICS MECHANISMS

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?