DEVELOPMENT OF REVISED SAPRC AROMATICS MECHANISMS

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Table 2 (continued) Label [a] Reaction and Products [b] BP39 CRES + NO3 = #.1 HNO3 + #.9 XN + #.7 HO2 + #.1 BZO + #.17 xHO2 + #.03 OH + #.17 RO2C + #.7 CATL + #.03 AFG3 + #.085 xAFG1 + #.085 xAFG2 + #.085 xGLY + #.085 xMGLY + #.170 yRAOOH BP83 PHEN + OH = #.7 HO2 + #.1 BZO + #.095 xHO2 + #.105 OH + #.095 RO2C + #.7 CATL + #.105 AFG3 + #.048 xAFG1 + #.048 xAFG2 + #.095 xGLY + #.095 yRAOOH BP84 PHEN + NO3 = #.1 HNO3 + #.9 XN + #.7 HO2 + #.1 BZO + #.095 xHO2 + #.105 OH + #.095 RO2C + #.7 CATL + #.105 AFG3 + #.048 xAFG1 + #.048 xAFG2 + #.095 xGLY + #.095 yRAOOH BP85 XYNL + OH = #.7 HO2 + #.07 BZO + #.23 xHO2 + #.23 RO2C + #.7 CATL + #.115 xAFG1 + #.115 xAFG2 + #.115 xGLY + #.115 xMGLY + #.23 yRAOOH BP86 XYNL + NO3 = #.07 HNO3 + #.93 XN + #.7 HO2 + #.07 BZO + #.23 xHO2 + #.23 RO2C + #.7 CATL + #.115 xAFG1 + #.115 xAFG2 + #.115 xGLY + #.115 xMGLY + #.23 yRAOOH BP87 CATL + OH = #.4 HO2 + #.2 BZO + #.2 xHO2 + #.2 OH + #.2 RO2C + #.2 AFG3 + #.1 xAFG1 + #.1 xAFG2 + #.1 xGLY + #.1 xMGLY + #.33 CNDPP + #.2 yRAOOH BP88 CATL + NO3 = #.2 HNO3 + #.8 XN + #.4 HO2 + #.2 BZO + #.2 xHO2 + #.2 OH + #.2 RO2C + #.2 AFG3 + #.1 xAFG1 + #.1 xAFG2 + #.1 xGLY + #.1 xMGLY + #.2 yRAOOH Rate Parameters [c] k(300) A Ea B Notes [d] 1.40e-11 7,9 2.74e-11 4.70e-13 -2.42 10,11 3.80e-12 10,12 7.38e-11 13,14 3.06e-11 13,15 2.00e-10 16 1.70e-10 17 [a] Underlined reaction label indicates that the reaction was added to the mechanism. If not underlined, it is the same label as used in the SAPRC-07 listing given by Carter (2010a). [b] 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. [c] 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 cm 3 molec -1 s -1 , Ea are kcal mol -1 , T is o K, and R=0.0019872 kcal mol -1 deg -1 . The following special rate constant expressions are used: 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)]}· F Z , 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. 12
Table 2 (continued) Phot Set = name: The absorption cross sections and (if applicable) quantum yields for the photolysis reaction are given by Carter (2010a), where “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. Same K as Rxn xx: Uses the same rate constant as the reaction in the base mechanism with the same label. k is variable parameter: xxx: The rate constant for this reaction of this chemical operator species is given by the indicated variable parameter, which is computed from peroxy radicals and NO x levels as given by Carter (2010a) and also in footnotes to Table A-2. [d] Footnotes discussing the rate constants and mechanisms used are given below. Unless indicated otherwise, the rate constants used are the same as those used in SAPRC-07 for the indicated reaction (Carter, 2010a). 1 Temperature dependence corrected. From NASA (2006), but unchanged in NASA (2011). Change would have no effect on simulations at 300 K, and have very minor or negligible effects on chamber or ambient simulations at normal temperatures. 2 Product distribution revised to be consistent with the most recent IUPAC (2009) recommendations. Three pathways are assumed for the HO2 + acyl peroxy radical reaction: (1) 41% O2 + peroxy acetic acid; (2) 15% O3 + acetic acid; and (3) 44% OH + O2 + CH3C(O)O·. The peroxy acetic acid is represented by acetic acid and the CH3C(O)O· is assumed to rapidly decompose to CO2 and methyl radicals. The mechanisms for reactions of HO2 with the other peroxyacyl radical model species are assumed to be analogous. 3 Rate constant revised and temperature dependence added based on the most recent IUPAC (2008a) recommendation. This results in a ~10% decrease in the rate constant at 300K. 4 Mechanism revised to be consistent with the most recent IUPAC (2008a) recommendation. Both OH and NO 3 reactions are assumed to involve initial formation of HC(O)C(O)·. IUPAC (2008a) does not give explicit recommendation for branching ratios for the subsequent reactions of this radicals, but the rate constants given there imply ~40% decomposition to HCO and CO and ~60% reaction with O 2 forming 50% HCO + 2 CO and 50% HC(O)C(O)OO· under atmospheric conditions at ~300K. This corresponds to the reactions indicated if it is assumed the major fate of HCO is HO 2 + CO. HC(O)C(O)OO· is represented by the HCOCO3 model species. Unlike other acyl peroxy radicals, data discussed by IUPAC (2008a) indicates that it reacts with NO 2 to form NO 3 + HCO + CO 2 , so it is not appropriate to lump it with acyl peroxy radicals that react to form PAN analogues. However, the rate constants for the HCOCO3 reactions are the same as those used for the lumped acyl peroxy radical RCO3, which are given by Carter (2010a) and also in Table A-2. The HC(O)C(O)OH and HC(O)C(O)OOH predicted to be formed in the HCOCO3 + HO2 reaction is represented by the GLY model species. 5 The reactions of AFG1 and AFG2 with O 3 were calculated to be of minor importance under chamber or atmospheric conditions of interest so these reactions were deleted from the mechanisms. The mechanisms and rate parameters for the reactions of these model species with OH radicals and by photolysis are unchanged. 6 The model species AFG4 is added to represent the reactions of monounsaturated 1,4-diketones, which are assumed to not to undergo photodecomposition to a significant extent, other than perhaps cis-trans isomerization (Calvert et al, 2002). These compounds were previously represented using AFG3, whose mechanism is based on those estimated for diunsaturated dicarbonyls. In this version of the mechanism they are treated separately because they are expected to form products of different reactivity. The only significant net loss process is assumed to be reaction with OH radicals, and its mechanism is estimated using the SAPRC-07 mechanism generation system, based on the structure for cis-3-hexene-2,5-dione. The rate constant is from 13
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: Table 2. Reactions that were modifi
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 and 42: MECHANISM EVALUATION Methods Chambe
Page 43 and 44: Table 9 (continued) ID TVA CSI Brie
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
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Phenol Number of Runs 5 50% Model E
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Although there is somewhat greater
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∆([O3]-[NO]) Model Error Full Sur
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constants and product yield paramet
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25 20 10 SAPRC-11 Reactivity 15 10
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there is an inconsistency between t
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e obtained from the AFG1 / (AFG1+AF
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higher NO x experiment. Note that t
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in this evaluation, as well as the
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develop chemically detailed or expl
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laboratory data and theories of atm
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REFERENCES Anderson, R.S., Czuba, E
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Carter, W. P. L. (2000a): “Docume
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IUPAC (2008e): http://www.iupac-kin
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White, S.J., M. Azzi, D. E. Angove,
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Table A-1 (continued) Type and Name
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Table A-1 (continued) Type and Name
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Table A-2. Listing of reactions and
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Table A-2 (continued) Label Reactio
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Table A-2 (continued) Phot Set = na
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Table B-1 (continued) Run New [a] C
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Table B-2. Summary of incremental r
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Table B-3 (continued) Run ID Surrog
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Table B-3 (continued) Run ID Surrog
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Table B-4. (continued) Cham. Set(s)
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Table B-4. (continued) Cham. Set(s)
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DEVELOPMENT OF REVISED SAPRC AROMATICS MECHANISMS

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