Figure 4.32: Mechanism of the reaction of OH with (1-ONO2,2-OOH)-IPN. Yields are for 298 K and 1 atm; branching ratios between OH-addition and -abstraction, epoxide formation and O2addition, and nitrate and alkoxy formation all vary with temperature and/or pressure. For the reduced mechanism, we combine the -IPN isomers into a single species, and scale the product yields of its subsequent reactions according to the relative contributions of the isomers. We also combine the various isomers of stable C5tetrafunctionalized products.
Figure 4.33: Mechanism of the reaction of OH with (3-OOH,4-ONO2)-IPN. Yields are for 298 K and 1 atm; branching ratios between OH-addition and -abstraction, epoxide formation and O2addition, and nitrate and alkoxy formation all vary with temperature and/or pressure. For the reduced mechanism, we combine the -IPN isomers into a single species, and scale the product yields of its subsequent reactions according to the relative contributions of the isomers. We also combine the various isomers of stable C5tetrafunctionalized products.
Figure 4.34: Mechanism of the reaction of OH with (1-ONO2,2,3-O,4-OH)-INHE.
The cisand trans isomers are not treated separately, as they are expected to react identically. Yields are for 298 K and 1 atm; branching ratios between nitrate and alkoxy formation in reactions with NO vary with both temperature and pressure. For both the full and reduced mechanisms, we simplify the INHE and ICN systems by combining some intermediate peroxy radicals and distributing their products accord- ing to the relative contributions of the isomers. For the reduced mechanism, we also combine the -INHE isomers into a single species, and scale their product yields similarly. We further combine the various isomers of stable C5 tetrafunctionalized products.
Figure 4.35: Mechanism of the reaction of OH with (1-OH,2,3-O,4-ONO2)-INHE.
The cisand trans isomers are not treated separately, as they are expected to react identically. Yields are for 298 K and 1 atm; branching ratios between nitrate and alkoxy formation in reactions with NO vary with both temperature and pressure. For both the full and reduced mechanisms, we simplify the INHE and ICN systems by combining some intermediate peroxy radicals and distributing their products accord- ing to the relative contributions of the isomers. For the reduced mechanism, we also combine the -INHE isomers into a single species, and scale their product yields similarly. We further combine the various isomers of stable C5 tetrafunctionalized products.
Figure 4.36: Mechanisms of the reactions of OH with (1,2-O,3-OH,4-ONO2)- and (1-ONO2,2-OH,3,4-O)-INHE. For both the full and reduced mechanisms, we simplify the INHE and ICN systems by combining some intermediate peroxy radicals and distributing their products according to the relative contributions of the isomers.
For the reduced mechanism, we also combine the -INHE isomers into a single species, and scale their product yields similarly. We further combine the various isomers of stable C5tetrafunctionalized products.
Figure 4.37: Mechanism of the reaction of OH with E-(1-OH,4-ONO2)-IHN. Z- (1-OH,4-ONO2)-IHN is expected to react identically. Yields are for 298 K and 1 atm; in reactions of peroxy radicals with NO, the relative contributions of the nitrate and alkoxy pathways vary with both temperature and pressure, and the branching ratio between IEPOX formation and O2addition also varies with pressure. For the reduced mechanism, we combine the -IHN isomers into a single species, and scale the product yields of its subsequent reactions according to the relative contributions of the isomers. We also combine the various isomers of stable C5tetrafunctionalized products.
Figure 4.38: Mechanism of the reaction of OH with E-(1-OOH,4-ONO2)-IPN.Z- (1-OOH, 4-ONO2)-IPN is expected to react identically. Yields are for 298 K and 1 atm; branching ratios between OH-addition and -abstraction, epoxide formation and O2addition, and nitrate and alkoxy formation all vary with temperature and/or pressure. For the reduced mechanism, we combine the -IPN isomers into a single species, and scale the product yields of its subsequent reactions according to the relative contributions of the isomers. We also combine the various isomers of stable C5tetrafunctionalized products.
Figure 4.39: Mechanism of the reaction of OH with E-(1-CO,4-ONO2)-ICN. Z- (1-CO,4-ONO2)-ICN is expected to react identically. The terminal radical formed by H-abstraction (upper left) is presumed to add oxygen and react further like the analogous (though not identical) acyl peroxy radical in Figure 13. Yields are for 298 K and 1 atm; branching ratios between OH-addition and -abstraction, epoxide formation and O2addition, and nitrate and alkoxy formation all vary with temperature and/or pressure. For the reduced mechanism, we combine the four isomers of peroxy radicals derived from the addition of OH and O2 to the -ICN isomers, and scale the product yields of its subsequent reactions with NO and HO2
according to the relative contributions of the isomers. We also combine the various isomers of stable C5tetrafunctionalized products.
Figure 4.40: Mechanisms following the abstraction of an aldehydic hydrogen from the -ICNs that form from the reaction of isoprene with NO3. Yields are for 298 K and 1 atm; branching ratios between epoxide formation and O2 addition, as well as nitrate and alkoxy formation, vary with temperature and/or pressure.
For the reduced mechanism, we group the ICN isomers together, and simplify the H-abstraction scheme to represent its effects on HOx and NOx budgets.
Figure 4.41: Reactions and products following the photolysis of the HPALD2.