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B1 7
B1
Appendix
B1 8
The specie R* in Equation B1-8 (or Equation 6.2A or Equation 11.14) is called a hydrocarbon radical. Like other free
radicals it is extremely reactive, as is shown in Equation B1-9.
R O2 /ROO
B1 9
B1 10
7
The hydroxyl radical, HO*, is not the same as the hydroxyl ion OH
(Chapter 1, Footnote 19). The former is neutral. The latter has a negative
charge. Some identify the hydroxyl radical as just OH, which can be confusing.
8
In this description, hydrocarbon solvents will be described as R-H,
where R is the main solvent structure (Figure 1.2) and H is
a hydrogen atom attached to that structure.
This description applies to all solvents except those which don't have
hydrogen atoms. Perchloroethylene is such an exception. Recall that the
unsaturated double bond between the two carbon atoms is very
reactive. Therefore, these compounds have a short atmospheric lifetime
and don't signicantly penetrate the upper atmosphere. In other words,
R doesn't exist in the upper atmosphere; R-H does exist.
9
This reaction is very important since it is the primary reaction pathway
by which most organic compounds initially participate in atmospheric
photochemical reaction processes. If the reaction of Equation B1-8 could
be impeded, VOCs would not form photochemical smog.
The reaction rate constant for Equation B1-8, called kOH, has been
and can be used to determine whether a solvent is VOC exempt. The
literature kOH value for ethane is 2.54 x 1013 cm3/molecule-sec.
Petitions for VOC exemption of solvents with kOH values larger than 2.54
x 1013 would likely be denied. kOH data may be found in Professor
Carter's XLS spreadsheet SAPRC07.XLS (Tab B) which is available from
his collection of materials referenced in Chapter 6, Endnote S.
10
R is the HC to which the aldehyde is attached (Figure 1.2).
11
There is a reaction between RO* and NO2, but it is relatively
unimportant in the atmosphere because of the many other ways that the
RO* radical can react. It also forms RONO2 (an organic nitrate), not RO2
+ NO. However, there is a second reaction of RO2 (ROO) with NO, [RO2 +
NO e> RONO2] that is a minor pathway for most RO2 radicals but
becomes increasingly important as the size of the RO2 radical increases.
This reaction is radical terminating and is the reason that the MIRs tend
to decrease as the size of the molecule increases.
12
Sometimes the hydroperoxide (H-O-O-*) is referred to as HO2.
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