Calculation of MIR through Group Contribution Methods

B2

Appendix

Table B2-1 Comparison of Outcomes about Reduction of Ozone Formation

Plot Analysis of Types
(Section 6.10)

Group Contribution
(Appendix B2)

Incorporate bromine, uorine,

or chlorine atoms
Incorporate a compact highly branched
structure such as t-butyl or methyl to
support substituents

Incorporate CH2 or CH (as in glycol

ethers, which dont have low MIR
values)

Avoid linear segments of 3 and 4 carbon

atoms, and primary and secondary
alcohols, and ethers

Avoid methyl groups, ethyl groups,

propyl groups, butyl groups, primary/
secondary OHs, and ethyl ethers

Incorporate ester groups

Incorporate ester groups, use single

oxygen atoms (as in ethers)

Figure B2-2); methyl acetate (MIR calculated 0.930, MIR

measured 0.067, green symbol in Figure B2-2); tertiary
butyl acetate (MIR calculated 0.628, MIR measured 0.721,
yellow symbol in Figure B2-2); and DBE-4G (MIR calculated 0.545, MIR measured 0.211, blue symbol in Figure
B2-2).


All four3 (not three) of these of these solvents are

classied as VOC exempt by US EPA.

Note that every one of the four solvents noted above has
a predicted MIR value considerably higher than that
measured. This outcome suggests that no matter how well
this correlation of group parameters describes measured
MIR performance (and this one does describe many
solvents perfectly), there is some other factor which
controls reaction of some VOC chemicals to produce
a maximum amount of ozone with various combinations
of UV light and NOx.
This author has no clue about the reason for this
outcome4, but believes that the information in the
appendix can be useful in identifying options for both
regulators and usersdas per Table B2-1.

3
Actually, there was a petition led in 1997 by the Synthetic Organic
Chemical Manufacturers Association in favor of exemption of both
DBE-4 and DBE-5 (dimethyl glutarate) from VOC status. In 2006, EPA
announced its intention to exempt DBE-4 from VOC status (Federal
Register/Vol. 71, No. 237/Monday, December 11, 2006/Unied Agenda
73885, 3064). However, without public announcement, the petition was
withdrawn sometime before 2009.
4
The independent analysis by Professor Yamato produces the same
outcome, except the MIR for three of the four exempt solvents is less
well predicted.

E.

APPLICATION OF RESULTS

It can be instructive to compare the results of this analysis

with that of Section 6.10 because they are based on
somewhat different approaches, but use the same data.


The approach in this appendix is based on statistical

correlation of the effects on ozone production (MIR)
with molecular groups of which solvents are composed.
The approach in Section 6.10 is based on human
analysis of plots of MIR vs. types of solvent.

F. SUMMARY
There is general agreement on some details of how to
synthesize or choose low VOC solventsduse of esters and
small branched structures, and avoidance of propyl and
butyl groups. But there is disagreement about specic
hydrocarbon structures, and four (three, actually) VOC
exempt solvents are not predicted to be so!
The main aw in this analysis is that it is based on too few
solventsdeven though others which might be included are
not useful (or used) for cleaning work. When a solvent has
a low MIR, all groups found in it are credited with that
benet, and the reverse. Some groups in Table B2-2 are
found in only two, three, or four solvents; others are found
in 20, 30, or 40 solvents. The incidence for each group is
listed in Table B2-2. It is the latter which has been used to
weight the recommendations in Table B2-2dat least about
20% of the solvents must contain a certain structural group
in order for it to be mentioned in the table.

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