United States
Environmental Protection
Agency
Environmental Sciences Research
Laboratory
Resewch Triangle Park NC 27711
EPA-600/3-79-040
April 1979
Research and Development
&EPA
Effect of
Diethylhydroxyl-
amine on Smog
Chamber Irradiations
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on the effects of pollution on humans, plant and animal spe-
cies, and materials. Problems are assessed for their long- and short-term influ-
ences. Investigations include formation, transport, and pathway studies to deter-
mine the fate of pollutants and their effects. This work provides the technical basis
for setting standards to minimize undesirable changes in living organisms in the
aquatic, terrestrial, and atmospheric environments.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/3-79-040
April 1979
EFFECT OF DIETHYLHYDROXYLAMINE
ON SMOG CHAMBER IRRADIATIONS
by
Larry T. Cupitt
Eric W. Corse
Environmental Science and Emissions Research
Northrop Services, Inc.
Environmental Sciences Center
Post Office Box 12313
Research Triangle Park, North Carolina 27709
Contract No. 68-02-2566
Project Officer
Joseph J. Bufalini
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
-------
DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for publica-
tion. Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
11
-------
ABSTRACT
The addition of diethylhydroxylamine (DEHA) to the urban atmosphere had
been suggested as a means of preventing photochemical smog. Smog chamber
studies were carried out to investigate the photochemical smog formation
characteristics of irradiated hydrocarbon-nitrogen oxides - DEHA mixtures.
Propylene and n-butane were the hydrocarbons used. The effects of DEHA
upon ozone formation, aerosol formation, peroxyacetyl nitrate formation,
nitric oxide-to-NO conversion, and hydrocarbon consumed are described. The
X
rate constant for the reaction
DEHA + OH products
was estimated as 4.1 + 3.4 X 10 ppm min . Possible reaction schemes for
DEHA in the photochemical smog mechanism are discussed.
The addition of DEHA to a HC/NO system inhibits the conversion of NO
X
to NO^ during the initial minutes of irradiation, but after continued
irradiation accelerates this conversion.
This report is submitted in fulfillment of Contract No. 68-02-2566 by
Northrop Services, Inc., under the sponsorship of the U.S. Environmental
Protection Agency. This work covers a period from November, 1976 to December,
1977, and work was completed as of May 1978.
iii
-------
CONTENTS
Abstract '< iii
Figures : vi
Tables ix
Abbreviations and Symbols x
Acknowledgments xii
1. Introduction 1
i
2. Experimental 2
3. Results 5
4. Discussion 26
DEHA Effects on Aspects of Smog Formation 26
Potential Mechanisms to Explain DEHA Effects on Smog
Formation 31
5. Conclusions 36
References 38
Appendix 40
-------
FIGURES
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Schematic diagram of chamber and. support equipment ....
Reaction profiles of DEHA-NO system
Reaction profiles of 0.25 ppm propylene-NO system ....
X
Reaction profiles of ~0.25 ppm propylene-NO -DEHA system .
Reaction profiles of 0.5 ppm propylene-NO system
Reaction profiles of ~0.5 ppm propylene-NO -DEHA system
X
Reaction profiles of 5.0 ppm propylene-NO system ....
X
Reaction profiles of ~5 ppm propylene-NO -DEHA system. . .
X
Reaction profiles of ~0.5 ppm n-butane-NO system ....
X
Reaction profiles of ~0.5 ppm n-butane-NO -DEHA system . .
X
Reaction profiles of 5.0 ppm n-butane-NO system
Reaction profiles of ~5 ppm n-butane-NO -DEHA system . . .
X
Reaction profiles of ~15 ppm n-butane-NO system
X
Reaction profiles of 15.0 ppm n-butane-NO -DEHA system . .
X
Effect of changes of [DEHA] o/ [HC] 0 on manifestations of
Page
... 3
... 8
... 9
... 10
... 11
... 12
... 13
... 14
... 15
... 16
... 17
... 18
... 19
... 20
"smog" for an initial HC concentration of ~0.25
ppm propylene 22
16 "Smog" manifestations for an initial HC concentration of
~0.5 ppm propylene 23
17 Effect of [DEHA]0/[HC]0 on "smog" manifestations for an
initial HC concentration of ~5 ppm propylene 24
18 Aerosol formation data versus time for runs with and
without DEHA 25
VI
-------
Number
19
20
A-l
A- 2
A- 3
A- 4
A- 5
A- 6
A- 7
A- 8
A- 9
A- 10
A- 11
A- 12
A- 13
A- 14
A- 15
A- 16
A- 17
A- 18
A- 19
A- 20
A-21
A- 22
A-23
Simulation profiles for HC, NO, N0_, 0 , and DEHA predicted
X
Reaction profiles of 0. 25 ppm propylene-NO system
X
Reaction profiles of 0. 25 ppm propylene— NO system
X
Reaction profiles of 0. 24 ppm propylene— NO —DEHA system. . .
X
Reaction profiles of 0. 26 ppm propylene— NO —DEHA system.
Reaction profiles of 0. 30 ppm propylene— NO -DEHA system. . .
X
Reaction profiles of 0. 30 ppm propylene-NO —DEHA system. . .
Reaction profiles of 0.49 ppm propylene— NO system
X
Reaction profiles of 0.48 ppm propylene— NO system
X
Reaction profiles of 0. 50 ppm propylene^NO system . * . . *
X
Reaction profiles of 0.60 ppm propylene-NO -DEHA system . .
Reaction profiles of 0. 50 ppm propylene-NO -DEHA system . .
Reaction profiles of 0. 54 ppm propylene— NO system
Reaction profiles of 0.47 ppm propylene— NO system
X
Reaction profiles of 0.50 ppm propylene-NO —DEHA system. . .
X
Reaction profiles of 0. 54 ppm propylene— NO system
X
Reaction profiles of 0. 55 ppm propylene-NO system
X
Reaction profiles of 0. 54 ppm propylene-NO —DEHA system. . .
X
Reaction profiles of 0.47 ppm propylene-NO system
Reaction profiles of 0. 52 ppm propylene-NO system
Reaction profiles of 0. 52 ppm propylene-NO system
X
Reaction profiles of 0. 50 ppm propylene-NO system
X
Reaction profiles of 0.55 ppm propylene-NO -DEHA system. . .
. Page
. . 32
. . 34
. . 41
. . 42
. . 43
. . 44
. . 45
. . 46
. . 47
. . 48
. . 49
. . 50
. . 51
. . 52
. . 53
. . 54
. . 55
. . 56
. . 57
. . 58
. . 59
. . '60
. . 61
. . 62
. . 63
VI1
-------
Number
A- 24
A-25
A- 26
A- 27
A- 28
A- 29
A- 30
A- 31
A- 32
A- 33
A- 34
A- 35
A- 36
A- 37
A- 38
A- 39
A-40
A- 41
A- 42
A- 43
A- 44
A- 45
A- 46
A-47
Reaction profiles of 5.0 ppm propylene-NO system
X
Reaction profiles of 5.2 ppm propylene-NO system
X
Reaction profiles of 5.1 ppm propylene-NO system
X
Reaction profiles of 5.3 ppm propylene-NO -DEHA system . . .
X
Reaction profiles of 4.7 ppm propylene-NO -DEHA system . . .
X
Reaction profiles of 4.9 ppm propylene-NO -DEHA system . . .
Reaction profiles of 5.0 ppm propylene-NO -DEHA system . . .
X
Reaction profiles of 4.7 ppm propylene-NO -DEHA system . . .
Reaction profiles of 0.49 ppm n-butane-NO system
X
Reaction profiles of 0.59 ppm n-butane-NO system
Reaction profiles of 0.48 ppm n-butane-NO system.
Reaction profiles of 0.46 ppm n-butane-NO -DEHA system . . .
X
Reaction profiles of 0. 55 ppm n-butane-NO -DEHA system . . .
X
Reaction profiles of 0. 59 ppm n-butane-NO -DEHA system . . .
Reaction profiles of 4.9 ppm n-butane-NO system
Reaction profiles of 4.9 ppm n-butane-NO system
X
Reaction profiles of 4.3 ppm n-butane-NO -DEHA system . . .
Reaction profiles of 4.7 ppm n-butane-NO -DEHA system . . .
X
Reaction profiles of 4.8 ppm n-butane-NO -DEHA system. . . .
Reaction profiles of 14.0 ppm n-butane-NO system
X
Reaction profiles of 14.3 ppm n-butane-NO system
Reaction profiles of 13.6 ppm n-butane-NO -DEHA system . . .
X
Reaction profiles of 13.5 ppm n-butane-NO -DEHA system . . .
X
Reaction profiles of NO system
Page
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
Vill
-------
TABLES
Number Page
1 Results of Irradiation of HC/NO /DEHA Mixture Using
Propylene 21
IX
-------
ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS
approx. — approximately
ARB — Aerosol Research Branch
°C — degree Celsius
cm — centimeter
DVM — digital voltmeter
EAA — electrical aerosol analyzer
EPA — U.S. Environmental Protection Agency
ERC — Environmental Research Center
°F — degree Fahrenheit
FID — flame ionization detection
ft — foot
FTIR — Fourier transform infrared spectroscopy
GC — gas chromatograph
hr — hour
in — inch
IR — infrared
1 — liter
MCA — multichannel analyzer
pm — micrometer
min — minute
MS — mass spectrometer
NBS — National Bureau of Standards
NSI — Northrop Services, Inc.
OPC — optical particle counter
ppb — part per billion
ppm — part per million
-------
RTP
sec
SYMBOLS
CH3CHO
C2H4
C2H5°H
C3H6
C4H10
DEHA
DENO
HC
HONO
2
H2
NO
N02
NO
x
N2
N2°
0
OH
°2
°3
PAN
THC
Research Triangle Park, North Carolina
second
acetaldehyde (ALD2) (C2H 0)
nitroe thane
ethylene
ethyl nitrite (NET) (nitroethane)
ethanol
ethyl nitrate (NIT)
propylene
n-butane
diethylhydroxylamine
(C2H5)2-N-0.
hydrocarbon
nitric acid
nitrous acid
hydroperoxide
hydrogen
water
nitric oxide
nitrogen dioxide
nitrogen oxides
nitrogen
nitrous oxide (N2O)
atomic oxygen
hydroxyl radical
oxygen
ozone
peroxyacetyl nitrate
total hydrocarbons
k first-order dissociation constant for NO_
[OH] steady-state hydroxyl radical concentration
S 5
XI
-------
ACKNOWLEDGMENTS
The authors especially thank Dr. T. A. Walter for his helpful discussions
of reaction mechanisms and intermediates. We also thank Mr. T. Winfield (for
assistance in analyzing for nitric acid), Mr. S. B. Joshi (for help in deter-
mining peroxyacetyl nitrate concentrations), and Mr. B. Gay and Dr. T. Knudsen
(for aid in analysis of diethylhydroxylamine).
XII
-------
SECTION 1
INTRODUCTION
The idea of treating polluted air with a chemical "air freshener" has
been bandied about in the literature for a number of years (1). The quest
for a "suitable" free radical scavenger led Heicklen and others to suggest
the use of DEHA as a photochemical smog inhibitor (2,3). Because of the
announced intention of Heicklen and co-workers "to add DEHA into urban atmo-
spheres to prevent the formation of photochemical smog" (4), and in an attempt
to resolve the controversy (5,6) regarding the efficacy of DEHA in inhibiting
the onset of the physical and chemical characteristics associated with smog
formation, this study was undertaken.
-------
SECTION 2
EXPERIMENTAL
A series of irradiation experiments was conducted in a smog chamber using
propylene (C H ) or n-butane (C H ) as the HC. NO in the ratio 4 parts NO
J O ^* Aw X
to 1 part NO were added to the chamber, and DEHA was either introduced or ex-
cluded in order to ascertain what differences were attributable to the role of
the inhibitor.
The irradiations were carried out in a 400-ft smog chamber described
elsewhere (7). A schematic diagram of the chamber and support equipment is
shown in Figure 1. An average value for k.. of 0.4 min was measured.
®
Cylinders of NO in nitrogen (N») and N0? in N_ from Scott Products were
used to charge the chamber with the initial NO concentrations. Propylene and
x ®
n-butane used for these runs were supplied by Matheson Gas Products . An-
®
hydrous DEHA from Pennwalt Corporation was used. Initially, DEHA was purified
by vacuum distillation (4). However, this purification was discontinued for
two reasons: (1) no difference in irradiations was attributable to use of the
purified material; and (2) any widespread application of DEHA to smog control
strategies would have to use unpurified commercial product.
NO and NO concentrations were monitored on two Bendix chemiluminescent
x
monitors. Periodic Saltzman determinations (8) of N0_ concentration were
®
made. 0 was measured on a Bendix Model 8002 0_ monitor. HC concentrations
®
were measured using an FID gas chromatograph (either a Perkin Elmer Model 900
® ®
or a modified Beckman 6800). Porapak Q columns were used to separate and
®
analyze the HC. DEHA in the gas phase was monitored using a Pennwalt 223
-------
t-
._. .1-11'
HIOWTI? I
ILO !J| HO nil
Till AM CpNI HOI
VAt Vf M'l
~~: :-—
j FlUER j
(COOttHG
| FM.1F.R !
IrARTJCLE^
; ni-TEn j
S/
..
lilt > >< >> "
UJ
®
-(5
run
-Cg) j
r-
3-WAY VAI.VC j— ,
P
Mr
\ /rx
I L
wAif.n .IACKMF.O A
—ilEA-"-.~-*c!!*M9-_/ I IpiinArii | Irupiriil I riiAtKOAi*| [ciiAncoAir| IcitAiicOATl
1 out sire
,1 "'"•'"••
WA1F.H 11HAIN
HEATED
I. IMF
(|)
I 3 WAf VAIVF
l^n^lHlt^rHinil
t
Av
MAKt: IIC
"""""•
~
• -^-
-------
amine packing in either a glass or Teflon column in the Perkin Elmer Model
900 GC. Bag samples from the chamber were analyzed for peroxyacetyl nitrate
®
(PAN) on the Perkin Elmer GC with an electron capture detector. Aerosol
®
formation was monitored with a Thermo Systems EAA. The dew point for each
®
run was held between 52-56°F and was monitored with an E G & G dew point
®
hygrometer. The internal chamber temperature was monitored with a YSI
calibrated thermistor.
-------
SECTION 3
RESULTS
The reaction profiles for 47 HC/NO /DEHA runs are displayed in the Appendix.
X.
For convenience, selected runs will also be reproduced in the present section.
For all of the runs reported here, the nominal initial concentrations of NO
and NO were 100 and 400 ppb, respectively. Stability measurements of DEHA and
HC gave gas-phase loss rates in the nonirradiated chamber that were experi-
mentally equivalent to the dilution losses.
Figure 2 shows the results of irradiating DEHA and NO , with no HC added.
Conversion of NO to N0_ was inhibited for about 6 hr, after which rapid con-
version of NO and quick formation of 0 occurred.
Figures 3 through 14 show the effects of irradiations with and without
DEHA for a variety of HC concentrations. In Figures 3 and 4, the propylene
concentration is ~0.25 ppm. In Figures 5 and 6, the propylene concentration
is ~0.5 ppm, and in Figures 7 and 8 the HC concentration is ~5 ppm. Figures
9 through 14 show irradiations of n-butane. HC concentration in Figures 9
and 10 is ~0.5 ppm; in Figures 11 and 12, ~5 ppm; and in Figures 13 and 14,
~15 ppm.
These graphs of irradiation runs demonstrate strikingly the effects of
DEHA on the system. During the initial portion of the run, the NO concentra-
tion increases as the NO_ is converted to NO and atomic oxygen (0) by irradia-
tion. HC consumption is decreased relative to the "no DEHA" profile, and O
formation is retarded. After the DEHA is consumed, the reaction proceeds with
-------
vigor! The NO conversion is very rapid, 0_ formation is accelerated, and the
maximum 0 concentration attained is increased.
Table 1 shows data taken from propylene runs. The first column lists the
Appendix figure number (e.g., "1" refers to Figure A-l). The second column
gives the initial propylene concentration, the third column tabulates the ini-
tial DEHA concentration, and the fourth shows the ratio [DEHA]0/[HC]0. The
next six columns represent various measurements of "smog formation." The time
to reach 90% of initial NO concentration (i.e., 10% conversion to NO and other
products) is listed in minutes in column five. The time at which only 10% of
[NO]0 remains as NO is given in the next column. The times in minutes for 0
to reach 40 ppb and to reach its maximum concentration are listed in the next
two columns, while the maximum O concentration obtained is given in column
nine. The effective O dosage for "1 day" (i.e., 11 hr of chamber irradia-
tion) is given in the tenth column.
The next five columns list pseudo-first-order rate constants for HC or
DEHA removal. (This assumes that concentrations of reactants other than HC or
DEHA are unchanging; i.e., that steady-state approximations are valid for
those species which react to remove the HC or DEHA.) The first two of these
columns apply only to irradiations to which no DEHA has been added. The first
column shows the rate constant calculated from data early in the reaction
(i.e., prior to a substantial 0 buildup), while the second column lists the
overall removal rate constant. The third column tabulates the HC removal rate
when DEHA was present, and the fourth gives the HC removal rate after the DEHA
has been consumed. Finally, the pseudo-first-order removal rate constant for
DEHA plus hydroxyl (OH) is estimated.
Figures 15 through 17 plot some of the data on "smog formation" listed in
Table 1 for the initial propylene concentrations of ~0.25, ~0.5, and ~5 ppm,
respectively. Figure 15 demonstrates some interesting results. At [DEHA]0/[HC],
= 0.2, the initial conversion of NO to NO is retarded; once the reaction
X
begins, however, the 90% conversion point (the + in the plot) is soon reached
and is achieved earlier than in the no-DEHA case. Therefore, under these
experimental conditions "smog formation" can be either retarded or enhanced,
6
-------
depending upon which characteristic one chooses to examine. Note also that,
while the onset of 0 production may be retarded, it is entirely possible that
the "1-day" 0 dosage may be enhanced. Comparison of Figure 15 with Table 1
shows that, while the "1-day" O dosage is reduced at high DEHA-to-HC ratios,
it comes about not because the potential for large values of [0_] is reduced,
3 max
but rather because the onset of 0 formation is delayed sufficiently long for
the integrated 0 -time profile for the first 11 hr of irradiation to be di-
minished.
Figures 5 and 6 demonstrate that PAN production seems to be increased
when DEHA is added to the system. Also, Figure 8 includes the profile of HNO.
formation as monitored by the method of Miller and Spicer (9).
®
Aerosol formation was monitored in a series of runs using the TSI Model
3030 EAA. Figure 18 compares the aerosol data for some 5 ppm propylene runs,
with and without DEHA.
-------
CD
60 I2O ISO 240 30O
360 420 48O S4O
1IME . minulei
66O 72O 780 840 9OO
Figure 2. Reaction profiles of DEHA-NO system.
-------
0.9
0.8-
O.7-
120 180 240 300 360 42O -»8O 54O 6OO 66O 72O 780 84O
60
TIME, minules
Figure 3. Reaction profiles of 0.25 ppm propylene-NO system.
X
-------
I.OH
O.9
o.a
0.7
O.6
60 I2O ISO
240 3OO 560 42O
TIME, minutes
4BO S40 CUO
Figure 4. Reaction profiles of ~0.25 ppm propylene-NO -DEHA system.
-------
0.6
60
I8O 24O 3OO
TIME, minutes
360
42O 480 540 6OO 66O
Figure 5. Reaction profiles of 0.5 ppm propylene-NO system.
-------
to
O.9-
0.8-
0.7-
0-6-
0.5-
O.4-
0.3-
0.2-
0.1-
30O J6O 42O
TIME . minutet
4BO 540 6OO 66O 72O 780
Figure 6. Reaction profiles of ~0.5 ppm propylene-NO -DEHA system.
-------
6.0-
S.O-
a
3.0-
2.0-
1.0-
0 J
O 30 60 9O 120
TIMC.minutet
Figure 7. Reaction profiles of 5.0 ppm propylene-NO system.
-------
6.O H
5.0
4.O-
3.0-
2.O-
I.O-
O-J
O.9-
O.8-
O.7-
O.6
0 NO,
Id NO
4 Oj
V Propylene
O OtHA
I 1 Sulumon
M HNOj , micro CCKllomeliy
NO.
TIME, minutes
Figure 8. Reaction profiles of ~5 ppm propylene-NO -DEHA system.
-------
0.6-J,
0.5
O.I -
6O 120 ISO 240 300 36O 42O 48O 54O 6OO 660 72O 780 840 900 9CO IO?O lOUO 1140 1200
TIME, imnules
Figure 9. Reaction profiles of ~0.5 ppm n-butane-NO system.
-------
0.9
IOZO 1080 I HO
TIME, minulei
Figure 10. Reaction profiles of ~0.5 ppm n-butane-NO -DEHA system.
X
-------
b.O-
3.0-
Z .0-
1.0-
O J
o.a
o eo
600 6OO
Figure 11. Reaction profiles of 5.0 ppm n-butane-NO system.
X
-------
1.0
O.9-
00
6.O-
5.0-
4.O .
3.0 -
2.O-
1.0-
60
I02O 1080 1140
TIME, minute*
Figure 12. Reaction profiles of ~5 ppm n-butane-NO -DEHA system.
-------
15.0-
14.0-
I3.O-
12.0-
11.0-
IO.O-
9.O-
f 8.0-
E
S 6.O-
5.O-
4.O-
3.0-
Z.O-
I .O-
0.9 -
O.8-
6O
120 I8O 24O
TIME, minutes
300 360
Figure 13. Reaction profiles of ~15 ppm n-butane-NO system.
X
-------
1.0-
0.9-
16.0
15.0-
14.0-
13.0-
12.0-
I I.O-
10.0-
• 9.O-
| 8.0-
" 7.0-
a. 6.0-
5.O-
4.0-
3.0-
2.0-
1.0-
0-J
60 120 180 240 300 360 42O 48O 54O 6OO
Figure 14. Reaction profiles of 15.0 ppm n-butane-NO -DEHA system.
-------
TABLE
1. RESULTS OF IRRADIATION OF HC/NO /DEHA MIXTURE USING PROPYLENE
X
K>
FICIJRE
1
2
3
4
5
6
7
10
13
21
22
11
23
12
15
25
26
27
28
29
30
31
"*••'<>
ppn
0.0
0.25
0.25
0.24
0.26
0.30
0.30
0.50
0.54
0.52
0.50
0.60
0.55
0.50
0.50
5.2
5.1
5.3
4.7
4.9
5.0
4.7
'Z'°
0.19
0.00
0.00
0.05
0.10
0.15
0.38
0.00
0.00
0.00
o.'oo
0.13
0.13
0.13
0.15
0.00
0.00
6.23
0.28
0.50
0.76
1.4
|DHIAI0
|ICI0
0.00
0.00
0.21
0.38
0.50
1.27
0.00
0.00
0.00
0.00
0.21
0.23
0.25
0.30
0.00
0.00
0.04
0.06
0.10
0.15
0.30
TIME FOR
0.9|NO]0
miji
380
25
25
46
274
253
474
14
8
8
11
191
226
168
215
2
1
45
42
85
175
310
o.]|iwi0
min
418
165
171
83
288
268
495
93
60
77
67
208
267
194
237
9
9
80
C5
132
245
353-
Ozone
= 40 ppb lOjIj^
mi n min
400
165
165
75
28R
266
495
81
55
64
67
204
252
189
234
R
7
115
125
ISO
300
402
840
750
780
480
900
660
930
430
405
360
340
*
715
-510
600
23
20
750
840
R40
990
1150
ppb
700
230
260
540
800
750
900
525
470
590
570
*
810
>700
630
330
320
760
760
740
700
800
"ONE
DAY"
1C Remwal
O3 Ozone UU1A
DOSAGE S70 ppb Overall Present
^m— nun min n\in nun
117
85
82
243
194
223
60
241
236
294
279
*
240
>253
213
22
23
245
255
183
98
65
.00655 .00655
.00550 .00550
.00513
— — .00134
.00151
— .00072
.00564 .00700
.00853 .01006
.00735 .00900
.00501 .00842
— — .00255
. 00094
— — . 00024
— — .00102
.00763
.00749
.00239
.00073
.00114
.00026
.00071
DEI [A
Consumed
min"1
-
—
.02-163
.02267
.01337
—
—
—
—
.02472
.02041
. 03047
.02387
—
—
.00773
.00822
.00555
.00545
.00298
^EHA
min 10 pun" min
-
—
.04748
.0)008
.01103
.00453
—
.00957
.00669
.00946
.00871
.01037
.01163
.OH947
.00446
.00931
-
3.3
2.7
2.6
2.3
1.4
2.6
14. 2
3.1
1.6
5.7
3.0
6.2
4.7
*F/-|uipment Failure During Run
-------
I
-------
o — [NO] = o.
.30-
.28-
.26-
.24-
.22-
.20-
.18-
.16-
o
r~~l 1 4-
o -ln
I
.12-
.10-
.08-
.06-
.04-
.02-
0-
(
+ - [NO] = o.
w D — [ 0 3] = 4C
ME& w
X — "ONE DAY
HC = 0.5 ppm
°» X
oXOf
^o — m Y
) 100 200 300 400 500
MINUTES
ppb
"ONE DAY" 03 DOSAGE IN ppm-minutes
Figure 16. "Smog" manifestations for an initial HC concentration of ~0.5 ppm
propylene.
23
-------
+ n
D
O -[NO] = 0.9[NO]0
+ -[NO] = o.i [NO]O
D - [ 03] - 40 ppb
X - "ONE DAY" 03 DOSAGE IN ppm-minules
HC- 5 ppm Propylene
1
100
1
200
300
t
400
500
MINUTES or ppm-minutes
Figure 17. Effect of [DEHA]0/[HC]0 on "smog" manifestations for an initial
HC concentration of ~5 ppm propylene.
24
-------
to
U1
250-
S NMO )
5O
200-
100-
0J
45
40-
30-
O 25-
20-
10-
SOLIO POINTS — NO OFHA
OPEN POINTS — OIHA AODEO
ISO 20O 220 24O 26O 280 3OO
MINUTES
Figure 18. Aerosol formation data versus time for runs with (open symbols) and without (filled symbols)
DEHA.
-------
SECTION 4
DISCUSSION
DEHA EFFECTS ON ASPECTS OF SMOG FORMATION
The results reported above illustrate that DEHA does indeed exhibit re-
markable influence on the progress of smog formation in chamber irradiations.
The effect of DEHA on a number of characteristics normally attributed to smog
formation will be discussed below.
NO Conversion
One of the earliest suggestions for using DEHA as an inhibiting agent
arose because of its ability to inhibit conversion of NO to N0_ (2). A series
of 10-min irradiations of NO/C,H./O0 were carried out, and the amount of N00
j b ^ £.
formed was monitored. DEHA was found to be one of the more efficient com-
pounds for retarding the formation of NO . The data presented herein confirm
that result: DEHA does inhibit the conversion of NO to NO products. Indeed,
in this system, N0? initially decreases while NO increases. But 10-min irradia-
tions do not tell the whole story, for — in all but the most reactive HC/NO
systems — the addition of DEHA first inhibits and then accelerates the con-
version of NO. As can be seen from Table 1, experimental conditions can be
found for which conversion of the first 10% of NO is retarded while conversion
of 90% of the NO is accelerated. (See also Figures 9 and 10 for the 0.5 ppm
n-butane runs and Figures 11 and 12 for the 15 ppm n-butane runs, where the
DEHA-added runs exhibit similar behavior.) This means that the effect of DEHA
in inhibiting NO conversion to products is ambiguous, and that short irradia-
tion experiments could show an inhibiting effect, while longer irradiations
would indicate an enhancement.
26
-------
03 Formation
The data in Table 1 and the reaction profiles in the Appendix all show
[0,] to be increased by the addition of DEHA to the reaction system. With
3 max
DEHA added to the propylene system, [0_] «750 ppb. This compares to
3 max
~250 ppb, ~550 ppb, and ~330 ppb for the 0.25 ppm, 0.5 ppm, and 5.0 ppm
propylene runs, respectively.
In fairly reactive.systems, the onset of 0 production (as represented by
the time at which the O concentration reaches 40 ppb) and the time for 0
maximum are retarded by DEHA. However, in the case illustrated by Figure A-4,
both onset of 0_ formation and the time for [O_] are advanced by the addi-
3 3 max
tion of DEHA. Coupled with an increased value for the O maximum, the "1-day"
0 dosage is three times as large with 50 ppb of DEHA in the system as with no
DEHA.
0 dosages were determined by measuring the area under the 0 concentra-
tion profile for the first 11 hr of irradiation. Schere and Demerjian (10)
give 1/2-hr average values of k for June 21 in Los Angeles. In our experi-
ments, the area under the sinusoidal-like step function was calculated to give
a k 'time product. The result was divided by the chamber k value of 0.4 to
determine the length of time of chamber irradiation equivalent to the Schere
and Demerjian k profile. This time was reduced by about 10% to represent the
solar irradiance on an average spring or summer day instead of for the longest
day of the year. (Data taken from Leighton (11) for a point at 35°N latitude
indicate that daily insolation for an average spring and summer day is about
89% of the daily insolation at summer solstice.) The result was that an 11-hr
irradiation in the chamber gave a k •time product equivalent to that of an
average spring/summer day in Los Angeles; the integrated dosages for 11-hr
irradiations are given in Table 1 and Figures 15 through 17.
In general, the time for onset of 0 production and the time to reach 0
•J J
maximum increase with increasing DEHA concentration. This affects the "1-day"
dosage figures, not by reducing the 0 -forming potential of the system but
27
-------
rather by moving the O profile out of the first 11-hr irradiation period.
Even so, the dosage figures are not lowered relative to the no-DEHA case until
a substantial amount of DEHA has been added.
PAN Formation
The addition of DEHA to the propylene-NO system roughly doubles the
maximum PAN concentration reached during irradiation (cf. Figures 5 and 6).
A similar result is reported by Pitts et al. (5).
Aerosol Formation
Figure 18 compares the aerosol growth dynamics of chamber irradiations
with and without DEHA. In both instances, the rapid production of aerosol
coincides with the onset of O formation. Without DEHA, a large number of
small droplets is formed. With DEHA in the system, the number of particles
formed is not so large as in the "no-DEHA" case, but they are larger in diame-
ter (as evident in the substantial increases in volume and surface area). This
means that there is considerably more material tied up in the aerosol when DEHA
is in the system. Also, only with DEHA added do the aerosol particles exceed
0.05 ym in diameter. Since 0.05 ym is (roughly) the smallest size particle
that can contribute to particulate light scattering (12), the net effect of
DEHA on visibility would seem to be increased degradation resulting from
particulate diffusion.
HC Consumption
A second major inhibiting characteristic (in addition to retarding NO
conversion) ascribed to DEHA is that it slows the rate of HC consumption
(4,6). This is to be expected of any compound which can effectively compete
with the HC for those reactive species which are capable of removing the HC.
Because the predominant reactive species early in an irradiation is OH (12),
any compound which reacts with OH at a rate substantially higher than that of
the HC should effect a decrease in the HC consumption rate — so long as its
reaction products do not in turn produce even more OH or other reactive species.
28
-------
Table 1 shows that DEHA does substantially reduce the HC consumption rate
as long as DEHA is present in the chamber. Once all the DEHA has been consumed,
however, the HC removal rate is accelerated and becomes as fast or faster than
the removal rate in the "no-DEHA" case.
Figures 9 through 14 demonstrate a similar general behavior for n-butane
(i.e., the HC removal rate is decreased as long as DEHA is present and is
increased after all the DEHA has been consumed).
The data listed in Table 1 for K „ , permit some interesting cal-
HC Removal ^
culations. If one assumes that HC removal prior to substantial buildup of O
is primarily due to reaction with OH (12), then the steady-state hydroxyl
radical concentration [OH] can be estimated as
ss
COHl = (k - k ) /k
ss HC Removal Dilution ' HC+OH
Using the data for k (with 0 ^ 70 ppb) together with values of 2.6
-4 -1 4 -1 -1
x 10 min and 3.6 x 10 ppm min for k_._ . and k (13), one
Dilution HC+OH
calculates an average OH concentration of 1.6 x 10 ppm, or about 4 x 10
radicals cm . This value is roughly equivalent to the yearly daytime average
[OH] of 5 x 10 radicals cm calculated by Weinstock (14) , and is less than
the daytime OH concentrations in ambient air measured by Niki et al. (15).
The validity of using HC removal rate data taken before [O ] reaches 70 ppb
can be checked by calculating the ratio of HC removed by OH to the HC removed
by 03:
_kHC+OH
kHC+03 [O ] [HC]
For the propylene data given in Table 1, the ratio is:
4 -1 -1 -7
(3.8 x 10 ppm min ) (1.6 x 10 ppm) _ .
R — — — ~ 5.1
(1.7 x 10 ppm min ) (0.070 ppm)
29
-------
This means that the HC removal rate is dominated (by a ratio of 5:1 or greater)
by the OH reaction until 0 exceeds 70 ppb. This calculation neglects HC
removal by other species like hydroperoxide (HO.) and 0, the concentrations of
which are kept exceedingly low by other species present in the system.
One may assume that when both DEHA and propylene are present in the
chamber they compete for the same reactive species. If that species is OH,
then one may estimate the reaction rate constant for DEHA plus OH by the
following equation:,
k *k
_ DEHA Removal HC + OH
DEHA + OH k
HC Removal (DEHA Present)
The last column in Table 1 shows the estimated values for DEHA + OH determined
from the experimental runs. The results give a value of 4.1 x 10 (±3.4 x 10 )
ppm min . This value is in good agreement with the direct measurement of
1.4 x 10 ppm min reported by Gorse et al. (16), especially in view of the
assumptions required to obtain the estimate. This value is approximately one-
half the "hard-sphere" estimate for a collisional rate constant and implies
that the reaction of DEHA with OH is very efficient.
The data show that the parent compound DEHA can act to inhibit many of the
manifestations of smog formation. However, as Figure 2 illustrates, DEHA is
an organic molecule which, when irradiated with NO , yields reactive products.
X
These primary or secondary products may, in turn, rapidly convert NO to NO? and
form copious quantities of 0 . This implies that the "reactivity" of DEHA
itself may set the limit on the extent of inhibition which is attainable by
injection of DEHA into the atmosphere. Indeed, the striking similarity of
Figure 2 (DEHA alone) and Figure 10 (DEHA added to 0.5 ppm n-butane) supports
the idea that, in reasonably unreactive systems, smog formation is directly
controlled by the reactivity of the DEHA itself.
30
-------
POTENTIAL MECHANISMS TO EXPLAIN DEHA EFFECTS ON SMOG FORMATION
The behavior of the chamber runs described above can be explained in
general terms by assuming that DEHA interacts with OH and other reactive
intermediates to form inert or less reactive products. (Indeed, the primary
applications for DEHA suggested by the manufacturer, Pennwalt, are as a radical
scavenger or "shortstopper" in polymerization or corrosion chemistry (17).)
Radical scavenging by DEHA would: (1) reduce the number of radicals capable
of reacting with HC, thus reducing the HC removal rate; and (2) intercept
atomic 0 so that irradiation would convert the NO- to NO with subsequent
suppression of 0 formation.
Attempts were made to adapt a reaction model for a propylene-NO system
X
developed by Dodge and Ascher (private communication) to explain the results
described above. Reactions for DEHA were added to the mechanism, based upon
reported product formation.
The products attributed by Heicklen (4) to addition of DEHA to a C_H /NO/
0_ irradiation system are: acetaldehyde (CH CHO) (C?H 0) (ALD2), ethyl nitrite
(C H NO ) (NET), ethyl nitrate (C H ONO ) (NIT), ethanol (C H OH), nitrous
acid (HONO), and nitrous oxide (NO) (N20). The reaction of O with DEHA (in
the presence of excess O or air) is reported to yield CH CHO and C»H NO?
essentially quantitatively and without inhibition (18).
One possible mechanism that explains all of the observed products is
shown in Figure 19. The first reaction step, abstraction of the hydroxyl
hydrogen, was suggested by Heicklen (4) and supported by Gorse e~b at. (16),
based upon liquid phase kinetic studies. Abstraction reactions are often very
fast; in the case of abstraction by OH, a very stable product, water (H_O), is
formed. The resulting radical, (C2H ) -N-0* or DENO, is interesting in that
resonant configurations may place the free electron on either the O or N atom.
The intermediate DENO or some subsequent product may itself be relatively
unreactive, since the rapid conversion of NO (and the other manifestations of
smog formation) is suppressed so long as DEHA is still present in the chamber.
31
-------
u>
NJ
RO
o ;
°3 r
DEHA OH ^
N02^
HONO^
H * OWJBS^^
H C-C — N — Et •*** — ~ y
> /
H,C-C— N-Et Et-N0-+Et
O ii i
II INO
Vv 4
/ \ EtO-
CH CHOA Et-NO
•D
+ H
EtN02 H^-C-O-O-
H^ r~ * LI r* _ P 1
•a v< — ^ — ^ rl-aVy o v. '
\ ^ O
0- I 0
Hr- c nu
.3. Vrf v^ vj n ,
0 x"
" * /^
u r n ri-i ^_ -r
C2H5-N-C2H5
V
0
(DENO)
^ \°\
\ \2
, E,,EtN02\
EtO2-
\0
EtO<^
DEHAX I
EtOH CH3CHO
^ 3 2 2
b. rw r>. -+. HP — n
/
/ *
/ NO (Ft^ N NO
^
02/
Eto^. Ji£^ E)0
\ F + O^ ^- P 1 1 ^
» C.TU • *" Un,v
\ 4°
E1NO2
^EtO-
\v
EtON02
or
CH3CHO 4 HONO
N02
Figure 19. Possible reaction mechanism for DEHA.
-------
Heicklen (4) reported an ~40-min inhibition period between onset of DEHA
removal and the appearance of CH CHO, nitroethane (CH CH.NO-) (EtNO ) and NO.
He suggests that the compound (Et) -N-NO may serve as an unidentified inter-
mediate in the reaction scheme. (The suggested reactions are included in
parentheses in Figure 19.) Some of the reactions included in the mechanism
must be considered to be speculative in nature. The paucity of thermodynamic
data makes theoretical predictions of possible reaction routes and rates
extremely difficult.
The photolytic rate constants in the model and an initial concentration
of HONO were adjusted to emulate the NO removal rate observed in the chamber
runs without DEHA. The model overpredicts 0 formation (therefore, the HC re-
moval rate is also too fast), a feature characteristic of this particular
model (Dodge and Ascher, private communication). Reactions involving DEHA
were then added to the mechanism. Initial attempts at modeling the entire
reaction scheme actually increased the overall reaction rate. For simplicity,
the DEHA reaction scheme was truncated with DENO, and the simulation was rerun
in an attempt to model the initial portion of the irradiation. Figure 20
shows a comparison of the simulations with and without DEHA added.
The simulations show that, with this particular reaction mechanism, the
addition of DEHA does indeed retard onset of O production and NO conversion
and slow the HC removal rate. The NO does increase initially, as is observed
experimentally (although the model achieves this primarily through reaction
of DEHA with HONO). The difficulties involved in modeling the initial NO
increase indicate that the mechanism may be either incomplete or inadequate
in regard to NO chemistry. This may also be the reason that the model tends
X
to over-predict 0 formation.
The rate constant used for Reaction (a)
DEHA + OH -> DENO + HO (a)
33
-------
i.o-
0.9-
0.8-
0.7H
0.6-
0.5
E
Q.
O.
O
(-
<
O
z
O
O
50
100 150 200 250
TIME--*- (minutes)
300 350
Figure 20. Simulation profiles for HC, NO, NO , 0,, and DEHA predicted by
kinetic model. Initial concentrations are: [HC]0 = 0.5 ppm
propylene; [NO]0 = 0.4 ppm; [NO ] = 0.1 ppm; [O ]0 = 0.0 ppm;
and [DEHA]0 = 0.0 or 0.125 ppm. Dotted lines are the "no DEHA"
case. Solid lines show simulation with DEHA included.
34
-------
varied between 1.4 x 10 ppm min and 4.1 x 10 ppm , with an intermediate
value of ~2.6 x 10 ppm min generally being used.
An upper limit of 0.02 ppm min was estimated for reaction (b)
DEHA + N02 ->• DENO + HONO (b)
based upon data obtained while charging the chamber for irradiations and from
data quoted by Heicklen (2). B. Gay detected by Fourier transform infrared
spectroscopy (FTIR) the rapid formation in the dark of HONO from the mixture
of NO and DEHA in a different chamber, but that rapid reaction may have been
influenced by wall effects.*
The rate constant for reaction of O and DEHA
0 + DEHA •*• DENO + OH + 0 (c)
was estimated as >1.3 ppm min from plots of the reaction of O with DEHA
published by Heicklen (18). A similar lower limit rate constant was used for
reaction (d):
O + DEHA -»• DENO + OH (d)
The reaction rate constant of HONO and DEHA was permitted to vary as
required:
HONO + DEHA -»• DENO + HO + NO (e)
Ratios of the subsequent reactions can be estimated from product distribu-
tions. The magnitudes of the rates must be adjusted to account for the actual
reactivity of the system.
*Gay (private communication). The formation of HONO in a nonirradiated mixture
of NO and DEHA was unmistakable, but because these two compounds have existed
in the gas phase in other chambers without rapid reaction, the results observed
by Gay may be attributable to surface effects. A subsequent 5-min irradiation
showed removal of both DEHA and HONO with no identifiable product buildup.
35
-------
SECTION 5
CONCLUSIONS
The results of adding DEHA to chamber irradiations of HC/NO systems were
X
empirically defined for propylene and n-butane.
As long as DEHA was present in the gas phase in the chamber, the physical
manifestations of smog formation were retarded or inhibited. However, DEHA is
an organic molecule which does react to produce "smog" itself; once it was con-
sumed, all of the manifestations of smog production were aggravated in the
test reaction systems. In particular, the chamber runs indicated that the
DEHA-consumed system produced: (1) increased 0 formation; (2) rapid con-
version of NO to NO ; (3) increased HC consumption; (4) increased PAN pro-
X
duction; (5) aerosol in greater volume and in a size distribution that is more
likely to affect visibility; and (6) a significantly different NO product
profile. These results have significant impact on any proposed control strategy
involving DEHA.
It has been suggested (4,6,16) that continual and sufficient introduction
of DEHA into the urban environment could significantly lower the exposure of
the urban population to smog. Under normal meterological conditions, this
conclusion is probably correct. However, addition of DEHA to the urban atmo-
sphere is much like "adding fuel to the fire." Should the concentration of
DEHA drop below "adequate" levels, the adverse effects of smog on the urban
population are likely to be exacerbated. In addition, these studies indicate
that the impact on rural areas downwind from the urban center may be significant
and undesirable. Under conditions of stagnant air over the urban center, the
necessary amount of DEHA to be injected on the second and subsequent days
36
-------
would have to be increased to overcome the reactivity of both the cumulative
HC and NO emissions and the buildup of DEHA reaction products. At some
X
point, DEHA concentrations would become unacceptable (on account of odor,
etc.), or the reactivity of the total organic chemical loading would become
sufficiently large to overwhelm the DEHA inhibition and produce smog effects
despite the presence of DEHA.
Finally, introduction of DEHA into the atmosphere may expose the populace
to some unknown NO product of DEHA. The runs presented above show that the
X
NO profile is significantly different with DEHA added to the system. The
X
high NO concentrations late in the DEHA runs cannot be accounted for by PAN,
X
NO , NO, and nitric acid (HNO,). CH CH NO and N0O (the major NO products
£. J j ^ £• £ X
identified by Heicklen (4)) could not be monitored because of gas chromato-
graphic insensitivity, but studies of the response of the chemiluminescent NO
X
instrument indicate that substantial concentrations of these compounds would
be required to account for the observed NO readings. This implies that some
X
other NO product (or a chemiluminescent interferent) must be formed during
X
the reaction. An attempt to analyze these NO products by FTIR was unsuccessful
X
because of experimental problems (Gay, private communication; see previous
footnote). The reaction scheme in Figure 19 suggests several possible inter-
), EtN=C
mediate NO products (EtNO, DENO, EtN=CHCH , etc.); Heicklen et al. (4) have
X -J
?
also suggested (C H ) -N-NO. The possible hazards of exposure to these or
other possible NO products of the reaction are currently unknown.
X
37
-------
REFERENCES
1. Stephens, E. R., R. H. Linnell, and L. Reckner. Atmospheric Photochemical
Reactions Inhibited by Iodine. Science 138:831, 1962.
2. Jayanty, R. K. M., R. Simonaitis, and J. Heicklen. The Inhibition of
Photochemical Smog. III. Inhibition by Diethylhydroxylamine, N-Methylani-
line, Triethylamine, Diethylamine, Ethylamine and Ammonia. Atmos. Environ.
8:1283, 1974.
3. Two New Approaches to Smog Control. Chemical and Engineering News 54(37):
32, 1976.
4. Stockburger, L. , B. K. T. Sie, and J. Heicklen. The Inhibition of Photo-
chemical Smog. V. Products of the Diethylhydroxylamine Inhibited Re-
action. Report No. 407-75, Center for Air Environment Studies, The
Pennsylvania State University, University Park, Pennsylvania, 1975.
5. Pitts, J. N., Jr., J. P. Smith, D. R. Fitz, and D. Grosjean. Enhancement
of Photochemical Smog by N,N'-Diethylhydroxylamine in Polluted Ambient
Air. Science 197:255, 1977.
6. Schaal, D., K. Partymiller, and J. Heicklen. The Inhibition of Photo-
chemical Smog. VII. inhibition of Diethylhydroxylamine at Atmospheric
Concentrations. Report No. 483-77, Center for Air Environment Studies,
The Pennsylvania State University, University Park, Pennsylvania, 1977.
7. Cupitt, L. T., and E. W. Corse. Status Report and DEHA Experiments.
ESG-TR-78-17, Northrop Services, Inc., Research Triangle Park, North
Carolina, 1978.
8. Selected Methods for the Measurement of Air Pollutants. Division of Air
Pollution, Public Health Service, U.S. Department of Health, Education,
and Welfare, 1965.
9. Miller, D., and C. Spicer. Measurement of Nitric Acid in Smog. J. Air
Pollution Control Assoc. 25:940, 1975.
10. Schere, K., and K. Demerjian. Calculation of Selected Photolytic Rate
Constants over a Diurnal Range: A Computer Algorithm. EPA-6001/4-77-015,
U.S. Environmental Protection Agency, 1977.
11. Leighton, P. A. Photochemistry of Air Pollution. Academic Press, New
York, 1961.
38
-------
12. Finlayson, B., and J. Pitts, Jr. Photochemistry of the Polluted Tropo-
sphere. Science 192:111, 1976.
13. Reaction Rate and Photochemical Data for Atmospheric Chemistry — 1977.
Circular No. 513, National Bureau of Standards, 1977.
14. Weinstock, B., and H. Niki. Carbon Monoxide Balance in Nature. Science
176:290, 1972.
15. Wang, C., L. Davis, Jr., C. Wu, S. Japur, H. Niki, and B. Weinstock.
Hydroxyl Radical Concentrations Measured in Ambient Air. Science 189:797,
1975.
16. Gorse, R., Jr., R. Lii, and B. Saunders. Hydroxyl Radical Reactivity
with Diethylhydroxylamine. Science 197:1365, 1977.
17. N, N-Diethylhydroxylamine: Reactions and Applications. PD-106, Product
Development Department, Industrial Chemicals Division, Pennwalt Corpora-
tion, 1969.
18. Olszyna, K., and J. Heicklen. The Inhibition of Photochemical Smog.
VI. The Reaction of 0- with Diethylhydroxylamine. Report No. 405-75,
Center for Air Environment Studies, The Pennsylvania State University,
University Park, Pennsylvania, 1975.
39
-------
APPENDIX
40
-------
I.O-
0.9-
o.e-
0.7-
6O I2O
84O 9OO
TIME ,
Figure A-l. Reaction profiles of DEHA-NO system.
-------
NJ
0.9
o.a
60 120 IBO 240 3OO 360 420 4SO 540 6OO 660 72O 760 B4O
Figure A-2. Reaction profiles of 0.25 ppm propylene-NO system.
X
-------
0.9
o.a
0.7H
o.e
O.I
60 12O ISO 24O 3OO
36O 4 2O 460
TIME, minulos
640 6OO 660 720 7BO 84O
Figure A-3. Reaction profiles of 0.25 ppm propylene-NO system.
-------
I.OH
0.9-1
O NO,
a NO
* 03
O OEHA
Propylen
I i Sail i man
I2O ISO 240 3OO 36O 42O 480 S40 60O 66O
Figure A-4. Reaction profiles of 0.24 ppm propylene-NO -DEHA system.
-------
Ui
O NO,
a NO
A Oj
O DEHA
Propylene
Soltzmon
ISO Z40 SOO 360 420 4BO 540
O.
78O 840 9OO
TIME, minute*
Figure A-5. Reaction profiles of 0.26 ppm propylene-NO -DEHA system.
-------
I.O
0.9
o.a
0.7
0.6-
o.s
0.4
0.3<
0.2
O.I
o NO,
B NO
A Oj
V Piopykiw
O UtHA
1 Sollimon
60 120 ISO
240 iOO J6O 420 4BO S4O 6OO
TIME, minulei
Figure A-6. Reaction profiles of 0.30 ppm propylene-NO -DEHA system.
X
-------
I.O-,
0.9-
0.8-
0.7-
0.6-
0.5-
0.4
O.i
0.2-
0.1 -
42O 48O 540 6OO 660 720 780 840 9OO
> 6O 120 180 240 3OO
Figure A-7. Reaction profiles of 0.30 ppm propylene-NO -DEHA system.
-------
00
I.O-
0.9-
0.8-
o.r-
O.6 -
o NO,
13 NO
A Oj
tf Prop»l*n«
I 1 Sottlfnon
6O IZO ISO 240 3OO 360 42O 480 540 600
Figure A-8. Reaction profiles of 0.49 ppm propylene-NO system.
-------
0.6-
0.51
0.4 -J
0.3-
0.2-
O.l -
0 60 I2O 180 24O JOO J60 420 460 540
Figure A-9. Reaction profiles of 0.48 ppm propylene-NO system.
-------
Ol
o
0.6-
0.5-6
0.4
E 0.3-
0.2-
0.1-
24O 3OO 360 42O 480 540 6OO 660
Figure A-10. Reaction profiles of 0.50 ppm propylene-NO system.
-------
(J1
o.e
O.7-
ISO Z4O 3OO 36O «ZQ 48O 54O 6OO
Figure A-ll. Reaction profiles of 0.60 ppm propylene-NO -DEHA system.
-------
O NOl
Ul
to
O.7-
0.6-
60
120 180 240 300 360 420 48O
TIME, minutes
540
Figure A-12. Reaction profiles of 0.50 ppm propylene-NO -DEHA system.
-------
0.9
O.8-
0.7-
0.6
0.5
0.4-J
0.3-
0.2-
0.1 -
O NO
B NO
A
60 120 180 240 3OO 36O 420 480 540 6OO
TIME, minutes
Figure A-13. Reaction profiles of 0.54 ppm propylene-NO system.
X
-------
en
0.9-
0.8-
0.7-
0.6-
0.5-
0.4
0.3-
O.2 -
0. I -
o NO,
D NO
* Oj
U Propylen<
1 Soil/man
120 180 240 KM) 360 42O 4 BO 540
Figure A-14. Reaction profiles of 0.47 ppm propylene-NO system.
-------
en
240 3OO 36O 420 480 54 O 600 660
0.9-
0.8-
0.7-
0.6-
0.3-i
0.4
O.S -
O.Z -
O.I -
60 120 180
TIME, minulos
Figure A-15. Reaction profiles of 0.50 ppm propylene-NO -DEHA system.
-------
0.6 -\
0.5 ^
0.4 e
0.2i
o-i -
O NO,
O NO
* Oj
tf Propylene
1 So Hi mun
0 6O
120 180 24O
TIME, minutes
Figure A-16. Reaction profiles of 0.54 ppm propylene-NO system.
X
-------
Ul
•-J
6O 120 ISO 240 30O
TIME, minutes
Figure A-17. Reaction profiles of 0.55 ppm propylene-NO system.
-------
CO
I.O
O.9 -
o.e
0.7-
0.6-
O.5-
0.44
0.3 -
O.2
GO 12O ISO 21O 3«) 360 42O 46O MO GOO 66O 720 7BO
Figure A-18. Reaction profiles of 0.54 ppm propylene-NO -DEHA system.
-------
vo
O.6
0.5
0.4,
O.3
0.2-
0.1
6O 120
180 240 300 360 42O
TIME . minutes
Figure A-19. Reaction profiles of 0.47 ppm propylene-NO system.
X
-------
O.6-
0.5-
0.4 -I I
0.3-
0.2 -
O.I J
60
120 ISO 24O JOO 36O
1IME. minutes
Figure A-20. Reaction profiles of 0.52 ppm propylene-NO system.
X
-------
0.6-
O.S-
E O.4 -I
0.3-
0.2-
O.l -
6O 12O 180 240 3OO J6O 42O 4BO 51O 6OO 66O
Figure A-21. Reaction profiles of 0.52 ppm propylene-NO system.
-------
en
NJ
O.6-
0.5
0.4-
0.3-
0.2-
0.1 -
O NO.
a NO
* Oj
V Propylent
1 Soil/mod
+ PAN
0 60 120 180 24O iOO J6O
TIME, minules
4BO 510 60O 660
Figure A-22. Reaction profiles of 0.50 ppm propylene-NO system.
X
-------
Co
O.9-
0.8-
0.7-
0.6-
0.5-
O.4 -
O.3-
0.2-
O.l -
6O I2O 180 240
300 36O 420
TIME . minulei
480 S4O 6OO 660 720 78O
Figure A-23. Reaction profiles of 0.55 ppm propylene-NO -DEHA system.
-------
6.0 H
3.0H
e
a.
I 3.O
2.0-\
• oH
O.6
0 30 6O 9O IOO
TIME, oimulei
Figure A-24. Reaction profiles of 5.0 ppm propylene-NO system.
-------
en
Ul
o NO.
a NO
Propylenc
3.0-
O.5
3.0-
1.0-
o-
0 SO 6O 9O I2O
TIME, cninutet
Figure A-25. Reaction profiles of 5.2 ppm propylene-NO system.
X
-------
o NO
6.0-
5.0-
4.0-
O.6
2.0-
1.0-
0 J
0 30 6O 90 I2O
TIME.mmuUt
Figure A-26. Reaction profiles of 5.1 ppm propylene-NO system.
-------
CTi
6.0 -
S.O .
J 4.O •
«
I
E
a
2.0-
1.07
O-
o.s
O.B -
0.7
O.6-
0 NO,
Itl NO
A 03
^ Propylene
O OtHA
I 1 Sail i man
•> HNOj .miciacoulomtlry
NO it
TIME, mingles
Figure A-27. Reaction profiles of 5.3 ppm propylene-NO -DEHA system.
-------
0.9H
6.0H
00
4.0-1
§
|
o.
I
I .OH
o-J
0 3O 60 90 120 ISO I8O 210 24O 27O JOO 36O 420 4BO S4O 6OO 66O 72O 78O 840 9OO
Figure A-28. Reaction profiles of 4.7 ppm propylene-NO -DEHA system.
-------
6.0-
5.0-
4.O-
I 3.0H
2.O-
I .0-
O-1
1 1 1 i i 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 r
6 3O 6O 9O 120 150 180 210 24O 270 30O 330 36O 39O ISO 4SO 48O 510 54O 57O 6OO 63O 66O 690 72O 75O 780 810 840 870 9OO
TIME , minutes
Figure A-29. Reaction profiles of 4.9 ppm propylene-NO -DEHA system.
X
-------
6.0-
5.0
«*
I 4.0-
1.0-
2.0-
1.0-
O-i
0.3
O.I -
' 1 1 1 1 1 1 1 *—*? *** 9 V *P—9 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
0 30 60 9O 120 ISO 180 2K> 24O 270 3OO 330 36O 39O
-------
6.0-
O 3O 6O 9O 120 ISO 180 210 240 27O iOO 3JO J6O 39O 420 46O 48O SIO 540 570 600 630 660 69O 720 75O 760 610 640 870 9OO 93O 96O i«O 1020 I05O 1060 1110 IHO
TIME, minutes
Figure A-31. Reaction profiles of 4.7 ppm propylene-NO -DEHA system.
-------
NJ
O 6O
84O .9OO 96O IO2O
Figure A-32. Reaction profiles of 0.49 ppm n-butane-NO system.
-------
0.6 -(
0.5J
0.4
0.3
0.2-
O.l -
360 420 480 540 60O660 T2O 78O 84O 9OO 96O
Figure A-33. Reaction profiles of 0.59 n-butane-NO system.
X
-------
O.4
0.2 -
60 120 ISO 24O MO 36O
10 BO
TIME , minutes
I26O IS20 IJ80 I44O I50O
Figure A-34. Reaction profiles of 0.48 ppm n-butane-NO system.
X
-------
72O /6U U4U 9OO 06O IO2O lOtIO II4U
Figure A-35. Reaction profiles of 0.46 ppm n-butane-NO -DEHA system.
X
-------
cr>
O.I
60
84O 9OO 961) IO20 IOUO II4O
1IME. minutM
Figure A-36. Reaction profiles of 0.55 ppm n-butane-NO -DEHA system.
X
-------
-J
-o
I.O-i
0.9H
O.I
IO8O IHO
TIME, minuies
Figure A-37. Reaction profiles of 0.59 ppm n-butane-NOx-DEHA system.
-------
-J
GO
6.O-
5.0-
4.0-
a>
• 3.O-
2.0-
1.0-
60 120
I6O 24O 3OO
TIME,minute*
36O 420
Figure A-38. Reaction profiles of 4.9 ppm n-butane-NO system.
-------
Ob
ti.O-
4.O -
3.0-
2 .O-
1.0-
0 J
6O 120 I BO
r
240 3OO 36O
TIME, minultt
420 46O 540
6OO
Figure A-39. Reaction profiles of 4.9 ppm n-butane-NO system.
-------
00
o
66O 720 7BO 840
loo
960 I02O
TIME.minulei
Figure A-40. Reaction profiles of 4.3 ppm n-butane-NO -DEHA system.
-------
00
5.0-
4.0 -
I 5-0-
2 .0 -
\ .0 -
480 540
TIME .minutes
780 840 9OO 960 1020 I08O
Figure A-41. Reaction profiles of 4.7 ppm n-butane-NO -DEHA system.
2C
-------
i.o-
O.9
o.a
00
to
6.0-
5.O-
4.O -
3.0 -
2.0
1.0-
O 1140
TIME. mmul«»
Figure A-42. Reaction profiles of 4.8 ppm n-butane-NO -DEHA system.
-------
en
U)
16.0-
15.O
14.0
13.0-
12.0
11.0-
10.0-
9.O-
J 8.0
o
I 7.0-
i
6.O-
50-
4.0-
3.O-
2.0-
I.O-
0 -
E
0.9-
0.8-
0.7-
0.6-
0.5-
0.4 '
0.3.
0.2-
0.1-
60
120 180 24O 300 36O
TIME . minulec
Figure A-43. Reaction profiles of 14.0 ppm n-butane-NO system.
-------
00
15.0
11.0
I3.0
I2.O-
II.O
IO.O
9.0
•
o a.o
f ,oH
a
a 6.O
3.O
3.0
Z.O
I .0
O
0.9 -
0.8
O.7-
0.6-
o
o
z
M
i
| 0.3
a
O.2-
O.l -
6O 120 180 24O
TIME, minute.
JOO 360
Figure A-44. Reaction profiles of 14.3 ppm n-butcUie-NO system.
X
-------
CO
(Jl
16.0-
15.0-
.0-
13.0-
12.0-
11.0-
IO.O-
• 9.O-
o
5 8.O-
7.0-
6.0-
3.0-
^.0-
3.O-
2.O-
1.0-
O-
l.O-
0.9-
0.8-
O.7-
O.6-
o NO,
a NO
* °s
O n-Butanc
O OEHA
' SalKmon
n-8ulaiw
6O 120 ISO 240 JOO 360 42O 480 54O 6OO
Figure A-45. Reaction profiles of 13.6 ppm n-butane-NO -DEHA system.
X
-------
00
16.0
15.0
M.O-I
I3.O-
I?..fl-
it.O-
IO.O-
9.O
•
| e.o
7.0
6 6.0-
c&
a
5.O-
4.O
3.O
2.O
I.O-j
O-
01
0.3
0.2
0.1-
84O 9OO 96O
Figure A-46. Reaction profiles of 13.5 ppm n-butane-NO -DEHA system.
X
-------
00
o.s-<
o.i
o.j-
O.2 -
O.I -
0 6O 120 180 Z40 3OO J6O 420 4 BO S4O GOO 66O
TIME, inlnules
780 84 O 90O
Figure A-47. Reaction profiles of NO system.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-6QO/3-79-040
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
EFFECT OF DIETHYLHYDROXYLAMINE ON SMOG CHAMBER
IRRADIATIONS
5. REPORT DATE
April 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
L. T. Cupitt
E. W. Corse
8. PERFORMING ORGANIZATION REPORT NO.
'9. PERFORMING ORGANIZATION NAME AND ADDRESS
Northrop Services Inc.
Environmental Sciences Center
Research Triangle Park, North Carolina
10. PROGRAM ELEMENT NO.
1AA603 AC-02 (FY-78)
11. CONTRACT/GRANT NO.
27709
Contract no. 68-02-2566
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory-RTF, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The addition of diethylhydroxylamine (DEHA) to the urban atmosphere had
been suggested as a means of preventing photochemical smog. Smog chamber studies
were carried out to investigate the photochemical smog formation characteristics
of irradiated hydrocarbon-nitrogen oxides - DEHA mixtures. Propylene and n-butane
were the hydrocarbons used. The effects of DEHA upon ozone formation, aerosol
formation, peroxyacetyl nitrate formation, nitric oxide-to-NO conversion, HHd
hydrocarbon consumed are described. The rate constant for thS reaction
DEHA + OH
products
was estimated as 4.1 + 3.4 X 10 ppm min . Possible reaction schemes for DEHA
in the photochemical smog mechanism are discussed.
The addition of DEHA to a HC/NO system inhibits the conversion of NO to
NO- during the initial minutes of irradiation, but after continued irradiation
accelerates this conversion.
7,
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
*
*
Air pollution
Hydroxyamine
Nitrogen oxides
Propylene
Butanes
Photochemical reactions
Test chambers
13B
07B
07C
07E
14B
8. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
100
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
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