EPA-600/3-77-109a
September 1977
Ecological Research Series
;\ AGENCY
Park, 27711
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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.
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EPA-600/3-77-109a
September 1977
EFFECT OF HYDROCARBON COMPOSITION ON
OXIDANT-HYDRCCARBON RELATIONSHIPS
Phase I. Exhaust Blends from Non-Catalyst
and Catalyst Equipped Vehicles
by
T. R. Powers
Exxon Research and Engineering Company
Linden, New Jersey 07036
Contract No. 68-02-1719
Project Officer
Joseph J. Bufalini
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
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
<
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DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
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 comnerical products constitute endorsement or recomnendation
for use.
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ABSTRACT
Oxidation catalysts on automobiles not only reduce the total amount of
hydrocarbon emissions, but also change the composition of these emissions
significantly. To explore the effect of this change on oxidant formation, 28
ten-hour irradiations were carried out in the Exxon Research Environmental
Chamber. Fourteen of these irradiations used a hydrocarbon blend represen-
tative of the non-methane, non-acetylene exhaust hydrocarbon emissions from a
non-catalyst equipped vehicle, and 14 used a blend representative of the same
fraction of the emissions from a catalyst equipped vehicle. Irradiations were
carried out at three hydrocarbon-to-nitrogen oxides ratios and with three
modes of chamber operation, chosen to simulate different meteorological condi-
tions.
The results of these experiments indicate that the composition change due
to oxidation catalysts will result in a significant alleviation, above that
due to hydrocarbon concentration change alone, of the local effects of auto-
motive tailpipe emissions.
111
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CONTENTS
Abstract iii
1. Introduction 1
2. Conclusions 3
3. Experimental Plan * 4
4. Methods and Procedures '5
Equipment 5
Chamber operating characteristics 5
Analytical methodology 6
Reagents and calibration gases .. 7
Procedure 8
5. Results and Discussion 11
Data organization and presentation -11
Data analysis 12
Results 12
Discussion 15
Appendices
A. Formulae used to calculate parameters^ -19
B. Calculated parameters and graphs 23
C. Calculated parameters and graphs 47
D. Analysis of variance tables 139
v
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SECTION 1
INTRODUCTION
The air quality standard for photochemical oxidant, 0.08 ppm, 1-hour
average, not to be exceeded more than once per year, is widely regarded as the
most difficult health-related standard to achieve.-1 This level is based on
upper respiratory effects, as developed in the document, "Air Quality Criteria
For Photochemical Qxidant". Oxidant is a secondary pollutant. That is, it is
formed as a result of chemical reactions between primary pollutants, in this
case, hydrocarbons (HC) and nitrogen oxides (MX.). Air quality standards for
hydrocarbons are based on the tendency of hydrocarbon to participate in re-
actions leading to oxidant formation. According to the Environmental Pro-
tection Agency (EPA), an air quality standard of 0.24 ppm non-methane hydro-
carbon (NMHC) is required to assure that the oxidant standard is not exceeded.
Most recently, a report from a National Academy of Science Panel, headed by
Professor Arthur Stern, concluded that the oxidant atr quality standard could
be attained via a NMHC standard of 0.75 ppm carbon (ppmC). This standard is
important to the nation, as the control of NMHC to very low levels in order to
control oxidant may result in significant changes in our society, including
urban land use, modes of transportation, and population density.
Another important recent development is the recognition that the com-
position of auto exhaust gas from vehicles equipped with oxidation catalysts
may have a composition significantly different from that of vehicles not
equipped with catalysts. The catalyst systems appear to preferentially remove
the more reactive hydrocarbon species. Thus, in addition to the large re-
duction in total hydrocarbon mass emissions, there is a further decline in
atmospheric reactivity associated with this composition change. Since hydro-
carbon -oxidant relationships are affected by the photochemical reactivity of
the hydrocarbon mixture, control strategies for oxidant abatement must be
reevaluated in light of the prospective change which began in September, 1974
when catalyst equipped vehicles were introduced. The difference in hydrocarbon
composition of the exhaust gas from these vehicles from that of vehicles not
equipped with catalysts should influence the hydrocarbon-oxidant relationship.
Further investigations may show that no general, nationwide hydrocarbon-
oxidant relationship is possible, since the formation of oxidant depends in
part on meteorological conditions, such as ventilation, sunlight intensity,
inversion layer height, etc. According to this reasoning, conditions favor-
able to oxidant formation in Los Angeles should not be used to establish NMHC
1Due to the subject matter of this report, the English System of Units was
used. For conversion to the International System of Units, see the conversion
table on p. 17.
1
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standards in New York City. Although a massive amount of aerometric data and
an equally impressive array of smog chamber data have been gathered over the
past decade, a clear picture of the true NMHC-oxidant relationship is still
not available.
The research program reported here is designed to begin to answsr some of
the questions about the NMHC-oxidant relationship by providing basic data on
HC-NCx-oxidant systems at ambient concentrations, under both static and dynamic
conditions. Specifically, the question of the effects of the introduction of
catalytic exhaust treatment of automobile exhaust on oxidant formation is
addressed in the following pages.
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SECTION 2
CONCLUSIONS
While extrapolation of the results of a smog chamber study like the one
reported here to the real world is subject to considerable uncertainty, it is
probably justifiable to apply trends observed in snog chamber studies to
actual atmospheric situations. The trends in these data indicate that signif-
icant alleviation of the local impact of automotive tailpipe emissions, above
that due to changes in mass of hydrocarbons emitted, can be expected uhen the
changeover to catalytic exhaust treatment is completed.
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SECTION 3
EXPERIMENTAL PLAN
In this program, two hydrocarbon blends, one modeled on the exhaust from
a non-catalyst equipped vehicle and the other on the exhaust from a vehicle
meeting the 0.41 g/mi. hydrocarbon, 3.4 g/mi carbon monoxide (CO), and 0.4
g/mi. NQx emission standards were compared using the Exxon Research Environ-
mental Chamber. Both blends were irradiated for 10 hours in the chamber under
three different initial hydrocarbon-to-NOx (HC/NQx) ratios and three different
modes of chamber operation, as given in the matrix below:
Initial HC/NOy
Chamber operating mode 2 4 8
static xxx
dilution x x
dynamic x x
All runs were replicated. Initial hydrocarbon concentration levels were 4 ppm
carbon for HC/NOx ratios of 4 and 8, and 2 ppm carbon for an BC/NOx ratio of
2. Initial NOx consisted of 30% nitrogen dioxide (NO2) and 70% nitric oxide
(NO).
Time/concentration profiles for ozone (03), NO, N02, peroxyacetylnitrate
(PAN), total hydrocarbons, condensation nuclei, and individual hydrocarbons
were determined. Oxidant was determined by the Neutral Buffered Potassium
Iodide method (NBKI) and formaldehyde was determined by the chromatropic acid
method at the beginning and end of the run only. Analysis of the data has
concentrated on blend-to-blend variations in those parameters of the profiles
directly concerned with ozone and oxidant levels. At the request of the
Project Officer, a pair of static runs was conducted using propylene at a
concentration of 3 ppm carbon and an KC/NOx ratio of 6. The purpose of the
runs was to provide data for inter-chamber comparison work among EPA con-
tractors. The data from these runs was not analyzed.
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SECTION 4
METHODS AND PROCEDURES
EQUIPMENT
Experimental work was carried out using the Exxon Research Environmental
Chamber facility. A description of the chamber and associated analytical
methodology follows.
The Environmental Chamber
The 4.25 m3 Exxon Research environmental chamber is made of an aluminum
frame with windows of Teflon film. The chamber resembles a flattened ellip-
tical cylinder with cross-sectional dimensions of 2.75 m x 1.83 m and a length
of 0.99 m. The chamber surface is calculated to be 16.1 m2, about 50% of
which is associated with the two Teflon windows, resulting in a surface-to-
volume ratio of 3.78 m""1. The chamber is equipped with a metered purified air
supply and metered vents which allow it to be run in dynamic modes.
Irradiation System
The irradiation system, designed to simulate ambient sunlight both in
light intensity and spectral distribution of energy, consists of SO fluores-
cent lamps, a combination of black and sun lamps. The light intensity in the
chamber was determined by an Eppley laboratories Model TUVR Solar Ultraviolet
Radiometer (290-380 nm) to be approximately 48 meal min-1 cm"2.
Air Supply
An air purification system, consisting of a charcoal absorption tower and
a platinum oxidation catalyst, provides pure air with less than 0.3 ppmC
hydrocarbon. The hydrocarbon was analyzed and found to be solely methane. A
measure of chamber background reactivity is obtained by irradiating this clean
air in the chamber with humidity for 10 hours. The maximum number of conden-
sation nuclei (CN) monitored was 182 CN/ml, which is three orders of magnitude
lower than that observed with irradiated auto exhaust diluted to atmospheric
levels. No increase in HC concentration was observed over the period of
irradiation, Oxidant levels reach a maximum of 0.015 ppm.
CHAMBER OPERATING CHARACTERISTICS
Leak Rate and Sampling Requirements
To ensure that the chamber contents will not be contaminated by atmos-
5
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phsric air, the chamber pressure is maintained at 0.13 kPa above atmospheric
pressure. This results in an unintentional leak rate of less than 1.5% hr."1
which is measured by monitoring the amount of makeup air added. This volume
is replaced with the purified air previously described. With the analytical
procedures currently employed, the total leak rate of the chamber is about 3%
hr.-1. This volume is dependent upon the number and type of analytical
measurements taken.
Relative Humidity and Temperature
The chamber is usually operated at approximately 30°C, the temperature
being maintained by the use of infrared lamps. Temperature stability is
adequate with a standard deviation of about 0.5°C over a 10-hour irradiation.
Initial chamber humidity can be varied by circulating the diluent chamber air
through a tank containing heated distilled water. The water temperature in
the tank is maintained at about 80°C to reduce the time required for humidi-
fication.
Cleanliness
To ensure chamber cleanliness and avoid run-to-run contamination, the
chamber is purged with pure air containing about 2 ppm ozone between experi-
ments. This has proven to be an effective means of maintaining chamber clean-
liness.
It is believed that the rate of ozone disappearance in a chamber is a
measure of chamber cleanliness. Ozone disappearance rates in air at 20%
relative humidity were measured with and without irradiation. These rates,
expressed as the half-life for 03 at 1 ppm, are shown below. The values
compare favorably with those of other chambers.
With irradiation, t, ,0 = 2.7 hours @ 20% R.H.
i/^
Dark reaction, t, /0 = 14 hours @ 20% R,H.
i/^
ANALYTICAL MEIHCDOLOGY
Total Hydrocarbons
Total hydrocarbons were measured with a Varian 1440 total hydrocarbon
analyzer with a sensitivity of ^10 ppbC, The analyzer was zeroed on the
chamber clean air supply and spanned on a commercially analyzed cylinder of
propane CO-5 ppm) in air.
Individual Hydrocarbons
Individual hydrocarbons were measured with a Perkin Elmer Model 900 Gas
Chromatograph with sub-ambient temperature programming capabilities. The
instrument was equipped with a column 1/8" outer diameter (O.D).; 5% UCW 98 on
80/100 mesh Chromosorb G AWDMCS. Fifty milliter samples were injected at
-70°C and the column oven temperature was raised at a rate of 8°C/min. to
180°C. The instrument is calibrated on the initial chamber hydrocarbon
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charge, widen is a metered dilution of a commercially analyzed cylinder.
Nitrogen Oxides
Nitrogen oxides were monitored with a TECO 14B nitrogen oxides analyzer.
The analyzer is calibrated on a commercially analyzed cylinder vising a TECO
Model 101 calibration unit.
Qxidants
Qxidants were determined by the Neutral Buffered Potassium Iodide Proce-
dure according to the Federal Reference Method (Fed. Reg. Vol. 36, #84, p.
8196), and corrected for N02 by subtracting 0.1 [N02].
Ozone
Ozone was measured with a REM Chemiluminescent Analyzer calibrated on the
ozone generator in the TECO 101 calibration unit. The ozone generator is
calibrated by Neutral Buffered Potassium Iodide according to the Federal
Reference Method.
Peroxyacetylnitrate
Peroxyacetylnitrate determinations were carried out with a Varian Model
1700 gas chromatograph with electron capture detector. Calibration is by
dilution of PAN mixtures synthesized in-house. Concentration of these mix-
tures is determined by long path infrared spectroscopy.
Formaldehyde
Formaldehyde concentrations were determined by the chromatropic acid
method (U.S. Dept. HEW, 999-AP-ll).
Condensation Nuclei
Condensation nuclei were monitored with an Environment One Condensation
Nuclei Monitor, which operates on the cloud chamber principle.
REAGENTS AND CALIBRATION GASES
All reagents and calibration gases were obtained as analyzed cylinders
from Scott Research Laboratories in Plumsteadville, Pennsylvania and used
without further purification.
Nitrogen Oxides
Separate cylinders of NO2 (^1000 ppm in hydrocarbon-free nitrogen) and NO
(vLOOO ppm in hydrocarbon-free nitrogen) were used to charge NOx for all runs.
Hydrocarbon Blend
Two different hydrocarbon blends were used in this study. Blend XL-228 is
a model blend for the non-methane, non-acetylene hydrocarbon fraction of the
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exhaust from a non-catalyst equipped vehicle. Blend A-11004 is a model blend
for the same fraction of the exhaust from a car meeting stringent CO. 41 g/mi.
HC, 3.4 g/mi. CO, 0.4 g/mi. N^) emission standards.
Hydrocarbon blends were derived from gas chromatographic data on auto
exhaust obtained at Exxon Research and Engineering. Details of these blends
are given in Table 1.
For a non-catalyst equipped car, two runs were used. These were analyses
of the emissions from a 1970 Chevrolet with a 5 . 7 liter engine run on the 1972
Federal Test Procedure. For the catalyst equipped car data, three runs from
another 1970 5.7 liter Chevrolet equipped with a Monel reduction catalyst
before a monolithic oxidation catalyst were used. This vehicle was run on the
1975 Federal Test Procedure. Both cars were run on a 37% aromatic fuel blended
from standard refinery blending components. The olefin data ware not used as
they were believed to be unrepresentative due to a large and probably spurious
trans-hexene-2 peak.
Using the sumnary of mole fraction data from each run, the following
parameters were calculated for non-catalyst equipped and catalyst equipped
emissions: average mole fractions of non-methane paraffins, olefins and aro-
matics; average carbon numbers of the whole mixture, non-methane paraffins,
olefins, and aromatics; the ratio of C2 olefins to C3 olefins; and the ratio
of C7 aromatics to C8 aromatics. The blends were constructed as follows:
Paraffins: The normal paraffin of carbon number closest
to the average non-methane paraffin carbon
number was chosen and put in at the average
non -methane paraffin mole fraction.
Olefins: Ethylene and propylene were chosen as olefin
model compounds and put at the C2 and C3 olefin
ratio calculated from the data. Total mole
fraction of olefins was set at the value derived
from the data.
Aromatics: Toluene and xylene were chosen as aromatic
model compounds and put in at the C7 to C8
aromatic ratio calculated from the data. Total
mole fraction of aromatics was set at the value
derived from the data.
Table 1 gives values of all the parameters calculated from the data, and also
gives values of the same parameters calculated from the blends used in this
work. The blends provide a good approximation to the available data on non-
methane, non-acetylene emissions from non-catalyst equipped and catalyst
equipped cars.
PROCEDURE
After an overnight flush with clean air, the chamber was pressurized to
0.13 kPa and checked for background ozone, oxidant, hydrocarbon, and NOx- If
these values were essentially zero, chamber humidity was set and the chamber
8
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TABLE 1. HYDROCARBON BLENDS AND CALCULATED PARAMETERS
HYDROCARBON BLENDS
Compounds
n-pentane
n-butane
ethylene
propylene
toluene
m-xylene
Mole Fraction
(Non-Catalyst Equipped Car) (Catalyst
XL-228
0.21
0.30
0.09
0.17
0.23
Equipped Car)
A-11004
0.51
0.18
0.04
0.17
0.10
CALCULATED PARAMETERS
Parameter Non-Catalyst Equipped Car
Experimental
mole fraction paraffins
mole fraction olefins
mole fraction aromatics
avg. paraffin carbon number
avg. olefin carbon number
avg. aromatic carbon number
avg. carbon number
C2/C3 olefin ratio
C7/C8 aromatic ratio
.19
.44
.38
5.06
2.35
7.88
4.94
3.3
.78
XL-228
.21
.39
.40
5.00
2.22
7.57
4.95
3.3
.71
Catalyst Equipped Car
Experimental
.53
.21
.25
4.44
2.47
7.30
4.73
4.74
1.62
A-11004
.51
.22
.27
4.00
2.18
7.41
4.52
4.5
1.70
Avg. Carbon Number Ratio
Non-Catalyst Equipped/Catalyst Equipped
Experimental
Blends
1.04
1.09
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was charged to the initial reactant levels in the following order:
1) N02 (to 30% of total NO*)*
2) NO (balance of total NOx)
3) hydrocarbon
Initial readings of all instruments were taken after charging and before
turning on the lights. Instruments were read at half-hour intervals for the
first 5 hours of each run and at hourly intervals for the second 5 hours.
Qxidant and formaldehyde were determined only at the end of the run after the
lights had been shut off. Three different modes of chamber operation were
used:
Static - Only air necessary to make up for samplings losses was
added. Results were corrected for this small dilution before re-
porting. Initial relative humidity was set at 12%.**
Dilution - The chamber was operated statically for the first 5 hours
of irradiation and then diluted at a rate of 10%/hour with purified
air. This mode was intended to simulate a temperature inversion
which holds throughout the morning and then breaks up. Results were
not corrected for dilution. Initial relative humidity was set at
20%.**
Dynamic - The chamber charge was diluted at a rate 10%/hour from the
beginning of the run with purified air and reactants at a concen-
tration 0.4 ppmC hydrocarbon and 0.1 ppm NO. This mode was intended
to represent the transport of a polluted air mass across a populated
area where it is diluted and simultaneously receives injections of
reactants. Results were not corrected for dilution. Initial re-
lative humidity was set at 70%.**
At the end of each run, the chamber was flushed for 8 hours with clean
air, treated with ozone at ^2 ppm for 2 hours with the lights on and flushed
overnight with clean air. To facilitate the determination of statistically
significant trends in the data, runs were performed in random order.
*except propylene runs, where all NOx was charged as ND.
**Due to an arithmetical error, average relative humidity was not held
constant over all running modes, so effects due to change in running mode
may be, in part, due to differences in relative humidity.
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SECTION 5
RESULTS AND DISCUSSION
DATA ORGANIZATION AND PRESENTATION
Raw data from each chamber run were punched on cards and fed into an IBM
1130 computer. The computer converted the raw instrument readings into con-
centrations in ppm, corrected these concentrations for dilution as necessary,
and output the results in graphical form. Smooth curves were drawn through
the line printer plots from the computer and further parameters were calcu-
lated from these curves. The formulae used to calculate these parameters are
listed in Appendix A. The computer output sheets are available from the
Project Officer. Calculated parameters and graphs for all runs appear in
Appendices B and C.
Propylene Runs
Two static runs using propylene were made at an initial concentration of
3 ppmC and an HC/NOx ratio of 6 in order to facilitate inter-chamber compar-
isons among EPA contractors. The low level of 03 production in these runs and
in preliminary runs with our test hydrocarbon blends indicated that there was
a deficiency in light intensity in the chamber. Modifications were made to
the windows and light banks to correct this deficiency. Since the propylene
runs do not reflect the condition of the chamber during the balance of the
program, no further analysis was performed. For the sake of completeness, the
graphs and calculated parameters for the runs are in Appendix B. The computer
output sheets are available from the Project Officer.
Runs at HC/NQ^. = 2
Runs at this level showed no evidence of reaction with either blend;
therefore, they were not analyzed further.
Runs at HC/NO^ = 4 and HC/NOy = 8
Runs at these levels showed evidence of reaction with both blends and in
all chamber operating modes. All of the subsequent analyses and conclusions
are based on these runs. For the sake of completeness, the graphs and calcu-
lated parameters for the runs are in Appendix C. The computer output sheets
are available from the Project Officer.
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Condensation Nuclei Data
Condensation nuclei concentrations (CNC) were of the order of 102/ml for
all runs. This extremely low absolute concentration level is near the limits
of detectability for our CNC counter. It is believed that any variability in
CNC readings is due to the noise inherent in operating the instrument at these
low levels, so no detailed analysis of these data was carried out.
DATA ANALYSIS
The 24 runs with HC/NOx = 4, and HC/NOx = 8, chamber running conditions
of static, dilution, and dynamic, and non-catalyst equipped and catalyst
equipped hydrocarbon blends form a completely replicated 3x2x2 factorial
experimental design. One of the basic characteristics of this design is that
factor effects, i.e., those due to HC/NQx, chamber running conditions, or
hydrocarbon blend, are completely clear of each other. The factor effects are
also clear of all two- and three-factor interaction effects and the inter-
action effects are clear of each other. Replication allows the variance in
the measurements to be estimated and the statistical significance of any
observed effects to be determined.
For these data, a three-factor analysis of variance was carried out for
the parameters in Table 2. CThe analysis of variance tables are given in
Appendix D.) This group includes all of the parameters necessary to make a
good assessment of the effects of the factors in the experimental matrix on
photochemical smog production. All of the single factor and two-way inter-
action effects significant at the 95% level were determined using the standard
F test for comparison of the variance due to the factor and the variance
determined from the replicate experiments. These significant effects are
given below.
It should be noted that very little significance can be attached to the
absence of an effect in this analysis. The experimental design and variance
of the measurements are such that the probability of not detecting an effect
of . 03 ppm in maximum 03, maximum N02, or final oxidant is '^50% when the test
for that effect is carried out at the 95% significance level.
RESULTS
Effects Due Only to Hydrocarbon Blend
Changing the hydrocarbon blend from non-catalyst equipped to catalyst
equipped (XL-228 to A-11004):
Decreased the maximum 1-hour average ozone concentration by 39%, from
an average of .23 ppm to an average of .14 ppm.
Increased the time to reach maximum ozone 33%, from an average of 5.4
hrs. to an average of 7.2 hrs.
Decreased maximum PAN concentration 53%, from an average of 0.015 ppm
to an average of 0.007 ppm.
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TABLE 2. PARAMETERS ANALYZED
Ozone, maximum 1-hour average
Ozone dose
>
Ozone, tine to maximum
NO2, maximum 1-hour average
N02, dose
N02, time to maximum
PAN, maximum
Oxidant, final
Formaldehyde, final
Total Hydrocarbon, average disappearance rate
Individual Hydrocarbon, average disappearance rate*
* Analyzed by simple analysis of variance for compound-to-compound
differences as missing data did not allow a full factor analysis.
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Decreased the average total hydrocarbon disappearance rate 38%, from
an average of 0.88 ppm/hr. to an average of 0.54 ppm/hr.
Effects Due Oily to Change in HC/NOy Ratio
Changing the HC/NQx ratio from 4 to 8 (or NQx concentration from 1.0 ppm
to 0.5 ppm):
Decreased time to maximum ozone by 26%, from 7.2 hrs. to 5.4 hrs.
Decreased N02 1-hour maximum average by 36%, from 0.45 ppm to 0.29
ppm.
Decreased NO2 dose by 43%, from 2.8 ppm hrs. to 1.6 ppm hrs.
It should be noted that in this set of experiments, EC concentration was
held constant. Therefore, a change in HC ratio may equally be thought of as
a change in total NC^ concentration.
Effects Due Only to Change in Chamber Running Mode
A change in chamber running conditions from static to dynamic:
Increased maximum 1-hour average ozone 39%, from an average of .18
ppm to an average of .25 ppm.
Decreased time to maximum ozone 60%, from an average of 8.7 hrs. to
an average of 3.5 hrs.
Decreased time to maximum N02 by 70%, from 2.2 hrs. to 0.7 hrs.
Increased maximum PAN concentration 171%, from an average of .007 ppm
to an average of .019 ppm.
Increased average total hydrocarbon disappearance rate 272%, from an
average of .36 ppm/hr, to an average of 1.34 ppm/hr.
Effects Due to Interactions Between Hydrocarbon
Blend and HC/NOy Ratio
Increasing initial HC/NQx from 4 to 8 left final oxidant concentration
unchanged for Blend XL-228 (non-catalyst) and increased final oxidant by 83%
for Blend A-11004 (catalyst).
Effects Due to Interactions Between Hydrocarbon
Blend and Chamber Running Mode
Changing hydrocarbon blend from XL-228 (non-catalyst) to A-11004 (cat-
alyst) increased time to maximum ozone:
19% for static runs, from an average of 8.0 to an average of 9.5.
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55% for dilution runs, from an average of 5.2 to an average of 8.1.
33% for dynamic runs, from an average of 3.0 to an average of 4.0.
Effects Due to Interactions Between HC/NO^ Ratio
and Chamber Running Mode
Increasing HC/NQx from 4 to 8:
Decreased maximum PAN 40% for static runs, from an average of 0.010
to an average of 0.006.
Increased maximum PAN 150% for dilution runs, from an average of
0.004 to an average of 0.010.
Decreased maximum PAN 14% for dynamic runs, from an average of 0.021
to an average of 0.018.
Increased average 1-hour maximum average 03 100% for dilution runs,
leaving it unchanged for static and dynamic runs.
Notes on Dosages
Dosage calculations, being integrals under experimental curves, are
highly dependent upce the time limits of the integration. Comparisons based
on total dose are subject to an experimental artifact: if the effect of a
change in experimental factor is to shift the 03 or NO2 maxima to a later
time, and the dose integral is still cut off in 10 hours from the start of the
run, the dose will be less, but it will be less because the production was
artifically terminated at the end of the run. To guard against this artifact,
no effects on dose are reported as significant unless the factor involved had
no effect on the time to maximum of the species in question.
DISCUSSION
Examination of the large number of statistically significant effects
shows that the findings of this study can be easily sumnarized.
The effects due to hydrocarbon blend, i.e. , a decrease in maximum 1-hour
average ozone and an increase in the time to reach it, a decrease in maximum
PAN, and a decrease in total hydrocarbon disappearance rate, can all be thought
of as effects which tend to lessen the short term (<10 hour) severity of
photochemical smog as one goes to the catalyst blend.
The behavior of the system in response to changes in HC/NCx ratio (or
equivalent ly in this study, NO^ level) is also quite simple. The only effects
found were a decrease in N02 levels with decreasing NQx and a decrease in time
to maximum ozone with decreasing
The behavior of the system in response to changes in chamber running mode
is also of interest. The most severe short term smog effects did not occur
under static or stagnant conditions but under dynamic conditions where con-
15
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siderable dilution of the air mass takes place. This dilution is contaminated
by air with a low level of hydrocarbons and ISD. This finding has implications
for control strategy formulation also as it indicates that a good assessment
of the potential severity of smog in a given day must consider the effects of
input precursors throughout the day as wsll as the effects of the precursors
present in the early morning.
The results of this study can then be stated in the following summary;
Changing hydrocarbon composition from a blend modeled on exhaust
from a non-catalyst equipped vehicle to a blend modeled on exhaust
from a catalyst equipped vehicle decreases the parameters associated
with the short term (<10 hour) severity of photochemical smog.
Changing the hydrocarbon-to-NDx ratio from 4 to 8 decreases the time
to 03 maximum, the maximum 1-hour average N02, and the N02 dosage.
Short term (<10 hour) smog effects are most severe under dynamic
running conditions.
16
-------
TABLE 3. CONVERSION TABLE TO S. I. UNITS
To Convert From
To
Multiply by
calorie
gram
hour
kilopascals (kPa)
liter
mile
minute
degree Celsius (°C)
joule
kilogram
second
newton/meter2
meter3
meter
second
degree Kelvin (°K)
4.186 8 E+00
1.000 000*E-03
3.600 000*E+03
1.000 000*E-K)3
1.000 000*E-03
1.609 344*E-K)3
6.000 000*E+01
t = t + 273.15
k c
17
-------
APPENDIX A
FORMULAE USED TO CALCULATE PARAMETERS
19
-------
= N02 photolysis rate constant
where all concentrations are determined at the intersection point of the NO
and 03 curves.
10
N02 Dose = ( [N02] dt ppm hrs.
o"
_n
.10
03 Dose = \ [03] dt ppm hrs.
maximum 1-hour average =
Oq(max) + 03(1/2 hr. before max) + 0^(1/2 hr. after max)
3
**N02 maximum 1-hour average =
NO?(max) + NO?(1/2 hr. before max) + 0^(1/2 hr. after max)
3
The project officer provided the following formulae:
ND initial
NO2 formation rate = 2T, /0 ppm/hr.
Tn ._ = time at wtiich N02 = 1/2 NO initial + NO2 initial
Maximum rate of OQ formation =
- Tl/4>
* This formula is from: O'Brian, Environ. Sci. Tech., 8, 579, 1974.
**The formulae provide a good approximation to the true average for the broad
maxima encountered in this vrork.
20
-------
where
TV,., = time to form 3/4 of 03 (max)
T, /0 = time to form 1/4 of 03 (max)
Average rate of 03 formation =
I/2
where
T, ,0 = time to form L/2 of 03 (max)
Maximum rate of hydrocarbon disappearance = HC. - HC
2
where
HC. = initial hydrocarbon concentration
HC. = final hydrocarbon concentration
T3/4 = time for disappearance of 3/4 (IHC. - 1HCf)
T,,. = time for disappearance of 1/4 (IHC. - lHCf)
21
-------
APPENDIX B
CALCULATED PARAMETERS AND GRAPHS
UNANALYZED RUNS
Propylene at 3 ppmC, HC/NOx = 6
XL-228 (Non-catalyst blend) at 2 ppmC, HC/NCk = 2
A-11004 (Catalyst blend) at 2 ppmC8 HC/NO = 2
Note: The E field specification (floating point)
notation was used for the ordinate and
abcissa values on the graphs in this
appendix. Explanation of notation:
QE -1 = 0 x ICT1
QE 1 = 0 x 10"1
23
-------
RUN NO. 9C: 3 ppmC PROPYLENE, 0.5 ppm NO, STATIC
FEBRUARY 4, 1975
Average Temperature = 31.25 ±0.15 °C
1 2 1
Average Dilution Rate = 0.227 x 10 ±0.153 x 10 hr chamber volumes
Concentrations are corrected for dilution
N02 Photolysis Rate Constant =1.27 min
N02 Formation Rate =0.31 ppm hr~
N00 Dose = 1.883 ppm hr
^
NO., is corrected for PAN
Maximum Rate of 0 Formation =0.22 ppm hr~
Average Rate of 0,, Formation = 0.10 ppm hr
Oo Dose = 1.678 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.28 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.50 ppmC hr~
Initial Oxidant by Neutral Buffered KI = 0.02 ppm
Final Oxidant by Neutral Buffered KI = 0.16 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.45 ppm
24
-------
co
H 8
H ii H ii n 'o -a rf
10
o
UJ
>c
LU
in
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o
25
-------
0 OJ -P
-------
27
-------
RUN NO 9E: 3.0 ppmC PROPYLENE, 0.5 ppm NO, STATIC
FEBRUARY 10, 1975
Average Temperature = 30.63 ± 0.32 °C
1 2 -1
Average Dilution Rate = 0.203 x 10 ± 0.101 x 10 hr chamber volumes
Concentrations are corrected for dilution
N00 Photolysis Rate constant = 1.26 min~
£t
NCL Formation Rate =0.57 ppm hr
N02 Dose = 1.678 ppm hr
NCL is corrected by PAN
Maximum Rate of 0_ Formation = 0.34 ppm hr~
Average Rate of 0,, Formation = 0.27 ppm hr~
0~ Dose = 1.718 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.46 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.45 ppmC hr
Initial Qxidant by Neutral Buffered KI = 0.01 ppm
Final Qxidant by Neutral Buffered KI = 0.17 ppm
Initial Formaldehyde by Cnromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.72 ppm
28
-------
UJ
o
I
UJ
UJ
-i
UJ
o
29
-------
30
-------
FH
a
I
1
P -H
O -P
.C C3
» -H o; in
i § "
g o h
H O
"
CO C 0)
H -H rH
CO
f
r\
UJ
CO
rv.
UJ
' + C
CM
UJ
-o
31
-------
RUN NO. 20: 2 ppm XL-228, 1 ppm NO , 0.3 ppm N09, STATIC
JUNE 23, 1975 x
Average Temperature = 33.86 ± 0.35 °C
-1 -2 -1
Average Dilution Rate = 0.143 x 10 ± 0.154 x 10 hr chamber volumes
Concentrations are corrected for dilution
NOp Photolysis Rate Constant = Cannot calculate.
No intersection of NO and 0,, curves.
N02 Formation Rate =0.11 ppm hr~
N00 Dose = 3.089 ppm hr
^j
N0~ is corrected for PAN
Maximum Rate of 0_ Formation = Cannot calculate.
Average Rate of 0^, Formation = Maximum 03 = 0.
03 Dose = 0.016 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.11 ppmC hr
Average Rate of total Hydrocarbon Disappearance = 0.14 ppmC hr
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = <0.01 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.08 ppm
32
-------
ft
.5
CO 8
H
11 ts
0 sS
O (5 w d 0
H -H rH
II II II II 0
oa co rt< m
-------
> OS CD
>> ft-p 3
X! P C iH .
-p ft 53 o >>
CD a P, -p x
rH CM CO
-P X
0) rH
O
"
CD cti
-P |JH
CD
H CD
-H rH
T3 cd
LU
O
c
U
OI
c
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UJ
34
-------
UJ
o
35
-------
RUN NO. 32: 2 ppm XL-228, 1 ppm NO , 0.3 ppm N09, STATIC
JULY 25, 1975X
Average Temperature = 33.18 ± 0.28 °C
-1 3 -1
Average Dilution Rate = 0.136 x 10 ± 0.814 x 10 hr chamber volumes
Concentrations are corrected for dilution
NCL Photolysis Rate Constant = Cannot calculate.
No intersection NO and 0« curves.
N00 Formation Rate = 0.30 ppm hr (used time at maximum NO ).
£ itL
N00 Dose = 3.197 ppm hr
£t
N00 is corrected for PAN
£
Maximum Rate of 0,, Formation = 0 ppm hr
Average Rate of 0« Formation = 0 ppm hr~
0 Dose = 0.004 ppm hr
O
Maximum Rate of Total Hydrocarbon Disappearance = 0.15 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.13 ppmC hr
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = <0.01 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0.09 ppm
36
-------
01
o
I
01
UJ
CO
01
r-
I
UJ
Ol
-------
o
en
^
g
1
-H O
Crf rH
S
C 0) CD (L>
CD
i-l
>>
>>
G 0)
CD C
C II
O rH
I
-P fa ffi O >> CO
3
Q)
rH
Co
CO
Ul
o
o
UJ
UJ
00
UJ
r-
Ul
o
38
-------
UJ
o
S
I
H
CD
rH
I
H
-P
"H$
d
UJ
O
UJ
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UJ
CO
tsi
UJ
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in
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.*
UJ
tfl
-------
RUN NO. 22: 2 ppm A-11004, 1 ppm NO . 0.3 ppm NO^ STATIC
JUNE 27, 1975X
Average Temperature = 32.86 ± 0.19 °C
-1 -3 -1
Average Dilution Rate = 0.141 x 10 ± 0.983 x 10 hr chamber volumes
Concentrations are corrected for dilution
NCL Photolysis Rate Constant = Cannot calculate.
No intersection of NO and 03 curves.
N02 Formation Rate =0.20 ppm hr~ (used time at maximum N02).
N00 Dose = 2.958 ppm hr
&
N00 is corrected for PAN
£
Maximum Rate of 0., Formation = <0.01 ppm hr~
O
Average Rate of 0» Formation = <0.01 ppm hr
0 Dose = 0.025 ppm hr
o
Maximum Rate of Total Hydrocarbon Disappearance =0.17 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.16 ppmC hr
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = <0.01 ppm
Initial Formaldehyde by Chromatropic Acid = <0.01 ppm
Final Rjrmaldehyde by Chromatropic Acid =0.06 ppm
40
-------
u.
O
I
01
Ul
O
I
UJ
I
LU
I
Ul
I
UJ
(V
Ml
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41
-------
' + O
CM
Ul
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Ul
o>
Ul
CD
IM
Ul
tu
o
CM
tu
in
tu
<*
CM
Ul
in
CM
IM
Ul
Ul
O
42
-------
RUN NO. 21: 2 ppm A-11004, 1 ppm NO , 0.3 ppm NO STATIC
JUNE 25, 1975 x ^
Average Tenperature = 32.81 ± 0.18 °C
-1 -3 -1
Average Dilution Rate = 0.130 x 10 ± 0.876 x 10 hr chamber volumes
Concentrations are corrected for dilution
N02 Photolysis Rate Constant = Cannot calculate.
No intersection of NO and 0~ curves.
NCL Formation Rate = 0.35 ppm hr~ (used time at maximum NCL).
NCL Dose = 2.895 ppm hr
^
N0 is corrected for PAN
Maximum Rate of 0 Formation = 0 formation nil
-------
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o
up
-J- «!
OJ
o
I
UJ
LU
CO
UJ
rsi
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LU
44
-------
ft
c
H
s
h '"r"
p -H
CM
II
C! CD Q) EH O
CD rH CD C 0> II -P
rH >> 2 CD C II O
>i ft 03 3 CD CD oj
X! O-PrHrH CJ-P'H
H -H rH
ii ii ii ii ii o -a us
rHCMCO'^lO
-------
APPENDIX C
CALCULATED PARAMETERS AND GRAPHS
UNANALYZED RUNS
XL-228 (Non-catalyst blend)
and
A-11004 (Catalyst blend)
at
4 ppnC, HC/NOX = 4, HC/NOX = 8
s±atic, dilution, and dynamic conditions
Note: The E field specification (floating point)
notation was used for the ordinate and
abcissa values on the graphs in this
appendix. Explanation of notation:
OE -1 = Ox 1CT1
OE 1 = 0 x 101
47
-------
RUN NO. 5R: 4 ppm XL-228, 1 ppm NO , STATIC
MAY 7, 1975 x
Average Temperature = 32.65 ± 0.06 °C
-1 -3 -1
Average Dilution Rate = 0.170 x 10 ± 0.707 x 10 hr chamber volumes
Concentrations are corrected for dilution
N02 Photolysis Rate Constant =0.69 min
N02 Formation Rate =0.15 ppm hr
N00 Dose = 3.287 ppm hr
N02 is corrected for PAN
Maximum Rate of 0~ Formation = 0.05 ppm hr~
Average Rate of 03 Formation = 0.03 ppm hr~
0,, Dose = 1.365 ppm hr
3
Maximum Rate of Total Hydrocarbon Disappearance =0.33 ppmC hr
Average Rate of Total Hydrocarbon Disappearance = 0.42 ppmC hr~
Initial Qxidant by Neutral Buffered KI = <.01 ppm
Final Qxidant by Neutral Buffered KI = 0.25 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.18 ppm
Maximum 1-hour Average 0., = 0.283 ppm
Maximum 1-hour Average NCL = 0.434 ppm
48
-------
IU
o
111
co
LU
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tu
in
I
w
I
IU
o
49
-------
CD
CD
C CD
S3 c
3 OJ
A
c
H
c
CO O
*T3o
.S2M
4-> X
H CD CM
O
gen
3 O ^
CH O
ii -P
11 Ǥ
CD
>> PH+-> . _, -
^OCrHrH Cti-P'H
-P^|CDO>>a3^^
CD ft &-P X M fi 0)
|| || || || || O TJ erf
f
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50
-------
til
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*
-f
Oi
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00
Ul
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Ul
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51
-------
RUN NO. 7R: 4 ppm XLn-228, 1 ppm NO , STATIC
MAY 9, 1975 X
Average Temperature = 32.81 ± 0.13 °C
-1 -S -1
Average Dilution Rate = 0.154 x 10 ± 0.668 x 10 hr chamber volumes
Concentrations are corrected for dilution
N02 Photolysis Rate Constant =0.94 min
N02 Formation Rate = 0.16 ppm hr~ ; Maximum NO^ does not reach T^.
Used time (2.2 hrs.) for Tlaximum value (0.50).
N02 Dose = 2.872 ppm hr
NOp is corrected for PAN
Maximum Rate of 0^ Formation = 0.06 ppm hr~
Average Rate of 03 Formation =0.04 ppm hr~
03 Dose = 1.733 ppm far
Maximum Rate of Total Hydrocarbon Disappearance =0.34 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.45 pprcC hr
Initial Qxidant by Neutral Buffered KI = <.01 ppm
Final Qxidant by Neutral Buffered KI = 0.16 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
final Formaldehyde by Chromatropic Acid =0.17 ppm
Maximum 1-hour Average 0,. = 0.297 ppm
Maximum 1-hour Average MX, = 0.493 ppm
52
-------
** O
IU
O
IU
a-
\u
CO
I
LU
O
Ul
ir\
t
IU
.*
I
IU
Ul
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53
-------
Ul
o
LJJ
f O
54
-------
» o
*
IM
CM
Ul
U)
in
CM
Ul
Ul
CM
CM
Ui
+ O
Ul
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55
-------
RUN NO. 16: 4 ppm A-11004, 1 ppm NO , 0.3 ppm NCL, STATIC
JUNE 11, 1975 x Z
Average Tenperature = 33.18 ± 0.04 °C
1 3 1
Average Dilution Rate = 0.145 x 10 ± 0.748 x 10 hr chamber volumes
Concentrations are corrected for dilution
NOp Photolysis Rate Constant = Cannot calculate.
No intersection of NO and 03 curves.
NCv, Formation Rate = 0.08 ppm hr~ (used time at maximum NO,,).
N02 Dose = 3.457 ppm hr
N00 is corrected for PAN
^
Maximum Rate of 0,, Formation = <.01 ppm hr~
Average Rate of 0~ Formation = <.01 ppm hr
o
0» Dose = 0.163 ppm hr
O
Maximum Rate of Total Hydrocarbon Disappearance =0.22 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.30 ppmC hr
Initial Oxidant by Neutral Buffered KI = 0 ppm
Final Oxidant by Neutral Buffered KI = 0.03 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.14 ppm
Maximum 1-hour Average 0., = 0.070 ppm
Maximum 1-hour Average NCL = 0.385 ppm
56
-------
UJ
o
I
UJ
UJ
00
UJ
r--
ai
o
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UJ
UJ
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UJ
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57
-------
58
-------
RUN NO. 28: 4 ppm A-11004, 1 ppm NO , 0.3 ppm N09, STATIC
JULY 16, 1975X -
Average Tenperature = 34.65 ± 0.33 °C
-1 2 1
Average Dilution Rate = 0.140 x 10 ± 0.185 x 10 hr chamber volumes
Concentrations are corrected for dilution
N02 Photolysis Rate Constant = Cannot calculate.
No intersection of NO and 03 curves.
N00 Formation Rate = 0.59 ppm hr (used time at maximum N00).
z £
N02 Dose = 3.271 ppm hr
N00 is corrected for PAN
^
Maximum Rate of 0_ Formation = 0 ppm hr
Average Rate of 0,, Formation = 0 ppm hr~
0 Dose = 0.000 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.28 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.21 ppmC hr~
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0.08 ppm
Maximum 1-hour Average Oo = 0 ppm
Maximum 1-hour Average N02 = 0.362 ppm
59
-------
til
o
I
til
01
CO
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UJ
UJ
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60
-------
0,
rq
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£ ° h
E-" O
II -p
. C _
- >> C 0) G II O
>. a a a 0) CD cd
3 Q+JrH ctf-pm
H -H pH
II II II II II O T! '
^ IN CO ^ lO < O I
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IU
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IU
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61
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01
tu
111
ID
«M
IU
-------
RUN NO. 9R: 4 ppm XL-228, 1 ppm NO , DILUTION
MAY 21, 1975 X
Average Temperature = 32.61 ± 0.03 °C
Average Dilution Rate = 0.532 x 10 ± 0.128 x 10"1 hr"1 chamber volumes
N02 Photolysis Rate Constant =0.83 min~
N0? Formation Rate = 0.09 ppm hr (used maximum value of N02 for T%).
N02 Dose = 2.738 ppm hr
>O~ is corrected for PAN
Maximum Rate of 0« Formation = 0.04 ppm hr
Average Rate of 0,, Formation = 0.02 ppm hr
0- Dose = 0.842 ppm hr
O
Maximum Rate of Total Hydrocarbon Disappearance =0.37 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.46 ppmC hr
Initial Qxidant by Neutral Buffered KI = <0.01 ppm
Final Qxidant by Neutral Buffered KI = 0.11 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Fomaldehyde by Chromatropic Acid =0.10 ppm
Maximum 1-hour Average 0_ = 0.152 ppm
o
Maximum 1-hour Average N02 = 0.468 ppm
63
-------
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en.
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Ul
ru
I
01
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64
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f--
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in
-------
RUN NO. 18: 4 ppm XL-228, 1 ppm NO , 0.3 ppm N09, DILUTION
JUNE 16, 1975 X Z
Average Temperature = 33.20 ± 0.03 °C
-1 -1 -1
Average Dilution Rate = 0.539 x 10 ± 0.135 x 10 hr chamber volumes
N02 Photolysis Rate Constant =0.82 min~
N02 Formation Rate =0.41 ppm hr~
N00 Dose = 2.587 ppm hr
NO2 is corrected for PAN
Maximum Rate of 0~ Formation =0.04 ppm hr~
Average Rate of 0~ Formation =0.03 ppm hr~
03 Dose = 1.047 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.40 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.46 ppmC hr~
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.13 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0.09 ppm
Maximum 1-hour Average 0., = 0.182 ppm
Maximum 1-hour Average NO = 0.483 ppm
^j
67
-------
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68
-------
at
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69
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70
-------
RUN NO. 17: 4 ppm A-11004, 1 ppm NO*, 0.3 ppm N09, DILUTION
JUNE 13, 1975 z
Average Temperature = 33.22 ± 0.13 °C
Average Dilution Rate = 0.561 x 10 ± 0.130 x 10 hr~ chamber volumes
N02 Photolysis Rate Constant =0.72 min~
N00 Formation Rate = 0.11 ppm hr (used time at maximum N00).
^j £
N02 Dose = 2.925 ppm hr
N02 is corrected for PAN
Maximum Rate of Ozone Formation =0.02 ppm hr~
Average Rate of Ozone Formation =0.01 ppm hr~
Ozone Dose = 0.425 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance = 0.25 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.29 ppmC hr~
Initial Oxidant by Neutral Buffered KI = <.01 ppm
Final Oxidant by Neutral Buffered KI = 0.09 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.09 ppm
Maximum 1-hour Average 0,, = 0.088 ppm
Maximum 1-hour Average N02 = 0.417 ppm
71
-------
Ul
o
I
Ul
UJ
00
Ul
o
111
in
I
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I
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72
-------
73
-------
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-------
RUN NO. 29: 4 ppm A-11004, 1 ppm NO , 0.3 ppm NO9, DILUTION
JULY 18, 1975X Z
Average Temperature = 34.11 ± 0.33 °C
Average Dilution Rate = 0.590 x 10"1 ± 0.142 x 10 hr chamber volumes
N02 Photolysis Rate Constant = Cannot calculate.
No intersection of NO and 0- curves.
N02 Formation Rate = 0.33 ppm hr~ (used time at maximum N09).
3 = 3.290 ppm hr
N02 is corrected for PAN
Maximum Rate of 0 Formation = 0 ppm hr
Average Rate of 0_ Formation = 0 ppm hr
O
0 Dose = 0.042 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.40 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.34 ppmC hr~
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.02 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.10 ppm
Maximum 1-hour Average 0=0 ppm
*J
Maximum 1-hour Average N00 = 0.432 ppm
75
-------
I
Ul
o
I
Ul
o
UJ
p-
ui
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Ul
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Ul
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76
-------
77
-------
f
04
VII
O
> + O
UJ
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UJ
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78
-------
RUN NO. 15: 4 ppm XL-228, 1 ppm NO , 0.3 ppm NCL, DYNAMIC
JUNE 9, 1975 X
Average Temperature = 33.15 ± 0.09 °C
-1 -3 -1
Average Dilution Rate = 0.956 x 10 ± 0.709 x 10 hr chamber volumes
N00 Photolysis Rate Constant =1.00 min
&
NCL Formation Rate = 0.36 ppm hr (used time at maximum ND0).
& £i
NO.
L Dose = 2.186 ppm hr
N0_ is corrected for PAN
Maximum Rate of 0Q Formation = 0.08 ppm hr~
-------
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UJ
UJ
oo
UJ
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UJ
in
I
1U
I
UJ
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80
-------
w
o
81
-------
RUN NO. 14: 4 ppm XL^-288, 1 ppm NO , 0.3 ppm N09, DYNAMIC
JUNE 6, 1975X
Average Temperature = 32.77 ± 0.04 °C
1 2 1
Average Dilution Rate = 0.983 x 10 ±0.530 x 10 hr chamber volumes
N00 Photolysis Rate Constant =1.33 min"1
£i
N00 Formation Rate = 0.8 ppm hr (used time at maximum N00).
*j £
N00 Dose = 2.248 ppm hr
£
N00 is corrected for PAN
&
Maximum Rate of 0,, Formation = 0.08 ppm hr~
O
Average Rate of 0^ Formation =0.14 ppm hr~
0 Dose = 1.872 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.74 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance = 2.1 ppmC hr~
Initial Oxidant by Neutral Buffered KI = <.01 ppm
Final Oxidant by Neutral Buffered KI = 0.07 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.07 ppm
Maximum 1-hour Average Oo = 0.2Q2 ppm
Maximum 1-hour Average N02 = 0.473 ppm
82
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RUN NO. 11: 4 ppm A-11004, 1 ppm NO , DYNAMIC
MAY 28, 1975 x
Average Temperature = 32.93 ± 0.04 °C
-1 -3 -1
Average Dilution Rate = 0.930 x 10 ± 0.700 x 10 hr chamber volumes
N00 Photolysis Rate Constant =0.87 min~
^
N00 Formation Rate = 0.65 ppm hr~ (used time at maximum N00).
£j £t
N00 Dose = 2.438 ppm hr
N02 is corrected for PAN
Maximum Rate of 0_ Formation = 0.08 ppm hr
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Average Rate of 0 Formation =0.09 ppm hr
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Oq Dose = 1.852 ppm hr
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Maximum Rate of Total Hydrocarbon Disappearance =0.41 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.95 ppmC hr
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.10 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0.07 ppm
Maximum 1-hour Average 03 = 0.252 ppm.
Maximum 1-hour Average N00 = 0.497 ppm
85
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RUN NO. 10R: 4 ppm A-11004, 1 ppm NO , 0.3 ppm NO9, DYNAMIC
MAY 30, 1975 x ^
Average Temperature = 32.86 ± 0.05 °C
-1 -3 -1
Average Dilution Rate = 0.945 x 10 ± 0.689 x 10 hr chamber volumes
NOp Photolysis Rate Constant =1.01 min
N00 Formation Rate =0.42 ppm hr~ (used time at maximum N00).
£* £
N00 Dose = 2.232 ppm hr
£
N00 is corrected for PAN
£
Maximum Rate of 0~ Formation = 0.08 ppm hr
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Average Rate of 0., Formation = 0.07 ppm hr~
0 Dose = 1.710 ppm hr
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Maximum Rate of Total Hydrocarbon Disappearance =0.61 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.81 ppmC hr
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.14 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.09 ppm
Maximum 1-hour Average 0 = ,0.237 ppm
Maximum 1-hour Average N02 = 0.490 ppm
88
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RUN NO. 26: 4 ppm XL-228, 0.5 ppm NO , 0.15 ppm NO STATIC
JULY 9, 1975 x
Average Temperature = 33.81 ± 0.35 °C
1 3 -1
Average Dilution Rate = 0.114 x 10 ± 0.999 x 10 hr chamber volumes
Concentrations are corrected for dilution
N02 Photolysis Rate Constant =0.73 min"
N00 Formation Rate = 0.08 ppm hr~ (used time at maximum N00).
^J £
N00 Dose = 1.582 ppm hr
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NO,., is corrected for PAN
Maximum Rate of 0,, Formation = 0.04 ppm hr~
Average Rate of 0_ Formation =0.03 ppm hr~
03 Dose = 1.274 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance = 0.38 ppmC hr
Average Rate of Total Hydrocarbon Disappearance= 0.46 ppmC hr"
Initial Qxidant by Neutral Buffered KI = 0 ppm
Final Oxidant by Neutral Buffered KI = 0.13 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.12 ppm
Maximum 1-hour Average 03 = 0.205 ppm
Maximum 1-hour Average MX, = 0.283 ppm
92
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RUN NO. 30: 4 ppm XL-228, 0.5 ppm NO , 0.15 ppm N09, STATIC
JULY 21, 1975X
Average Temperature = 33.52 ± 0.31 °C
-1 -2 -1
Average Dilution Rate = 0.133 x 10 ± 0.108 x 10 hr chamber volumes
Concentrations are corrected for dilution
N02 Photolysis Rate Constant =0.59 min
N02 Formation Rate =0.17 ppm hr
N00 Dose = 2.039 ppm hr
^
N09 is corrected for PAN
Maximum Rate of 0« Formation =0.02 ppm hr
Average Rate of 0,-. Formation = 0.02 ppm hr~
03 Dose = 0.668 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.34 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.45 ppmC hr~
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.13 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0 . 17 ppm
Maximum 1-hour Average 0., = 0.110 ppm
Maximum 1-hour Average NCu = 0.483 ppm
95
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RUN NO. 12: 4 ppm A-11004, 0.5 ppm NO , 0.15 ppm N09, STATIC
JUNE 2, 1975 x Z
Average Temperature = 32.72 ± 0.02 °C
-1 -3 -1
Average Dilution Rate = 0.140 x 10 ± 0.986 x 10 hr chamber volumes
Concentrations are corrected for dilution
NOp Photolysis Rate Constant =0.89 min~
N00 Formation Rate = 0.09 ppm hr (used time at maximum N00).
£ £1
N02 Dose = 1.824 ppm hr
N00 is corrected for PAN
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.Maximum Rate of 0« Formation = 0.03 ppm hr
Average Rate of 0,, Formation = 0.03 ppm hr
0 Dose = 1.108 ppm hr
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Maximum Rate of Total Hydrocarbon Disappearance =0.24 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.34 ppmC hr~
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.17 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0.14 ppm
Maximum 1-hour Average 0_ = 0.195 ppm
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Maximum 1-hour Average NCL = 0.292 ppm
99
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RUN NO. 31: 4 ppm A-11004, 0.5 ppm NO , 0.15 ppm N09, STATIC
JULY 23, 1975 x
Average Temperature = 33.97 ± 0.38 °C
1 -3 1
Average Dilution Rate = 0.121 x 10 ± 0.881 x 10 hr chamber volumes
Concentrations are corrected for dilution
. -1
NO.
L Photolysis Rate Constant =0.61 min
N00 Formation Rate = 0.08 ppm hr~ (used time at maximum N00).
£* £
N02 Dose = 2.001 ppm hr
N02 is corrected for PAN
Maximum Rate of 0« Formation =0.09 ppm hr~
Average Rate of 0_ Formation =0.06 ppm hr~
03 Dose = 0.306 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.16 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.21 ppmC hr~
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.09 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.10 ppm
Maximum 1-hour Average 0~ = 0.265 ppm
Maximum 1-hour Average NO = 0.260 ppm
103
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RUN NO. 6R: 4 ppm XL-228, 0.5 ppm NO , DILUTION
MAY 15, 1975 x
Average Temperature = 32.76 ± 0.09 °C
1 2 1
Average Dilution Rate = 0.638 x 10 ± 0.999 x 10 hr chamber volumes
N02 Photolysis Rate Constant =1.02 min
N02 Formation Rate = 0.18 ppm hr~ (used time at maximum N02).
N02 Dose = 1.229 ppm hr
N09 is corrected for PAN
Maximum Rate of 0,, Formation = 0.11 ppm hr
Average Rate of 03 Formation =0.08 ppm hr
0 Dose = 1.487 ppm hr
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Maximum Rate of Total Hydrocarbon Disappearance =0.40 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.62 ppmC hr~
Initial Oxidant by Neutral Buffered KI = 0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.08 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.09 ppm
Maximum 1-hour Average 0~ = 0.255 ppm
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Maximum 1-hour Average N00 = 0.245 ppm
£j
107
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RUN NO. 13: 4 ppm XL-228, 0.5 ppm NO , 0.15 ppm N09, DILUTION
JUNE 4, 1975 x
Average Temperature = 32.90 ± 0.05 °C
Average Dilution Rate = 0.578 x 10~ ± 0.142 x 10~ hr~ chamber volumes
N02 Photolysis Rate Constant =0.9 min~
N00 Formation Rate = 0.18 ppm hr~ (used maximum N00 value for time).
^ £i
NO,
>2 Dose = 1.288 ppm hr
N02 is corrected for PAN
Maximum Rate of 0,, Formation = 0.13 ppm hr
Average Rate of 0Q Formation =0.09 ppm hr
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03 Dose = 1.653 ppm. hr
Maximum Rate of Total Hydrocarbon Disappearance =0.39 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.67 ppmC hr
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.09 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0.09 ppm
Maximum 1-hour Average 0Q = 0.272 ppm
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Maximum 1-hour Average N00 = 0.277 ppm
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RUN NO. 25: 4 ppm A-11004, 0.5 ppm NO , 0.15 ppm NO DILUTION
JULY 7, 1975 X
Average Temperature = 32.70 ± 0.18 °C
Average Dilution Rate = 0.529 x 10 ± 0.133 x 10~ hr"1 chamber volumes
NOp Photolysis Rate Constant =0.65 min~
NCu Formation Rate = 0.09 ppm hr" (used time at maximum N02).
N02 Dose = 1.484 ppm hr
MXj is corrected for PAN
Maximum Rate of 0_ Formation = 0.04 ppm hr~
Average Rate of 0,, Formation = 0.03 ppm hr~
0,, Dose = 1.019 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.30 ppmC hr"
Average Rate of Total Hydrocarbon Disappearance =0.31 ppmC hr
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI= 0.10 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.07 ppm
Maximum 1-hour Average 0Q - 0.162 ppm
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Maximum 1-hour Average J£> = 0.263 ppm
115
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RUN NO. 23: 4 ppm A-11004, 0.5 ppm NO , DILUTION
JUNE 30, 1975 x
Average Temperature = 32.68 ± 0.19 °C
Average Dilution Rate = 0.548 x 10~ ± 0.135 x 10 hr"1 chamber volumes
N02 Photolysis Rate Constant =0.92 min~
N02 Formation Rate = 0.10 ppm hr~ (used time at maximum NO2).
N02 Dose = 1.607 ppm hr
N09 is corrected for PAN
Maximum Rate of 0^ Formation = 0.05 ppm hr
Average Rate of 0^ Formation =0.03 ppm hr~
03 Dose = 1.052 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.33 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.35 ppmC hr~
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.11 ppm
Initial Formaldehyde by Chromatropic Acid = <0.01 ppm
Final Formaldehyde by Chromatropic Acid = 0.08 ppm
Maximum 1-hour Average 0Q = 0.165 ppm
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Maximum 1-hour Average NO2 = 0.282 ppm
119
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RUN NO. 8R: 4 ppm XL-228, 0.5 ppm NO , DYNAMIC
MAY 19, 1975 X
Average Temperature = 32.70 ± 0.04 °C
1 2 1
Average Dilution Rate = 0.938 x 10 ± 0.123 x 10 hr chamber volumes
N02 Photolysis Rate Constant =1.23 rnin"
N02 Formation Rate =0.4 ppm hr~
N00 Dose = 1.616 ppm hr
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Maximum Rate of 0« Formation = 0.19 ppm hr
Average Rate of 0~ Formation = 0.29 ppm hr~
03 Dose = 1.743 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.58 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance = 1.45 ppmC hr~
Initial Oxidant by Neutral Buffered KI = O.01 ppm
Final Oxidant by Neutral Buffered KI = 0.11 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0.07 ppm
Maximum 1-hour Average 0~ = 0.258 ppm
Maximum 1-hour Average NCL = 0.252 ppm
122
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RUN NO. 19: XL-228, 0.5 ppm NO , 0.15 ppm N09, DYNAMIC
JUNE 18,X1975
Average Temperature = 35.68 ± 0.68 °C
-1 2 1
Average Dilution Rate = 0.925 x 10 ± 0.258 x 10 hr chamber volumes
N00 Photolysis Rate Constant =3.80 min~
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N00 Formation Rate =0.19 hr"1
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NO Dose = 1.483 ppm hr
N02 is corrected for PAN
Maximum Rate of 0,. Formation = 0.24 ppm hr
Average Rate of 0,. Formation = 0.36 ppm hr~
03 Dose = 2.135 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.57 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =1.46 ppmC hr~
Initial Oxidant By Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.10 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.06 ppm
Maximum 1-hour Average 0^ = 0.287 ppm
Maximum 1-hour Average N00 = 0.273 ppm
126
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RUN NO. 24: 4 ppm A-11004, 0.5 ppm NO , 0.15 ppm N0p, DYNAMIC
JULY 2, 1975 X
Average Temperature = 32.61 ± 0.17 °C
-1 2 -1
Average Dilution Rate = 0.914 x 10 ± 0.350 x 10 hr chamber volumes
N02 Photolysis Rate Constant =0.84 rain"
N00 Formation Rate =0.34 ppm hr (used time at maximum N00).
£ £
N00 Dose = 1.370 ppm hr
£
N00 is corrected for PAN
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Maximum Rate of 0,, Formation = 0.10 ppm hr~
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Average Rate of 0., Formation =0.10 ppm hr
Q Dose = 2.061 ppm hr
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Maximum Rate of Total Hydrocarbon Disappearance =0.51 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.87 ppmC hr
Initial Oxidant by Neutral Buffered KI = <0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.16 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.09 ppm
Maximum 1-hour Average Or, = 0.283 ppm
Maximum 1-hour Average 1CL = 0.265 ppm
130
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RUN NO. 27: 4 ppm A-11004, 0.5 ppm NO , 0.15 ppm NCL, DYNAMIC
JULY 14, 1975 X
Average Temperature = 33.86 ± 0.35 °C
1 3 1
Average Dilution Rate = 0.930 x 10 ± 0.510 x 10 hr chamber volumes
N02 Photolysis Rate Constant =0.98 min~
N02 Formation Rate = 0.29 ppm hr~
N00 Dose = 1.826 ppm hr
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N02 is corrected for PAN
Maximum Rate of 0~ Formation =0.11 ppm hr
Average Rate of 03 Formation =0.21 ppm hr~
03 Dose = 0.972 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.56 ppmC hr
Average Rate of Total Hydrocarbon Disappearance = 1.53 ppmC hr
Initial Oxidant by Neutral Buffered KI = 0.01 ppm
Final Oxidant by Neutral Buffered KI = 0.03 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.06 ppm
Maximum 1-hour Average 03 = 0.163 ppm
Maximum 1-hour Average N02 = 0.280 ppm
134
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APPENDIX D
ANALYSIS OF VARIANCE TABLES
139
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EXPLANATION OF SYMBOLS
Factor Symbol
Chamber Running Mode T
HC/NO C
Hydrocarbon Blend B
Factor
T
C
B
Level 1
static
4
XL-228
Level 2
dilution
8
A-11004
Level 3
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-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO 2.
PA-600/3-77-109a
TITLE ANDSUBTITLE
EFFECT OF HYDROCARBON COMPOSITION ON OXIDANT-
HYDROCARBOX RELATIONSHIPS Phase I. Exhaust Blends
from Non-Catalyst and Catalyst Equipped Vehicles
ALTHOR(S)
T. R. Powers
PERFORMING ORGANIZATION NAME AND ADDRESS
Exxon Research and Engineering Company
Linden, New Jersey 07036
2 SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory-RTF, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
3. RECIPIENT'S ACCESSION-NO.
5. REPORT DATE
September 1977
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
1AA008
11. CONTRACT/GRANT NO.
68-02-1719
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/600/09
5. SUPPLEMENTARY NOTES
6. ABSTRACT
Oxidation catalysts on automobiles not only reduce the total amount of
hydrocarbon emissions, but also change the composition of these emissions
significantly. To explore the effect of this change on oxidant formation,
28 ten-hour irradiations were carried out in the Exxon Research Environmental
Chamber. Fourteen of these irradiations used a hydrocarbon blend representative
of the non-methane, non-acetylene exhaust hydrocarbon emissions from a non-
catalyst equipped vehicle, and 14 used a blend representative of the same
fraction of the emissions from a catalyst equipped vehicle. Irradiations were
carried out at three hydrocarbon-to-nitrogen oxides ratios and with three
modes of chamber operation, chosen to simulate different meteorological condi-
tions.
The results of these experiments indicate that the composition change due
to oxidation catalysts will result in a significant alleviation, above that due
to hydrocarbon concentration change alone, of the local effects of automotive
tailpipe emissions.
7. KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
* Air pollution Test chambers
* Hydrocarbons * Irradiation
* Ozone
Automobiles
* Exhaust emissions
Catalytic converters
Oxidation
13. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
b.lDENTIFIERS/OPEN ENDED TERMS
19. SECURITY CLASS (This Report)
UNCLASSIFIED
20. SECURITY CLASS (This page)
UNCLASSIFIED
c. COSATI Field/Group
13B 18H
07C
07B
13F
21B
07A
14B
21. NO. OF PAGES
157
22. PRICE
Form 2220-1 (9-73)
151
-------
INSTRUCTIONS
1. REPORT NUMBER
Insert the EPA report number as it appears on the cover of the publication.
2. LEAVE BLANK
3. RECIPIENTS ACCESSION NUMBER
Reserved for use by each report recipient.
4. TITLE AND SUBTITLE
Title should indicate clearly and briefly the subject coverage of the report, and be displayed prominently. Set subtitle, if used, in smaller
type or otherwise subordinate it to main title. When a report is prepared in more than one volume, repeat the primary title, add volume
number and include subtitle for the specific title.
5. REPORT DATE
Each report shall carry a date indicating at least month and year. Indicate the basis on which it was selected (e.g., date of issue, date of
approval, date of preparation, etc.).
6. PERFORMING ORGANIZATION CODE
Leave blank.
7. AUTHOR
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