EPA-600/3-77-109b
September 1977
Ecological Research Series
EFFECT 0F
Phase II. Blend of Total
PROTECTION
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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 pol lutants 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-600/3-77-10Qb
September 1977
EFFECT OF HYDROCARBON COMPOSITION ON
OXIDANT-HYDRCCARBON RELATIONSHIPS
Phase II. Blend of Total Hydrocarbon Emissions
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
LIBRARY
U. S. ENVIRQmVC'.'TAL PROTECTION
EK$QN, N. J. Uool?
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DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for publi-
cation. 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 comnercial products constitute endorsement or
recommendation for use.
11
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ABSTRACT
Phase I of this contract effort explored the effect of the change in auto
exhaust hydrocarbon composition due to the installation of catalytic exhaust
control on automobiles on the formation of atmospheric oxidant. In Phase I,
28 experimental and 2 comparison smog chamber irradiations were performed
under static, dilution, and dynamic flow conditions. Fourteen of these runs
used a hydrocarbon mixture representative of the non-tnethane, non-acetylene
exhaust hydrocarbon emissions from a non-catalyst equipped car, and 14 used
a hydrocarbon mixture representative of the same fraction of the emissions
from a car equipped with an oxidation catalyst. The production of oxidant
and other parameters of the reaction were followed, and the data was analyzed
for significant changes in oxidant formation with hydrocarbon composition.
In Phase II, a third hydrocarbon blend modeled on the total hydrocarbon
emissions (exhaust, refueling, and evaporative) from a catalyst-equipped
vehicle was run under the conditions used in Phase I. The results of these
runs were compared against the Phase I results in terms of significant effects
on photochemical smog formation.
In the Phase II tests, the blend based on total vehicle hydrocarbon
emissions produced significantly less severe photochemical smog manifestations
than either of the other two blends. The clear stratification of the blends
in terms of maximum 1-hour average ozone production and the apparent linear
decrease of maximum 1-hour average ozone with increasing paraffin mole fraction
indicate that the concept of hydrocarbon reactivity is applicable to smog
chamber data taken with long irradiations (10-hour ^ 2 solar days) and under
a variety of simulated meteorological conditions, including ventilation with
clean and polluted air. Of the three reactivity scales tested, all under-
estimated the reactivity differences between the blends. However, the oldest
scale developed by Altshuller in 1966 fits the data better than two recently
proposed scales. Further work is necessary to determine whether a scale
capable of accurately predicting over a wide range of conditions and blend
compositions can be developed.
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CONTENTS
Abstract iii
1. Introduction 1
2. Conclusions 2
3. Experimental Plan 3
4. Methods and Procedures 4
Equipment 4
Chamber operating characteristics 4
Analytical methodology 5
Reagents and calibration gases 6
Procedure 7
5. Results and Discussion 10
Data organization and presentation 10
Data analysis 10
Results 12
Discussion 14
References 15
Appendices
A. Formulae used to calculate parameters 19
B. Calculated parameters and graphs 23
C. Analysis of variance tables 93
v
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SECTION 1
INTRODUCTION
As control of the hydrocarbon (HC) emissions from automobile exhaust
becomes increasingly strict, other sources of hydrocarbon loss connected with
vehicle operation become increasingly important. Recent work at Exxon Re-
search allows the estimation of losses from two of these sources: (1) evap-
oration from the fuel system, and (2) refueling emissions.
Evaporative losses occur during normal diurnal thermal cycling of the
vehicle fuel system and during changes in the fuel system temperature due to
vehicle operation. These losses have been subject to control since 1971 at a
level of 2 g EC/test, with a test simulating one day's operation. Using
10,000 mi/year/ vehicle, evaporative losses from vehicles meeting this stan-
dard amount to MD.07 g/mi.*
Refueling losses occur when liquid is pumped into a vehicle fuel tank,
displacing hydrocarbon vapors into the atmosphere. Control of such losses has
been proposed for the major metropolitan areas. Exxon Research has measured
refueling losses for an uncontrolled vehicle using a laboratory simulation and
found them to range from 2 g/gal. to 5 g/gal. of fuel dispensed, depending on
temperature and fuel vapor pressure. Under typical late sunnier conditions,
emissions are ^0.24 g/mi. at a projected 1980 fuel economy of 17 mpg. We have
also obtained detailed compositional data for hydrocarbon emissions from this
source.
The sum of losses from these two sources, 0.31 g/gal., is 75% of the 1978
exhaust hydrocarbon emission standards. Given the magnitude of this contri-
bution to total vehicle emissions, these losses should certainly be taken into
account when assessing the impact of controls on the oxidant-forming potential
of vehicle hydrocarbon emissions. This report covers smog chamber studies of
a hydrocarbon blend modeled on the total emissions from a vehicle which meets
the strict (0.41 g/mi.) exhaust emission standards using an oxidation catalyst.
*Due to the nature of the measurements in this report, the English System of
Units was used. For conversion to the International System of Units, see the
conversion table on p. 18.
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SECTION 2
CONCLUSIONS
The data from this work indicate that the oxidant-forming potential of
the composite hydrocarbon mix, including exhaust, evaporative, and refueling
emissions, is less than that of the exhaust emissions alone. It is, there-
fore, important to consider all three sources of hydrocarbons when assessing
the impact of motor vehicle operations on oxidant air quality. For example,
the effect of transportation controls on a region would be overestimated if
the total quantity of hydrocarbons removed were considered to have the oxidant -
forming potential of exhaust.
It also appears that the concept of hydrocarbon reactivity is applicable
to the prediction of oxidant levels during long term (10-hour) irradiations
under a variety of simulated meteorological conditions. This finding, with
irradiations approximately equivalent to 2 solar days of real world exposure
and runs including ventilation of the system with both clean and polluted air,
indicates that a valid reactivity scale for use under transport conditions is
feasible. Of three reactivity scales tested, all underestimated the reac-
tivity differences between the blends. The scale proposed by Altshuller in
1966 did, however, give a better fit to the data than two more recently pro-
posed scales. Further work is necessary to determine if a scale capable of
accurately predicting over a wide range of conditions and blend compositions
can be developed.
In evaluating the implications of the above results, the uncertainties
involved in extrapolating smog chamber data to the real world should be noted.
In general, only trends, not absolute results, should be applied to actual
atmospheric situations.
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SECTION 3 .
EXPERIMENTAL PLAN
The oxidant -forming potential of a hydrocarbon blend modeled on the total
emissions from a vehicle which meets the strict exhaust emission standards
(0.41 g/mi) was studied in the Exxon Research Environmental Chamber. Ten -hour
irradiations were carried out under three different initial hydrocarbon -to-NQx
ratios and three different modes of chamber operation, as given in the matrix
below:
Initial HC/NDx
Chamber Operating Mode 2^ 4_ 8_
static XXX
dilution X X
dynamic X X
Initial hydrocarbon concentration levels were 4 ppm carbon for HC/NOx ratios
of 4 and 8, and 2 ppm carbon for an HC/NOx ratio of 2. Initial nitrogen
oxides (NOx) consisted of 30% nitrogen dioxide (NO2) and 70% nitric oxide
(NO).
Time /concent rat ion 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 (NBKI) method and formaldehyde was determined by the chromatropic acid
method at the beginning and end of the run only. This experimental design is
identical to that used in Phase I of this contract effort. It allows direct
comparison of the oxidant -forming potential of this blend to that of the
catalyst and non-catalyst exhaust blends tested in Phase I. The analysis and
discussion in Phase II have focused on such comparisons.
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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 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 or1. 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 80 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 reached 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-
pheric air, the chamber pressure is maintained at 0.13 kPa above atmospheric
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pressure. This results in an unintentional leak rate of less than 1.5% hr. l,
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-
f ication .
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 /Q = 2.7 hours @ 20% R.H.
Dark reaction, t, /0 = 14 hours @ 20% R.H.
i/z
ANALYTICAL METHCDOLOGY
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 corrmercially analyzed cylinder of
propane (0.5 ppm) in air.
Individual Hydrocarbons
Individual hydrocarbons were measured with a Perkin Elmer Model 900 Gas
Chromatograph with sub-ambient temperature programning capabilities. The
instrument was equipped with a column 1/8" 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 instru-
ment is calibrated on the initial chamber hydrocarbon charge, which is a
metered dilution of a corrmercially analyzed cylinder.
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Nitrogen Oxides
Nitrogen oxides were monitored with a TECO 14B nitrogen oxides analyzer.
The analyzer is calibrated on a comnercially analyzed cylinder losing 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 NO2 by subtracting 0.1 (N02).
Ozone
Ozone was measured with a REM Chemiluininescent 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 N02 (^1000 ppm in hydrocarbon-free nitrogen) and NO
(^1000 ppm in hydrocarbon-free nitrogen) were used to charge NOx for all runs.
Hydrocarbon Blend
The hydrocarbon blend used in this study was derived from gas chroma-
tographic data taken at Exxon Research and Engineering Co. The catalyst
exhaust data was the same as that used to derive the catalyst blend for Phase
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I. Refueling emissions were as measured from 9 Ib. Reid Vapor Pressure (RVP)
fuel dispensed at a temperature of 80°F into a fuel tank containing the same
fuel at 90°F. Emissions from this particular run were 4.26 g/gal. of dis-
pensed fuel. It was assumed that evaporative losses had the same composition
as refueling losses. The composition of the final blend was constructed by
summing the mole fractions of paraffins, olefins, and aromatics from exhaust
with 3/4 of their counterparts from refueling and dividing the total by 1.75.
Isopentene, the most conmon olefin in the refueling losses, was chosen as
typical of olefin losses from that source. C2/C3 olefin and C7/C8 aromatic
ratios were taken from the exhaust data. Methane and acetylene from exhaust
were not considered, as they are photochemically unreactive. Table 1 gives
the composition of the hydrocarbon blend used and compares parameters calcu-
lated from this blend with the same parameters from the chromatographic data.
PROCEDURE
After an overnight flush with clean air, the chamber was pressurized to
0.13 kPa above atmospheric pressure and checked for background ozone, oxidant,
hydrocarbon, and NOjj. If these values were essentially zero, chamber humidity
was set and the chamber was charged to the initial reactant levels in the
following order:
1) NO2 (to 30% of total
2) NO (balance of total
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.
Oxidant 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 sampling losses was added.
Results were corrected for this small dilution before reporting.
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%.
**Due to an arithmetical error, average relative humidity was not held constant
over all running modes, so effects due to change in running modes may be, in
part, due to differences in relative humidity.
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TABLE 1. PHASE II HYDROCARBON BLEND AND CALCULATED PARAMETERS
COMPOSITION OF HYDROCARBON BLEND
Compound
Mole Fraction
ethylene
propylene
n-butane
isopentene
toluene
xylene
0.10
0.02
0.67
0.07
0.08
0.06
CALCULATED PARAMETERS
Parameter
mole fraction paraffins
mole fraction olefins
mole fraction aromatics
average paraffin carbon #
average olefin carbon #
average aromatic carbon #
C2/C3 olefin ratio
Cy/Ce aromatic ratio
Target Value
(Chromatographic data)
0.65
0.20
0.15
4.50
3.75
7.30
4.7
1.62
Blend Value
0.67
0.19
0.14
4.0
3.2
7.4
5.0
1.33
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• Dynamic - The chamber charge was diluted at a rate of 10%/hour from
the beginning of the run with purified air and reactants at a con-
centration of 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 in-
jections of reactants. Results were not corrected for dilution.
Initial relative 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.
**Due to an arithmetical error, average relative humidity was not held constant
over all running modes, so effects due to change in running modes 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 raw instrument readings into concen-
trations 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 calculated
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 Appendix B.
Runs at HC/NCy = 2
Runs at this level showed no evidence of reaction. They were not analyzed
further.
Runs at HC/NCy = 4 and HC/NCy = 8
Runs at these levels showed evidence of reaction in all chamber operating
modes. All of the subsequent analyses and conclusions are based on these
runs.
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
CMC 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 12 runs with HC/NC^ = 4, and HC/NOx = 8, chamber running conditions
of static, dilution, and dynamic ,and non-catalyst and catalyst hydrocarbon
blends form a completely replicated 3x2 factorial experimental design. One
of the basic characteristics of this design is that factor effects, i.e.,
those due to HC/NOx and chamber running conditions, are completely clear of
all two-factor interaction effects, and the interaction effects are clear of
each other. Replication allows the variance in the measurements to be esti-
mated and the statistical significance of any observed effects to be deter-
mined.
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TABLE 2. PARAMETERS ANALYZED
Ozone, maximum 1-hour average
Ozone, time to maximum
N02, maximum 1-hour average
N02, time to maximum
PAN, maximum
Oxidant, final
Formaldehyde, final
Total Hydrocarbon, average disappearance rate
Individual Hydrocarbons, 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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For these data, analysis of variance was carried out for the parameters
in Table 2. (The analysis of variance tables are given in Appendix C.) 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 interaction effects signifi-
cant 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 repli-
cate experiments. Significant blend effects were determined by comparing the
mean parameter levels from this set of runs with the mean levels from the
Phase I data. The Phase I blends were modeled after the non-acetylene, non-
methane fraction of exhaust emissions from catalyst equipped and non-catalyst
equipped automobiles. Table 3 gives the composition of these blends. The
standard t test was used to determine whether differences due to changing
blend were significant at the 95% level. All significant effects found in the
present study and all significant blend effects are given below in RESULTS.
(The 95% confidence intervals used in this test and plotted in the following
figures are ^2 times the standard deviation.)
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
(the 8 risk) of .03 ppm in maximum ozone, maximum N02, or final oxidant is
^50% when the test for that effect is carried out at the 95% significance
level.
TABLE 3. PHASE I HYDROCARBON BLENDS
Compound Mole Fraction
Non-Catalyst Equipped Car Catalyst Equipped Car
n-pentane 0.21
n-butane — 0.51
ethylene 0.30 0.18
propylene 0.09 0.04
toluene 0.17 0.17
m-xylene 0.23 0.10
RESULTS
Effect Due Only to Change in HC/NOy Ratio
Changing the HC/NOx ratio from 4 to 8 (or NOx concentration from 1.0 ppm
to 0.5 ppm):
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• Decreased maximum 1-hour average N02 41%, from 0.41 ppm to 0.24 ppm,
and
• Increased time to maximum N02 70%, from 1.0 to 1.7 hours.
It should be noted that in this set of experiments, HC concentration was
held constant. Therefore, a change in HC ratio may equally be thought of as
a change in total NOx concentration.
Effects Due Only to Change in Chamber Running Mode
A change in chamber running conditions from static to dilution:
• Decreased time to maximum N02 50%, from 2.2 hours to 1.1 hours.
A change in chamber running conditions from static to dynamic:
• Decreased time to maximum ozone 55%, from 8.9 hours to 4.0 hours,
• Decreased time to maximum N02 64%, from 2.2 hours to 0.8 hours, and
• Increased average total hydrocarbon disappearance rate 280%, from
0.23 ppmC/hour to 0.87 ppmC/hour.
Effects due to Interactions Between HC/NOy Ratio and Chamber Running Mode
Changing HC/NCx ratio from 4 to 8 increased the time to N02 maximum 2.9
hours for static runs and did not change it significantly for dilution and
dynamic runs.
Effects Due Only to Change in Hydrocarbon Blend
Changing hydrocarbon blend from one modeled on non-catalyst exhaust to
one modeled on catalyst exhaust plus refueling losses plus evaporative emis-
sions:
• Decreased maximum 1-hour average 03 78%, from 0.23 ppm to 0.05 ppm,
• Increased time to maximum ozone 19%, from 5.4 hours to 6.4 hours,
• Decreased maximum 1-hour average ND2 15%, from 0.39 ppm to 0.33 ppm,
• Decreased maximum PAN 87%, from 0.015 ppm to 0.002 ppm,
• Decreased final oxidant 67%, from 0.12 ppm to 0.04 ppm,
• Decreased final formaldehyde 42%, from 0.12 ppm to 0.07 ppm, and
• Decreased average total hydrocarbon disappearance rate 49%, from 0.88
ppmC/hour to 0.45 ppmC/hour.
Changing the hydrocarbon blend from one modeled on catalyst -treated
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exhaust to one modeled on the same exhaust plus evaporative emissions plus
refueling losses:
• Decreased maximum 1-hour average 03 64%, from 0.14 ppm to 0.05 ppm,
and
• Decreased final oxidant 56%, from 0.09 ppm to 0.04 ppm.
Individual Hydrocarbon Disappearance Rates for Static Runs
Of the six hydrocarbons studied, four (ethylene, toluene, xylene and
propylene) did not differ significantly in disappearance rate. The average
for this group was 0.009 ppm/hour. Isopentene disappeared significantly
faster at 0.05 ppm/hr., while n-butane had a significantly slower rate of
0.002 ppm/hr.
Note on Dosages
Dosage calculations, being integrals under experimental curves, are
highly dependent upon 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 ND£ 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 only because the production
was artificially terminated at the end of the run. Since the probability of
missing a significant shift in time to maximum in this experiment is high (for
a shift of 1 hour p = 0.7 for time to 03 maximum), no effects on dose are
reported as significant.
DISCUSSICN
Examination of the statistically significant effects shows that the find-
ings of this study can be easily summarized.
• The blend used in this study generally produced less severe manifes-
tations of photochemical smog than the blends used in Phase I.
• Changing HC/Npx ratio (or equivalently in this study, NOx concen-
tration) significantly effected only the maximum 1-hour average ND2
concentration and the time to reach it.
• Changes in running mode produced significant effects only in times to
maxima of 03 and N02 and total hydrocarbon disappearance rate.
A clear ranking of the three blends in terms of the severity of photo-
chemical smog produced under our reaction conditions can be deduced from the
significant effect presented in Phase II and from the significant effects
found in Phase I of this program. The Phase II blend clearly produces the
least severe smog, exhibiting significant decrease from both other blends in
maximum 1-hour average ozone and final (10-hour) oxidant, and significant
decreases from the non-catalyst blend in maximum 1-hour average N02 , maximum
PAN, and 10-hour formaldehyde. The catalyst blend from Phase I is next in
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severity, showing significant increases in maximum i-hour average O3 and final
(10-hour) oxidant over the Phase II blend, but remaining significantly less
(Phase I results) than the non-catalyst blend in maximum 1-hour average ozone
and in maximum PAN. In addition, maxima in ozone occur significantly later in
time for both the Phase II and catalyst blends as compared to the non-catalyst
blend.
The data in this program do not allow analysis in terms of individual
hydrocarbon reactivities as the three blends contain six hydrocarbons, which
translates into a system of three equations and five unknowns. In fact, since
the olefin and aromatic mole fractions are essentially equal within each of
the blends, no good solution for reactivities on the basis of class can be
found. It is clear, however, that ozone production drops off as mole fraction
of paraffins increases and the drop-off is approximately linear over the range
studied (Figure 1). TMs observation is interesting in that it indicates that
the concept of hydrocarbon class reactivities might be applicable to data
gathered in long term (10-hour) irradiation under a variety of simulated
meteorological conditions, as well as to data from the more cannon 5-hour
static irradiation runs.
Previously proposed reactivity scales were tested to see if they provided
an adequate explanation for the difference in oxidant levels seen with these
blends. Figure 2 shows a plot of measured vs. calculated relative ozone con-
centrations for the Phase I blends relative to the Phase II blend. Three
different reactivity scales were used (1-3). All these scales underestimate
the reactivity differences between the blends. The oldest scale, proposed by
Altshuller in 1966, provided a better fit to the data than the two scales
recently proposed by EPA and the California Air Resources Board. Additional
work with blends in which class or compound effects can be clearly discerned
is necessary to determine whether a scale capable of predicting over a wide
range of blend compositions and running conditions can be developed.
REFERENCES
1. Altshuller, A. P., JAPCA, 16, p. 257, May, 1966.
2. Dimitriades, B., Proceedings of the Solvent Reactivity Conference,
EPA-650/3-74-010, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina, p. 19.
3. State of California Air Resources Board. Progress Report on Hydrocarbon
Reactivity. Staff Report, June 12, 1975.
15
-------
.25
.2
o
H
.15
rH
fi
.05
0
NON-CATALYST EQUIPPED
BLEM)
CATALYST EQUIPPED
BLEND
T
TWO STANDARD
DEVIATIONS
1
TOTAL EMISSIONS
BLEND
.5
MOLE FRACTION PARAFFINS
1.0
Figure 1. Average maximum 1-hour average ozone concentration
vs. mole fraction of paraffins.
16
-------
\
\
\
\
\
\
/-^. cr
C:i CD
CD O
CD «H
CH 0
\
"O
0
PH
\
"
\
\
\
oo
CO
8
•H
I
S
i
3
fc
£
£
*
Q)
SP
&
^
O
1
\
\
\
8
(M
-------
TABLE 4. CONVERSION TABLE TO S. I. UNITS
To Convert From
calorie
gram
hour
kilopascals (kPa)
mile
minute
pound
degree Fahrenheit (_°F)
To
joule
kilogram
second
newton/meter2
meter
second
kilogram
degree kelvin
Multiply by
4.186 8 E+00
1.000 000*E-03
3.600 000*E+03
1.000 000*E+03
1.609 344*E+03
6.000 000*E+01
4.535 924 E-01
(°K) t. = (t, + 4S9.67)/, ,
18
-------
APPENDIX A
FORMULAE USED TO CALCULATE PARAMETERS
19
-------
K- = N02 photolysis rate constant
"D ' IJ&1 <29'5> --' *
where all concentrations are determined at the intersection point of the NO
and 03 curves.
N02 Dose = [NO2] dt ppm hrs.
*
0
03 Dose = \ [O3] dt ppm hrs.
**O3 maximum 1-hour average =
O^(max) + 03(1/2 hr. before max) + 0^(1/2 hr. after max)
3
**N02 maximum 1-hour average =
N02(max) + ND?(l/2 hr. before max) + 0^(1/2 hr. after max)
3
The project officer provided the following formulae:
NO initial
NO? formation rate = 2T, /0 ppm/hr.
where
T /0 = time at which ND2 = 1/2 NO initial + N02 initial
Maximum rate of Oo formation = 75^
2
* This formula is from: 0'Brian, Environ. Sci. Tech., .8, 579, 1974.
**The formulae provide a good approximation to the true average for the broad
maxima encountered in this work.
20
-------
where
T3/4 = time to form 3/4 of 03 (max)
T, ,0 = time to form 1/4 of 03 (max)
Average rate of 03 formation = j
where
T, /0 = time to form 1/2 of 03 (max)
LftL
HP — HC"
Maximum rate of hydrocarbon disappearance = "i ~ 'f
where
HC. = initial hydrocarbon concentration
HCf = final hydrocarbon concentration
T . = time for disappearance of 3/4 (IHC. - THC )
T^/4 = time for disappearance of 1/4 (IHC± - IHC )
21
-------
APPENDIX B
CALCULATED PARAMETERS AND GRAPHS
23
-------
RUN NO. 38: 2 ppm XL-263, 1 ppm NO , 0.3 ppm NO STATIC
SEPTEMBER 2, 1975 X
Average Temperature = 32.95 ± 0.20 °C
-1 -2 -1
Average Dilution Rate = 0.130 x 10 ± 0.122 x 10 hr chamber volumes
Concentrations are corrected for dilution
N02 Photolysis Rate Constant = Cannot calculate
Ifo intersection of NO and 0,, curves
NOr, Formation Rate = 0.06 ppm hr
N02 Dose = 3.538 ppm hr
N02 is corrected for PAN
Maximum Rate of Ozone Formation = 0 ppm hr
Average Rate of Ozone Formation = 0 ppm hr
Ozone Dose = 0.001 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.08 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.13 ppmC hr
Initial Oxidant by Neutral Buffered KI = 0 ppm
Final Oxidant by Neutral Buffered KI = 0 ppm
Initial Formaldehyde by Chromatropic Acid - 0 ppm
Final Formaldehyde by Chromatropic Acid =0.05 ppm
Maximum 1-hour 0« Average = 0
Maximum 1-hour NCU Average = 0.45
Average Hydrocarbon Disappearance Rate: (1) ethylene = 0.0031
(2) propylene = 0
(3) butane = 0.0007
(4) i-pentene = 0
(5) toluene = 0.0222
(6) xylene = 0.0057
24
-------
I
UJ
I
Hi
o-
LJ
cc
UJ
•O
I
UJ
UJ
•*•
I
UJ
I
UJ
UJ
o
25
-------
tu
-< o
26
-------
01
o
ID
+ O
+ o
o
UJ
27
-------
tu
+ o
uj
O
28
-------
RUN NO. 35: 4 ppm XL-263, 1 ppm NOx, 0.3 ppm NOo, STATIC
AUGUST 20, 1975
Average Temperature = 33.02 ± 0.23 °C
-1 -3 -1
Average Dilution Rate = 0.136 x 10 ± 0.861 x 10 hr chamber volumes
Concentrations are corrected for dilution
N00 Photolysis Rate Constant =0.59 min
£i
N00 Formation Rate = 0.21 ppm hr~ (used time at maximum N00).
£i £j
N02 Dose = 4.098 ppm hr
N00 is corrected for PAN
^
Maximum Rate of CU Formation = 0.02 ppm hr
Average Rate of CL Formation =0.01 ppm hr
CL Dose = 0.509 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.20 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.29 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 = 0.26 ppm
Maximum 1-hour 0« Average = 0.13
Maximum 1-hour N02 Average = 0.35
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0069
(2) propylene = 0.0094
(3) butane = 0.0017
(4) i-pentene = 0.0640
(5) toluene = 0.0092
(6) xylene = 0.0110
29
-------
LU
o
I
LU
UJ
00
I
UJ
I
LU
I
LU
in
I
LU
LU
CM
I
LU
I
LU
O
30
-------
31
-------
•f
o
+ o
o
32
-------
£ o
O 02
LU
o
UJ
a-
UJ
ac
rg
uj
(NJ
UJ
CVJ
UJ
UJ
o
33
-------
RUN NO. 33: 4 ppm XL-263, 1 ppm NOX, 0.3 ppm NO2, DILUTION
AUGUST 14, 1975
Average Temperature = 33.29 ± 0.33 °C
Average Dilution Rate = 0.583 x 10~ + 0.155 x 10"1 hr"1 chamber volumes
NOp Photolysis Rate Constant = Cannot calculate.
No intersection of NO and Oq curves.
ij
N02 Formation Rate =0.27 ppm hr" (used time at maximum N09).
N00 Dose = 3.402 ppm hr
^
is corrected for PAN
Maximum Rate of 0,, Formation = 0 ppm hr
~
Average Rate of Oq Formation = 0 ppm hr
o
0 Dose = 0.018 ppm hr
O
Uaximum Rate of Total Hydrocarbon Disappearance = 0,32 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0,24 ppmC hr~
Initial Oxidant by Neutral Buffered KE = 0 ppm
Final Qxidant by Neutral Buffered KI = 0.03 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0.07 ppm
Maximum 1-hour 0^ Average = 0.004
Maximum 1-hour N00 Average =0.48
^
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0104
(2) propylene = 0.0030
(3) butane = 0.0035
C4) i-pentene = 0.0711
(5) toluene = 0.0075
(6) xylene = 0.0133
(T. = 0.1088)
34
-------
I
UJ
o
I
LU
LU
CO
I
LU
LU
in
I
LU
CO
LU
(NJ
I
LU
LU
O
35
-------
36
-------
o
UJ
37
-------
IU
+ o
a
•H
CO
UJ
o
38
-------
RUN NO. 34: 4 ppm XL-263, 0.5 ppm NO , 0.15 ppm N09, DILUTION
AUGUST 18, 1975X
Average Temperature = 33.50 ± 0.26 °C
Average Dilution Rate = 0.584 x 10"1 ± 0.153 x 10~ hr~ chamber volumes.
N00 Photolysis Rate Constant =0.59 min
j^j
N09 Formation Rate =0.11 ppm hr (used time at maximum N09).
ICL Dose = 1.775 ppm hr
NCL is corrected for PAN
Maximum Rate of 0,, Formation = 0.02 ppm hr
o
Average Rate of 0,, Formation = 0.02 ppm hr
0~ Dose = 0.741 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.30 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 = 0.11 ppm
Initial Formaldehyde by Chroniatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.07 ppm
Maximum 1-hour 0_ Average =0.11
Maximum 1-hour N00 Average =0.28
Zj
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0106
(2) propylene = 0.0076
(3) butane = 0.0038
(4) i-pentene = 0.0660
(5) toluene = 0.0055
(6) xylene = 0.0241
39
-------
UJ
o
UJ
o-
UJ
CO
I
UJ
I
UJ
if\
UJ
IM
UJ
O
40
-------
41
-------
+
o
UJ
o
42
-------
s
£H
a
1
O
-2
Oj -P «H
w oj
03 C CD
•H -H rH
O TJ
-------
RUN NO. 36: 4 ppm XLr-263, 1 ppm NOx, °-3 PF™ NO DYNAMIC
AUGUST 26, 1975 ^
Average Temperature = 34.63 ± 0.17 °C
Average Dilution Rate = 0.102 x 10° ± 0.127 x 10 hr"1 chamber volumes
NOu Photolysis Rate Constant =0.70 min
N00 Formation Rate = 0.53 ppm hr~ (used time at maximum N00).
£ 2
N02 Dose = 2.344 ppm hr
NO,-, is corrected for PAN
Maximum Rate of Ozone Formation =0.04 ppm hr"
Average Rate of Ozone Formation =0.06 ppm hr
Ozone Dose = 0.903 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance = 0.47 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.88 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 =0.05 ppm
Maximum 1-hour 0~ Average = 0.13
Maximum 1-hour NCL Average = 0.47
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0511
(2) propylene = 0.0200
(3) butane = 0.0127
(4) i-pentene = (-KX))
(5) toluene = 0.0340
(6) xylene = 0.0151
44
-------
UJ
o
UJ
(f
JJ
00
LU
•£>
I
UJ
UJ
rvj
I
01
UJ
O
45
-------
*
o
IU
o
o
UJ
111
•o
o
UJ
o
UJ
UJ
CM
O
UJ
46
-------
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o
a
g
-Hoj
-P O
3
0) II
8" a)
rH rf -P
>, W rf
X CO G 0>
II
G
-r-t iH
T3 oJ
^0
O K!
' -f
o
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o
LU
O
LU
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47
-------
til
+ o
Ul
CO
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LU
in
ui
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JJ
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48
-------
RUN NO. 37: 4 ppm XLr-263, 0.5 ppm NO , 0.15 ppm N09, DYNAMIC
AUGUST 28, 1975X
Average Temperature = 32.88 + 0.20 °C
Average Dilution Rate = 0.106 x 10° ± 0.277 x Id" hr"~ chamber volumes
N09 Photolysis Rate Constant =0.44 rnin"
^
_^
N00 Formation Rate = 0.30 ppm hr (used time at maximum N00).
/ £
iN00 Dose = 2.335 ppm hr
NO,., is corrected for PAN
Maximum Rate of 03 Formation = 0.04 ppm hr~
Average Rate of 0^ Formation =0.04 ppm hr
03 Dose = 0.230 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.43 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.78 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 =0.04 ppm
Maximum 1-hour 0^, Average = 0.06
O
Maximum 1-hour N00 Average =0.25
^
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0255
(2) propylene = 0.0145
(3) butane = 0.0092
(4) i-pentene = (-KX))
(5) toluene = 0.0134
(6) xylene = 0.0400
49
-------
JJ
o
I
UI
I
UJ
00
I
UJ
UJ
.o
I
ui
in
UJ
eg
I
iu
o
50
-------
M §
in -Hcsi
3 -P O
•5 § i-H
O
02 C II
Q) CD SO
> § a 0 ii o
>> a a gj 3 a) as
J3 O -P o
-------
UJ
t O
UJ
O
I +
O
01
52
-------
RUN NO. 39: 2 ppm XL-263, 1 ppm NOx, 0.3 ppm N09, STATIC
SEPTEMBER 4, 1975
Average Temperature = 33.13 ± 0.27 °C
Average Dilution Rate = 0.138 x 10 ± 0.103 x 10 hr~~ chamber volumes
Concentrations are corrected for dilution
N02 Photolysis Rate Constant = Cannot calculate.
No intersection of NO and 0« curves.
NOp Formation Rate = Cannot calculate.
Zero in denominator .
N02 Dose = 3.584 ppm hr
N00 is corrected for PAN
&
Maximum Rate of Oq Formation = 0 ppm hr~
O
Average Rate of 0~ Formation = 0 ppm hr~
Og Dose = 0.003 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.07 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.12 ppmC hr~
Initial Oxidant by Neutral Buffered KI = 0 ppm
Final Oxidant by Neutral Buffered KI = 0 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.05 ppm
1-hour Maximum Oo Average = 0
1-hour Maximum NCL Average = 0.53
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0050
(2) propylene =
(3) butane = 0.0005
(4) i-pentene =
(5) toluene = 0.0024
(6) xylene = 0.0046
53
-------
CO
+
«»• -t
* c\» . V • +
Ut
O
I
at
l
in
in
tu
m
I
uu
CM
Ul
O
54
-------
§
•H> S S3 i ft co 0 J3 r
O
UJ
0
01
oo
"J
-o
55
-------
+••••*+•*•
ft
fl
•H
s
•!-|(X
•H O
Ctf rH
P
0 (N
m o
ECU
•rH O
^6^
(u H ii -p
> 65 cJ
« i
•H C 0)
O -H rH
CC T3 Cd
§££
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56
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57
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RUN NO. 40: 4 ppm XL-263, 0.5 ppm NOx, 0,. 15 ppm N00, DYNAMIC
SEPTEMBER 8, 1975
Average Temperature = 33.18 ± 0.23 °C
-1 -o -l
Average Dilution Rate = 0.927 x 10 ± 0.159 x 10 hr chamber volumes
N02 Photolysis Rate Constant =0.73 rnin"
N00 Formation Rate = 0.36 ppm hr (used time at maximum N00).
M ^
N02 Dose = 0.694 ppm hr
NOo is corrected for PAN
-1
Mayimim Rate of Oo Formation =0.03 ppm hr
Average Rate of 0~ Formation =0.05 ppm hr~
Oo Dose = 0.764 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance = 0.40 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance = 1.13 ppmC hr*
Initial Qxidant by Neutral Buffered KI = 0 ppm
Final Qxidant by Neutral Buffered KI = 0.03 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid =0.04 ppm
Maximim 1-hour 0,, Average = 0.10
Maximum 1-hour NCU Average = 0.22
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0587
(2) propylene = 0.0177
(3) butane = 0.0122
(4) i-pentene =
(5) toluene = 0.0188
(6) xylene = 0.0430
58
-------
I
LU
O
ID
•O
I
IU
IU
og
IU
O
59
-------
o
Ul
UJ
CO
o
UJ
Ul
in
o
Ul
60
-------
•f
o
Ul
o
a
o
Ul
01
r-
+• o
o
61
-------
LU
+ O
I
CM
UJ
UJ
co
rx
UJ
UJ
-O
62
-------
RUN NO. 41: 4 ppra XL-263, 0.5 ppm NOx, 0.15 ppm NO DILUTION
September 17, 1975 ^
Average Temperature = 33.20 ± 0.23 °C
-1 -1 -1
Average Dilution Rate = 0.538 x 10 ± 0.136 x 10 hr chamber volumes
N00 Photolysis Rate Constant = Cannot calculate.
fo
-1
No intersection of NO and 03 curves.
NO.
U Formation Rate = 0.16 ppm hr (used time at maximum NCL).
N02 Dose = 1.936 ppm hr
N02 is corrected for PAN
Maximum Rate of 03 Formation =0.50 ppm hr
Average Rate of Oq Formation =0.04 ppm hr
o
0 Dose = 0.105 ppm hr
o
Maximum Rate of Total Hydrocarbon Disappearance =0.30 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.26 ppmC hr
Initial Oxidant by Neutral Buffered KI = 0 ppm
Final Oxidant by Neutral Buffered KI = 0.01 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0.04 ppm
Maximum 1-hour 0« Average = 0.017
Maximum 1-hour NO,-, Average = 0.24
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0090
(2) propylene = 0.0033
(3) butane = 0.0029
(4) i-pentene = 0.0581
(5) toluene = 0.0081
(6) xylene = 0.0128
63
-------
LU
co
UJ
r-
i
LU
•o
UJ
U1
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UJ
til
ro
LU
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64
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a
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•H
§
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G
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(PC fl
a 33 53 CD
CD rH CD -P C
rH >> B fl 0)
>> ft co CD 3
Jd &4J ftH
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OJ P, £ -H
II II II II
rH CM CO •rJH
O
O
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0 Ctf
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s
0) TO
O
UJ
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LU
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66
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at
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RUN NO. 42: 4 ppn XL-263, 0.5 ppm NO , 0.15 ppm N09 STATIC
SEPTEMBER 19, 1975 x "
Average Temperature = 33.31 ± 0.25 °C
Average Dilution Rate = 0.125 x 10~ ± 0.782 x 10~3 hr"1 chamber volumes
Concentrations are corrected for dilution
NCu Photolysis Rate Constant = Cannot calculate.
No 0« curve.
NCu Formation Rate =0.05 ppm hr (used time at maximum N00).
^j £
N02 Dose = 2.065 ppm hr
N00 is corrected for PAN
^j
Maximum Rate of 0,, Formation = 0 ppm hr
Average Rate of 03 Formation = 0 ppm hr~
03 Dose = 0.060 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.12 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance =0.22 ppmC hr~
Initial Qxidant by Neutral Buffered KI = 0 ppm
Final Oxidant by Neutral Buffered KI = 0 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chroraatropic Acid =0.04 ppm
Maximum 1-hour 0,, Average = 0 ppm
Maximum 1-hour NCL Average = 0.225
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0057
(2) propylene = o.0160
(3) butane = 0.0019
(4) i-pentene = 0.0320
(5) toluene = 0.0121
(6) xylene = 0.0111
68
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+ o
•1- •
•
in
+ c-
in
in
•
•
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69
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71
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72
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RUN NO. 43: 4 ppm XL-263, 1 ppm NOx, 0.3 ppm NO2, DYNAMIC
September 23, 1975
Average Temperature = 33.31 ± 0.24 °C
-1 —2 -1
Average Dilution Rate = 0.960 x 10 ± 0.132 x 10 hr chamber volumes
N02 Photolysis Rate Constant = Cannot calculate.
No intersection of NO and 0.-. curves.
NOp Formation Rate = 0.22 ppm hr (used time at maximum N02).
N02 Dose = 2.505 ppm hr
N02 is corrected for PAN
Maximum Rate of 0« Formation =0.02 ppm hr
Average Rate of 0Q Formation =0.01 ppm hr
O
03 Dose = 0.238 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.42 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.68 ppmC hr
Initial Oxidant by Neutral Buffered KI = 0 ppm
Final Oxidant by Neutral Buffered KI = 0.01 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0.04 ppm
Maximum 1-hour 0,-, Average = 0.05
Maximum 1-hour N02 Average =0.38
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0250
(2) propylene = none shown on GC
(3) butane = 0.0079
(4) i-pentene = only first reading
shown on GC
(5) toluene = 0.0117
(6) xylene = 0.0280
73
-------
I
UJ
o
I
UJ
LU
CO
I
UJ
ui
•o
UI
irt
UJ
fl
UJ
o
74
-------
CO
a
-H CM
-P o
> ^ fl
fe a
-p fi s i o w oj
II II II II II 'p 73
in csi co ^ m <
-------
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a
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3
1
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RUN NO. 44: 4 ppm XL-263, 0.5 ppm NOx, 0.15 ppm NO STATIC
SEPTEMBER 25, 1975 Z
Average Temperature = 33.20 ± 0.24 °C
-1 -^ -1
Average Dilution Rate = 0.120 x 10 ± 0.869 x 10 hr chamber volumes
Concentrations are corrected for dilution
NOp Photolysis Rate Constant = Cannot calculate.
No intersection No and 0,.. curves.
NO- Formation Rate =0.07 ppm hr~
NO0 Dose = 2.239 ppm hr
^
NO,, is corrected for PAN
Maximum Rate of 0~ Formation = 0.05 ppm hr~
Average Rate of O« Formation = 0.002 pptn hr~
Oo Dose = 0.119 ppm hr
n
Average Rate of Total Hydrocarbon Disappearance =0.26 ppmC hr"
Maximum Rate of Total Hydrocarbon Disappearance =0.10 ppmC hr
Initial Oxidant by Neutral Buffered KI = 0 ppm
Final Oxidant by Neutral Buffered KI = 0 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chromatropic Acid = 0.07 ppm
Maximum 1-hour 0« Average =0.02
Maximum 1-hour N00 Average =0.25
^
Average Hydrocarbon Disappearance Rate: (1) ethylene = 0.0078
(2) propylene = not detected by GC
(3) butane = 0.0046
(4) i-pentene = GC showed only
initial point
C5) toluene = 0.0074
(6) xylene = 0,0092
78
-------
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uu
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79
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-P O
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•rt -H i—I
li O IS ctf
. -Q it O
' + O
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01
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+....+....+•
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RUN
NO. 45: 4 ppm XL-263, 1 ppm NQx, 0.3 ppm NO , DILUTION
SEPTEMBER 29, 1975
Average Temperature = 33.15 ± 0.23 °C
Average Dilution Rate = 0.556 x 10 ± 0.136 x 10~ hr~ chamber volumes
NO Photolysis Rate Constant = Cannot calculate.
No intersection of NO and 0« curves.
NOp Formation Rate =0.18 ppm hr
N02 Dose = 2.892 ppm hr
N02 is corrected for PAN
Maximum Rate of 0^ Formation = 0 ppm hr
Average Rate of 0~ Formation = 0 ppm hr
03 Dose = 0.017 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance =0.27 ppmC hr
Average Rate of Total Hydrocarbon Disappearance =0.24 ppmC hr
Initial Oxidant by Neutral Buffered KI = 0 ppm
Final Oxidant by Neutral Bufffered KI = 0.04 ppm
Initial Formaldehyde by Chromatropic Acid = 0 ppm
Final Formaldehyde by Chramtropic Acid = 0.04 ppm
Maximum 1-hour 0,, Average = .001
Maximum 1-hour N0? Average =0.36
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0068
(2) propylene = 0.0032
(3) butane = 0.0029
(4) i-pentene = 0.0533
(5) toluene = 0.0059
(6) xylene = 0.0157
83
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RUN NO. 46: 4 ppm XL-263, 1 ppm NO , 0.3 ppm N09, STATIC
OCTOBER 1, 1975 X
Average Temperature = 33.18 ± 0.23 °C
-1 -3 -1
Average Dilution Rate = 0.118 x 10 ± 0.782 x 10 hr chamber volumes
Concentrations are corrected for dilution
N09 Photolysis Rate Constant = Cannot calculate.
No intersection of NO and 0« curves.
N09 Formation Rate =0.64 ppm hr
N09 Dose = 3.538 ppm hr
£i
NO9 is corrected for PAN
Maximum Rate of 0~ Formation = 0 ppm hr
Average Rate of 03 Formation = 0 ppm hr
0 Dose = 0.005 ppm hr
Maximum Rate of Total Hydrocarbon Disappearance = 0.10 ppmC hr~
Average Rate of Total Hydrocarbon Disappearance = 0.15 pprnC hr~
Initial Oxidant by Neutral Buffered KI = 0 ppra
Final Oxidant by Neutral Buffered KI = 0 ppm
Initial Formaldehyde by Cnromatropic Acid = 0 ppm
final Formaldehyde by Chromatropic Acid =0.06 ppm
Maximum 1-hour Oo Average = 0
Maximum 1-hour N00 Average = 0.385
£
Average Hydrocarbon Disappearance Rates: (1) ethylene = 0.0086
(2) propylene = 0.0072
(3) toluene = 0.0014
(4) i-p^mtene = 0.0533
(5) toluene = 0.0037
(6) xylene = 0.0127
88
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APPENDIX C
ANALYSIS OF VARIANCE TABLES
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
1 REPORT NO.
EPA-6QQ/3-77-ir)9h
3. RECIPIENT'S ACCESSIOr*NO.
4 TITLE AND SUBTITLE
EFFECT OF HYDROCARBON COMPOSITION ON OXIDANT-
HYDROCARBON RELATIONSHIPS
Phase II. Blend of Total Hydrocarbon Emissions
5. REPORT DATE
September 1977
6. PERFORMING ORGANIZATION CODE
7 AOTHCR(S)
8. PERFORMING ORGANIZATION REPORT NO.
T.R. Powers
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Exxon Research and Engineering Company
Linden, New Jersey 07036
10. PROGRAM ELEMENT NO.
1AA008
11. CONTRACT/GRANT NO.
68-02-1719
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory - RTP, NC
Office of Research and Development
Environmental Protection Agency
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
To assess the formation of atmospheric oxidants resulting from exhaust emitted
by catalyst-equpped vehicles,chamber irradiations were conducted using a
hydrocarbon blend representing total hydrocarbon emissions (exhaust, refueling
and evaporation). Results were compared with previous irradiation results using
a hydrocarbon blend representing non-methane, non-acetylene exhaust emissions
from non-catalyst vehicles or catalyst-equipped vehicles. The blend representing
total hydrocarbon emissions produced significantly less oxidants than either of the
other two blends.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
*Air pollution
*Hydrocarbons
*0zone
Automobiles
*Exhaust emissions
Catalytic converters
Oxidation
Test chambers
*Irradiation
13B
07C
07B
13F
21B
07A
14B
18H
13 DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO OF PAGES
no
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
104
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