EPA-650/2-75-014
December 1974
Environmental Protection Technology Series
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environ-
mental Protection Agency, have been grouped into series. These broad
categories were established to facilitate further development and applica-
tion of environmental technology. Elimination of traditional grouping was
consciously planned to foster technology transfer and maximum interface
in related field?. These 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
9. MISCELLANEOUS
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to
develop and demonstrate instrumentation, equipment and methodology
to repair or prevent environmental degradation from point and non-
point sources of pollution. This work provides the new or improved
technology required for the control and treatment of pollution sources
to meet environmental quality standards.
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EPA-650/2-75-014
EFFECT
OF GASOLINE ADDITIVES
ON GASEOUS EMISSIONS
by
R. W. Hum, J. R. Allsup, anclF. Cox
Fuels and Combustion Research Group
Bartlesville Energy Research Center
Bureau of Mines
Bartlesville, Oklahoma 74003
Interagency Agreement No. EPA-IAG-097(D)
ROAP No. 26AAE
Program Element No. 1AA002
EPA Project Officer: J. E. Sigsby, Jr.
Chemistry and Physics Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
December 1974
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EPA REVIEW NOTICE
This report has been reviewed by the National Environmental Research
Center - Research Triangle Park, Office of Research and Development,
EPA, and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
This document is available to the public for sale through the National
Technical Information Service, Springfield, Virginia 22161.
11
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TABLE OF CONTENTS
Page
Foreword viii
Objective „ 1
Experimental apparatus 1
Engines and vehicles 1
Fuel 2
Instrumentation 2
Experimenta 1 procedures 6
Organic manganese analysis --methodology 6
Inorganic manganese analysis —methodology 7
Analyses for nitrogen compounds --methodology 7
Emission measurement—methodology 8
Results and discussion 9
Manganese determination-methodology background 9
Manganese determination—test results 10
Nitrogen compound determination=-methodology background .... 12
Nitrogen compound determination--test results 17
Engine deposits 17
Induction system 17
Carburetor. 17
Intake manifold passages 17
Intake valves 17
Combustion chamber 18
Piston heads „....„ „. 18
iii
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TABLE OF CONTENTS--Continued
Page
Engine head 18
Spark plugs 18
Exhaust valve stems... 18
Conclusions 19
References ?.C
APPENDIX A.-Tabulated data 32
APPENDIX Bo - Photographs of engine components 49
ILLUSTRATIONS
1. The detection system for organic manganese analysis.. 21
2. Chromatographic system for analysis of nitrogen compounds... 22
3. Exhaust analysis for MCMT 23
4. Effect of mileage accumulation on exhaust emissions, AK33X
vehicle 24
4A. Effect of mileage accumulation on manganese emissions,
AK33X vehicle „ „ 24
5. Effect of mileage accumulation on exhaust emissions,
stationary engine A with AK33X 25
5A. Effect of mileage accumulation on manganese emissions,
stationary engine A with AK33X 25
6. Effect of mileage accumulation on exhaust emissions,
stationary engine B with AK33X 26
6A. Effect of mileage accumulation on manganese emissions,
stationary engine B with AK33X 26
iv
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ILLUSTRATIONS--Continued
Page
7. Effect of mileage accumulation on exhaust emissions,
stationary engine A with F310 „ 27
8. Effect of mileage accumulation on exhaust emissions,
stationary engine B with F310 , 27
9. Effect of mileage accumulation on exhaust emissions, control
vehicle 28
10. Effect of mileage accumulation on exhaust emissions, F310
vehicle 28
11. Total CVS exhaust hydrocarbons by GLC 29
12. Chromatogram or synthetic amines and pyridine 30
13. Chromatogram or synthetic amines and pyridine 30
14. Chromatogram or acidic and neutral nitrogen compounds
(synthetic sample) 30
ISA. Chromatogram for acidic and neutral nitrogen compounds
(exhaust sample) 31
15B. Chromatogram for acidic and neutral nitrogen compounds
(exhaust sample after 1.0 hours) 31
15C. Chromatogram for acidic and neutral nitrogen compounds
(exhaust sample after 1.5 hours) 31
15D. Chromatogram for acidic and neutral nitrogen compounds
(exhaust sample after 2.0 hours) 31
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ILLUSTRATIONS—Continued
Page
B-l. Carburetor bases for the AK33X, F310, and control vehicles 50
B-2. Carburetor bases for the stationary engines 51
B-3. Intake and exhaust ports for the AK33X, F310, and control vehicles... 52
B-4. Intake and exhaust ports for the stationary engines 53
B-5. Intake valve stems for the AK33X, F310, and control vehicles 54
B-6. Intake valve stems for the stationary engines 55
B-7. Piston head for the AK33X, F310, and control vehicles 56
B-8. Piston head for the stationary engines 57
B-9. Cylinder heads for the AK33X, F310, and control vehicles ... 58
B-10. Cylinder heads for the stationary engines 59
B-ll. Exhaust valve stems for the AK33X, F310, and control vehicles 60
B-12. Exhaust valve stems for the stationary engines 61
B-13. Spark plugs for the AK33X, F310, and control vehicles 62
B-14. Spark plugs for the stationary engines 63
B-15. Piston and engine head for AK33X engine A 64
VI
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TABLES
1. New engine break-in procedure (28 hours) 3
2. Inspection data for Indolene Motor Fuel HO III 4
3. Inspection data for unleaded gasoline blend 5
A-l. Detailed hydrocarbon analysis, F310 vehicle 33
A-2. Detailed hydrocarbon analysis, AK33X vehicle 35
A-3. Detailed hydrocarbon analysis, control vehicle 37
A-4. Detailed hydrocarbon analysis, stationary engine A 39
A-5. Detailed hydrocarbon analysis, stationary engine B 42
A-6. Effect of mileage accumulation on exhaust emissions, stationary
engine A 44
A-7. Effect of mileage accumulation on exhaust emissions, stationary
engine B 45
A-8. Effect of mileage accumulation on exhaust emissions, F310 vehicle... 46
A-9. Effect of mileage accumulation on exhaust emissions, AK33X vehicle.. 47
A-10. Effect of mileage accumulation on exhaust emissions, control
vehicle 48
vii
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FOREWORD
This report presents a summary of work performed by the Fuels Combustion Research
Group, Bartlesville Energy Research Center, Bureau of Mines, for the Environ-
mental Protection Agency, (EPA), Office of Research and Monitoring under Inter-
agency agreement number EPA-IAG-097(D).
Mr. John E. Sigsby, Jr., was the Project Officer for EPA. The program at
Bartlesville was directed by R. W. Hurn, Research Supervisor; J. R. Allsup,
Mechanical Engineer, was the Project Leader; Frank Cox, Research Chemist, was
responsible for the analytical development work and was assisted by D. E.
Seizinger, Research Chemist, and Dr. James Vogh, Research Chemist. Others who
contributed to the experimental work were L. Wilson, D. Thompson, S. Bishop,
and L. Nichols, Engineering Technicians. J. M. Clingenpeel, Chemical Engineer,
and R. F. Stevens, Mechanical Engineering Technician, assisted in the aldehyde
and other routine chemical measurements.
viii
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OBJECTIVE
The need to assess the effects of fuel additives upon auto emissions has
become increasingly pressing as the number and variety of additive materials
have been expanded to meet a growing desire for increased engine life and per-
formance. To be complete, such an assessment must include not only information
pertinent to the direct contribution of the additives themselves to the appear-
ance or composition of objectionable pollutants, but also the indirect con-
tribution resulting from the use of these materials.
The primary objective of this study is to provide data to the Environmental
Protection Agency (EPA) which will serve as a basis to establish the methodology
essential to standardization of additive effect testing. A complete and
meaningful test methodology of this type necessarily involves two elements:
1. determination of the levels and composition of emitted pollutants, and;
2. control and management of the emission source. The first element is the
basic concern since the capability to establish the amounts and types of
objectionable materials emitted by a source is requisite to recognition of the
extent and/or existence of objectionable materials. This study is intended
to supply basic analytical concepts and procedures which may be applicable
to additive effect testing. Control and management of emission sources must
be applied with discretion in accordance with the desired goal. Specifically,
ignition spark timing and dwell are independent of any effect caused by the
use of a gasoline additive while air-fuel ratio and idle speed may be markedly
affected by carburetor and induction system deposits which may, in turn, be
altered by the use of an additive. Insofar as the control and management of
these parameters are concerned, as well as pretest preparation of the emission
sources, the methodology described in this report is considered by the investi-
gators to be compatible with the production of meaningful data for the determi-
nation of gasoline additive effects. On the other hand, it is not within the
scope of the study objective to establish a standard mileage accumulation
procedure, but rather to produce data derived from: 1. Vehicles in "typical"
user service, and; 2. engines under controlled duty cycle conditions.
The secondary objective, a natural extension of the primary objectives discussed
above, is to provide data indicating the effect, if any, of each of two fuel
additives upon the character and/or composition of pollutants emitted by two
test engines and three test vehicles.
EXPERIMENTAL APPARATUS
A. Engines and Vehicles
Gaseous emissions from three 1972 Chevrolet Impalas and two Chevrolet
stationary engines were measured. The vehicles were 1972 models with
350 cubic-inch-displacement (CID) engines, two-barrel carburetors,
and automatic transmissions. Mileage on the vehicles at the time of
acquisition ranged from 1,500 to 3,000 miles; therefore, no break-in
mileage was accumulated. The stationary engines were new 1972 350-
CID Chevrolet engines with two-barrel carburetors. They were coupled
to eddy-current dynamometers via automatic transmissions. Stationary
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engine break-in was according to the EPA 28-hour schedule (table 1).
Vehicle inspection and refueling were conducted by technicians
assigned to the project.
B. Fuel
Due to delays in receipt of the EPA fuel, the program was begun using
Indolene clear as the basic fuel. Approximately 5,200 miles were
accumulated on the three vehicles using Indolene fuel. One test cycle
with stationary engine B using clear fuel for 5,000 miles and F310 for
5,000 miles was completed before the change to EPA fuel was made.
Inspection data for the Indolene and EPA fuels are given in tables 2
and 3, respectively.
C. Instrumentation
Analyses of exhaust components which were included in the program and
are considered to be routine are:
1. Total hydrocarbon (HC) by flame ionization detection (FID)—
Beckman 400.
2. Nitrogen dioxide (N0£) and oxides of nitrogen (NOX) by chemilum-
inescence—Thermo Electron 10A.
3. Carbon monoxide (CO) and carbon dioxide (C02) by nondispersive
infrared (NDIR)—Beckman 315.
4. Detailed hydrocarbon by gas-liquid chromatography (GLC) and
FID—modified Perkin-Elmer 900 (1-2).
5. Total aldehydes by 3-methyl-2-benzothiazolone hydrozone (MBTH)
colorimetry—Spectronic 20 (3).
The samples for total aldehyde analysis were metered directly from the
constant volume sampling (CVS) system into the MBTH reagent solution.
With this exception, samples for all routine analyses were collected
from the CVS system in light-proof Tedlar bags.
Instrumentation prepared for additive specific exhaust components
include:
1. F&M 810 chromatograph fitted with FID, alkali flame, and elctron
capture as optional detectors.
2. F&M 810 chromatograph fitted with FID and alkali flame parallel
detectors and two-pen recorder.
3. Perkin-Elmer 900 fitted with a Coulson electrolytic conductivity
detector (figure 1).
4. F&M 810 chromatograph oven system fitted with modified Beckman
DU spectrophotometer (figure 2).
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TABLE 1. = New engine break°in procedure (28 hours)
1. Warm up engine to 180° F coolant outlet temperature at 1,000 rpm,
no load. Set spark advance and best idle according to manufacturer's
specifications.
2. Run 1 hour at 1,500 rpm, no load, automatic spark advance and fuel
flow. Shut down, retorque cylinder heads, and drain and change
lubricating oil.
3. Run cycle 1:
Manifold vacuum,
RPM
1,500
2,000
2,400
2,600
2,000
inches Hg
15.0
14.0
14.0
14.0
11.0
Time,
hours
1.0
1.0
1.0
1.0
1.0
5.0
4. Run cycle 2:
Manifold vacuum,
RPM
1,500
2,000
2,500
3,000
2,000
inches Hg
7.0
7.0
7.0
7.0
7.0
Time,
hours
0.2
.6
1.0
1.0
.2
5. Repeat cycle 2.
6. Run cycle 3:
Manifold vacuum,
RPM
2,000
2,500
3,000
3,500
2,800
inches Hg
WOT*
WOT
WOT
WOT
WOT
Time,
hours
1.0
1.0
1.0
.5
.5
4.0 x 4 cycles
= 16 hours
* Wide open throttle.
-3-
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TABLE 2. - Inspection data for Indolene Motor Fuel HO III
API gravity
Distillation, %F:
Initial boiling point
107o Evap.
50% Evap.
90% Evap,,
Maximum
10% Slope
Reid Vapor Pressure
Oxidation stability, min.
Gum, mg/100 ml (after
Heptane wash)
TMEL, grm. lead/gal
Sulfur weight, %
Olefin, %
Aromatic, %
Saturates, %
Octane Research (Clear)
Octane Research (3 cc TEL/gal)
Phosphorus, gms/gal
Sensitivity (Clear)
Sensitivity (3 cc TEL/gal)
ASTM
method
D287
D86
D86
D86
D86
D86
D86
D323
D525
D381
D526
D1266
D1319
D1319
D1319
D2699
D2699
ACM 21.00
Specification
control limit
58.0-61.0
75=95
120-135
200-230
300-325
NMT 415
NMT 3.2
8.7-9.2
NLT 600
NMT 4.0
Nil
NMT 0.10
NMT 10
NMT 35
Remainder
96.0-98.5
NLT 103.0
NMT 0.01
7,0-10.5
NMT 9oO
Sample No.
D-18032
59.1
94
133
224
323
412
2.7
8.7
1440+
1.6
0.02
0.017
5.6
32.6
61.8
97.1
104.1
0.0
10.3
8.3
-4-
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TABLE 3. - Inspection data for unleaded gasoline blend
Research Octane Number
Motor Octane Number
Ron-Mon
Reid Vapor Pressure, psia
Distillation, ASTM D-86, °F:
10%
50%
95%
100%
API gravity at 60° F
FIA Analysis, %:
Aromatics
Olefins
Paraffins
ASTM gum, mg/100 ml
Stability, hrs
Sulfur, ppm
Phosphorous , ppm
Lead, g/gal
Diene Number, meq/ liter
2/
Fuel Composition, LV % - :
Benzene
Toluene
n=Butane
Isopentane
n-pentane
Results
93.2
84.7
8.5
10.2
123
199
325
383
61.6
24.0
8.3
67.7
0.57
24+
127-7
1
0.00004
0.0
0.1
8.1
8.0
8.3
5.4
Specification
Minimum
91.5
82
8
9.8
-
-
320
-
-
24
7
62
tonobservable
24+
-
=
=
-
-
-
-
-
0
Maximum
93.5
85
10
10.2
140
250
350
380
-
28
10
69
-
100
30
0.01
1
4
15
12
12
8
NOTE.-Fuel was inhibited with 5 lbs/1000 bbls of Du Pont 22
oxidation inhibitor.
I/ Fails specification, waiver obtained from customer.
2/ Benzene and toluene were determined by infrared analysis
by direct calibration techniques.
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EXPERIMENTAL PROCEDURES
The methods for analysis of HC, NC>2, NOX, CO, and C02 are well established and
will not be discussed in detail.
A. Organic Manganese Analysis—Methodology
Sample collection was accomplished by drawing diluted exhaust from
the CVS system with a Metal Bellows pump. The sample was pumped
through a 4 in x 3/8 in O.D. stainless steel column packed with
Chromosorb 102 at ice temperature. Sample flow was measured with a
rotometer placed downstream from the collection column.
The sample was recovered and analyzed according to the following
procedure:
1. To prevent loss of light sensitive manganese compounds, workup
should be carried out in semi-darkness.
2. Backflush the Chromosorb 102 collection column with acetone to
a total volume of about 5 ml.
3. To the acetone solution, add 0.2 ml of a sec-butylbenzene solu-
tion of a known weight of cyclopentadienylmanganesetricarbonyl (CMT-
internal standard).
4. Extract the acetone solution three times with 2 ml volumes of
pentane.
5. Bubble dry nitrogen through the pentane solution until it is
evaporated to about 0.3 ml of organic (upper) phase (water generally
separates from the organic material upon evaporation).
6. Note the exact volume of the organic layer.
7. Inject 20 yl into a chromatograph equipped with a flame photo-
metric detector (modified Beckman DU).
8. Quantitate by peak height relative to that of the CMT internal
standard.
Fuel, lube oil, and intake valve deposits were also analyzed for
organic manganese content. The fuel was diluted to a specific volume
with a benzene solution of CMT and injected into the chromatograph.
Methylcyclopentadienylmanganesetricarbonyl (MCMT) content was calculated
from relative peak heights. The lube oil was also analyzed in this
manner. Weighed samples of deposits from the manifold side of the
intake valves were digested in a known volume of benzene containing
CMT and chromatographed.
Conditions for the chromatographic determination were:
1. Column: 11-1/2 feet x 1/8 in O.D. stainless steel tubing packed
with 4 pet Apiezon L on 90/100 mesh Anachrom ABS.
2. Carrier: helium flowing at 55 cc/min
3. Temperature program: 8° C/min from 100° C to 180° C
4. Emission line measured: 403.3 my
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B. Inorganic Manganese Analysis—Methodology
A Gelman, Type A, glass fiber filter was placed in the sample line
as near as possible to the CVS system. As sample was drawn by the
sample pump for delivery to the Chromosorb 102 column, exhaust partic-
ulates were collected on the filter. Since MCMT has an appreciable
vapor pressure, it was assumed that all organic manganese was swept
through and only inorganic manganese retained by the filter. The
filter was analyzed for inorganic manganese in the following manner.
1. Place the entire glass fiber filter in a Teflon beaker and
digest with 3N HC1 near 80° C for 15 minutes.
2. Quantitatively transfer beaker contents to a plastic filtering
apparatus containing an acid washed cellulose membrane.
3. Thoroughly wash the filtering apparatus and retained solids
with 3N HC1.
4. Transfer the filtrate first to a Teflon beaker for heat evapo-
ration to a few milliliters, then to a 25 ml volumetric flask.
5. Dilute to volume with 1.5N HC1 and analyze by atomic absorption
(flame) spectroscopy.
6. Use 1.5N HC1 as an instrument blank and correct data according
to the value obtained from parallel analysis of an unused glass fiber
filter.
Deposits from the manifold side of the intake valves and combustion
chamber deposits were semi-quantitatively analyzed for total manganese
content by neutron activation analysis.
C. Analyses for Nitrogen Compounds—Methodology
Sample collection for nitrogen compound analysis is exceptionally
difficult due to their wide variety of chemical and physical properties.
Several collection methods were attempted but proved to be inadequate.
As a result, vapor samples were taken directly from the CVS system (or
bag) and injected into the PE-900 chromatograph via a 25cc gas sample
loop.
Differences in the properties of the nitrogen compounds made it
necessary to analyze with three separate chromatographic columns.
Chromatographic conditions for the analysis of ammonia, light aliphatic
amines, and pyridine were:
1. Column: 10 feet x 1/8 in O.D. stainless steel tubing packed with
15 pet Carbowax 600 plus 10 pet KOH on 80/100 mesh Gas-Chrom R
2. Carrier: Helium flowing at 48 cc/min
3. Temperature program: Hold at 25° C for 2 minutes, then program
at 5° C/min to 120° C
Substances such as acetonitrile, pyrrolidine, and cyclohexylamine can
also be analyzed on this column.
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Chromatographic conditions for the analysis of all of the preceding
nitrogen compounds (but with less resolution), N-nitros amines,
nitroso aromatics, nitro aromatics, aromatic nitriles, and aromatic
amines were:
1. Column: 3 feet x 1/8 in O.D. stainless steel tubing packed with
15 pet Carbowax 1540 plus 10 pet KOH on 80/100 mesh GC-22
2. Carrier: helium flowing at 52 cc/min
3. Temperature program: Hold at 35° C for 2 minutes, then program
at 6.5° C/min to 180° C
Molecular size for this column is limited to about CQ.
Chromatographic conditions for the analysis of cyanogen, hydrogen
cyanide, nitromethane, and acetonitrile were:
1. Column: 2-1/2 feet x 1/8 in O.D. stainless steel tubing packed
with Carbopack B treated with 3 to 4 drops of H^PO,
2. Carrier: helium flowing at 42-1/2 cc/min
3. Temperature program: -70° C for 6 minutes then 13° C/min to
180° C
Detection capability for the nitrogen analyses was provided by a
Coulson electrolytic conductivity cell. Nickel wire was used as the
reduction catalyst, the furnace temperature was 700° C, and the
hydrogen flow through the quartz catalyst tube was 17 cc/min. To
prevent moisture condensation, the conductivity cell was warmed by
heating tape from the furnace exit to the gas-water mixing chamber.
D. Emission Measurement—Methodology
Initially, all engines to be tested (both vehicle and stationary) were
adjusted to factory specifications. Engine parameters were then
periodically checked during the study and, in this case, were found
to remain very nearly constant. In additive testing, ignition timing
and dwell are independent of additive effects and should be kept con-
sistent throughout any series of tests. On the other hand, air-fuel
ratio and idle speed may be influenced by the action of an additive
upon carburetor and induction system deposits and, therefore, should
not be mechanically altered during a series of tests unless it can be
determined that a change in those parameters is due to some malfunction.
For mileage accumulation, the vehicles were put into "typical" user
service by assignment of the vehicles to BERC employees whose normal
routes consisted of about equal amounts of city and highway driving.
The stationary engines were operated repetitively over the LA-4 test
schedule in order to accumulate mileage. Prior to testing, each
vehicle was driven for 10 minutes at 50 mph to purge the charcoal can-
ister (evaporative loss trap), then immediately placed in a soak area
at about 75° F and allowed to stand overnight. Stationary engine test
preparation consisted of a shut-down period lasting at least five hours.
Exhaust was tested as the vehicles and engines were being operated
according to the LA-4 test schedule on chassis and stationary engine
dynamometers. A single CVS bag sample was collected at a constant rate
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for the duration of the test. The Roots blower in the CVS pumped a
nominal 330 cfm. This sample was analyzed for total HC, N02, NOX, CO,
C02, and individual hydrocarbon compounds. CO, HC, and NOX were cal-
culated in accordance with the Federal Register, Vol. 36, No. 128,
Friday, July 2, 1971, section 1201.87.
A test cycle for the engine or vehicle, includes a period of mileage
accumulation with additive-free fuel (4,000-5,000 miles) to establish
baseline emissions and a period of mileage accumulation with the fuel
plus additive to establish the effect, if any, of the additive upon
emission levels or trends. Four test cycles were completed with the
two stationary engines; each engine being tested with AK33X additive
at 0.125gMn per gallon fuel and F310 additive at 14.2 ml additive
plus carrier per gallon fuel. Mileage accumulation with additive-
containing fuel was 4,000-5,000 miles.
One test cycle was completed with each of three vehicles. After base-
line emissions were established (approximately 5,000 miles) one vehicle
was switched to fuel containing AK33X, F310 was added to the fuel for
the second vehicle, and the third vehicle remained on additive-free
fuel. Slightly more than 9,000 miles were accumulated with additive-
containing fuel.
As each test cycle was completed, each engine (both stationary and
vehicle) was disassembled and photographed. Samples of engine deposits
were taken and, when AK33X had been the additive used, the deposits
were analyzed for organic manganese. The oil from the engines and
vehicle using AK33X was also analyzed for organic manganese.
RESULTS AND DISCUSSION
A. Manganese Determination-Methodology Background
The primary objective of the study is to provide methodology which can
be applied to the determination of the effect of gasoline additives
upon emissions and the fate of the additive itself. While the method
for organic manganese analysis was developed specifically for this
program, the method (or modifications of the method) should be appli-
cable to the analysis of other organo-metallic compounds. As for in-
organic manganese analyses, atomic absorption methods are well
established for this and other metallic ions.
Chromosorb 102 was very effective as a sample collection medium.
Retention capability was high and recovery from the column was simple
and efficient. A collection efficiency check was made by applying
0.943 yg of CMT to the upstream end of the 4 in x 3/8 in O.D.
Chromosorb 102 column. After exposure to 275 liters of CVS exhaust
flowing at 12 liters/min, nearly 99 pet (0.932 yg) of the sample was
recovered by direct analysis of the acetone wash. A large variety of
porous polymers is commercially available. Stability and diverse
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physical and chemical properties (pore size, surface area, acid-base
properties, polarity, etc) make them likely candidates for application
to collection of other volatile organo-metallics.
In the early stages of method development, n-tridecane was added to
the recovered sample to minimize loss of the MCMT during evaporation.
No problems occured with small chromatographic injections, but when
the sample size was increased to 20 yl, the n-C-j^ caused MCMT peak
spreading. Chromatographic response, in terms of peak height, was
then dependent upon sample size as well as concentration. This problem
was circumvented by replacing n-C^3 with sec-butylbenzene. MCMT
evaporative loss with sec-butylbenzene was about 5 pet, but addition
of the internal standard (CMT) before the extraction process negates
work-up losses. One possible improvement to the method might be to
remove most of the moisture from the porous polymer column with a
dry nitrogen purge prior to recovery, wash the column with acetone
(or pentane), add the internal standard, evaporate to a small volume,
and inject a portion into the chromatograph.
The detection system (figure 1) for organic manganese analysis con-
sisted of a Beckman DU Spectrophotometer equipped with standard photo-
multiplier and flame attachments and the Spectral Energy Recording
Adapter (SERA) to allow transfer of the photomultiplier signal to a
strip chart recorder. The only modification to the system was inter-
change of the burner oxygen and fuel supply lines. Oxygen and fuel
supplied to the burner in this manner produce an exceptionally small
flame which, in turn, allows more precise optical focus by limiting
the volume in which the sample is oxidized. Chromatographic effluent
was fed to the flame through a heated line connected to the sample
capillary of the burner.
Nickel, iron, and chromium trifluoracetylacetonates have been chromato-
graphed and detected in this laboratory with the manganese instrumen-
tation. The less stable corresponding manganese chelate decomposed
within the chromatographic system. One consideration to be given with
respect to chromatographic flame emission analysis is that, although
the method may (in many instances) be made specific for the desired
element, the triple resonance line of manganese is relatively intense.
When coupled with the chromatograph as little as 10~H moles of
manganese can be detected with each injection. The sensitivity for
other elements may limit the usefulness of the method. Trace quanti-
ties of some elements, such as phosphorous and lead, are not suited
to detection by flame emission.
B. Manganese Determination—Test Results
Figure 3 shows the results of a typical analysis. It is apparent
from this chromatogram that; (1) only extremely high concentrations
of hydrocarbons are capable of producing interference (and then only
if they are eluted from the column with the internal standard or
desired compound), (2) peak quality is good, and (3) complete separa-
tion of the desired components is achieved. The peaks in the figure
represent 1.07 x 10~10 moles CMT (known quantity) and 3.79 x 10"11
-10-
-------
moles MCMT (calculated value). The sample was prepared according to
the procedure given previously and calculation back to the CVS
exhaust concentration gives a value of 5.10 x 10~^ ppb. Thus, the
gaseous sample stream concentration that is detectable by the method
is less than 2 x 10~^ ppb.
The procedure for manganese determination was developed early in
the program; therefore, the data for AK33X additive related materials
are complete. Figures 4A, 5A, and 6A show the manganese present in
the exhaust when AK33X is a fuel component. The organic manganese
(MCMT) maximum exhaust levels varied considerably for the two
stationary engines and the vehicle ranging from 1 yg/mile to 5 yg/mile.
Expressed in other terms, these values represent CVS exhaust concen-
trations of 1.40 x 10~2 ppb and 7.45 x 10~^ ppb, respectively. Up
to 0.042 percent of the MCMT consumed was emitted unaltered and no
organic fragments of the molecule were detectable in the exhaust.
Under similar conditions, Ethyl Corporation has previously reported
(4) considerably higher values. Engine characteristics, propor-
tional sampling, trapping methods, or the inability of the Ethyl
Corporation method to detect the organic molecule itself may have
been factors in the differences in the reported values; but the most
likely contributor was the exceptionally high concentration of manga-
nese (1.25 gMn/gal) in the fuel used for the Ethyl Corporation tests.
It is interesting to note, though not unlikely, that comparison of
figures 4 with 4A, 5 with 5A, and 6 with 6A show that changes in hydro-
carbon emission levels are generally accompanied by corresponding
changes in MCMT emission levels. Both hydrocarbon and MCMT emis-
sions were increasing at 4,000-5,000 miles with additive. The
stationary engine cycles were terminated at about this point. Con-
tinued mileage accumulation with the vehicle shows hydrocarbons and
MCMT decreasing somewhat to an apparent stabilization. The hydro-
carbon emission trend using AK33X additive is more easily recognizable
by direct comparison of the total hydrocarbon emissions to those using
clear fuel or F310 additive (figure 11). The values for figure 11
were taken from the detailed hydrocarbon analysis tables contained in
Appendix A.
Inorganic manganese emissions from the stationary engines, figures
5A and 6A, tend to increase along with the MCMT emissions. Figure 4A,
however, fails to indicate a trend for inorganic manganese emissions
from the vehicle. One possible explanation for this is the relatively
mild duty cycle of the stationary engines (repetitive Federal test
cycles) in comparison to the vehicle (user service). This assumption
was given credence by visual comparison of combustion chamber deposits
(to be discussed later in this report).
Manganese mass balance was low with an exhaust emission range of
4 to 30 percent of ingested material. Since the combustion efficiency
of MCMT was 99.4 pet or better, this is due largely to engine and
exhaust system retention of inorganic manganese. Intake manifold
deposits ranged from 4.2 pet to 5.7 pet manganese (only 0.03 pet or
less of this was MCMT). From 7.3 pet to 13.1 pet of the combustion
chamber deposits was manganese. Nonhomogeneity of particulates within
-11-
-------
• the CVS stream and losses within the CVS system could contribute to
erroneous values for the inorganic manganese actually emitted, but
program emphasis was not placed upon particulate sampling.
Engine lube oil used in conjunction with AK33X additive testing
was analyzed for MCMT content and found to range from 0.95 yg/ml to
2.68 yg/ml depending upon mileage accumulation and lube oil added
during the test cycle. Lack of test procedure information (MCMT
lube oil levels immediately before addition of make-up oil) prevents
quantitation of MCMT bypass, but estimates made from the levels
found in the oil indicate approximately 2 yg/mile. This is comparable
to the MCMT levels released to the atmosphere through the exhaust
system. Insofar as a potential health hazard is concerned, organic
manganese in the lube oil should be given special consideration for
two reasons: (1) it is retained by solution in a definite volume of
liquid as opposed to eventual dilution by diffusion in the atmosphere
and (2) lube oil is an efficient U.V. light filter which prevents
photochemical decomposition (there was no detectable difference
between fresh samples and those exposed to fluorescent lighting for
up to five months).
Periodic checks of the fuel confirmed that the manganese concentration
was within 15 pet of the desired level.
C. Nitrogen Compound Determination—Methodology Background
Isolation of the proposed nitrogen bearing compounds from exhaust
would be an awesome project within itself. Nonspecific detection
systems produce complex exhaust chromatograms in which not all compo-
nents appear individually, especially those present at low concen-
trations. The development of the chromatographic techniques for
analysis of these compounds was undertaken with this in mind.
Four types of detection systems with some degree of specificity were
available; electron capture, alkali flame ionization, microcoulometry,
and electrolytic conductivity. Electron capture was considered
primarily for confirmation of the presence of aromatic nitro compounds
and N-nitrosoamines, the latter to be accomplished by conversion to
nitramines with hydrogen peroxide and trifluoroacetic anhydride or
trifluoroacetic acid. With careful attention to parameter adjustments,
alkali flame ionization can be made to differentiate between most
organic nitrogen compounds and hydrocarbons with essentially complete
specificity. The response of nitrogen compounds to alkali flame, how-
ever, is not solely dependent upon the number of nitrogen atoms, but
also the molecular structure. Nitro compound and hydrogen cyanide
responses were comparatively small and ammonia failed to respond de-
tectably. The failure of ammonia .to respond led to experiments in which
ammonia was mixed with the carrier gas to reduce amine tailing. A
column packed with Ucon LB550X-KOH on Chromosorb W was being considered
at that time for amine separation and the effectiveness of ammonia in
the carrier was demonstrated, but detector specificity for nitrogen
-12-
-------
compounds as compared to hydrocarbons was decreased from complete to
about 10:1. Another characteristic of the alkali flame detector
which was considered in judging its applicability was its extreme
sensitivity to temperature and gas flow fluctuations.
The remaining two detectors are comparable in terms of nitrogen sensi-
tivity and selectivity. The selectivity is good for both, and both
respond to any nitrogen compound which is reduced to ammonia when
exposed to nickel catalyst in a hydrogen atmosphere at elevated temper-
atures. The Coulson electrolytic conductivity detector was chosen over
the Dohrmann microcoulometer because of its relative simplicity of
operation and maintenance. The electrolytic conductivity cell requires
no periodic cleaning, electrode maintenance, or electrolyte preparation;
up to the point of bubble formation within the electrode capillary,
hydrogen and carrier flows can be varied over a considerable range
without significant damage to peak quality or detector response; light
coke deposits can easily be removed from the nickel wire catalyst by
in situ treatment with oxygen; and the detector functions satisfactorily
with background signals up to about 4 mV. The cell water and/or water
conditioning resins must be changed periodically when the background
signal becomes excessive, but under normal conditions, this occurs
only after several weeks of continuous operation.
The variety of nitrogen compounds of interest was considered when
selecting materials for chromatographic columns. Liquid phases con-
taining nitrogen compounds were rejected a priori to minimize the
probability of excessive background signal and reduced peak signal due
to column bleed. The acid-base properties of the compounds to be
separated were considered as the principal factor in determining
chromatographic behavior. Several column materials and variations were
tested before those which performed acceptably for the entire spectrum
of compounds to be analyzed. Chromosorb 103 and several variations
of Carbowax-KOH combinations were tested for amine analysis. Porapak
Q, S, and QS, Carbosieve B, and Carbopack A were tested for hydrogen
cyanide analysis. The neutral compounds were found to give good qual-
ity chromatograms when separated by the columns prepared for analysis
of the basic or acidic components.
The nitrogen compound classes proposed for study were amines, pyridines,
N-nitrosoamines, and nitro compounds. Individual compounds included
were hydrogen cyanide and cyanogen. On first analysis, it appears that
the basic compounds (amines and pyridines) can be isolated from the
remaining compounds via salt formation with hydrochloric acid and
extraction of the neutral and acidic compounds. Further examination,
however, reveals that the neutral and acidic compounds become sensi-
tized, to various degrees, to hydrolysis upon addition of mineral acid.
Furthermore, hydrolysis of compounds containing the -C:N group produces
ammonium ion and N-nitrosoamines produce secondary amines; thus inter-
fering with the analysis of the basic compounds. At best, this method
of collection and/or isolation is applicable to the basic compounds,
and only then if consideration is given to the fact that some of the
analyzed components may be hydrolysis products of non-basic nitrogenous
compounds.
-13-
-------
Not only the wide range of physical properties (vapor pressure, solu-
bility, acid base character, etc.) but also the complex chemistry of
these nitrogen compounds is responsible for the difficulty in their
collection, recovery, and analysis. Common exhaust products with
which these compounds may react under favorable conditions include
water, nitrogen oxides (plus water), aldehydes, ketones, phenols,
and unsaturates. In addition, reactions may take place among the
nitrogen bearing species. Hydrogen cyanide may polymerize, nitroso
compounds may dimerize or react with aromatic amines, and ammonia or
amines add to nitriles under favorable conditions. The presence of
some nitrogen compounds enhances the reactivity of other nitrogen
compounds. For instance, ammonia enters into the addition of hydrogen
cyanide to aldehydes or ketones, and alkylamines or pyridines act as
condensing agents for nitroparaffins and aldehydes or ketones.
In light of the foregoing discussion, it is evident that (1) reactions
may proceed during sample collection and processing and (2) maintenance
of sample integrity during this period is likely to be difficult.
Initial efforts concerning sample collection were based on the idea of
class separation during sampling. A sample collection train was
constructed consisting of a wet cation exchange column, a wet anion
exchange column, and a cold trap at dry ice temperature. A methanol
scrubber at ice temperature was subsequently installed upstream from
the cold trap to prevent plugging by water freeze-out • The ion exchange
resins were wetted by water condensed from the sample stream. Hope-
fully, amines and pyridines would be retained by the cation exchange
column, hydrogen cyanide (and possibly nitroparaffins) retained by the
anion exchange column, and neutral compounds trapped by the cold solvent.
The system was tested by spiking an exhaust stream with the various
compounds. When practical, known quantities were injected; but the
purities of hydrogen cyanide, cyanogen, and N-nitrosoamines were not
known and only manufacturer estimates were available for the aqueous
solutions of light aliphatic amines. Recovery calculations were based
on the detector response to pyridine (known purity) and the number of
nitrogen atoms per molecule as well as detector response to equivalent
amounts of the individual compounds injected directly into the chromato-
graph. The system was partially successful. Amine and pyridine
recoveries from the cation exchange column were in the 50 to 75 percent
range with comparable nitrile and N-nitrosoamine recoveries from the
cold solvent scrubber. Minimum detection levels were estimated for
those compounds recoverable from this system. These levels for un-
diluted exhaust were:
1. Pyridine - 0.02 ppm
2. Aromatic amines - 0.02 ppm
3. C-j^-C^ aliphatic amines - 0.10 ppm
4. Nitriles - 0.30 ppm
5. C2~^4 N-nitrosoamines - 0.15 ppm
These figures are only estimates since the efficiency of the system and
test repeatability were not considered to be adequate. Hydrogen
cyanide, cyanogen, and nitroparaffins were, for practical purposes,
-14-
-------
lost; however, the chromatographic technique for these compounds had
not yet been fully developed.
Methanol alone cannot be used as a solvent for scrubbing the sample
stream. Chromatograms of a methanol solution of the various nitrogen
compounds gave peaks which did not correspond to any of the individual
compounds. Some of these unidentified peaks diminished or grew upon
standing, giving evidence of slow, continuing reactions within the
solution. Water solutions of formic and acetic acid were also checked
for potential as scrubber solutions, but experimentation indicated
that the basic nitrogen compounds could not be concentrated by evapora-
tion and recovered in the original form.
All of the previously discussed sample collection techniques failed
to establish the presence of nitrogen bearing compounds (other than
NOX) in auto exhaust even with F310 additive present in the fuel.
This is not surprising since testing with synthetic samples gave evi-
dence that none of the techniques were sufficiently quantitative or
repeatable.
At this point, a different approach was taken in an effort to demon-
strate the presence or absence of the nitrogen compounds in exhaust
at some detectable limit that could be established with a reasonable
degree of confidence. Direct chromatographic injection of the exhaust
(discussed in the Experimental Procedures Section of this report) pro-
vides a means to obtain an exhaust component profile that is least
likely to be altered from the true composition. No intermediate
sampling or recovery steps are involved with this technique, and the
chromatographic response can be related directly back to the exhaust
concentration. Even with this simple introduction system, some pre-
cautions are essential. Separate, preconditioned syringes and sample
loops are necessary for acidic or basic component analysis. For
instance, total loss of small amounts of ammonia results for subsequent
injection into the sample loop used for hydrogen cyanide analysis.
The chromatographic system for the analysis of nitrogen compounds is
illustrated in figure 2. The Coulson electrolytic conductivity.
detector was calibrated with known quantities of pyridine and the
response found to be very nearly 5 x 10~10 nitrogen atom per millivolt.
Operating at 4 mV full scale the noise level is slightly less .than one
division (0.04 mV). Considering the detection limit to be twice the
noise level, 4 x 10"^ nitrogen atom becomes the limit. With a 25 cc
sample loop, this converts to 0.04 ppm nitrogen atom in the diluted
(CVS) exhaust. This is up to twenty times less sensitive than the
estimated detection limits for the sampling train collection technique,
but the reliability of direct, gaseous sampling tends to compensate
for this loss. Results of CVS exhaust analyses by direct injection
were:
-15-
-------
1. HCN - 1.0-1.5 ppm found and confirmed.
2. CH3N02 - 0.2-0.3 ppm found and confirmed.
3. NCCN - trace possible but presence not confirmed.
4. CHgCN - trace possible but low levels are rapidly destroyed
by exhaust.
5. NH3 - possible exhaust component but interference peak prevented
definite identification.
Nitrogen compounds either not present or present at levels below
0.04 ppm include:
1. Aliphatic and aromatic amines
2. Pyridine
3. €3 and larger aliphatic and aromatic nitriles
4. G£ and larger aliphatic and aromatic nitro compounds
5. C2~C^ N-nitrosoamines
Hydrogen cyanide and nitromethane consistently appear in exhaust
chromatograms regardless of the presence of F310 additive in the fuel.
Though relatively stable in exhaust, the appearance of cyanogen was
intermittent and could be due to sample syringe hold-over from
previous analysis of synthetics. This is also true of acetonitrile,
but experimental evidence shows this compound to be unstable in
exhaust as well. Vapor samples give a chromatographic peak near the
retention time of ammonia even in the absence of the compound, thus
small quantities could be present and remain hidden. No chromatographic
peaks appeared corresponding to any of the remaining nitrogen compounds,
so, if present, their exhaust concentrations were below the detection
limit.
Chromatography of the basic nitrogen compounds is illustrated in
figures 12 and 13. Amines and pyridine were separated to show peak
quality. Approximate locations are indicated for other amines and
compounds representative of the neutral classes which are eluted from
these columns. Vapor samples injected downstream from the column have
shown that the major portion of the tailing effect takes place within
the detector rather than the column. Figures 14 and 15 are chromato-
grams of synthetic and exhaust components, respectively, which are
eluted from the Carbopack B-^PC-A column. For figure 15A, 25 cc of
gaseous sample was drawn from the sample line and immediately injected
into the chromatograph. Samples for figures 15B, 15C, and 15D were
taken from a single CVS cold-start bag after aging 1 hour, 1.5 hours,
and 2 hours in the absence of light. Comparison of the exhaust
chromatograms can leave little doubt that there is continuous sample
deterioration. With age, hydrogen cyanide decreases and nitromethane
decreases and/or is swamped by a growing peak. Peak A diminishes with
time and peaks B, C, D, E, and F appear and grow at various times and
rates. Little effort was directed toward identification of the
lettered peaks, but oxides of nitrogen are eluted in areas A-B and
E-F giving responses similar to those of the aged exhaust sample.
-16-
-------
D. Nitrogen Compound Determination—Test Results
The methodology for nitrogen compound analysis was not adequately
developed in time to obtain meaningful data pertinent to the effect
of F310 additive on nitrogenous emissions.
Routine emission measurements, however, failed to show any trends
that might be attributable to the presence of F310 additive in the
fuel (figures 7, 8, and 10).
ENGINE DEPOSITS
A. Induction System
1. Carburetor
Carburetor throats and bases were examined for deposit buildup.
The deposits were found to be almost equally independent of fuel
additive or duty cycle. Deposits on the carburetor bases are,
as well as the following items, shown pictorally in Appendix B.
2. Intake Manifold Passages
The deposits were generally equal in amount from both additives
in the stationary engines. The F310 additive resulted In softer
tar-like deposits in the intake passages of the stationary engines
compared to more crusty deposits resulting from all other engine
and vehicle conditions. The clear fueled vehicle contained more
deposits in the intake passages than did the other vehicles or
engines. The F310 additive vehicle produced unusually clean in-
take passages as compared to those of the other two vehicles or the
stationary engines even after F310 use. This suggests that the
cleaning ability of the additive is dependent upon duty cycle.
It is reasonable to postulate that the higher air flow and turbu-
lence in the intake manifold associated with the more severe duty
of the vehicle would lead to cleaner surfaces provided the deposits
produced were comparable in consistency to those produced by the
lighter duty cycle.
3. Intake Valves
The intake valve stems had considerably less deposits in both
vehicles and engines using the F310 than the clear or AK33X
additive, independent of duty cycle. In addition the deposit
material was generally softer and more pliable using the F310.
The vehicle using the clear fuel produced the greatest amount of
valve stem deposit.
-17-
-------
B. Combustion Chamber
1. Piston Heads
Deposits produced on the piston heads while using the F310 were
generally heavier in amount and more flaky in composition than
the other conditions. The AK33X produced deposits that were very
fine, almost powdery in composition while the clear fuel resulted
in deposit composition intermediate between the two. Deposits
from the F310 and clear tests were similar in color with a typical
black-grey color. In contrast, the deposits produced from the
AK33X were an unusual reddish-tan color. The color was character-
istic of the combustion chamber surfaces when AK33X was used
independent of engine or vehicle duty cycle. Some color photo-
graphs are included in Appendix B to show the characteristic color
associated with the AK33X additive.
2. Engine Head
Deposits on the engine heads were similar in amounts and compo-
sition to deposits on the piston heads just described; the major
exception being extremely white deposits on the exhaust valve
face of the stationary engines which used F310. This effect was
present but much less pronounced with the vehicles than with the
engines suggesting a duty effect.
3. Spark Plugs
Spark plug deposits from the AK33X fuel again showed the charac-
teristic reddish color and, in addition, on one stationary
engine the deposits were so great that the spark gap was being
bridged. The deposits were still very soft and fine. The vehicle
using AK33X did not have nearly so great a quantity of plug
deposits as the engine, also the second engine test with the AK33X
additive resulted in less plug deposits than the first test.
Undoubtedly the duty cycle has a great effect on plug deposits
using the AK33X additive. The plug deposits from tests other than
those using AK33X were similar in color and composition.
4. Exhaust Valve Stems
Deposits on all the exhaust valve stems were similar in amounts
and composition. The reddish color continued on the exhaust valves
using the AK33X, while the valves of the engine using F310 exhibited
a pronounced white color. The white color, however, was not present
on the valve stems of the vehicle using F310.
-18-
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CONCLUSIONS
The methodology for control and management of the vehicles and engines, pretest
preparation, test operation, and sampling for routine exhaust measurements is
discussed in detail in the Emission Measurement section of this report. This
methodology was selected on the basis of previous knowledge and experience prior
to this study and is, therefore, not a product of the study. While the investi-
gators feel that the procedures are applicable to gasoline additive testing,
they should not be considered as procedural recommendations.
Two analytical methods were developed, with varied degrees of success, for the
study. The method for specific analysis of the MCMT molecule was successful
with a detection capability at the 10~^ ppb level in vapor samples. Up to
0.042 percent of the antiknock compound in AK33X additive was found to survive
the combustion process and exhaust emissions were in the 1 to 5 yg/mile range.
The analytical method for exhaust nitrogen compounds was only partially success-
ful and was not developed early enough to determine if F310 additive had any
effect upon exhaust emissions. For vapor samples, the detection capability of
the technique described in this report is 0.04 ppm nitrogen atom. Hydrogen
cyanide at 1.0 to 1.5 ppm and nitromethane at 0.2 to 0.3 ppm were found in CVS
exhaust samples. Traces of cyanogen and acetonitrile were indicated but not
firmly established. Continuous sample deterioration with respect to nitrogen
compounds was illustrated by consecutive analyses of an aging exhaust sample.
Tests with AK33X additive gave the following results:
1. No organic fragments of the MCMT molecule were found in the exhaust.
2. MCMT in the exhaust increased with mileage for the first 4,000 to
5,000 miles then decreased somewhat to a stable level.
3. Generally, changes in MCMT exhaust level were accompanied by corre-
sponding changes (in the same direction) in hydrocarbon level.
4. MCMT levels in the lube oil ranged from 0.95 yg/mile to 2.68 yg/mile;
UV light filtration by the oil prevented photochemical decomposition.
5. With a mild duty cycle, inorganic manganese emissions gradually in-
creased with mileage (at least for the first 5,000 miles); there was essentially
no change upon mileage accumulation with a more severe duty cycle.
6. Manganese mass balances were low (4 to 30 pet); deposit analysis showed
that much of the manganese was retained by the engine.
No test results were obtained for exhaust nitrogen compounds, but routine emis-
sion measurements gave no indication of trends that might be attributable to
the presence of F310 additive in the fuel.
The effect of duty cycle upon engine deposits was indicated by:
1. Exceptionally clean intake manifold passages using F310 additive with
the vehicle (more severe duty cycle)•
2. Exceptionally white deposits on the exhaust valve faces using F310
additive with the stationary engines (mild duty cycle).
3. Heavy spark plug deposits using AK33X with the stationary engines
(mild duty cycle).
-19-
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REFERENCES
1. Dimitriades, B., and D. E. Seizinger. A Procedure for Routine Use in
Chromatographic Analysis of Automotive Hydrocarbon Emissions. Environ-
mental Science and Technology, v. 5, No. 3, March 1971, pp. 223-229.
2. Dimitriades, B., C. J. Raible, and C. A.-Wilson. Interpretation of Gas
Chromatographic Spectra in Routine Analysis of Exhaust Hydrocarbons.
Bureau of Mines Report of Investigations No. 7700, 1972, 19 pp.
3. Coordinating Research Council, Inc. Oxygenates in Automotive Exhaust Gas:
Part I. Techniques for Determining Aldehydes by the MBTH Method. Report
No. 415, June 1968, 21 pp.
A. Brandt, M., et al. Information for the National Research Council Con-
cerning Methylcyclopentadienyl Manganese Tricarbonyl. Ethyl Corporation
communication, September 8, 1972.
-20-
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I
NJ
Helium-
Oxygen
Hydrogen
Chromotograph
Burner
Beckmon Model DV
Spectrophotometer
Spectral
energy
recording
adopter
Recorder
FIGURE I.-The detection system for organic manganese analysis.
-------
I
r-O
Helium
Hydrogen
D.C. Bridge Conductivety cell / Furonce
Scrubber
Coulson electrolytic conductivety detector
FIGURE 2.-Chromotographic system for analysis of nitrogen compounds.
-------
80
70
60
50
40
o
6
I
O
o
in
30
20
10
10
6 4
TIME, mi nutes
FIGURE 3.-Exhaust analysis for MCMT.
-23-
-------
AK 33X additive
. I25g Mn/gal
2,000
4,000
6,000 8,000
MILES
10,000
12,000
14,000
FIGURE 4.-Effect of mileage accumulation on exhaust emissions
AK 33X vehicle .
'i 3
10
E
Inorganic Mnx
Organic Mn x
Clear fuel
AK 33X additive
.I25g Mn/gal -
2,000
4,000
6,000 8,000
MILES
I 0,000
12,000 14,000
FIGURE 4A.-Effect of mileage accumulation on manganese
emissions AK33X vehicle.
-24-
-------
E
o
i 2
UJ
Clear fuel
AK33X additive
.I25g Mn/gal
I
I
2,000
4,000 6,000
MILES
8,000
10,000
FIGURE 5.-Effect of mileage accumulation on exhaust emissions
stationary engine A with AK33X .
£
o
* 2
in
—
5
UJ
Clear fuel
KEY
AK33X additive
. 125 g Mn/gal
I Inorganic Mn x I03
Organic Mn x I06
2,000
4,000 6,000
MIL ES
8,000
10,000
FIGURE 5A.-Effect of mileage accumulation on manganese emissions
stationary engine A with AK33X .
-25-
-------
o>
.n"3
z
o
CO x 10
Clear fuel
AK 33 X additive
.I25g Mn/gal
2,000
4,000 6,000
MIL ES
8,000
10,000
FIGURE 6.-Effect of mileage accumulation on exhaust emissions
stationary engine B with AK33X .
0>
E
E
o
o>
- 2
w
•z.
o
(/)
Clear fuel
AK 33X additive
.I25g Mn/gol
KEY
• Inorganic Mn x I03
• Organic Mn x 10^
2,000
4,000 6,000
MILES
8,000
10,000
FIGURE 6A.-Effect of mileage accumulation on manganese emissions
stationary engine B with AK33X.
-26-
-------
V
•- 4
E
o
O
HC
Cleor fuel
F3IO additive
14.2 ml/gal
Hive I
gal 1
2,000
4,000 6,000
MILES
8,000
10,000
FIGURE 7.-Effect of mileage accumulation on exhaust emissions
stationary engine A with F3IO.
~ 4
z
o
to
in
UJ
HC
Clear fueI
F 310 additive
' 14.2 ml/gal ~
2,000
4,000 6,000
MILES
8,000
10,000
FIGURE 8.-Effect of mileage accumulation on exhaust emissions
stationary engine B with F3IO.
-27-
-------
6
o
o>
. 4
V)
z
o
V) -i
Clear f ue I
2,000 4,000 6,000 8,000 10,000
MILES
IZ.OOO 14,000
FIGURE 9.-Effect of mileage accumulation on exhaust emissions
control vehicle.
COx 10
in
Z
O
C lea r f ue I
F 310 additive
14.2 ml/gal
2,000 4,000 6,000 8,000 10,000
MILES
12,000 14,000
FIGURE lO.-Effect of mileage accumulation on exhaust emissions
F 310 vehicle ,
-28-
-------
280
260 —
140
2,000
4,000 6,000
MILES WITH ADDITIVE
8,000
10,000
175
150
o 125
JC.
X
0}
en
o
o 100
E
75
50
Stationary engine A
F3IO
175
150
125
100
75
50
Stationary engine B
AK33X
F 310
'0 1,000 2,000 3,000 4,000 5,000 0 1,000 2,000 3,000 4,000 5,000
MILES WITH ADDITIVE
FIGURE 11.-Total CVS exhaust hydrocarbons by GLC .
-29-
-------
20
3 feet Carbowax-KOH
Carrier: He, 52 cc/minute
Initial temperature: 35*C for 6minutes
Final temperature : I80°C
Temperature prog ram ;6.5°C/minute
• Indicated retention time
*f, 5
M
r
u Z
~o T
| " 0
5
|,
in
0
10
O
z
z
CJ
"?>
X
(J
0
z
z
CJ
in
-------
100
80
60
40
20
0
100
BO
60
40
20
HCN
Fresh sample
CH3N02
Jl
I
©
Bag sample
10 15
TIME, minutes
FIGURE 15.- Chroma tog ram for acidic and neutral nitrogen compounds, CVS
exhaust, .04 mV/division .
-31-
-------
APPENDIX A.--TABULATED DATA
-32-
-------
TABLE A-l. - Detailed Hydrocarbon Analysts
Accumulated mileage..
Fuel
Peak
No, Compound
Is b a
isobut lene
14 n-Pentane, 2-tnethyl-l-butene.
18 Cyclopentane, 3-methyl-l-
20 2-Methylpentane,
2,3~dimethyl-l-butene
22 1-Hexene, 2-ethyl-l-butene. . .
24 Methylcyclopentane,
3-methyltrana-2-pentene. . . .
27 Cyclohexene,
2t3-dlmethylpentane,
32 2,4-Dimethylhexane,
35 Toluene, 2 ,3-dimethylhexane. .
41 2,5-Ditnethylheptane,
- y
py ib
1 " ' y Vib
50 sec-Butylbenzene, £-decane...
4,750
Indolene + F-310
CVS
exhaust
17.39
19.95
2.54
23.45
12.46
.81
6.64
4.61
.98
1.20
.28
3.46
.16
1.59
.58
.24
1.16
.13
1.23
1.33
.72
.13
.69
.70
1.44
9.84
2.94
.99
7.59
.84
.44
2.32
3.09
3.48
29.71
2.28
1.21
1.58
.32
.18
.13
2.46
5.92
3.56
.31
1.89
.84
.75
3.82
.42
CVS
exhaust
with
scrubber
17.39
2.54
.11
.21
2.24
3.46
1.08
.08
1.23
1.22
.74
.67
.53
1.40
.19
2.10
.81
7.44
.67
.34
2.38
3.05
3.48
1.07
.62
.52
1.24
.27
.14
.12
.06
.13
.18
.02
.15
.07
.17
.14
F-310 Vehicle. DDmC
6,070
Indolene+ F-310
CVS
exhaust
16.56
15.77
1.94
19.96
8.63
.29
4.94
2.67
.61
.75
.12
1.77
.09
.89
.34
.14
.73
.07
.62
.69
.38
.06
.35
.39
.77
7.78
1.40
.47
3.72
.37
.19
1.27
1.45
1.63
21.25
.68
.85
.16
.07
.04
1.65
4.29
2.56
.22
1.40
.63
.54
3.63
CVS
exhaust
with
scrubber
16.56
1.94
.14
.10
1.01
1.77
.53
.04
.62
.63
.40
.36
.27
.68
.15
1.06
.41
3.72
.32
.17
1.22
1.46
1.63
.51
.31
.26
.63
.13
.07
.08
.04
.08
.12
.01
.03
.10
.11
.09
7,420
EPA + F-310
CVS
exhaust
12.81
18.88
1.67
18.24
9.61
4.85
3.49
.79
.96
.38
2.99
.25
2.39
.34
.19
.52
4.26
.44
.69
.38
.40
.26
.37
.40
6.37
2.62
.57
4.57
.82
.44
.96
.50
.39
18.81
2.16
1.44
.36
.90
.12
.31
1.67
4.83
2.72
.24
1.33
.54
.53
2.45
.68
CVS
exhaust
with
scrubber
12.81
1.67
.15
.07
1.81
2.99
2.25
5.08
.44
.43
.22
.15
.15
.17
.02
2.07
.38
4.57
.53
.25
.80
.61
.39
.33
.92
.95
.24
.68
.02
.16
.06
.32
.04
.07
.09
8,550
EPA + F-310
CVS
exhaust
12.95
18.12
1.53
18.11
9.20
.97
4.63
4.26
.77
.93
.34
3.92
.25
3.12
.36
.20
.52
5.25
.51
.78
.40
.40
.26
.39
.32
5.52
3.15
.60
5.63
.89
.48
.97
.48
.25
19.32
2.40
1.55
.20
.85
.06
.20
1.46
4.72
2.35
.16
1.11
.47
.43
1.69
.49
CVS
exhaust
with
scrubber
12.95
1.53
.07
.10
2.50
3.92
3.01
5.66
.51
.53
.31
.21
.17
.14
.04
2.71
.49
5.63
.67
.34
.92
.47
.25
.30
.97
1.01
.07
.68
.02
.19
.10
.35
.04
.06
.07
9,150
EPA+ F-310
CVS
exhaust
12.76
17.88
1.59
16.70
7.41
.32
4.37
3.81
.52
.42
.05
3.54
.10
2.90
.25
.09
.36
5.76
.40
.47
.20
.15
.16
.26
.15
5.38
3.63
.67
6.88
1.31
.57
1.23
.63
.32
21.40
2.95
1.94
.23
1.10
.07
.27
1.61
5.28
2.56
.20
1.26
.10
.52
1.91
.53
CVS
exhaust
with
scrubber
12.76
1.59
.32
.16
2.26
3.54
2.78
5,01
.40
.43
.27
.23
.18
. .18
.04
3.23
.59
6.88
.87
.44
1.21
.64
.32
.39
1.20
1.28
.10
.97
.06
.30
.17
.49
.06
.08
.02
.12
*Total hydrocarbons by GC 205.70 144.90 160.65 157.19 156.35
Includes exhaust hydrocarbons not reported in detailed analysis.
-33-
-------
TABLE A-l. - Detailed Hydrocarbon Analysis
F-310 Vehicle. ppmC--Continued
Accumulated mileage... 9
Fuel EPA-
CVS
Peak exhaust
No. Compound
1 Methane 12.91
2 Ethylene 18.40
3 Ethane 1.59
4 Acetylene 18.27
5 Propylene, propane 9.57
6 Isobutane
7 Butene-l, Isobutylene 4.86
8 n-Butane, 1,3-butadlene 3.93
9 trans-2-Butene .75
10 c_l£-2-Butene 1.05
11 3-Methyl-l-butene .40
12 Isopentane 3.05
13 Pentene-1 .07
14 n-Pentane, 2-roethyl-l-butene 2.71
15 trans-2-Pentene .23
16 c_is-2-Pentene .09
17 2-Methyl-2-butene .36
18 Cyclopentane, 3-methyl-l-
pentene 5.51
19 2,3-Dimethylbutane .36
20 2-Methylpentane,
2,3-dlmethyl-l-butene .41
21 3-Methylpentane .17
22 1-Hexene, 2-ethyl-l-butene.. .12
23 n-Hexane, cls-3-hexene .16
24 Methylcyclopentane,
3-methyltrans-2-pentene... .25
25 2,4-Dlmethylpentane .09
26 Benzene, cyclohexane 6.06
27 Cyclohexene,
2,3-dimethy Ipentane,
2-tnethylhexane 3.71
28 3-Methylhexane .70
29 Isooctane 6.73
30 n-Heptane .98
31 Methylcyclohexane .53
32 2,4-Dlmethylhexane,
2,5-dimethylhexane 1.16
33 2,3,4-Trtmethylpentane .59
34 2,3,3-Trimethylpentane .29
35 Toluene, 2,3-dimethylhexane. 22.54
36 2-Methylheptane 2.55
37 3-Methylheptane 1-69
38 2,2,5-Trimethylhexane .19
39 n-Octane -98
40 2,3,5-Trlmethylhexane .06
41 2,5-Dimethylheptane,
3,5-dimethylheptane .23
42 Ethylbenzene 1.66
43 £-Xylene, m-xylene 5.47
44 o-Xylene 2-65
45 n-Propylbenzene -18
46 l-Methyl-3-ethylbenzene 1-33
47 l-Methyl-2-ethylbenzene .52
48 Mesltylene -45
49 1,2,4-Trimethylbenzene 1.76
50 sec-Butylbenzene, ii-decane.. .^7
CVS
exhaust
with
scrubber
CVS •
sxhaust
CVS
exhaust
with
scrubber
EPA + F-310
CVS
exhaust
CVS
exhaust
with
scrubber
CVS
exhaust
CVS
exhaust
with
scrubber
CVS
exhaust
CVS
exhaust
with
scrubber
12.91
.20
.10
3.05
2.43
4.53
.36
.37
.21
.16
.14
.12
.04
3.19
.59
6.73
.84
.43
1.16
.59
.29
,36
1.15
1.20
.09
.87
.04
.29
.14
.45
.01
.06
.08
.02
.11
13.65
18.64
1.57
18.90
8.08
4.87
3.84
.41
.44
.04
3.41
.10
2.93
.21
.08
.35
5.58
.32
.34
.15
.12
.15
.20
.10
6.35
3.15
.57
5.96
.82
.43
.99
.50
.19
21.75
2.19
1.43
.31
.81
.01
.15
1.60
5.36
2.58
.11
1.22
.49
.41
1.86
.39
13.65
.42
.40
5.07
.32
.28
.16
.11
.08
.45
2.89
.52
5.96
.69
.36
.95
.50
.19
.28
1.09
1.09
.11
.76
.01
.19
.09
.41
.15
.08
.07
.09
11.85
16.81
1.52
16.99
7.96
.67
4.20
4.29
.60
.73
.14
4.10
.13
3.29
.26
.12
.40
6.24
.43
.51
.23
.17
.16
.20
.09
5.15
3.32
.60
6.37
.87
.47
1.08
.56
.25
20.52
2.54
1.67
.16
.96
.04
.21
1.54
5.51
2.52
.15
1.46
.57
.48
1.89
.44
11.85
.13
.10
3.19
5.57
.43
.42
.22
.14
.11
.04
3.09
.55
6.37
.78
.41
1.03
.57
.25
.30
1.02
1.07
.07
.79
.03
.26
1.27
.44
.19
.11
.11
9.84
15.00
1.32
13.67
7.73
4.06
3.37
.39
.75
.07
3.31
.14
2.92
.27
.16
.41
5.61
.37
.40
.26
.20
.24
.29
.19
4.98
3.43
.66
6.72
1.04
.53
1.19
.63
.33
20.73
2.02
1.58
.15
.96
.07
.29
1.66
5.33
2.52
.26
1.29
.53
.55
1.65
.26
9.84
1.32
.19
.09
1.93
3.31
2.67
5.24
.37
.39
.18
.17
.15
.05
3.19
.59
6.72
.86
.44
1.00
.61
.33
•4?
1.40
1.37
.10
.87
.04
.28
.13
.44
.17
.10
.11
10.15
17.69
1.59
15.84
9.03
4.76
4.07
.67
.98
.29
3.80
.17
3.27
.28
.16
.47
6.33
.47
.49
.34
.29
.25
.34
.22
5.31
3.76
.68
7.18
1.07
.56
1.21
.61
.30
23.02
2.69
1.78
.19
1.00
.06
.25
1.78
5.68
2.76
.23
1.44
.54
.46
1.91
.55
10.15
1.59
.09
.09
2.20
3.80
3.06
.5.50
.47
.51
.33
.22
.20
.05
3.51
.66
7.18
.96
.50
1.17
.63
.30
.36
1.14
1.12
.09
.82
.03
.25
.16
.45
.04
.22
.13
.15
.13
*Total hydrocarbons by GC.
163.61
153.27
166.86
* Includes exhaust hydrocarbons not reported in detailed analysis.
-34-
-------
TABLE A-2. - Detailed Hydrocarbon Analysis
Accumulated mileage..
Fuel
Peak
No. Compound
3 Ethane
8 n-Butane, 1,3-butadiene
9 trans-2-Butene
14 n-Pentane, 2-methyl-l-butene
15 trans-2-Pentene
18 Cyclopentane, 3-methyl-l-
20 2-Methylpentane,
2,3-dimethyl-l-butene
22 1-Hexene, 2-ethyl-l-butene. .
24 Methylcyclopentane,
3-methyltrans-2-pentene. . .
27 Cyclohexene,
2 , 3-dltnethylpentane ,
32 2,4-Dltnethylhexane,
35 Toluene, 2 ,3-dimethylhexane.
41 2,5-Dtmethylheptane,
47 l-Methyl-2-ethylbenzene
50 sec-Butylbenzene, n-decane..
4,740
Indolene + AK33X
CVS
exhaust
17.49
19.75
2.50
24.75
12.77
1.21
6.25
5.26
1.08
1.45
.36
3.98
.22
1.77
.61
.28
1.17
.19
1.31
1.48
.85
.21
.75
.73
1.40
9.61
2.59
1.04
7.09
.76
.38
2.11
2.87
3.22
28.32
2.12
1.15
1.46
.28
.14
.08
2.39
6.06
3.68
.37
2.13
.98
.87
4.40
.50
CVS
exhaust
with
scrubber
17.49
2.50
.14
.29
2.93
3.98
1.22
.09
1.31
1.28
.82
.75
.53
1.32
.19
1.99
.78
7.09
.62
.30
2.20
2.89
3.22
.95
.55
.40
1.04
.21
.13
.11
.06
.13
.20
.09
.24
.12
.28
.22
AK33X Vehicle. ppmC
5,305
Indolene + AK33X
CVS
exhaust
17.10
19.02
2.55
23.31
12.39
1.20
6.27
4.40
1.04
1.51
.46
2.91
.14
1.40
.46
.21
1.01
.13
.98
1.12
.63
.14
.57
.55
1.06
8.78
2.00
.68
5.56
.56
.28
1.66
2.24
2.48
25.18
1.63
.84
1.15
.24
.13
.10
2.30
5.43
3.31
.38
2.00
.90
.82
4.18
.57
CVS
exhaust
with
scrubber
17.10
2.55
.15
.25
2.10
2.91
.95
.07
.98
1.01
.66
.62
.44
1.11
.17
1.52
.60
5.56
.54
.27
1.74
2.16
2.48
.78
.46
.38
.90
.21
.11
.09
.05
.11
.16
.01
.03
.13
.06
.13
.11
7.170
EPA-f AK33X
CVS
exhaust
14.61
23.32
2.27
21.47
12.32
6.40
5.03
.88
1.44
.43
4.15
.32
3.28
.45
.27
.70
5.29
.60
.60
.52
.47
.36
.50
.49
7.46
3.15
.64
5.59
.74
.37
1.06
.67
.48
24.09
2.11
1.33
.36
.76
.06
.19
2.02
5.87
3.20
.17
1.48
.63
.53
2.54
.60
CVS
exhaust
with
scrubber
14.61
2.27
.18
.13
2.65
4.15
2.99
5.37
.60
.59
.28
.25
.22
.30
.05
2.43
.50
5.59
.67
.31
1.03
.64
.48
.36
.80
.81
.27
.59
.02
.15
.01
.30
.04
.08
.03
.12
8.030
EPA + AK33X
CVS
exhaust
16.01
24.35
2.40
23.95
11.05
6.36
4.78
.68
.68
.07
4.50
.14
3.69
.36
.15
.58
6.73,
.63
.69
.31
.15
.28
.36
.33
8.08
4.17
.84
8.47
1.17
.60
1.60
1.07
.79
29.85
3.21
2.03
.54
1.12
.07
.25
2.40
7.42
3.77
.24
2.16
.80
.76
2.95
.64
CVS
exhaust
with
scrubber
16.01
2.40
.15
.13
2.32
4.50
3.43
5.88
.63
.63
.37
.34
.31
.38
.09
3.78
.77
8.47
1.02
.50
1.60
1.06
.79
.52
1.24
1.29
.41
.93
.05
.25
.10
.46
.01
.06
.13
.01
.03
.13
9.434
EPA + AK33X
CVS
exhaust
18.07
28.45
2.76
27.36
14.82
7.74
7.08
1.07
1.67
.50
6.88
.40
5.73
.59
.34
.83
10.65
.85
1.28
.71
.59
.51
.71
.55
8.40
5.92
1.23
11.08
1.70
.90
1.94
.96
.48
35.69
4.09
2.74
.30
1.60
.10
.40
2.93
9.22
4.41
.33
2.31
.94
.84
3.21
.80
CVS
exhaust
with
scrubber
18.07
2.76
.24
.21
4.19
6.88
5.50
10.31
.85
.94
.54
.48
.40
.34
.12
5.40
1.06
11.08
1.48
.74
1.92
.96
.48
.59
1.93
2.06
.16
1.53
.09
.49
.39
.82
.12
.10
.19
.28
.26
*Total hydrocarbons by CO.... 212.42 191.64 190.29 210.72 271.80
Includes exhaust hydrocarbons not reported in detatled analysis.
-35-
-------
TABLE A-2. - Deta11ed Hydrocarbon Analys is
Accumulated mileage...
Fuel
Peak
No . Compound
3 Ethane
8 n_-Butane, 1,3-butadtene
lit n-Pentane, 2-methyl-l-butene
17 2-Methyl-2-butene
18 Cyclopentane, 3-methyl-l-
20 2-Methylpentane,
22 1-Hexene, 2-ethyl-l-butene. .
24 Methylcyclopentane,
3-methyltran8-2-pentene. . .
26 Benzene, cyclohexane
27 Cyclohexene,
2,3-dimethylpentane,
32 2,4-Dlmethylhexane,
35 Toluene, 2,3-dtmethylhexane.
41 2,5-Dimethylheptane,
44 o-Xylene
46 l-Methyl-3-ethylbenzene
47 l-Methyl-2-ethylbenzene
49 1,2,4-Trlmethylbenzene
50 sec-Butylbenzene, n_-decane..
10.353
EPA + AK33X
CVS
exhaust
15.90
31.22
3.09
26.87
16.05
1.46
8.40
6.70
1.15
1.66
.30
5.45
.28
4.57
.47
.23
.65.
8.24
.59
.78
.37
.27
.29
.35
.17
9.00
4.38
.87
8.18
1.26
.65
1.26
.64
.30
32.29
3.54
2.25
.65
1.27
.08
.31
2.80
8.31
4.25
.31
2.29
.86
.77
3.52
.81
CVS
Exhaust
with
scrubber
15.90
3.09
.53
.48
3.54
5.45
4.29
7.72
.59
.64
.34
.30
.26
.21
.07
3.96
.78
8.18
1.11
.58
1.23
.64
.30
.39
1.27
1.35
.25
.94
.03
.25
.16
.47
.18
.09
.10
.10
AK33X Vehicle, ppmC--Continued
11,390
EPA+ AK33X
CVS
exhaust
17.01
26.91
3.02
22.25
14.17
7.38
5.32
.95
1.47
.33
3.90
.15
3.70
.31
.13
.49
6.91
.45
.56
.24
.15
.25
.32
.14
7.92
4.09
.85
. 7.43
1.13
.59
1.17
.59
.28
29.44
3.12
2.02
.21
1.14
.07
.27
2.56
7.55
3.87
.25
2.09
.76
.65
2.79
.67
CVS
Exhaust
with
scrubber
17.01
3.02
.36
.13
2.13
3.90
3.17
6.22
.45
.51
.26
.24
.21
.14
.08
3.61
.72
7.43
1.00
.51
1.16
.60
.28
.35
1.19
1.28
.10
.97
.06
.34
.11
.53
.01
.19
.11
.11
.12
12.140
EPA+ AK33X
. CVS
exhaust
15.85
27.62
2.81
22.31
14.10
7.44
5.40
.77
1.87
.21
3.99
.18
3.53
.37
.18
.51
6.30
.35
.41
.21
.16
.23
.27
.14
8.39
3.21
.64
6.20
.93
.48
1.01
.49
.20
28.57
2.44
1.62
.15
.95
.05
.26
2.55
7.44
3.76
.29
2.07
.77
.68
2.64
.64
CVS
Exhaust
with
scrubber
15.85
2.81
.21
.12
2.45
3.99
3.15
4.87
.35
.37
.17
.15
.15
.11
.05
2.93
.57
6.20
.86
.43
1.02
.51
.20
.31
1.08
1.13
.08
.89
.04
.31
.20
.50
.20
.11
.11
.11
12,740
EPA + AK33X.
CVS
exhaust
14.15
26.73
2.78
22.12
13.98
7.09
5.82
.84
1.05
.09 '
4.76
.13
4.13
.30
.11
.46
7.75
.47
.48
.20
.14
.21
.29
.13
7.31
4.37
.83
8.08
1.29
.67
1.42
.68
.32
30.16 '
3.57
2.32
.25
1.25
.06
.27
2.60
7.94
3.89
.22
.22
.78
.71
2.73
.56
CVS
Exhaust
with
scrubber
14.15
2.78
.13
.12
2.89
4.76
3.75
6.23
'.47
.47
.21
.17
.18
.14
.05
3.85
.72
8.08
1.04
.51
1.35
.67
.32
.43
1.58
1.63
.09
1.15
.02
.26
.16
.65
:24
.15
.15
.14
14,050
EPA+ AK33X
CVS
exhaust
12.27
25.94
2.65
18.80
14.16
7.39
5.67
1.22
1.60
.47
4.25
.16
3.62
.30
.13
.50
6.59
.45
.51
.22
.20
.18
.23
.10
6.52
3.64
.69
6.65
.94
.54
1.14
.52
.22
26.23
3.38
2.12
.23
1.06
.05
.21
2.33
6.65
3.39
.20
1.82
.66
.60
2.96
.83
CVS
Exhaust
with
scrubber
12.27
2.65
.13
.13
2.62
4.25
3.31
5.26
.45
.47
.28
.20
.15
.12
.03
3.10
.59
6.65
.82
.42
1.12
.52
.22
.27
1.04
1.09
.07
.78
.03
.21
.07
.37
.12
.07
.06
.07
*Total hydrocarbons by GC.... 247.22 217.74 211.23 ' 212.18 200.46
* Includes exhaust hydrocarbons not reported In detailed analysis.
-36-
-------
TABLE A-3. - Detailed Hydrocarbon Analysis
Accumulated mileage..
Fuel
Peak
No. Compound
14 £-Pentane, 2-methyl-l-butene
15 trans-2-Pentene
18 Cyclopentane, 3-methyl-l-
20 2-Methylpentane,
2,3-dimethyl-l-butene
22 1-Hexene, 2-ethyl-l-butene. .
23 n-Hexane, cis-3-hexene
24 Methylcyclopentane,
3-methyltrans-2-pentene. . .
27 Cyclohexene,
2,3-dimethylpentane,
32 2,4-Dimethylhexane,
35 Toluene, 2,3-dimethylhexane.
41 2 , 5-Dimethy Iheptane,
y m lene
2 X*! ne' ~
~ y
46 l-Methyl-3-ethylbenzene
47 l-Methyl-2-ethylbenzene
49 1 ,2,4-Trtmethylbenzene
50 sec-Butylbenzene, n-decane..
*Total hydrocarbons by GC....
4,550
Indolene
CVS
exhaust
16.86
17.79
2.22
23.96
11.01
.98
5.82
4.93
.95
1.06
.31
4.46
.24
1.95
.69
.32
1.35
.22
1.63
1.83
1.03
.26
.92
.92
1.91
8.70
3.33
1.17
9.90
1.12
.52
2.91
3.95
4.49
29.56
2.62
1.42
1.92
.39
.24
.19
2.39
5.73
3.35
.42
2.00
.92
.88
3.91
.72
CVS
exhaust
with
scrubber
16.86
2.22
.10
.27
2.98
4.46
1.35
.10
1.63
1.62
.98
.91
.67
1.77
.24
2.75
1.04
9.57
.82
.41
2.93
3.99
4.48
1.29
.73
.57
1.45
.31
.18
.15
.08
.16
.22
.07
.26
.12
.31
.14
216.16
Control Vehicle, ppmC
5,950
Indolene
CVS
exhaust
17.40
17.07
2.20
24.65
10.62
.70
5.72
3.77
.83
1.11
.32
3.43
.19
1.59
.56
.28
1.15
.14
1.23
1.24
.75
.16
.68
.65
1.35
8.69
2.42
.83
7.08
.73
.38
2.22
3.06
3.46
26.36
1.91
.96
1.50
.32
.18
.13
2.29
5.62
3.26
.49
2.15
.99
.94
4.12
.77
CVS
exhaust
with
scrubber
17.40
2.20
.13
.16
1.92
3.43
1.07
.09
1.23
1.23
.79
.72
.54
1.39
.27
2.01
.76
7.08
.59
.31
2.28
3.05
3.46
1.04
.60
.49
1.25
.26
.16
.15
.08
.16
.23
.05
.21
.10
.24
.15
7,700
EPA
CVS
exhaust
12.04
17.02
1.48
17.05
'8.48
4.41
3.28
.61
.95
.34
2.93
.26
2.36
.35
.23
.54
4.04
.43
.43
.42
.43
.26
.38
.36
5.99
2.46
.55
4.53
.76
.41
.93
.50
.40
16.77
1.71
1.22
.29
.88
.13
.34
1.62
4.27
2.47
.26
1.04
.50
.46
1.72
.58
CVS
exhaust
with
scrubber
12.04
1.48
.13
.08
1.81
2.93
2.18
4.16
.43
.39
.17
.16
.17
.19
.02
2.06
.39
4.53
.54
.26
.81
.63
.40
.38
.94
.97
.26
.59
.01
.15
.01
.33
.05
.09
.02
.11
8.725
EPA
CVS
exhaust
13.77
18.34
1.52
19.40
9.35
.99
4.77
4.20
.73
.97
.42
3.90
.08
3.30
.16
.06
.34
6.42
.41
.42
.17
.10
.16
.22
.13
6.04
3.72
.71
7.10
.99
.51
1.20
.64
.36
21.37
2.39
1.58
.22
.95
.06
.25
1.57
5.09
2.38
.13
1.25
.48
.42
1.58
.42
CVS
exhaust
with
scrubber
13.77
1.52
.10
.09
2.39
3.90
3.01
5.22
.41
.40
.19
.15
.15
.14
.07
3.44
.62
7.10
.83
.41
1.17
.72
.36
.37
1.16
1.20
.12
.80
.02
.20
.09
.39
.05
.09
.08
9,865
EPA
CVS
exhaust
13.45
17.92
1.48
18.36
7.42
.26
4.30
4.13
.50
.51
.07
3.77
.12
3.03
.25
.11
.39
5.78
.39
.47
.22
.16
.16
.26
.17
5.80
3.56
.66
6.72
.96
.53
1.21
.63
.31
21.26
2.53
1.74
.19
1.15
.09
.32
1.67
5.57
2.60
.14
1.30
.49
.42
1.59
.39
CVS
exhaust
with
scrubber
13.45
1.48
.24
.13
2.56
3.77
2.90
4.76
.39
.41
.26
.23
.18
.20
.09
3.12
.57
6.72
.87
.43
1.21
.65
.31
.40
1.20
1.30
.10
1.01
.07
.34
.18
.51
.06
.10
.09
198.66 153.15 163.42 157.81
Includes exhaust hydrocarbons not reported in detailed
-37-
-------
TABLE A-3. - Detailed Hydrocarbon Analysis
Control Vehicle^ ppmC*-Continued
Accumulated mileage...
Fuel
Peak
No. Compound
14 ri-Pentane, 2-methyl-l-butene.
18 Cyclopentane, 3-methyl-l-
20 2-Methylpentane,
22 1-Hexene, 2-ethyl-l-butene. . .
24 Methylcyclopentane,
3-methyltrans-2-pentene. . . .
27 Cyclohexene,
2,3-dimethylpentane,
32 2,4-Dimethylhexane,
35 Toluene, 2,3-dimethylhexane. .
41 2 , 5-Dimethy Iheptane ,
50 sec-Buty Ibenzene, n-decane. . .
10.3
EP
CVS
exhaust
14.85
16.92
1 35
21 98
7 90
.52
3.95
3 88
57
71
.19
3 60
2.90
.30
5 30
38
43
.19
.15
.13
.20
12
5 43
52
5 17
.74
.39
89
17.38
1.89
1 25
.11
72
.03
.14
1.29
4.36
2.08
. 11
1.03
.41
34
1.43
.28
20
\
CVS
exhaust
with
scrubber
14.85
1.35
H
.08
2.28
3.60
2.76
5.12
38
.37
.18
.21
.16
13
14
47
5 17
.68
.35
87
43
18
.23
.79
83
04
59
.01
.18
.10
.36
.04
.24
.14
14
.16
11.7
EP)
CVS
exhaust
12.51
16.09
1 37
17 75
71
3 88
4 07
64
83
27
4 38
23
3.18
13
04
6 31
32
31
.11
.07
17
.24
15
5 03
57
5 85
.79
.41
93
47
19
17.59
1.96
1 29
.12
.75
.03
.15
1.27
4.28
2.02
.14
1.10
.42
.37
1.45
.34
25
\
CVS
exhaust
with
scrubber
12.51
1 37
.11
2 51
4 38
2.14
4 04
32
32
.16
.10
.17
13
04
.52
5.85
.71
.36
93
48
19
.25
.86
.89
.05
.63
.02
.16
.08
.33
.14
.08
.09
.10
12.4
EP
CVS
exhaust
10.76
15.96
1 40
3 95
3 69
06
3 43
2.93
25
35
37
.23
.19
.18
.21
12
5 00
3 03
.57
5.71
.84
.44
96
52
23
18.45
2.00
1.36
.12
.85
.04
.19
1.41
4.77
2.19
.17
1.15
.45
.39
1.55
.39
90
\
CVS
exhaust
with
scrubber
10.76
09
3 43
2.63
5 02
35
.14
14
.15
05
50
5.71
.71
.36
84
51
23
.32
1.09
1.14
.07
.81
.02
.22
.11
.44
.17
.10
.11
.09
!3.fl
EP
CVS
exhaust
10.44
14 82
3 76
34
3.52
96
.52
.55
35
.50
4 95
87
8.12
1.38
.77
1 26
68
31
20.30
2.84
1.87
.18
1.05
.03
.22
1.48
5.32
2.30
.14
1.23
.47
.40
1.45
.33
40
\
CVS
exhaust
with
scrubber
10 44
3.43
63
.34
26
.21
04
70
8.12
1.00
.51
1 21
69
31
.34
1.21
1.29
.09
.86
.02
.22
.15
.43
.14
.08
.09
.08
*Total hydrocarbons by GC.
147.32
138.63
157.41
Includes exhaust hydrocarbons not reported In detailed analysis.
-38-
-------
TABLE A-4. - Detailed Hydrocarbon Analysis
Accumulated mileage..
Fuel
Peak
No. Compound
8 n_-Butane, 1 ,3-butadiene
11 3-Methyl-l-butene
14 n-Pentane, 2-methyl-l-butene
18 Cyclopentane, 3-methyl-l-
20 2-Methylpentane,
2,3-dimethyl-l-butene
22 1-Hexene, 2-ethyl-l-butene. .
24 Methylcyclopentane,
3-methyltrans-2-pentene. . .
26 Benzene, cyclohexane
27 Cyclohexene,
2 , 3-dimethy Ipentane ,
32 2,4-Dlmethylhexane,
35 Toluene, 2,3-dimethylhexane.
41 2,5-Dimethylheptane,
47 l-Methyl-2-ethylbenzene
50 aec-Butylbenzene, n-decane..
VcTotal hydrocarbons by GC....
1,080
Indolene
CVS
exhaust
9.28
10.56
1.10
11.67
6.57
.93
3.20
4.77
.71
.72
.18
4.15
.17
1.64
.54
.24
.96
.17
1.26
1.35
.75
.16
.65
.62
1.21
4.70
2.18
.82
5.92
.62
.30
1.67
2.39
2.70
16.96
1.47
.75
1.05
.19
.11
.07
1.31
2.97
1.75
.18
.98
.39
.39
2.19
131.75
CVS
exhaust
with
scrubber
9.28
1.10
.34
3.49
4.24
1.22
.08
1.29
1.26
.80
.72
.45
1.14
.14
1.65
.61
5.70
.47
.23
1.67
2.33
2.68
.74
.41
.28
.87
.15
.08
.05
.02
.06
.07
.07
.13
Stationary Engine A. ppmC
2,080
Indolene
CVS
exhaust
7.68
11.07
1.32
11.34
6.47
.43
3.48
2.57
.51
1.01
.19
1.63
.13
.85
.48
.27
.69
.10
.51
.53
.37
.16
.30
.26
.52
4.46
.87
.29
2.50
.19
.09
.66
.95
1.07
11.47
.67
.31
.42
.05
.03
.02
.96
2.07
1.48
.12
.70
.27
.30
1.48
.18
CVS
exhaust
with
scrubber
7.68
1.32
.20
1.33
1.63
.50
.05
.51
.53
.37
.29
.20
.53
.09
.68
.24
2. 39
.16
.08
.67
.93
1.05
.28
.15
.07
.34
.06
.04
.02
.04
.09
.02
.02
.03
2,930
Indolene
CVS
exhaust
6.83
10.20
1.24
10.47
5.49
.31
2.90
1.91
.40
.36
.10
1.10
.06
.56
.30
.09
.46
.08
.39
.46
.25
.09
.21
.23
.47
3.97
.83
.27
2.55
.24
.10
.65
.76
.88
10.46
.42
.58
.07
.03
.02
.86
1.79
1.33
.09
.57
.24
.28
1.80
CVS
exhaust
with
scrubber
6.83
1.24
.13
.92
1.10
.33
.02
.39
.40
.25
.20
.14
.38
.05
.55
.21
2.02
.16
.07
.64
.75
.88
.26
.15
.12
.31
.05
.03
.02
.01
.03
.02
.02
.01
.03
.06
4,950
Indolene
CVS
exhaust
7.53
11.07
1.28
10.42
6.48
.76
3.39
2.43
.62
.68
.27
1.53
.13
.74
.32
.14
.64
.13
.53
.67
.40
.23
.31
.34
.64
4.23
1.10
.36
2.66
.37
.20
.95
1.01
1.21
12.05
.57
.65
.14
.11
.12
1.08
2.16
1.56
.18
1.00
.35
.50
2.17
CVS
exhaust
with
scrubber
7.53
1.28
.07
.13
1.18
1.53
.43
.03
.53
.53
.36
.26
.20
.51
.06
.76
.28
2.67
.21
.11
.95
1.00
1.21
.32
.18
.12
.37
.06
.04
.03
.01
.03
.03
.02
.05
.02
.01
.02
5,000
Indolene + AK33X
CVS
exhaust
6.58
10.44
1.24
10.42
6.97
.33
3.30
3.21
.47
.63
.14
2.45
.12
1.08
.41
.20
.75
.12
.77
.76
.49
.12
.40
.43
.80
4.32
1.28
.45
3.64
.39
.20
1.03
1.40
1.61
13.00
.95
.51
.68
.14
.09
.07
1.08
2.26
1.53
.14
1.04
.31
.31
1.70
.34
CVS
exhaust
with
scrubber
6.58
1.24
.02
.17
1.99
2.45
.67
.05
.77
.75
.49
.36
.27
.69
.08
1.06
.39
3.64
.34
.17
1.01
1.42
1.61
.46
.25
.18
.50
.10
.06
.04
.01
.05
.04
.01
.04
.02
.04
.03
92.13 89.77 95.01 98.78
* Includes exhaust hydrocarbons not reported in detailed analysis.
-39-
-------
TABLE A-4. - Detailed Hydrocarbon Analysis
Stationary Engine A, ppmC--
Continued
Accumulated mileage.. S
Fuel E
CVS
Peak exhaust
No. Compound
1 Methane 7.23
2 Ethylene 11.46
3 Ethane .87
it Acetylene 10.65
5 Propylene, propane 5.00
6 Isobutane .64
7 Butene-1, Isobutylene 2.29
8 n-Butane, 1,3-butadiene 2.95
9 trans-2-Butene .48
10 cis-2-Butene .57
11 3-Methyl-l-butene .19
12 Isopentane 3.02
13 Pentene-1 : .14
14 n_-Pentane, 2-methyl-l-butene 2.32
15 trans-2-Pencene .25
16 cis-2-PenCene .11
17 2-Methyl-2-butene .31
18 Cyclopentane, 3-methyl-l-
pentene 4.14
19 2,3-Dlmethylbutane .34
20 2-Methylpentane,
2,3-dimethyl-l-butene .47
21 3-Methylpentane .25
22 1-Hexene, 2-ethyl-l-butene.. .25
23 n-Hexane, cis-3-hexene .16
24 Methylcyclopentane,
3-methyltrans-2-pentene... .23
25 2,4-Dimethylpentane .17
26 Benzene, cyclohexane 3.05
27 Cyclohexene,
2,3-dimethylpentane,
2-methylhexane 2.01
28 3-Methylhexane .36
29 Isooctane 3.89
30 n-Heptane .55
31 Methylcyclohexane .28
32 2,4-Dimethylhexane,
2,5-dimethylhexane .59
33 2,3,4-Trimethylpentane .29
34 2,3,3-Trimethylpentane .15
35 Toluene, 2,3-dimethylhexane. 10.11
36 2-Methylheptane 1.29
37 3-Methylheptane .83
38 2,2,5-Trimethylhexane .08
39 n-Octane .43
40 2,3 5-Trimethylhexane .04
41 2,5-Dimethylheptane,
3 ,5-dimethylheptane .12
42 Ethylbenzene .74
43 £-Xylene, m-xylene 2.27
44 o-Xylene 1.24
45 n-PropyIbenzene .10
46 l-Methyl-3-ethyIbenzene .56
47 l-Methyl-2-ethylbenzene .22
48 Mesitylene .19
49 1,2,4-Trimethy Ibenzene 1.12
50 sec-BucyIbenzene, ri-decane.. .32
CVS
exhaust
with
scrubber-
5.000
EPA + F-310
CVS
exhaust
cvs
exhaust
ilth
scrubber
6.400
EPA 4- F-310
CVS
exhaust
CVS
exhaust
with
scrubber
8.250
EPA + F-310
CVS
exhaust
CVS
exhaust
with
scrubber
9.130
EPA + F-310
CVS
sxhaust
CVS
exhaust
with
scrubber
7.23
.87
.06
.11
3.02
2.35
4.16
.34
.33
.17
.10
.08
.01
1.89
.33
3.89
.49
.22
.56
.29
.15
.19
.51
.54
.04
.45
.02
.07
.04
.16
.02
.03
7.85
14.57
1.18
12.07
5.77
.33
3.15
3.64
.43
.51
.09
3.43
.11
2.74
.24
.11
.34
5.10
.35
.44
.20
.17
.15
.24
.12
4.29
2.55
.47
4.61
.66
.36
.79
.40
.22
14.82
1.70
1.14
.13
.70
.05
.21
1.20
3.65
2.00
.18
.95
.41
.39
1.77
.51
7.85
1.18
.26
.16
3.43
2.62
4.30
.35
.37
.24
.14
.11
.02
2.23
.40
4.61
.59
.29
.77
.39
.22
.26
.76
.81
.07
.67
.07
.26
.40
.32
.05
.07
.09
7.49
10.99
.87
9.95
4.36
.22
2.49
2.51
.31
.39
.07
2.44
.08
2.00
.16
.07
.25
3.63
.25
.24
.14
.12
.09
.15
.07
3.31
1.87
.39
3.42
.47
.24
.53
.26
.11
11.11
1.21
.76
.07
.40
.08
.82
2.67
1.34
.07
.67
.26
.22
1.03
.32
7.49
.18
.06
2.44
1.86
3.36
.25
.24
.09
.08
.08
.07
.04
1.80
.29
3.42
.39
.20
.49
.26
.11
.15
.45
.46
.03
.31
.09
.03
.17
.07
.04
.04
.01
.06
7.77
11.47
.92
10.97
3.84
2.46
2.18
.22
.36
.03
1.99
.07
1.70
.14
.08
.23
3.08
.20
.20
.11
.08
.10
.11
.05
3.31
1.53
.28
2.68
.40
.20
.39
.21
.08
10.02
1.00
.62
.06
.30
.01
.06
.72
2.26
1.20
.12
.57
.25
.21
.96
.39
7.77
.92
.04
.04
1.21
1.99
1.51
2.70
.20
.19
.08
.07
.05
.02
1.33
.24
2.68
.34
.17
.33
.18
.08
.11
.32
.33
.02
.25
.01
.09
.03
.11
.04
.02
.02
.03
7.09
11.84
.90
10.48
5.22
2.64
2.54
.33
.46
.07
2.29
.08
1.88
.16
.07
.26
3.35
.24
.23
.15
.12
.10
.12
.05
3.29
1.71
.34
3.01
.44
.45
.22
.09
10.61
1.09
.68
.06
.35
.01
.06
.78
2.39
1.33
.17
.67
.30
.26
1.09
.42
7.09
.06
.05
2.29
1.72
2.95
.24
.23
.10
.07
.07
.06
.02
1.48
.26
3.01
.38
.19
.46
.23
.09
.15
.41
.41
.04
.29
.01
.09
.07
.17
.06
.03
.03
.04
''•Total hydrocarbons by GC.
92.51
89.54
82.53
89.43
Includes exhaust hydrocarbons not reported in detailed analysis.
-40-
-------
TABLE A-4. - Detailed Hydrocarbon Analysis
Accumulated mileage.,*
Fuel
Peak
No. Compound
8 n-Butane, 1,3-butadiene
14 n-Pentane, 2-methyl-l-butene
18 Cyclopentane, 3-raethyl-l-
20 2-Methylpentane,
2,3-dlmethyl-l-butene. ....
22 1-Hexene, 2-ethyl-l-butene. ,
24 Methylcyclopentane,
3-methyltrans-2-pentene. . .
27 Cyclohexene,
2,3-dimethylpentane,
32 2,4-Diroethylhexane,
35 Toluene, 2,3-dimethylhexane.
41 2,5-Dimethylheptane,
46 l-Methyl-3-ethylbenzene
47 l-Methyl-2-ethylbenzene
50 sec-Butylbenzene, n-decane..
*Total hydrocarbons by GC....
6j090
Indolene + AK33X
CVS
exhaust
9.50
14.82
1.85
15.70
8.67
1.10
4.09
3.34
.78
1.04
.30
2.18
.19
1.02
.42
.21
.75
.18
.69
.82
.46
.15
.35
.35
.68
5.49
1.28
.44
3.53
.40
.20
.95
1.20
1.37
15.22
.60
.86
.14
.09
.07
1.24
2.59
1.84
.14
1.09
.36
.36
2.18
120.24
CVS
exhaust
with
scrubber
9.50
1.85
.05
.17
1.79
2.18
.59
.05
.69
.70
.45
.34
.24
.63
.08
.98
.37
3.53
.31
.15
.91
1.28
1.37
.44
.23
.18
.48
.11
.05
.04
.01
.05
.06
.01
.04
.01
.03
.03
Stationary Ensine A, ppmC--
Continued
8,180
Indolene + AK33X
CVS
exhaust
9.00
13.85
1.87
14.24
8.18
1.01
3.80
3.48
.79
1.00
.30
2.06
.08
.93
.36
.14
.68
.08
.66
.68
.39
.08
.34
.34
.71
5.38
1.22
.51
3.56
.34
.19
.93
1.28
1.49
14.78
.92
.41
.69
.10
.04
.04
1.31
2.69
1.95
.17
.89
.34
.36
2.00
CVS
exhaust
with
scrubber
9.00
1.87
.05
.18
1.58
2.06
.61
.05
.66
.65
.40
.32
.23
.62
.09
1.00
.37
3.44
.30
.15
.99
1.27
1.49
.45
.25
.21
.52
.11
.06
.05
.03
.07
.12
.01
.05
.02
.08
.04
9,140
Indolene 4- AK33X
CVS
exhaust
8.61
12.25
1.46
13.04
7.45
1.14
3.68
5.63
.85
.99
.37
5.36
.29
2.20
.76
.35
1.27
.22
1.71
1.83
1.03
.27
.88
.86
1.71
5.07
2.79
.95
8.09
.97
.50
2.42
3.39
3.92
21.44
2.09
1.09
1.56
.32
.20
.11
1.65
3.80
2.28
.31
1.35
.59
.61
2.92
.61
CVS
exhaust
with
scrubber
8.61
1.38
.19
.40
4.06
5.36
1.67
.14
1.71
1.69
1.15
1.04
.72
1.79
.29
Z.48
.94
8.09
.82
.43
2.53
3.31
3.92
1.15
.67 '
.64
1.30
.32
.18
.19
.11
.17
.26
.03
.18
.09
.21
.15
10,040
Indolene + AK33X
' CVS
exhaust
8.66
12.88
1.43
13.85
6.72
.63
3.74
5.12
.70
.94
.29
4.75
.22
1.98
.74
.39
1.26
.22
1.53
1.66
.92
.22
.75
.74
1.50
5.30
2.48
.83
7.09
.71
.35
2.07
2.96
3.37
20.57
1.56
.74
1.21
.23
.12
.08
1.60
3.58
2.23
.28
1.91
.55
.58
2.67
.49
CVS
exhaust
with
scrubber
8.66
1.43
.22
.48
3.47
4.75
1.56
.16
1.53
1.55
1.09
.92
.60
1.46
.22
2.10
.77
7.09
.57
.29
2.14
2.94
3.37
.95
.52
.40
1.04
.21
.12
.08
. .04
.09
.10
.02
.13
.05
.10
.06
10.060
Indolene + AK33X
CVS
exhaust
7.37
14.44
1.76
12.73
8.00
.80
4.25
3.58
.74
.90
.34
2.50
.15
1.15
.47
.20
.83
.17
.85
.81
.56
.23
.44
.34
.91
5.01
1.54
.50
4.20
.58
.28
1.25
1.62
1.91
16.67
.64
.97
.17
.12
.10
1.46
2.78
2.05
.28
1.47
.48
.49
3.31
CVS
exhaust
with
scrubber
7.37
1.76
.18
.19
1.86
2.50
.68
.05
.85
.82
.53
.41
.29
.78
.10
1.17
.43
4.20
.35
.18
1.22
1.64
1.91
.56
.30
.24
.63
.10
.07
.05
.02
.06
.06
.01
.06
.01
.05
.03
115.23 158.19 147.40 125.67
* Includes exhaust hydrocarbons not reported in detailed analysis
-41-
-------
TABLE A-5. - Detailed Hydrocarbon Analysis
Accumulated mileage..
Fuel
Peak
No . Compound
8 n-Butane, 1 f 3-butadtene
9 trans-2-Butene
11 3-Methyl-l-butene .
14 n-Pentane, 2-methyl-l-butene
17 2-Methyl-2-butene
18 Cyclopentane, 3-roethyl-l-
20 2-Methylpentane,
2,3-dimethyl-l-butene
22 1-Hexene, 2-ethyl-l-butene. .
24 Methylcyclopentane,
3-methyltrans-2-pentene. . .
27 Cyclohexene,
2 , 3-dimethylpentane ,
32 2,4-Dimethylhexane,
35 Toluene, 2,3-dlmethylhexane.
41 2,5-Dimethylheptane,
47 l-Methyl-2-ethylbenzene
50 ' sec-Butylbenzene , n-decane..
4.000
Indolene + AK33X
CVS
exhaust
7.11
11.28
1.18
10.39
6.70
.40
3.76
3.26
.59
.72
.22
2.52
.13
1.17
.46
.20
.86
.15
.85
.82
.53
.15
.43
.44
.88
4.89
1.59
.54
4.34
.46
.24
1.40
1.70
1.96
15.70
1.11
.55
.78
.16
.09
.05
1.25
2.83
1.85
1.18
1.33
.40
.40
2.21
.39
CVS
exhaust
with
scrubber
7.11
1.18
.07
.18
1.85
2.52
.73
.06
.85
.81
.47
.42
.30
.79
.10
1.21
.45
4.34
.37
.17
1.44
1.67
1.96
.56
.32
.26
.65
.14
.11
.11
.02
.06
.05
.01
.05
.01
.04
.03
Stationary EnRine B. ppmC
4^930
Indolene + AK33X
CVS
exhaust
9.70
13.03
1.46
12.28
9.06
.92
4.71
3.54
.89
1.23
.37
2.71
.25
1.33
.57
.28
1.02
.22
.94
1.17
.66
.25
.51
.54
1.06
5.80
1.68
.58
4.86
.45
.21
1.62
1.98
2.23
19.16
1.32
.64
.93
.16
.08
.06
1.59
3.75
2.30
.29
1.87
.60
.57
2.85
.50
CVS
exhaust
with
scrubber
9.70
1.46
.10
.17
1.80
2.71
.88
.10
.94
.97
.68
.61
.40
1.04
.24
1.40
.53
4.86
.50
.25
1.65
1.95
2.23
.65
.37
.30
.76
.21
.10
.07
.03
.08
.07
.02
.12
.05
.13
.10
6_,164
Indolene + AK33X
CVS
exhaust
11.24-
15.47
1.81
15.42
10.38
1.03
4.97
3.46
.74
.23
2.43
.09
1.15
.44
.16
.89
.12
.86
.91
.51
.09
.45
.46
.91
6.41
1.70
.66
5.09
.47
.22
1.57
2.01
2.24
22.42
.78
1.06
.17
.08
.05
1.75
4.08
2.64
.24
1.47
.59
.56
3.26
.48
CVS
exhaust
with
scrubber
-
8V515
EPA + AK33X
CVS
exhaust
8.03
20.34
1.60
11.97
9.03
.66
5.32
5.59
.75
.97
.26
5.23
.20
4.24
.42
.22
.65
7.50
.57
.56
.43
.39
.29
.38
.27
4.96
3.88
.73
7.26
1.03
.53
1.22
.62
.31
22.29
2.46
1.65
.16
.93
.05
.23
1.72
5.28
2.68
.16
1.36
.49
.41
1.93
.42
CVS
exhaust
with
scrubber
S.03
1.60
.71
.45
3.43
5.23
4.08
6.06
.57
.65
• .49
.43
.18
.15
.05
3.31
.63
7.26
.89
.44
1.16
.60
.31
.36
1.20
1.24
.08
.81
.02
.23
.11
.44
.17
.10
.11
.11
4.350
EPA + F-310
CVS
exhaust
10.36
15.08
1.05
15.14
7.18
.65
3.86
4.05
.56
.67
.19
3.90
.18
3.14
.29
.15
.47
5.63
' .45
.43
.31
.29'
.20
• .27
.17
' 4.49
- 2.87
.54
4.90
.89 '
.46
.89
.43
.23
16.50
2.06
1.34
.16
.75
.06
.19
1.32
4.24
2.18
.22
1.23
.48 '
.42
1.75
.56
CVS
exhaust
with
scrubber
10.36
1.05
.07
.10
2.52
3.90
2.92
5.45
.45
.42
.20
.14
.16
.12
.03
2.40
.44
4.90
.63
.32
.75
.41
.23
.31
.94
.92
.07
.69
.03
.19
.18
.40
.26
.15
.11 _
.18
*Total hydrocarbons by GC.... 116.98 137.23 144.58 163.93 138.36
* Includes exhaust hydrocarbons not reported in detailed analysis
-42-
-------
TABLE A-5. - Detailed Hydrocarbon Analysis
Stationary Engine B, ppmC-—
Continued
Accumulated mileage..
Fuel
Peak
No. Compound
3 Ethane
9 trans-2-Butene
11 3-Methyl-l-butene
14 n-Pentane, 2-methyl-l-butene. .
17 2-Methyl-2-butene
18 Cyclopentane, 3-methyl-l-
20 2-Methylpentane,
22 1-Hexene, 2-ethyl-l-butene. . . .
24 Methylcyclopentane,
3-methyltrans-2-pentene
27 Cyclohexene,
2-3-dimethylpentane,
32 2,4-Dimethylhexane,
35 Toluene, 2,3-dimethylhexane. . .
41 2,5-Dimethylheptane,
50 sec-Butylbenzene, n-decane....
5.5'
EPA +
CVS
exhaust
11 36
14.14
.99
15 77
6 91
78
3 63
3 47
.63
81
33
3 27
12
2.67
.25
12
36
5.01
38
.49
.22
.19
.16
.23
.14
4 25
2.59
.47
4.82
.74
39
.76
38
.19
15.00
1.88
1.19
.13
.64
.03
.13
1.14
3.86
1.92
.14
1.04
.40
.35
1.42
.39
126.48
lO
•-310
CVS
exhaust
with
scrubber
11.36
.99
.07
.09
1 92
3 27
2.53
4.61
.38
.39
.18
.12
.12
.10
.04
2.39
.43
4.82
.59
.30
.76
.38
.19
.22
.77
.81
.05
.57
.02
.17
.10
.34
.
.27
.08
.12
.06
.13
6,12
EPA + ]
CVS
exhaust
8 31
11.85
.77
11.41
5.68
89
3 00
5 67
.56
69
22
4 31
11
3.14
.25
.12
.36
5.22
.37
.45
.21
.15
.14
.20
.11
3.43
2.37
.43
4.43
.65
.35
.71
.36
.18
13.36
1.64
1.06
.12
.53
.10
1.00
3.45
1.67
.10
.93
.35
.32
1.34
.36
112.15
5
-310
CVS
exhaust
with
scrubber
8 31
.77
06
21
4 37
4 31
3.00
4.41
.37
.37
.18
.12
.10
.09
.02
2.20
.39
4.43
.54
.30
.68
.35
.18
.20
.69
.69
.03
.48
.10
.06
.23
.
.
.09
.05
.06
.
.05
7,0
EPA +
CVS
exhaust
7 .25
11.87
.75
9.94
4.39
. 16
2 80
2 12
.33
21
04
1 95
10
1.62
.18
.08
.25
3.16
.26
.37
.18
.17
.12
.16
.09
2.87
1.84
.33
3.25
.57
.32
.53
.26
.12
10.74
1.49
.89
.10
.35
.07
.80
2.65
1.40
.07
.67
.26
.23
1.15
,18
88.10
70
•-310
CVS
exhaust
with
scrubber
7 25
.75
.06
06
1 13
1 95
1.52
3.10
.26
.25
.10
.08
.09
.07
.02
1.59
.28
3.25
.39
.21
.49
.26
.12
.14
.54
.53
.03
.32
.
.07
.03
.15
_
_
.06
.03
.03
_
.05
7,92
EPA + 1
CVS
exhaust
7 39
11.75
.64
9 89
5 85
66
3 15
2 65
.52
68
21
2 48
11
2.08
.19
.09
.32
3.81
.31
.31
.25
.23
.17
.21
.13
3.10
2.06
.37
3.82
.58
.29
.61
.31
.15
11.68
1.51
.95
.11
.49
.02
.10
.85
2.85
1.43
.12
.77
.30
.29
1.64
.52
97.76
0
-310
CVS
exhaust
with
scrubber
7 39
.64
07
07
1 38
2 48
1.92
3.38
.31
.32
.18
.17
.14
.15
.05
1.88
.35
3.82
.45
.23
.56
.31
.15
.18
.65
.63
.05
.43
_
.10
.05
.21
_
_
.12
.07
.09
_
.10
Includes exhaust hydrocarbons not reported in detailed analysis.
-43-
-------
TABLE A-6. - Effect of mileage accumulation on exhaust emissions
Stationary Engine A
Miles
Test
temp . ,
°F
Barometric
pressure,
mmHg
Fuel
consumed,
Ibs/test
Emissions
CO
HC
NOX,
uncbrrected
.NOx,
FTP corrected
grams /mile
Total
aldehydes
MCMT x 106
Inorganic
Mn x 10°
MCMT
percent
emitted
CLEAR FUEL
0
1,080
1,400
2,080
2,930
3,900
4,950
100
76
85
91
83
90
86
750.5
755.6
741.5
749.7
745.5
742.5
743.3
4.30
4.23
4.05
4.17
4.21
4.29
4.11
22.0
23.5
23.4
22.5
18.6
17.9
17.5
2.18
1.97
1.39
1.51
1.24
-
1.29
2.34
2.53
2.47
2.35
2.53
2.59
2.45
3.42
2.83
3.12
3.18
3.38
3.66
2.86
0.00
CHANGE TO FUEL CONTAINING AK33X ADDITIVE - 0.125 gMn/GAL
NEW SPARK PLUGS INSTALLED
3.74
1,006':
84 | 747.6
4-. 16 :
15.0 | 2.11 | 3.00
NEW TEST CYCLE
0
963
1,120
2,930
4,012
4,940
88
84
85
80 •
76
94
741.1
744.0
743 .1
"743.2
751,9.
746.4
4.61
4.25
4.47 '
3.85
4.07
3.73 •
26.3
19.8
17.7'"
27.2
27.6
- 23. 6 '
1.64
1.39
1.41
1.86 '
1.84
1.86
- 2.05 "
2.01
2.28
2.09
2.66
2.27
0.146
1.02
48
79
2.32
76
65
2.97
CHANGE TO FUEL CONTAINING F-310 ADDITIVE - 14.2 ML/GAL
5,000
6,400
8,250
9,130
82
60
68
75
748.2
740.0
744.2
757.0
4.02
4.23 "'
4.20
4.07
21.0.
29.3
27.4
24.9
•1.79
1.50
1.50
1.44
-2.. 52 -
2.56
3.00
2.76
3.12 .
2.18
2.61
2.56
0.108
.052
.071
.101
0.000
' 5,000
-P- 6,090
1 8,180'
•9 , 140
10,040
85
95
83
77
84
744.3
740.0
745.0
747.8
742.7
4.23
4.34
4.80
4.30
4.14
21.6
22.6
18.9
16.1
15.9
1.62
1.85
1.80
2.50
2.72
2.51
2.72
2.70
2.93
2.78
2.73
4.02
3.14
3.07
3.79
0.074
.074
.103
.125
.148
0.00
.00
.37
2.46
2.99
992
1,747
2,127
2,527
1,691
0.000
.000
.003
.021
.027
1,111
0.009
-------
TABLE A-7. - Effect of mileage accumulation on exhaust emissions
Stationary Engine B
Miles
Test
temp.,
°F
Barometric
pressure
mmHg
Fuel
cons umed ,
Ibs/test
Emissions
CO
HC
NOX,
uncorrected
NOX,
FTP corrected
grams /mile
Total
aldehydes
MCMT x 106
Inorganic
Mn x 106
MCMT
percent
emitted
CLEAR FUEL
0
1,240
2,030
3,990
80
90
93
78
747.1
749.6
749.9
746.4
2.96
4.65
4.04
4.44
18.2
16.1
16.5
20.5
1.37
1.59
1.62
1.79
1.56
2.42
1.97
2.33
1.79
2.75
2.45
2.86
CHANGE TO FUEL CONTAINING AK33X ADDITIVE - 0.125 gMn/GAL
4,000
4,930
5,870
8,515
9,085
85
75
74
80
71
755.0
754.0
747.8
746.0
745.3
4.56
4.07
4.29
4.96
4.79
23.0
35.0
25.5
24.9
36.7
1.82
2.17
1.85
2.52
2.98
2.67
2.50
2.79
2.80
3.29
3.57
2.59
2.77
2.89
3.09
0.109
.164
.130
.130
-
Trace
<0.50
.35
.58
.87
1,031
1,267
1,746
608
2,266
Trace
O.005
.003
.004
.008
NEW TEST CYCLE
0
1,420 -
2,840
3,650
4,050
76
66
71
74
78
740.0
744.2
740.5
748.7
., 739.0
4.89
4.88 .
4.92
5.08 •
5.04
25.1
38.4
33.8
38.9
34.8
1.68
1.98
2.15
2.09
1.73
2.64
3.72
3.49
4.15
3.64
2.61
3.27
3.59
3.84
4.27
CHANGE TO FUEL CONTAINING F-310 ADDITIVE - 14.2 ML/GAL
4,350
5,540
6,125
7,070
7,930
78
70
76
71
80
739.1
743.3
749.3
741.4
755.7
4.89
4.91
4.98
5.24
5.39
32.8
45.3
38.6
34.1
43.0
1.81
1.77
1.66
1.55
1.66
3.82
3.96
4.45
3.99
4.82
4.36
87
08
00
4.10
0.091
.089
.094
.103
.092
-------
TABLE A- 8. - Effect of mileage accumulation on exhaust emissions
F-310 Vehicle
Miles '
Test
temp.,
°F
Barometric
pressure
mmHg
Fuel
consumed,
Ibs/test
Emissions, grams/mile
CO
HC
NOX,
uncorrected
NOX)
FTP corrected
Total
aldehydes
MCMT x 106
Inorganic
Mn x 106
MCMT
percent
emitted
CLEAR FUEL
0
1,710
2,743
4,030
4,700
72
67
83
82
93
748.2
745.0
745.9
748.8
741.6
4.60
3.46
4.61
4.92
4.62
59.5
69.6
65.5
65.6
62.1
2.76
2.96
2.62
2.51
2.77
4.78
5.46
4.40
3.86
4.44
4.55
5.08
5.33
5.06
5.81
CHANGE TO FUEL CONTAINING F-310 ADDITIVE - 14.2 ML/GAL
4,750
6,070
7,420
8,550
9,150
9,550
10,550
11,880
12,840
13,940
81
86
94
79
80
84
76
66
66
66
745.9
742.5
749.6
743.2
742.2
740.0
744.0
751.1
737.9
744.0
4.77
4.92
4.98
4.77
4.43
4.62
4.66
4.70
4.70
4.67
64.7
75.8
62.2
58.0
63.4
63.2
66.5
52.7
45.7
49.7
3.11
2.85
2.41
2.39
2.73
2.66
2.66
2.58
2.53
2.53
4.00
4.02
4.40
4.43
3.60
3.59
3.81
5.03
5.63
5.48
4.91
6.51
6.45
5.58
4.57
4.99
4.60
5.63
5.25
5.00
0.086
.093
.065
.089
.072
.077
.090
.105
.054
.086
-------
TABLE A-9. - Effect of mileage accumulation on exhaust emissions
AK33X Vehicle
Miles
Test
temp.,
°F
Barometric
pressure
mmHg
Fuel
consumed,
Ibs/test
Emissions, grams /mile
CO
HC
NOX,
un corrected
NOX,
FTP corrected
Total
aldehydes
MCMT x 106
Inorganic
Mn x 106
MCMT
percent
emitted
CLEAR FUEL
0
1,600
, 1,910
-P- 3,190
71 4,010
4,700
86
80
77
83
80
90
741.1
744.5
739.0
745.9
747.7
748.0
5.07
4.94
4.74
4.58
5.24
4.16
74.4
74.4
79.5
59.3
78.3
63.5
3.09
3.43
3.72
2.89
2.80
2.92
4.34
5.65
4.68
4.89
4.51
3.97
4.85
5.96
4.93
5.93
6.09
5.16
CHANGE TO FUEL CONTAINING AK33X ADDITIVE - 0.125 gMn/GAL
4,740
5,305
7,170
8,030
9,434
10,353
11,390
12,140
12,740
14,050
90
80
87
81
60
70
62
55
76
63
750.0
746.6
744.4
744.1
752.0
744.0
750.4
740.3
742.5
755.5
4.86
4.35
4.89
4.89
5.02
4.96
4.66
4.72
4.56
5.00
61.9
57.4
79.2
57.8
69.7
70.3
56.3
58.8
51.8
56.4
3.02
2.98
2.87
3.69
4.29
3.97
3.52
3.47
3.63
3.52
4.03
4.57
4.54
4.43
5.53
4.70
5.45
5.59
4.84
6.22
5.88
5.48
5.77
5.68
5.04
5.00
5.45
5.59
5.31
5.53
0.088
-
.089
.109
.105
.126
.096
.096
.085
.093
-
1.86
0.80
4.97
4.63
1.29
.82
1.70
2.98
1.44
915
1,857
905
1,440
846
800
1,452
500
1,471
1,095
-
0.016
.006
.037
.042
.010
.007
.013
.024
.011
-------
TABLE A-10.- Effect of mileage accumulation on exhaust emissions
Control Vehicle
Miles
Test
temp.,
°F
Barometric
pressure
mmHg
Fuel
consumed,
Ibs/test
Emissions, grams/mile
CO
HC
NOX,
uncorrected
NOX,
FTP corrected
Total
aldehydes
MCMT x 106
Inorganic
Mn x 106
MCMT
percent
emitted
CLEAR FUEL
0
1,400
, 2,250
oo 3,200
4,550
5,950
7,700
8,725
9,865
10,320
11,200
11,725
12,490
13,490
13,840
65
67
83
85
95
85
92
84
80
70
89
74
60
82
65
748.6
745.0
745.9
748.8
748.4
747.8
746.0
744.1
742.5
744.6
740.2
748.0
740.3
737.5
740.0
4.76
4.59
4.68
5.03
4.89
4.73
5.00
4.77
4.34
4.27
5.03
4.41
4.63
4.57
4.50
46.7
48.3
59.2
66.6
63.6
65.7
82.7
67.3
70.2
63.3
80.2
57.8
52.9
59.8
53.0
2.92
2.65
2.81
2.69
2.78
2.99
2.07
2.64
2.65
2.43
2.96
2.30
2.00
2.28
2.47
5.18
5.28
4.27
4.51
3.70
4.52
4.28
3.91
4.23
4.08
4.17
4.78
5.12
4.28
5.32
4.62
4.78
5.18
5.97
5.60
6.80
5.97
5.65
5.01
4.39
6.47
4.86
5.29
5.03
4.85
-
-
-
—
0.103
.093
.083
.069
.086
.092
.096
-
-
.066
-------
APPENDIX B.--PHOTOGRAPHS OF ENGINE COMPONENTS
-49-
-------
AK33X vehicle
F3IO vehicle
•
_:
Control vehicle
FIGURE B-l.-Carburetor bases for the AK33X, F3IO, and control vehicles.
-------
AK33X engine A
AK33X engine B
F3IO engine A F3IO engine B
FIGURE B-2.-Carburetor bases for the stationary engines.
-------
AK33X vehicle
F3IO vehicle
I
j-
ho
i
Control vehicle
FIGURE B-3.- Intake and exhaust ports for the AK33X, F3IO, and control vehicles.
-------
:
-^
AK33X engine B
F3I 0 engine A
F3IO engine B
FIGURE B-4. - Intake and exhaust ports for the stationary engines.
-------
AK33X vehicle
F3IO vehicle
Control vehicle
FIGURE B-5.-Intake valve stems for the AK33X, F3IO, and control vehicles.
-54-
-------
AK33X engine A
AK33X engine B
F3IO engine A F3IO engine B
FIGURE B-6.-Intake valve stems for the stationary engines.
-55-
-------
-•
:
AK33X vehicle
* • *
"
F3IO vehicle
Control vehicle
FIGURE B-7.-Piston head for the AK33X, F3IO, and control vehicles.
-------
AK33X engine A
AK33X engine B
1
F310 engine A F3IO engine B
FIGURE B-8.-Piston head for the stationary engines.
-------
I
Ln
30
I
AK33X vehicle
F3IO vehicle
-.
•
Control vehicle
FIGURE B-9.-Cylinder heads for the AK33X, F3IO, and control vehicles.
-------
I
AK33X engine A
AK33X engine B
:
.
:,
F3IO engine A
F3IO engine B
FIGURE B-IO.-Cylinder heads for the stationary engines.
-------
n
AK33X vehicle
F3IO vehicle
Control vehicle
FIGURE B-ll.- Exhaust valve stems for the AK33X, F3IO, and control vehicles.
-60-
-------
AK33X engine A
AK33X engine B
F.3IO engine A F3IO engine B
FIGURE B-12.-Exhaust valve stems for the stationary engines.
-61-
-------
AK33X vehicle
F3IO vehicle
Control vehicle
FIGURE B-l3.-Spark plugs for the AK33X, F3IO,and control vehicles.
-------
UJ
AK33X engine A
AK33X engine B
F 310 engine A
F3IO engine B
FIGURE B-l4.-Spark plugs for the stationary engines.
-------
Piston head--AK33X engine A
Cylinder head--AK33X engine A
FIGURE B-15.- Piston and engine head for AK33X
engine A .
64
------- |