EPA-AA-TSS-PA-86-03
Analysis of Fuel Samples
from Baltimore, Detroit, and Philadelphia
(Report from Work Assignment 8, Contract 68-03-3192
with Southwest Research Institute)
Mary Ann Warner-Selph and Charles T. Hare
Southwest Research Institute
Craig A. Harvey and Jonathan Adler, EPA
July 1986
NOTICE
Technical Reports do not necessarily represent final EPA
decisions or positions. They are intended to present technical
analysis of issues using data which are currently available.
The purpose in the release of such reports is to facilitate the
exchange of technical information and to inform the public of
technical developments which may form the basis for a final EPA
decision, position or regulatory action.
Technical Support Staff
Emission Control Technology Division
Office of Mobile Sources
Office of Air and Radiation
U.S. Environmental Protection Agency
-------
I. INTRODUCTION
The objective of this Work Assignment was to analyze
samples of in-use gasoline from a representative selection of
gasoline outlets that were not major (national) brands. The
samples were obtained under Work Assignment No. 1 of Contract
68-03-3192 from three cities: Baltimore, Detroit, and
Philadelphia. Thirty-nine fuel samples originated from
Baltimore, 36 from Detroit, and 48 from Philadelphia, for a
total of 123 samples. Single samples from most of the major
brand outlets in each city were included for comparison.
Selection of "minor" (regional) outlets was done using a
random selection weighted by sales volume as reported by the
Lundberg Letter. In other words, each minor outlet listed by
Lundberg for each of the three cities was assigned a
probability of selection proportional to its reported sales
volume. Then, using a random number generator, forty minor
outlets from each city were selected so as to ensure that
thirty currently operational outlets could be found during
sample collection. (The Lundberg data were not fully up to
date for some of the outlets, so some of the outlets no longer
existed.) The major outlets (and ARCO Oxinol outlets) were
chosen arbitrarily with some emphasis on selecting larger
volume outlets of each brand. Premium Gasoline was chosen for
every fourth sample; current data indicate that 25% of unleaded
gasoline sold is premium grade.
Fuel samples were collected and stored in sealed cans as
is done with MVMA fuel samples. For the first few months of
storage these cans were kept in a refrigerated enclosure. Due
to space limitations they were then moved to an underground
unrefrigerated storage room with an estimated temperature of
about 60°F.
These cities and this sampling bias toward non-major
outlets were chosen for a combination of reasons. The MVMA
national fuel survey includes mostly major brand outlets, while
non-major outlets tend to have a greater use of alcohol blends,
which EPA wished to characterize. Also, in Philadelphia, ARCO
markets a gaspline/Oxinol1 blend, and only one sample of this
was included in the summer 1984 MVMA survey. Therefore eleven
samples of this fuel were collected and analyzed in this
program. Section V of this report provides a comparison of
summer 1984 MVMA data with the results of this program.
1 A fuel additive composed of methanol and tertiary butyl
alcohol (TBA).
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-2-
All samples were analyzed for Reid Vapor Pressure (RVP),
distillation temperature curve, methanol, ethanol, tertiary
butyl alcohol (TEA), water content, and lead content. In
addition, the "Evaporative Index"2 (El) was calculated for
each fuel. This parameter was developed by DuPont to correlate
volatility characteristics of fuels to the evaporative
emissions of vehicles. Fuel control and reference samples were
also analyzed to fulfill quality assurance requirements for
this Work Assignment. The reference fuel samples were used to
determine procedural accuracy and repeatability. The control
fuel samples were analyzed periodically to assure repeatability
and reproducibility. , ;
The test plan was written up as part of the Work Plan,
which is included as Appendix A. The test plan describes the
analysis sequence for control samples, reference samples, and
fuel samples. Reference and control samples were analyzed in
duplicate prior to fuel sample analysis. Batches of
approximately twenty fuel samples were analyzed for RVP,
distillation temperature curve, alcohols, water content, and
lead content, alternating with duplicate analyses of control
samples.
Fuel samples were originally scheduled for all analyses at
the Engines, Fuels and Lubricants Division of Southwest
Research Institute (SwRI). Due to scheduling difficulties,
however, it became necessary to have the water and distillation
analyses conducted at other laboratories. The measurement of
water was conducted at the Fuels and Lubricants Research
Division of SwRI. Fuel distillations were conducted by King
Laboratories in San Antonio. All other analyses were conducted
at SwRI by the Engines, Fuels and Lubricants Division.
II. ANALYTICAL PROCEDURES
The analytical procedures and calculations used in
evaluating the gasoline samples are as follows:
REID VAPOR PRESSURE (RVP) - Automatic RVP Instrument
Method. It has. been determined by the ASTM that the
conventional "wet-bomb" method (ASTM-D-323) is not
satisfactory for analysis of gasoline-alcohol blends. The
Automatic RVP Instrument, developed at SwRI and used to
analyze all MVNA survey samples, has been found to be a
satisfactory alternate method. This method is described
in Appendix B.
El = 0.85 RVP +0.14 (percent evaporated at 200°F)
- 0.32 (percent evaporated at 100°F).
-------
-3-
DISTILLATION - ASTM D-86.
METHANOL, ETHANOL, AND TERTIARY BUTYL ALCOHOL (Volume
Percent) - Water Extraction/Gas Chromatography. There are
currently no standard ASTM Procedures for determination of
alcohols in gasoline. SwRI has developed a reliable
analytical procedure based on extraction of the gasoline
with 2 volumes of water and gas chromatography of the
extract using a flame ionization detector. Full details
are given in Appendix B. This method is used to analyze
MVMA survey samples.
WATER (Weight Percent) - ASTM D-1533' Karl Fischer
Automatic Titration (pyridine free), using the Photo Volt
Aquatest IV instrument.
LEAD (Weight Percent) - ASTM D-3237, Atomic Absorption
Spectrometry.
EVAPORATIVE INDEX (El) - From RVP and distillation data:
El = 0.85XRVP - 0.32x(% EVAP @100°F) + 0.14x(%EVAP @200°F)
r
III. RESULTS
A description of the fuel samples is given in Appendix C.
The fuels, which were obtained from Baltimore, Detroit, and
Philadelphia, are designated as either regular unleaded or
premium unleaded. The locations of the gas stations where the
fuel samples were obtained are also given in Appendix C.
Table 1 summarizes the average RVP data grouped by city
and by alcohol content. The results of RVP, distillation,
alcohol, water, and lead analyses are listed in Tables 2, 3,
and 4 for fuel samples from Baltimore, Detroit, and
Philadelphia, respectively. RVP was measured in psi,
distillation in °F, alcohols (methanol, ethanol, and TEA) in
percent by volume, water by weight percent, and lead in g/gal.
Fuel samples were collected in mid September, 1984, from
Baltimore, Detroit, and Philadelphia. The recommended limits
for RVP (as given in ASTM Designation: D439-83) of gasoline are
based on the month of the year as well as location. The ASTM
specification for maximum gasoline. RVP in Baltimore in
September is 11.5 psi (Class C). The ASTM specification for
maximum RVP in Detroit and Philadelphia in September is 13.5
psi (class C/D), but September is a transition month, so fuel
conforming to the 11.5 psi standard may also be sold. The
specification for both of these cities in August is 11.5 psi.
Seventy-seven percent of the Baltimore fuel samples had
measured RVP below 11.5 psi, ten percent had measured RVP
between 12.4 and 12.7 psi, and thirteen percent were above 12.7
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-4-
psi. Thirty-one percent of the Detroit samples and
twenty-three percent of the Philadelphia samples (or 3,0% if the
Oxinol samples are excluded) had RVP less than or equal to 11.5
psi. All the fuel samples from Detroit, and ninety-six percent
of the Philadelphia fuel samples had measured RVP less than
13.5 psi. The highest RVP of any of the Philadelphia samples
was 13.7 psi.
The average RVP for the samples in Philadelphia not
containing alcohol (less than 3% total alcohol) was 11.9 psi,
while the average RVP for the gasoline/alcohol blend samples
was 13.3 psi. All of the samples in Philadelphia which
contained alcohol were Oxinol samples. It is possible that all
of the Oxinol samples were formulated to a class D
specification, which would explain why their RVP's were so much
higher than the other samples. For Detroit, the average RVP of
samples with alcohol (all of which contained 7.7 - 10.5%
ethanol) was 12.4 psi, while the average RVP for samples
without alcohol was 11.8 psi.
Alcohol content and water content of the fuel samples
appeared to be related variables. These values were plotted
and are presented in Figure 1. Two major clusters of data are
apparent: relatively low alcohol with low water and relatively
high alcohol with high water. When total alcohol (methanol,
ethanol, and TBA) was less than 1.0 percent (by volume) of the
fuel sample, water content was less than or equal to 0.05
percent (by weight). When total alcohols exceeded 7.0 percent,
water content was greater than or equal to 0.15 percent of the
fuel sample. One fuel sample had a high water content relative
to the other samples. Sample 70, with 8.0 percent total
alcohol, had a water content of 0.48 percent.
The distillation curve data from the fuel samples are
given in Tables 5, 6, and 7 for Baltimore, Detroit, and
Philadelphia. In general, the samples which contained alcohol
needed lower temperatures to achieve a given amount of
evaporation than those which did not contain alcohol. The
Evaporative Index was calculated from RVP and distillation
curve data. These El values are reported in Table 8. Figure 2
shows the frequency distributions of the El values of the
samples grouped by city and fuel type. The distillation values
of some control samples, which were periodically analyzed with
the three-city fuel samples, were out of the range specified in
the Quality Assurance Plan. This situation is discussed in the
Quality Assurance Assessment section, and should be taken into
consideration when using the distillation and El values for the
sampled fuels.
The EPA specified maximum lead level in unleaded gasoline
is 0.05 g/gal. All but one fuel sample had lead concentrations
below this level. Fuel sample 58 contained 0.83 g/gal-of lead.
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-5-
Table 1 Summary of RVP Data, Grouped by
City and Alcohol Content
Avq. RVP (psi)
Brand less than more than
City Distribution" 3% alcohol 3% alcohol
Baltimore
Detroit
Philadelphia
* Oxinol is considered separately from national and regional
groups.
National
Regional
National
Regional
National
Regional
(Oxinol)
11.3
11.1
11.2
12.0
12.0
11.9
12.:7
12/4
13.3
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-6-
Table 2. RVP, Alcohol Fraction, Water Fraction,
and Lead Content of Baltimore Fuel Samples
Sample
Identification3
1 AMOCO (R)
2 ARCO(R)
3 BPOU(R)
4 Exxon (P)
5 Getty (R)
6 Gulf(R)
7 Mobil (R)
8 Shell (P)
9 Sunoco (R)
10 Texaco (R)
11 Merit (R)
12 Merit (P)
13 Crown (R)
1* Crown (R)
15 Crown (R)
16 Crown (P)
17 Citgo(R)
18 Merit (R)
19 Crown (R)
20 Hess(R)
21 Crown (P)
22 Crown (R)
RVP, psi
Automatic
11.0*
11.20
11.13
10.52
12.46
11.21
11.37
11.09
11.93
11.21
11.50
10.8*
10.47
11.25
10.99
10.40
11.20
10.96
10.29
11.43
10.72
10.36
% by Volume
Methanol Ethanoi TBA
NATIONAL
~b « 0.42.
0.14
0.37
__
._
0.11
0.19
..
0.15
0.54
REGIONAL
__
0.12
-- 0.54
--
0.14 0.11
-- -- --
Water,
Wgt. %
0.01
0.01
0.02
0.02
0.01
0.01
0.01
0.02
0.02
0.02
0.01
0.02
0.01
0.01
0.02
0.02
0.02
0.02
0.02
0.02
0.04
0.05
Lead,
g/gal
0.005
0.006
0.007
0.003
0.001
0.004
0.007
0.006
0.003
0.008
0.007
0.008
0.004
0.005
0.005
0.003
0.006
0.010
0.004
0.006
0.002
0.005
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-7-
Table 2. (Cont'd) RVP, Alcohol Fraction, Water Fraction,
and Lead Content of Baltimore Fuel Samples
Sample
Identification3
23 Crown (R)
21 Crown (R)
25 Merit (P)
26 BPOil(R)
27 Crown (R)
28 Merit (R)
29 Citgo(R)
30 Citgo(R)
31 Citgo(R)
32 BPOU(R)
33 No Brand (R)
3* Big Red (R)
35 Crown (R)
36 BPOil(P)
37 7-11 (R)
38 Merit (R)
39 Crown (P)
Avg. with alcohol0
Avg. without alcohol
S.D. with alcoholc
S.O. without alcohol
RVP. psi % by Volume
Automatic Methanoi Ethanoi
REGIONAL
10.62
10.79
10.91 0.11
12.62
10.91
11.61
12.51
10.86 0.15.
10.73 0.17
12.67 0.12
11.81
11.63
10.23
10.56
11.58
11. *9
10.72
000
11.2 0.02 0
0 ' 0 0
0.6 0.05 0
- Water,
TBA Wet. %
'
0.0*
'* 0.05
0.05
0.03
0.03
0.0*
0.0*
0.15 0.03
0.15 0.03
0.03
0.22 0.0*
0.0*
0.0*
0.03
0.02
. 0.0*
0.10 0.03
0 0
0.08. 0.03
0 " 0
0.15 0.01
Lead,
g/gal
0.00*
0.00*
0.006
0.00*
0.005
0.006
0.00*
0.005
0.010
0.00*
0.006
0.010
0.00*
0.003
0.010
0.006
0,002
0
0.005
0
0.002
a3% total alcohols
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Table 3.
and
Sample
Identification3
40 Boron (R)
41 Shell (R)
42 Union 76 (R)
43 Sunoco (R)
44 Union 76 (R)
45 AMOCO (P)
46 Mobil (P)
47 Total (R)
48 No Brand (R)
49 Speedway (P)
50 Martin (R)
51 No Brand (R)
52 Total (R)
53 Total (P)
54 Total (R)
55 Speedway (R)
56 Total (P)
57 Clark (R)
58 Citgo(R)
59 Tulsa(R)
60 Total (P)
RVP, Alcohol Fraction, Water Fraction,
Lead Content of Detroit Fuel Samples
RVP. psi % by Volume
Automatic Methanol Ethanol
NATIONAL
12.11 -b
11.06
12.74 ~ 7.70
11.22
10.36
11.32
11.05
REGIONAL
12.09
12.39
11-. 46
12.09
10.88 10.1
11.02
12.27 10.3
12.00
12.40
11.97 10.1
12.75
11.94
13.22 10.2
11.10 10.5
.Water,
TBA Wgt. %
0.04
0.03
0.20
0.01
0.02
0.04
0.04
0.02
0.03
0.03
0.02
0.20
0.02
0.19
0.02'
0.02
0.21
0.02
0.02
0.17
0.21
Lead,
g/gal
0.002
0.002
0.005
0.001
0.001
0.003
0.002
0.004
0.001
0.002
0.005
0.001
0.004
0.016
0.004
0.001
0.004
0.003
0.83C
0.001
0.004
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-9-
Table 3. (Cont'd) RVP, Alcohol Fraction,
and Lead Content of Detroit Fuel
Sample
% by Volume
Water Fraction,
Samples
Water, Lead,
4
Identification3
61 Speedway (R)
62 Clark (R)
63 Total (R)
6* Pennzoil (R)
65 Clark (R)
66 No Brand (R)
67 Gas & Go (R)
68 Host(P)
69 Citgo(R)
70 Martin (R)
71 Tulsa(R)
72 Hi-Fy(P)
73 Clark (R)
7* Total (R)
75 Total (R)
Avg. with alcohol^
Avg. without alcohol
S.D. with alcohold
S.D. without alcohol
_ j t
Automatic
12.19
13.19
11.46
11.66
12.89
13.06
12.23
12.41
13.34
13.19
12.38
12.03
11.64
11.85
10.46
12.4
11.8
0.8
0.7
Methanol Ethanol
REGIONAL
9.22
9.38
9.83'
8.89
9.86
9.77
._
0.16
0 9.6
0 0.01
0 0.8
0 0.03
TEA Wgt. %
0.04
- '* 0.05
0.04
0.04
0.04
0.18
0.04
0.22
0.19
0.48
0.20
0.19
0.04
0.04
0.04
0 0.22
0 0.03
0 0.08
0 0.01
g/gal
0.001
0.002
0.004
0.002
0.002
0.003
0.002
0.005
0.004
0.005
0.002
0.002
0.002
0.005
0.003
0.004
0.003
0.004
0.001
a(R) = Regular, (P) = Premium
b=<0.1%
C5ample 58 lead value not included in averaging
^Includes samples with > 3% total alcohols
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-10-
Table 4. RVP, Alcohol Fraction, Water Fraction,
and Lead Content of Philadelphia Fuel Samples
Sample
Identification3
76 BPOil(R)
77 Gulf(R)
78 Amoco (R)
79 Exxon (P)
80 Sunoco (R)
81 Mobil (R)
82 Texaco (R)
83 Citgo(R)
84 Hess(R)
85 BPOil(R)
86 Alert (P)
87 Merit (R)
88 Hess(R)
89 Hess(R)
90 Citgo(P)
91 Golden (R)
92 BPOU(R)
93 7-11 (R)
94 BPOU(P)
95 Citgo(R)
RVP, psi
Automatic
13.38
11.79
11.71
10.66
11.80
11.84
12.74
12.48
12.31
12.81
12.99
11.91
10.93
10.58
12.22
11.63
11.40
12.37
9.76
12.14
% by Volume
Methanol Ethanoi TBA
NATIONAL
-b
0.19
2.08
0.21
..
__
REGIONAL
0.40
0.13
..
__
0.13
__
1.60
._
0.18 0.18
0.64
0.70
Water,
Wgt. %
0.02
0.03
0.08
0.03
0.04
0.03
0.03
0.03
0.03
0.02
0.02
0.03
0.03
0.02
0.04
0.03
0.03
0.03
0.03
0.04
Lead,
<0.001
<0.001
0.009
0.003
0.002
0.002
0.001
0.002
0.003
0.001
0.001
0.003
0.005
0.005
0.005
0.003
0.005
0.002
0.002
0.002
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-11-
Table 4. (Cont'd) RVP, Alcohol Fraction, Water Fraction,
and Lead Content of Philadelphia Fuel Samples
Sample
Identification*
96 Merit (R)
97 Merit (R)
98 Hess(P)
99 Merit (R)
100 T.F.C.O. (R)
101 Merit (R)
102 Hess(P)
103 Hess(R)
104 BP Oil (R)
105 Hess(R)
106 BPOil(P)
107 Citgo(R)
108 Merit (R)
109 Alert (R)
110 Merit (P)
111 Citgo(R)
112 Wm. Penn(R)
113 ARCO(R)
11* ARCO(R)
115 ARCO(R)
RVP. osi % by Volume
Automatic Methanol Ethanoi
REGIONAL
11.48
11.08
11.97
11.47
12.08
11.12
12.04
11.86
13.11
11.93
13.01
12.31
11.38
12.53
11.16
12.13
12.02
*
OXINOL
13.38 4.13
13.61 4.03
13.52 4.00
TBA
0.10,.
0.10
0.11
0.12
0.14
0.45
0.14
0.60
--
3.76
3.75
3.65
Water,
Wgt. %
0.03
0.03
0.04
0.04
0.05
0.04
0.05
0.03
0.03
0.03
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.16
0.19
0.17
Lead,
g/gal
0.004
0.004
0.006
0.005
0.006
0.005
0.007
0.003
0.001
0.003
0.001
0.002
0.004
0.001
0.004
0.002
0.002
0.002
0.002
0.002
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-12-
Table 4. (Cont'd) RVP, Alcohol Fraction, Water Fraction,
and Lead Content of Philadelphia Fuel Samples
Sample
Identification3
116 ARCO(R)
117 ARCO(P)
118 ARCO(R)
119 ARCO(R)
120 ARCO(R)
121 ARCO(P)
122 ARCO(R)
123 ARCO(R)
Avg. with alcohol0
Avg. without alcohol
S.D. with alcohoic
S.D. without alcohol
RVP, psi
Automatic
13. 48
12.71
13.19
13.46
13.74
12.90
13.19
13.16
13.3
11.9
0.3
0.8
%by
Methanol
OXINOL
4.18
4.32
4.06
3.94
4.03
4.06
3.81
4.20
4.1
0.02
0.1
0.05
Volume
Ethanol
--
V
^^
v«
0
0
0
0
TBA
3.77
3.96
3.72
3.61
3.72
3.64
3.67
3.76
3.7
0.21
0.1
0.44
Water,
Wgt. %
0.16
'* 0.15
0.17
0.17
0.16
0.16
0.23
0.15
0.17
0.03
0.02
0.01
Lead,
g/gal
0.002
0.002
0.002
0.002
0.003
0.002
0.002
0,002
0.002
0.003
0.000
0.002
*(RT= Regular, (P) = Premium
b=<0.1%
Includes samples with >3% total alcohols
-------
0.3
0.2
ao
T-l
0)
2 o.i
0.0
-13-
0
-------
Table 5. Distillation Data from Baltimore Fuel Samples
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
I2a
13
14
15
16
17
18
2?a
22
23
24
25
26
27
28
29
30
31
33
34 '
35
36
37
38
39
Temperature, °F at % Evaporated
IBP 5%
National
91 115
91 120
88 108
95 122
81 99
84 108
84 112
89 116
83 109
94 113
Regional
90 114
87 106
90 124
89 115
93 122
93 122
99 122
100 124
92 114
98 119
100 129
98 125
99 122
93 116
94 123
91 121
99 120
99 126
97 118
97 124
91 120
102 128
102 139
97 117
91 113
100 131
10%
126
133
117
133
107
120
122
127
120
123
123
120
138
126
133
135
129
131
128
130
142
138
134
128
135
132
131
139
129
138
134
136
156
129
124
146
15%
135
144
124
140
115
129
132
136
129
132
133
131
147
136
144
147
136
140
140
140
153
147
144
136
146
140
142
143
138
147
144
144
168
138
133
156
20%
145
151
135
149
122
138
141
145
140
142
143
141
156
148
154
158
147
149
150
151
158
156
152
147
156
151
151
153
149
156
151
158
178
149
143
165
30%
165
160
158
170
137
156
160
158
160
163
162
161
172
169
175
176
167
171
174
172
169
176
170
158
174
171
167
176
171
177
169
179
190
169
165
185
40%
190
181
183
192
160
180
185
175
183
188
182
187
190
193
195
192
190
194
201
195
192
198
188
190
194
194
187
196
194
199
186
203
205
192
190
207
50%
216
212
211
217
181
208
207
193
207
208
210
214
210
216
214
219
216
221
221
222
217
218
201
214
212
212
212
219
221
219
205
217
230
212
219
228
60%
242
237
239
239
210
234
235
219
234 .
240
240
233
234
233
241
241
242
246
241
246
234
243
225
239
235
243
235
241
246
244
225
240
247
230
246
246
70%
268
264
268
264
241
264
264
235
264
267
268
248
262
266
268
263
271
273
262
270
268
270
243
265
263
261
262
268
273
271
251
268
269
257
273
262
80%
300
297
305
300
281
300
300
257
298
301
300
271
295
298
302
297
306
306
291
302
300
306
265
296
293
297
295
306
307
301
275
302
299
297
307
297
90%
345
342
356
342
325
356
343
298
351
342
342
305
338
345
343
330
352
349
330
340
342
345
300
334
338
346
331
356
349
340
351
340
334
363
351
329
95% EP
372 418
372 414
394 420
358 399
356 390
387 430
372 421
334 379
385 424
380 418
378 412
343 385
365 417
376 421
380 424
361 402
390 419
376 423
357 403
370 410
369 423
376 421
328 382
366 398
364 414
381 419
360 403
396 432
383 423
369 417
390 423
376 421
355 410
405 433
379 423
367 419
alnstruinent 02
bNo data
Residue (%) Recovered (%)
1.5
1.5
1.5
1.0
1.5
1.5
1.0
1.5
1.0
1.0
98.5
98.0
97.5
98.5
98.5
98.5
98.5
98.0
98.5
98.5
98.0
98.0
98.0
98.5
98.5
98.5
98.0
98.0
99.0
99.0
99.0
98.5
99.0
97.0
99.0
98.0
98.5
98.0
98.0
98.5
98.0
98.5
99.0
98.0
99.0
98.0
-------
Table 6. Distillation Data from Detroit Fuel Samples
Sample
Number IBP
Temperature, °F at % Evaporated
5%
10%
15%
20%
30%
40%
50%
60%
70%
80%
90%
95% EP
National
40a 87
41 95
42 96
43 86
44 98
45 95
46a 89
107
118
112
108
120
124
116
120
. 130
118
120
131
139
135
131
140
123
133
' 139
149
' 153
145
150
128
143
147
160
170
173
171
139
163
165
181
203
201
194
150
182
186
205 '
218
228
210
192
210
214
230
230
253
236
230 |
240
241
245
243
279
260
263
269
269
273
263
309
288
297
304
305
316
298
348
326
342
350
346
347
337
386 425
360 424
378 412
400 440
382 425
370 403
372 421
Regional
47 89
48a 86
49 92
50 90
5la 99
52a 91
53 95
54 87
55 86
57 94
58 86
59 94
60 102
61 84
62 87
63 89
64 91
65 90
66 84
67 91
68 91
69 90
70 98
71 90
72 96
73 97
74 89
75a 96
aliistruineiit It 2
bNo data
108
105
136
111
116
109
113
108
117
115
110
114
122
106
110
112
124
114
113
III
108
104
115
109
111
122
112
117
119
118
143
117
122
119
120
120
130
128
121
121
127
118
120
122
136
126
120
124
117
113
122
118
117
134
121
130
130
130
153
121
127
128
125
130
. 139
140
130
128
133
129
130
130
148
135
126
136
123
118
129
126
124
145
130
140
140
140
168
131
131
138
130
140
150
150
138
134
137
144
140
138
160
145
131
149
131
123
132
132
130
156
139
143
158
167
198
151
141
146
139
161
168
171
156
144
146
167
163
158
187
165
141
180
144
133
145
145
144
178
158
157
184
195
218
174
150
181
150
187
188
193
177
155
158
196
192
179
214
190
151
208
153
144
155
155
156
203
182
ISO
214
223
233
200
172
208
177
215
219
218
197
206
187
221
237
206
239
214
181
235
189
154
210
199
208
230
207
207
240
250
250
229
222
235
228
243
244
240
228
238
229
250
243
234
262
247
225
261
234
208
244
238
219
257
236
236
269
276
273
259
254
264
260
275
271
268
260
266
266
279
270
265
288
279
254
288
265
248
274
260
264
284
264
264
302
309
307
293
285
300
293
307
310
304
301
302
302
318
308
300
311
315
293
318
299
288
309
300
298
318
295
298
340
351
350
341
330
325
337
346
357
355
350
352
345
372
362
337
354
365
347
367
343
336
362
347
343
358
330
332
369 429
381 419
390 420
375 426
361 409
362 420
365 412
381 426
397 427
390 426
382 424
384 421
374 414
414 425
404 424
363 423
392 437
399 430
379 420
403 430
372 420
374 406
406 425
383 420
381 403
394 434
366 410
364 417
1.5
1.0
1.5
1.0
1.0
1.0
1.5
.0
.0
.5
.0
.0
.0
.0
.0
.5
.0
.5
.5
.0
.5
.5
.0
.0
.5
.0
.5
.5
.5
.5
.0
.5
.5
.0
.0
Recovered (%)
98.0
99.0
98.5
98.5
98.5
98.5
98.0
99.0
99.0
97.0
99.0
99.0
99.0
99.0
98.0
97.0
98.5
98.5
98.5
99.0
97.0
97.5
99.0
99.0
97.5
99.0
97.5
98.5
98.0
98.0
99.0
98.0
98.0
99.0
99.0
Ul
I
-------
Table 7. Distillation Data from Philadelphia Fuel Samples
Number
IBP
3%
10%
U*
' JM4 '
mi"
~W~
M*
co«
70%
80%
90%
m
JP
National
76
77
7Sa
79
to
lla
82
89
91
90
90
88
90
92
107
121
108
109
110
114
110
120
132
116
120
119
121
120
130
141
12)
130
126
130
I2S
141
149
13)
141
137
140
13)
164
1))
1)6
162
1)4
162
149
188
17)
ISO
190
179
186
160
206
201
20S
218
206
212
182
232
223
238
238
241
240
208
2)9
246
2)8
2)7
277
270
241
289
27)
307
290
310
308
276
326
321
34)
336
3)3
3))
31)
3)6
3)6
370
3)7
386
387
346
399
408
419
403
42)
416
402
Regional
83*
S4a
8$
86*
87a
88
89
90*
913
92*»
936
94*
9)3
963
97
98a
99»
100*
101
102^
103
104
10)
106
I07a
108
109
110
Ilia
1123
113
114
11)
116
Il7a
ii8a
Il9a
1203
121
122
123
86
8)
90
84
87
86
90
8)
90
94
86
88
92
93
90
87
92
84
88
90
94
83
86
91
8)
90
85
93
Oninol
88
92
92
91
90
89
90
90
9J
91
86
108
100
120
119
101
114
II)
107
114
.
132
109
108
107
III
110
103
121
106
112
III
114
137
10)
112
112
116
108
100
102
106
106
107
III
101
104
103
III
III
101
122
III
131
140
113
126
126
117
129
144
120
120
IIS
122
122
II)
131
120
120 .
12)
122
1)3
118
123
124
130
120
III
109
113
III
113
120
110
110
110
IIS
117
110
132
121
140
1)7
123
136
13)
128
139
D)
130
I2S
127
131
132
124
136
134
12S
136
130
166
127
131
133
140
131
119
117
117
117
117
12)
II)
II)
116
122
121
II)
140
130
149
17)
131
146
14)
137
I4S
170
140
137
136
141
140
134
143
14)
137
144
137
177
137
141
140
1)0
140
128
123
122
122
123
133
121
121
121
129
126
120
1)4
149
167
201
DO
164
160
160
162
19)
160
1)8
1)6
163
160
1)4
164
172
1)2
148
1)6
184
1)8
160
1)7
170
160
148
136
13)
134
136
1)8
134
134
133
144
142
133
17)
169
183
217
172
IS)
181
1S4
190
214
ISO
ISI
180
192
181
17)
182
197
1)4
162
178
211
176
181
177
183
182
172
1)7
1)6
1)6
1)7
186
1)6
I))
1)4
171
163
1)7
200
190
207
232
197
19)
20)
207
220
228
203
208
207
218
198
206
206
219
199
I8S
203
227
200
210
19)
201
204
204
177
178
181
IS3
217
182
ISO
179
196
191
183
222
219
226
24)
22)
221
234
236
248
241
226
236
236
238
228
242
23)
236
227
214
238
241
222
23)
217
234
226
242
210
208
212
209
246
211
208
206
226
218
212
246
2)0
2)1
267
2)6
248
2)3
264
277
260
2)0
266
264
2)6
260
276
26)
2)4
2)8
242
260
260
244
264
246
2)4
2)0
282
246
242
247
244
26S
244
24)
241
2)9
248
24)
27S
286
283
300
292
281
299
297
31)
288
280
297
301
280
297
311
297
278
294
276
29)
290
27S
296
27S
280
283
311
284
280
2SO
279
294
281
280
281
293
284
279
318
330
313
340
334
314
339
340
360
317
316
334
340
330
338
3)3
337
330
333
314
336
328
3IS
332
320
314
316
3)3
3D
314
319
318
334
323
323
321
331
32)
3D
3)1
3)7
3)1
388
362
344
369
372
394
344
343
362
370
368
370
387
360
372
364
343
372
368
34S
3)9
3)3
346
3)6
384
3)8
3)8
3)7
3)8
3)8
346
343
3)7
371
3)8
343
389
384
399
39S
400
402
414
412
421
399
406
40)
411
408
401
421
40)
412
40)
394
406
406
393
408
399
404
407
421
410
401
404
401
400
401
406
399
408
400
406
instrument 12
bNo data
Residue (%) Recovered (%)
I.)
I.)
1.0
1.0
1.0
I.)
1.0
98.0
98.)
99.0
99.0
99.0
98.0
98.)
98.0
98.0
98.)
96.)
98.0
99.0
99.0
98.0
97.)
99.0
99.)
99.0
98.)
97.)
97.)
97.)
99.0
9S.O
98.0
98.)
98.0
97.0
98.)
99.0
98.)
99.0
9S.O
99.0
99.0
98.)
99.0
98.
97.
98.
98.
98.
98.0
99.0
99.0
O\
I
-------
-17-
-Table 8. Evaporative Index (El) of Fuel Samples'
Baltimore Detroit Philadelphia
Sample El
76 16.8
77 16.5
78 15.7
79 14.3
80 15.9
81 15.7
82 18.0
83 16.4
84 16.2
85 16.9
86 14.1
87 15.7
88 15.8
89 15.1
90 15.8
91 15.1
92b
93b
94 12.6
95 16.2
96 15.4
97 15.1
98 15.4
99 15.9
100 15.5
101 15.7
102 14.8
103 16.2
104 17.9
105 16.4
106 15.3
107 16.3
108 15.5
109 17.1
110 15.8
111 15.9
112 15.4
113d 18.0
114d 18.7
115d 18.4
116d 18.5
117d 16.1
118d 17.5
119d 18.3
120d 18.6
121d 17.5
122d 18.0
12:
Avg
Std dev 1.3
Sample El
1 14.9
2 15.4
3 14.8
4 14.7
5 16.7
6 15.1
7 15.2
8 16.1
9 15.6
10 15.4
11 15.5
12 14.2
13 14.6
14 14.8
15 14.8
16 14.4
17 15.5
18 15.1
19 b
20b
21 14.1
22 14.5
23 15.1
24 14.7
25 16.1
26 16.2
27 15.0
28 15.4
29 16.8
30 14.9
31 14.7
32b
33 15.4
34 15.9
35 14.0
36 14.1
37 15.7
38 15.2
39 14.2
Avg 15.1
Std dev 0.7
a El =. 0.85 x RVP
(% Evap @100
Sample
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56b
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
Avg
Std dev
- 0.32 x
°F) +
El
14.7
15.2
17. 7C
14.9
14.9
14.6
12.7
15.2
15.2
13.5
16.5
16. 9e
15.1
17. 6C
15.3
15.7
16.3
16.4
17. 6C
16. 9C
14.8
16.0
15.7
14.3
16.3
17. 6e
14.7
17. lc
18. 3C
17. 7C
16. 7C
16. 5C
15.0
15.9
15.2
15.8
1.3
0.14 x (% Evap @200°F)
b No data
c Gasohol fuels
( approximately
d Oxinol fuels
10% ethanol)
-------
-18-
DETROIT DETROIT BALTIMORE PHILADELPHIA PHILADELPHIA
MIDPOINT GASOHOL GASOLINE GASOLINE GASOLINE OXINOL
12.6 + +X + +X *
13.0 + + + + +
13.4 + +X + . + +
13.8 + + + + +
14.2 + *X +XXXXX *XX +
14.6 + +XXX +XXXXXX + +
15.0 ( +XXXXX ^XXXXXXXXX +XXXX +
15.4 + +XXXXX +XXXXXXXX +XXXXXX +
15.8 * +XXX +XXX +XXXXXXXXXX +
16.2 + +XXX -t-XXX +XXXX +X
16.6 +XX +XX +X +XXX *
17.0 "^AAA "*" "*"A "* AAA *
17.4+ + + -i- +XXX
17.8 +XXXX +X + +X +
18.2 +X + + +X +XXX
18.6 + * + + +XXXX
19.0 + + + + +
Figure 2. Distributions of Evaporative Index
-------
-19-
IV. QUALITY ASSURANCE ASSESSMENT
Six refernce and two control fuels were subjected to
several initial analyses. Descriptions of these fuels are
listed below. Reference fuel 4 was replaced with Reference
fuel 6, which has 500 ppm (0.05 weight percent) of added
water. Reference fuel 4 was spiked with 100 ppm (0.01 weight
percent) water, which appeared to be at the detectability
limits of the water analysis method for use with
gasoline-alcohol blends.
Fuel Sample Description '_
Reference 1 2,2-dimethylbutane, 9.9 psi at 100°F (for RVP analysis)
Reference 2 5% methanol, 5% TEA in unleaded Indolene (by volume)
Reference 3 10% ethanol in unleaded Indolene (by volume)
Reference 5 Two lead samples provided by the EPA: 5a = 0.717 g/gal,
5b = 0.0166 mg/gal
Reference 6 0.05 weight percent (500 ppm) added water in Reference 2
Control 1 Unleaded Indolene
Control 2 Same fuel batch as Reference 2
The samples were analyzed according to the schedule shown
in Table 9, and the results are given in Table 10. Detailed
listings of distillation data for Reference 2 (also called
Control 2) and Control 1 are presented in Appendix D. With one
exception, the reported values fell within the precision,
accuracy, and confidence limits specified in the quality
assurance plan (Table 11). An exception occurred with
Reference I, in which one of the RVP values using the ASTM D323
method was outside the limit specified in the QA plan by 0.1
psi. The ASTM D323 method appears to give a somewhat wider
dispersion of values than initially anticipated. After
discussion with the EPA Project Officer, it was decided to
accept the RVP values and SwRI was authorized to proceed with
sample analyses.
Analysis of an initial Reference 1 sample was considerably
outside reasonable limits, indicating some apparent problem
with that sample. Therefore, that sample was discarded and
another Reference l sample was used.
In addition to the initial analyses of reference and
control fuels, the two control samples were analyzed in
duplicate between batches of samples. The results of the Reid
vapor pressure analyses of Controls 1 and 2 are given in Table
12. The average Control 1 RVP for both the automatic and the
bomb methods was 8.9 psi. The average Control 2 RVP using the
-------
-20-
automatic method was'10.5 psi, and for the bomb method it was
10.4 psi. All but one set of controls fell within the quality
assurance guidelines. The controls analyzed between sample
batches 4 and 5 were slightly outside the reproducibility
specifications of only one value in 20, differing by more than
0.6 psi. A fresh set of controls was analyzed and several
samples within batch 5 were re-analyzed. The new control
values agreed within the allowed limits, and the re-analyzed
samples of batch 5 agreed within two percent of the original
values.
Alcohol analyses of Control 1 showed less than 0.1 percent
methanol, ethanol, and TEA for all analyses. 'The results of
analyses of Control 2 for alcohols are presented in Table 13.
The average measured methanol level in the standards was 5.0,
percent and the average measured level of TBA was 4.7 percent.
Ethanol was not detected in any of the samples (detectability
limit is 0.1 percent). The measurement of methanol fell within
the range given in the Quality Assurance Plan, however, several
TBA measurements were out of the range given for TBA. Some
measured TBA values were up to ten percent lower than the
concentrations to which the corresponding controls were
prepared. One possible explanation is that samples giving low
TBA values may have been drawn from a fuel can which was lower
in TBA than other cans. It is also possible that the
variability in the procedure for measuring TBA is on the order
of ten percent rather than five percent.
Water analysis results for the control samples are given
in Table 14. The average water content was about 0.1 weight
percent for Control 2 and about 0.02 weight percent for Control
1. Considerable variation in measured water levels occurred.
The reason for the variation is not known. However, since the
water content of the initial samples was about half of the
latter values, it can be speculated that the controls absorbed
water from the atmosphere over time. Repeatabilities have not
been previously established for water analysis of
gasoline-methanol blends, or even for gasolines not containing
alcohols. Analysis of the control fuels for lead yielded lead
values less than the detection limit of the method, 0.001 g/gal
of lead.
The two specified control samples and an additional fuel
sample, a regular unleaded gasoline on which distillation data
were available, were analyzed for distillation temperature
curve. Due to stringent time constraints, two instruments were
utilized to analyze the controls and samples. The second
instrument, however, was not available until over half the
total analyses had been completed.
-------
-21-
This situation came about as a result of several factors.
The samples were collected in a previous project in late summer
of 1984, with the understanding that analyses would be
conducted in the fall of 1984 in the same manner as was applied
in the analyses given in Report EPA 460/3-84-009. In that
study, a reasonable number of data checks were applied to those
analyses considered to be of primary importance to the intended
usage of the data. The laboratory at SwRI that was scheduled
to conduct the fuels analyses has a relatively relaxed schedule
in the fall and spring, and a very hectic schedule in the
winter and summer.
Authorization to proceed with the analyses was not
received until well into the spring of 1985. With the
incorporation of numerous quality assurance requirements to be
conducted prior to beginning analyses of the fuel samples, it
was not possible to begin these analyses before the beginning
of the already busy summer schedule. The laboratory at the
time, thought it was still possible to conduct the analyses,
but it eventually became evident that the distillation analyses
could not be completed before the September 30, 1985 deadline.
Therefore, an effort was made to locate another fuel analysis
laboratory, and one was located in San Antonio. With the
verbal approval of the EPA Project Officer, the fuels were
delivered to that laboratory for distillation analyses on a
rush basis. A question has become evident on the
reproducibility of the two instruments used, relative to one of
the control fuels. Due to the September 30 deadline, however,
it was not possible to incorporate any additional evaluations
in an attempt to resolve the question. It also should be
pointed out that the ASTM is reviewing the precision for ASTM
D86, and that it is not clear how to specifically apply the
given precisions to the data generated.
The results from the analyses of control and the
additional fuel sample (SwRI Fuel EM-616-F) are given in
Appendix D, and are summarized in Tables 15 and 16. The
repeatability between duplicate injections for Control fuels 1
and 2 were within the guidelines in the Quality Assurance Plan
for 19 out of 20 analyses (95 percent). Duplicate distillation
analyses were not. performed on fuel EM-616-F. The
reproducibilities of distillation temperatures for Controls 1
and 2 on each instrument separately were also within the
quality assurance guidelines. Reproducibility between the two
instruments for Control fuel 1 and EM-616 were outside the 95%
guidelines given by ASTM. Again, however, it should be noted
that the precision for ASTM D86 is under review, and that
specific applications of the precision values given by ASTM are
not defined.
-------
-22-
Table 9. Schedule for Initial Analysis of Reference
and Control Samples
Number of Evaluations
Sample RVP
Number Automatic
Reference I
Reference 2
(Control 2)
Reference 3
Reference 5a
Reference 5b
Reference 6
Control 1
2b
2
0
0
0
0
2
RVP, ASTM
D323(bomb)
2
2
0
0
0
0
2
Distillation
0
2
0
0
0
0
2
Alcohols*
0:
2
2
0
0
0
2
Water
0
2
0
0
0
2
2
Lead
0
2
0
2
2
0
2
aMethanol, ethanol, TBA
repetitive analyses
-------
Table 10. Results of Initial Analyses of Reference and Control Sample
Sample RVP, psi
Number Automatic
Reference 1 10. la
Reference 2 10.6,10.7
(Control 2)
Reference 3
Reference 5a
Final analyses
Reference 5b
Final analyses
Reference 6C
Control 1 8.8,9.1
RVH, psi Distillation,
ASTM °F at % Evap/ Alcohols, % by vol.
D323(bomb) 10% 50% 90% Methanol Ethanol TBA Water, wt % Lead, g/gal
9.7,9.2,9.3 -- b
10.3,10.6 - - 5.21,5.16 < 0.1, < 0.1 5.08,5.01 0.037,0.039 < 0.001, < 0.001
<0.l, <0.l 10.1,10.1 <0.1,<0.l
0.07,0.07 jj,
to
1
0.015,0.015
0.0899,0.0830
9.0,9.1 -- - -- <0.1, <0.1 <0.1, <0.l <0.l, <0.1 0.011,0.009 <0.001,
-------
-24-
Table 11. Objectives for Precision, Accuracy, and Completeness
Analytical
Procedure
Alcohol
Content
Distillation
Lead Content
RVP
RVP
Precision3
Experimental Repeat- Reproduo-
Reference Conditions ability ibility.
FID Chroma- Fuel Sample
tography
(SwRI)
2.5%b'c' 5%b'c
c,e
c,e
ASTM D86 Fuel Sample
ASTM D3237 Fuel Sample 0.005g/galc 0.01g/galc
ASTM D323 Fuel Sample 0.25 psic'9 0.55 psic'g
Automatic RVPFuel Sample 0.25 psic'n 0.55 psic'9
Instrument
Method
Water Content ASTM D-1744 Fuel Sample
Complete-
Accuracy ness 3
>95%
f
d
d
d
>95%
>95%
>95%
>95%
>95%
.The ASTM defines precision in terms of repeatability and reproducibility.
The percents given are percents of the measured alcohols content.
Based on 95% confidence limits (i.e., 19 out of 20 measurements should
,be within the limits given) .
vChe measured concentration for the blended standard solution should be within
five percent of the concentration to which it was blended.
Repeatability and reproducibility are given in Fig. 2 and Fig. 3 in
ASTM D86; these criteria can not be reduced to only a few numerical
f values.
Accura'cy is obtained through procedural operating requirements (i.e., by
following the procedure ) .
u samples having an RVP of 0 to 15 psi.
The Automatic RVP Instrument Method is designed to be an efficient re-
placement to the ASTM D323 method and has the same precision given for
.ASTM D323.
.The precision has not been determined for use with gasoline samples.
Unless stated otherwise in a specific work plan, the objective for com-
pleteness will be 95%, or better.
To be determined.
Reproduced from section 3E of Quality Assurance Project Plan
for this contract.
-------
Table 12. RVP of Control Fuel Samples as Measured by two Methods
Control 1Unleaded Indolene Control 2Indolene-Alcohol Blenda
Auto., psi
1 2
Initial - first set 8.8 9.1
- repeat
Later repeat -9.1
Between batches
land 2 8.9 8.9
Between batches
2 and 3 9.0 8.8
Between batches
3 and 1 8.7 8.9
Between batches
4 and 5 8.4b 8.4b
Between batches
5 and 6 8.9 9.2
Between batches
6 and 7 8.9 8.9
Between batch
7 and reruns
from batch 5C 8.9 9.0
Avg.
i
AVR.
9.0
9.1
8.9
8.9
8.8
8.4
9.0
8.9
9.0
8.9
Bomb, psi
1 2 AVR.
9.0 9.1 9.1 '
9.4 9.4
.
8.9 9.0 9.0
9.0 8.9 9.0
8.9 8.8 8.9
8.3b 8.lb 8.2b
8.9 9.0 9.0
8.8 9.0 8.9
8.9 8.9
8.9
Auto, psi
1 2
10.9 10.9
10.6 10.7
10.5
10.6 10.5
10.5 10.4
10.5 10.3
10. 2b 10.3
10.6 10.6
10.6 10.5
10.6 10.6
AVR.
10.9
10.6
10.5
10.6
10.4
10.4
10.3
10.6
10.6
10.6
10.5
Bomb, psi
1 2 AVR.
10.6 10.8 10.7
10.3 10.6 10.4
10.5 10.5
10.5 10.5 10.5
10.4 10.4 10.4
10.4 10.4 10.4
10. 0>> 10.lt> 10. 1
10.5 10.5 10.5
10.5 10.5 10.5
10.4
10.4
1
10
Ul
1
aFive percent methanol and five percent TBA (by volume) added to unleaded indolene
bThese RVP values were outside the reproducibility specification of 0.6 psi.
The two cans of fuel samples were discarded and fresh samples were analyzed
for the remaining analyses.
c£very fifth sample of the fifth batch was reanalyzed with the fresh standard
-------
-26-
Table 13. Alcohol Content of Control Sample 2*
Alcohol Content in Percent by Volume
Methanol Ethanol TBA
~T" "T"" Avg. "T~ T~ 1 2~ AvgT
Initial
First set 5.21 5.16 5.2 0.0 0.0 5.08 5.01 5.0
Later repeat 4.86 4.9 0.0 4*68 4.7
Between batches
land 2 4.95 4.96 0.0 0.0 4.73 4.74
Repeat 4.86 4.9 0.0 4.65 4.7
Between batches
2 and 3 4.85 4.85 0.0 0.0 4.68 4.65
Repeat 5.13 4.9 0.0 4.89 4.7
Between batches
3 and 4 5.08 5.11 0.0 0.0 4.87 4.88
Repeat 4.95 5.0 0.0 4.78 4.8
Between batches
4 and 5 4.93 4.92 4.9 0.0 0.0 4.76 4.76 4.8
Between batches
5 and 6 4.87 4.87 4.9 0.0 0.0 4.53 4.51 4.5
Between batches
6 and 7 4.89 4.91 4.9 0.0 0.0 4.54 4.55 4.6
After batch 7
Repeat
Later repeat
5.02
5.01
4.90
4.86
4.98
4.98
4.93
4.86
5.05
5.02 5.0
4.85
5.01
.4.89
4.86
5.01
4.9
Avg. ' 5.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
4.66
4.65
4.84
4.77
4.85
4.88
4.87
4.75
4.68
4.64
4.77
4.88
4.80
4.83
4.87
Avg.
4.7
4.8
4.7
sample 2 is unleaded Indolene with 5 percent methanol and
5 percent TBA added (by volume)
bAbout 40 percent of the values varied over 0.25 volume percent from
the five volume percent TBA that was added. See text for pertinent
discussion
C0.0 means <0.1%
-------
-27-
Table 14. Water Content of Control Fuel Samples
Water Content in Weight Percent
Initial
First set
Later repeat
Between batches
1 and 2
Repeat
Between batches
2 and 3
Repeat
Between batches
3 and 4
Repeat
Between batches
4 and 5
Repeat
Between batches
5 and 6
Between batches
6 and 7
After batch 7
Control 1
Unleaded Indolene
1
Avg.
0.011 0.009 0.010
0.007 0.009 0.008
0.025 0.024 0.02*
0.009 0.009
0.029 0.030 0.030
0.039
0.032
0.025
0.030
0.031
0.032
0.035
0.032
0.031
0.028 0.02* 0.026
0.033 0.030 0.032
0.03* 0.03* 0.03*
Avg. 0.02
Control 2
Unleaded Indolene
+5% Methanol +5% TBA
1
AYR.
0.037 0.039 0.038
0.087 0.093 0.090
0.107 0.121
0.120 0.116
0.1*2 0.132
0.139 0.138
0.103 0.103 0.103
0.108 0.126
0.117 0.113
0.10* 0.108 0.106
0.125 0.127 0.126
0.152 0.1*9 0.150
Avg. 0.1
-------
Table 15. Distillation Temperature Repeatability of Control Fuels
Temperature Difference at Percent Evaporated, °F
Control
Fuel Instrument IBP 5% 10% 15% 20% 30% 40% 50% 60% 70% 80%
1 1 43331322223
2 1 33321231233
1 2 344b3333334b3
2 2 5,21221112 24b
Precision for ASTM D86 is under review.
Indications are that precision for IBP and EP may be indeterminate.
"One °F above values given in guidelines
CTwo or more °F above values given in guidelines
dASTM D86 bases the repeatability guidelines on 95% probability
and makes the statement given in the preceeding note a.
Table 16. Distillation Temperature Reproducibility
Temperature Difference at Percent Evaporated, °F
Control
Fuel Instrument IBP 5% 10% 15% 20% 30% 40% 50% 60% 70% 80%
Guidelines in ASTM D86a '12 10 76666 66 6 7
1 1 7667b6744«69C
2 1 45533432454
1 2 76 8b 43343343
2 2 5643334 56 7b8C
I 142 12 I8C I8C I3C 9C 7b 5 6 6 10^ I|C
2 142 5664344 567b8b
616 142 39 IOC 8C IOC IOC 2 56 3 7
'Precision for ASTM D86 is under review.
Indications are that precision for IBP and EP may be indeterminate.
"One °F above values given in guidelines
cTwo or more °F above values given in guidelines
dASTM O86 bases the repeatability guidelines on 95% probability
Number of Values
Above Guidlines
Acceptance
90% 95% EP Observed Basis*. d
3 8C 2 1 3
132 0 3 to 4
1 2 8c>d 2 1 to 2
3 3 6b>d 2 1 to 2
of Control Fuels
Number of Values
Above Guidlines
Acceptance
90% 95% EP Observed Basis3' d
10 13 10
6 |4b I2C 0 5 to 6
553 4 7
128 1 3
4 5 "6 ' ' 2 3
9 |4b 28C 30 8 to 9
777 2 12
I3C 9 |6<: 7 5 to 6
1
to
00
1
-------
-29-
V. COMPARISON WITH MVMA SURVEY DATA
ASTM guidelines indicate that the samples from Baltimore
should be class C in September while those from Detroit and
Philadelphia may be either class C or D. There are some
samples of Oxinol which were collected from ARCO stations in
Philadelphia which are examined separately here. The data are
further stratified by the type of petroleum company, that is
whether it is a regional (e.g., small or independent) or
national company as listed in the report.
MVMA does not take samples in September, so direct
comparisons with MVMA data for the same month and city are not
possible. However, it is possible to compare the results in
this study with the data in the MVMA national survey for fuels
with the same ASTM class. The distributions of the RVP, lead,
methanol, ethanol, and butyl alcohol within the groups of data
were compared to MVMA survey data from June and December of
1984. The MVMA data used for the comparison to the
Philadelphia and Detroit distributions include all fuels taken
from class C or D areas/seasons. The data from the two classes
are simply combined for all of the parameters except RVP. RVP
is the parameter most likely to be affected by the ASTM class.
The comparison between the RVP data taken in this program and
that of the MVMA survey is shown by the histograms in figure
3. The data used for the comparison to the Baltimore samples
include only fuels from class C areas/seasons. These analyses
show that the distributions of measurements from the national
companies were distributed roughly equally to those of the
regional companies, except as noted.
RVP
The Baltimore samples have RVP's which were slightly
higher than those of the class C fuels in the MVMA
surveys. Ninety percent of the Baltimore samples fall in
the range of 10.4 - 12.6 psi; ninety percent of the MVMA
class C fuels fall in the range of 9.5 - 12.0 psi. The
RVP distributions of the Detroit and Philadelphia samples
(not including the Oxinol samples which were taken in
Philadelphia) fell between the distributions for class C
and class D, but they were closer to that of class D. The
ninety percent range for these two cities is 10.6 - 13.4
psi. The Oxinol samples had higher RVP's, ranging from
12.7-13.7.
Lead
The lead levels found in the samples taken by SwRI
are close to but slightly higher than those found in the
MVMA survey.
-------
Sample Distribution
OB
PI
ft
H-
B
n
at
^j
o>
ft
n
H-
ft
^x
o
a IS
M" £T
O M
HJ ft!
a
elphia
Exclud
&
^*
MIDPOINT
8.8000
9.2000
9.6000
10.000
10.400
10.800
1 1 .200
1 1 .600
12.000
12.400
12.800
13.200
13.600
14.000
14.400
14.800
MIDPOINT
8.8000
9.2000
9.6000
10.000
10.400
10.800
1 1 .200
1 1 .600
12.000
12.400
12.800
13.200
13.600
14.000
14.400
14.800
15.200
MIDPOINT
8.8000
9.2000
9.6000
10.000
10.400
10.800
1 1 .200
1 1 .600
12.000
12.400
12.800
13.200
13.600
14.000
14.400
14.800
15.200
National
Brands
0 +
0 +
0 +
0 +
1 +X
0 +
7 tXXXXXXX
0 +
1 +X
1 +X
0 +
0 +
0 +
0 *
0 +
0 +
0 +
0 +
0 +
0 +
1 +X
0 +
4 +XXXX
0 +
1 +X
0 +
1 +X
0 +
0 +
0 +
0 +
0 +
0 +
0 +
0 +
0 +
0 +
1 +X
0 +
2 +XX
2 +XX
0 -i-
J +X
1 +X
0 +
0 *
0 *
0 +
Regional
Brands
0 +
0 +
0 +
0 +
6 +XXXXXX
1 1 +XXXXXXXXXXX
2 +XX
6 +XXXXXX
1 +X
1 +X
2 +XX
0 +
0 +
0 +
0 +
0 +
0 +
0 +
0 +
0 +
1 +X
1 +X
2 +XX
4 *XXXX
8 +XXXXXXXX
6 +XXXXXX
2 +XX
5 +XXXXX
0 +
0 +
0 +
0 +
0 +
0 +
1 +X
0 +
1 +X
1 +X
4 *XXXX
4 +XXXX
9 +XXXXXXXXX
6 +XXXXXX
2 +XX
2 +XX
0 +
0 +
0 +
0 *
2 +X,
3 +x:
14 +x;
16 +x:
21 +x;
27 +x;
40 +x;
38 +x:
12 +x;
4 +x;
1 +X
1 +X
1 +X
0 *
0 *
0 +
2 +Xi
3 +x;
14 -t-x;
16 +X)
21 +X)
27 +X)
40 +X)
38 +X)
12 +X)
4 +X)
1 +X
1 +X
1 +X
0 +
0 +
0 +
0 +
2 +XJ
3 +X>
14 +X)
16 +X>
21 +X>
27 +X)
40 +X>
38 +X>
12 +X>
4 +X>
1 +X
1 +X
1 +X
0 +
0 +
0 +
0 +
Figure 3. Histograms of RVP
MVMA Reference Distributions
Class C
Class D
+XXXXXXXXXXXXXX
+XXXXXXXXXXXXXXXX
+XXXXXXXXXXXXXXXXXXXXX
+XXXXXXXXXXXXXXXXXXXXXXXXXXX
+XXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX
xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
+XXXXXXXXXXXX
xxxxxxxxxxxxxx
16- -t-XXXXXXXXXXXXXXXX
21 +XXXXXXXXXXXXXXXXXXXXX
xxxxxxxxxxxxxxxxxxxxxxxxxxx
40 +XXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX
38 +XXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX
+XXXXXXXXXXXXXX
+XXXXXXXXXXXXXXXX
xxxxxxxxxxxxxxxxxxxxx
+XXXXXXXXXXXXXXXXXXXXXXXXXXX
-t-XXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX
xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
xxxxxxxxxxxx
0 +
0 +
0 *
0 +
1 +X
2 +XX
2 +XX
5 +XXXXX
16 +XXXXXXXXXXXXXXXX
26 +XXXXXXXXXXXXXXXXXXXXXXXXXX
24 +XXXXXXXXXXXXXXXXXXXXXXXX
23 +XXXXXXXXXXXXXXXXXXXXXXX
12 +XXXXXXXXXXXX
0 +
1 +X
1 +X
1 +X
0
0
0
0
1
2
2
5
16
26
24
23
12
0
1
1
1
o
I
+X
+XX
+ XX
+XXXXX
+XXXXXXXXXXXXXXXX
+XXXXXXXXXXXXXXXXXXXXXXXXXX
+XXXXXXXXXXXXXXXXXXXXXXXX
+XXXXXXXXXXXXXXXXXXXXXXX
+XXXXXXXXXXXX
+X
+X
+X
-------
-31-
Methanol
Less than 0.25% methanol is found at the ninety
fifth percentile in all of the groups except the Oxinol.
The Oxinol samples have roughly four percent methanol.
Ethanol
One of the seven national samples taken in Detroit
had 7.7% ethanol. Eleven of the twenty nine regional
samples had approximately 9% ethanol. None of the other
samples contained significant amounts of ethanol. The
MVMA survey shows only small amounts of ethanol (0.1%) at
the ninety-fifth percentile.
Butyl Alcohol
Small amounts of butyl alcohol (up to 0.6%) are
present in many of the samples measured by SwRI. One of
the national brand samples from Philadelphia contains 2.1%
butyl alcohol, and one of the regional brand samples from
Philadelphia contains 1.6%. The samples of Oxinol have
roughly 3.7% butyl alcohol. The rest have levels below
1%. The MVMA survey reports no more than 0.1% butyl
alcohol at the ninety-fifth percentile.
-------
APPENDIX A
Work Plan
-------
SOUTHWEST RESEARCH INSTITUTE
POST OFFICE ORAWEB 28610 6220 CULEBRA ROAD SAN ANTONIO. TEXAS. USA 78284 (512) 684-8111-TELEX 76-7387
ENGINES. EMISSIONS AND VEHICLE RESEARCH DIVISION
TWX: 91047MOM
March "19', 1-985
TO: Mr. Albert W. Ahlquist, Contracting Officer
Contracts Management Division
Contracts Branch A
Environmental Protection Agency
Cincinnati, OH 45268
FROM: Charles M. Urban and Charles T. Hare
Department of Emissions Research
Southwest Research Institute
6220 Culebra Road
San Antonio, TX 78284
SUBJECT: Revision B to the Work Plan in response to Work Assignment No. 8 of
Contract 68-03-3192, received by SwRI on December 20, 1984
and revised by verbal technical directives in February and March
1985; SwRI Project 03-7774.
Contract Title: "Pollution Control Assessment for the
Emission Control Technology Division,
Aon Arbor, Michigan"
Assignment 8 Title: "Analysis of Fuel Samples" (Analysis
of In-Use Gasolines and Gasoline/
Methanol Blends)
I. INTRODUCTION
Southwest Research Institute will comply with the revised technical
and quality assurance (Q/A) type requirements of Work Assignment Number 8,
and will put forth efforts to do so within the 1985 fiscal year. It will
be necessary, however, to coordinate this effort with analyses of fuel
samples from MVMA and other currently scheduled fuel surveys. The initial
Scope of Work for Work Assignment Number 8 is attached as an Appendix for
information purposes.
II. STATEMENT OF TECHNICAL APPROACH
This Work Plan describes the manner in which our understanding of
the requirements will be met. Should there be a necessity for changes in
the Work Plan which are within the level of effort proposed, they can be
documented in a letter or a monthly progress report.
A. Gasoline and Blend Analysis
The following analyses will be performed on each of the one
hundred thirty (130) gasoline samples collected from three cities under
SAN ANTONIO, TEXAS
WITH 0 » * i c « s IN HOUSTON. T e x A s . AND WASHINGTON, o c
A-2
-------
Work Assignment No. 14 of Contract 68-03-3162,'and on selected reference
and control samples:
1. RVP - Automatic B.VP Instrument Method. The
Automatic KVP instrument developed at SwBI
is used to analyze all MVMA survey samples.
2. Distillation - ASTM D-86.
3* Jfethanol, Ethanol, and Tertiary Butyl Alcohol
(Volume Percent) - Water Extraction/Gas Chroma-
tography. This SwRI-developed analytical pro-
cedure is based on extraction of Che gasoline
with 2 volumes of water and gas chromatography
of the extract using a flame ionization detector.
4. Water (Weight Percent) - ASTM D-1744, Karl Fischer
Titration.
5. Lead Content (Weight *) - ASTM D-3237, Atomic
Absorption Spectrometry.
6. FE7I and El volatility indices - In accord with the.
Statement of'Work*, no calculations of indices have
been Included in this Work Plan.
The procedures described are the same as were previously used
in the fuel analyses conducted under Work Assignment No. 14 of EPA Con-
tract No. 68-03-3162. They were reported in the final report EPA 460/3-
84-009.
B. Discussion of the Procedures and Q/A
The ASTM maintains system accuracy by equipment calibration
and/or by Internal standards as appropriate to the specific analyses.
This approach is essentially the same as used in Che Code of Federal
Regulations for emissions measurements. The quality assurance guide-
lines given in QAMS-005/80 and in referenced handbooks and manuals are
specific only for environmental measurements. A major difficulty relative
to chis Work Assignment has been chat definitive guidelines for applying
EPA QA requirements to fuel.analyses were not available.
The ASTM incorporates quality control into its procedures, Co
Che maTrinrnm extent they consider co be practical for widespread use.
When attempting co apply Section 5.11 of QAMS-005/80 co a project,
several questions arise:
What specific level of control is essential?
Who is co decermine level of concrol applied?
Is che same level of concrol co be applied to all analyses?.
What degree of quality assurance is co be applied Co che
reference standards used?
A-3
-------
The Initial approach taken in developing this Work Plan was to attempt
to provide an adequate response without having definition of the specific
requirements. This revision Incorporates the specific requests from the
EPA Project Officer.
C. Test Plan - Including Quality Control and Assurance Provisions
As has been decided, several specific quality control and-
assurance efforts have been incorporated into this Work. Assignment. The
revised test plan incorporating those provisions is as follows:
1. Obtain or develop reference fuel samples ("to determine
procedural accuracy and repeatability):
RVP - Fuel Rl - pure grade 2,2-dimethybutane
(Neohexane), 9,9 psi at 100° F
Distillation - none (D86 provides empirical results)
Alcohols - Fuel H2 - 5% pure grade methanol and 5%
pure grade TBA in unleaded Indo1ene
Fuel R3 - 10% pure grade ethanol in unleaded
Indolene
Water content - Fuel R4 - Fuel R2 plus 0.100 weight
percent water
Lead content - Fuel R5 - Reference samples from the EPA
2. Develop control fuel samples (run periodically for
repeatability and reproducibility) :
Fuel Cl - unleaded Indolene
Fuel C2 - same fuel batch as Reference Fuel R2
3. Conduct Reference and Control Fuel analyses:
RVP (automatic and ASTM D323) - Two repetitive
evaluations of the following fuel set - Rl, Cl, C2
. Distillation" - Two repetitive evaluations of the
following" fuels - Q, C2
Alcohols - Two repetitive evaluations of Che following
fuel set - R3, Q, C2
- Water Content - Two repetitive evaluations of the
following fuel set - R4, Q, C2
Lead Content - Two repetitive evaluations of the
following fuels - R5, CL, C2
NOTE:. A third evaluation will be run for any result falling outside the
Q/A repeatability objectives.
A-4
-------
4. After accuracy and repeatability have been established,
evaluate the fuel samples* To the extent possible, conduct
the evaluation in sets per city sampled (control fuels to
be used are Indolene, Cl, and Indolene -I- 5% M&TBA, 02) :
BALTIMORE (=40 fuels)
a. Check tiae elapsed since last analyses of control samples*
b. Analyze 20 fuel samples (without ASTM D323)
c.- Replicate tests of control fuels (with ASTM D323)
d. Hepeat b and c
* If over one week, run single test of control fuels (with
ASTM D323)
DETROIT («40 fuels)
Same sequence as for BALTIMORE
PHILADELPHIA ("40 malors & minors)
Same sequence as for BALTIMORE
PHTT.ATWiPHIA (g10 Oadnol samples)
Steps a, b (except only 10 fuel samples), and c of the
sequence used for BALTIMORE
NOTE: Run a repeat of any control sample result falling outside the Q/A
reproducibility objectives. If-the repeat result is outside the Q/A
objectives for reproducibility, determine the reason and resolve the
cause-for being outside the control limits.
D. Reporting
Data will be reported in the monthly progress reports in the
form of a complete set of all data for each of the cities in which fuel
samples were taken. All data generated under this Work Assignment, along
with a Q/A assessment, will be provided as a Submittal of Test Results at
the end of the project. The format for this submittal will be similar Co
that used in Work Assignment No. 18 under EPA Contract 68-03-3162. This
submittal will provide a. brief description of what was done and will
report all the data generated. It is planned to report the data separately
for each of the three cities using the formats previously used in Tables 1
-------
through 3 in the Final. Report EPA 460/3-84-009. In accord with the
Statement of Work, no provisions are included in this Work Plan for any
analyses of other than the Q/A results.
III. SCHEDULE OP COMPLETION.
The Statement of Work for Assignment Number 8 requests a technical
effort period of performance of 3 months. We project that obtaining the
reference standards, blending .the control fuels, verifying-accuracy and
repeatability, and conducting the analyses of the gasoline and control
samples, will require five months.
IV. STAFF ASSIGNMENTS .
The Task Leader and principal investigator of the Division 08 effort
called for in Work Assignment No. 8 will be Kathleen M. Olson. Project
Manager is Charles T. Hare of the Department of Emissions Research, and
the Division 03 Task Leader will be Charles M. Urban.
V. PROJECTED LABOR HOURS BY CATEGORY AND OTHER DIRECT COSTS
Based on our understanding of the requirements of the Work Assignment,
we project the following breakdown of employee utilization by category:
Labor Category Div. 03 Employee Hours Projected
Professional Level 4 6
Professional Level 3 12
Professional Level 2 40
Professional Level 1 16
Senior Technical 16
Technical 16
Clerical 32
Laboratory Assistant 8
.Total 146
We also project the following other elements of direct cost, not
including fee:
Direct Cost Elements Cost, Exclusive of Fee
Fuel Analyses (Div 08) $36,456
Purchased parts and
supplies 650
Photography, report
services, and com-
munications
Total
A-6
-------
VI. SUMMARY
Southwest Research Institute has replied in accord with our
understanding of Work Assignment No. 8, as revised verbally, Con-
tract No. 68-03-3192, in a full and complete manner. Should any
technical questions arise, please contact Mr. Hare at Area Code 512,
684-5111, extension 2646, or Mr. Urban at exntesion 2644.. If cost
questions arise, please contact. Gerald R, Krisch at extension 2236.
Submitted by:
Charles M. Urban Charles T. Hare
Senior Research Engineer Manager, Advanced Technology
Department of Emissions Research Department of Emissions Research
Engines, Emissions and Vehicl'e Engines j Emissions and Vehicle
Research Division Research Division
A-7
-------
APPENDIX B
ANALYTICAL PROCEDURES
B-l Alcohol Content of Unleaded Gasoline
-------
APPENDIX B-l
ALCOHOL CONTENT IN UNLEADED GASOLINE
% Methanol, Ethanol, and TEA in Gasoline
An internal standard, isopropanol, is added in known concentrations, along
with a pre-determined volume of gasoline sample, to distilled water. The
alcohols present in the gasoline are extracted with the distilled water and the
extract is introduced into a gas chromatography column. The eluted alcohols
are detected by a flame ionization detector and peak areas are measured with
an integrator. The peak areas are applied to the appropriate calibration curve,
from which the volume percent is obtained.
Method
1. Insert the column for alcohols in side "A" of G.C. - Column-SS
Porapak QS 80-100 mesh.
2. Set instrument on FID.
3. Carrier gas is helium - Auxiliary gases are hydrogen and air to light
the detector.
Conditions
He - Carrier gas 25 cc/min at 60 psi
Hydrogen 30 cc/min at 13.5 psi
Air 250 cc/min at 28 psi
Temperature
Oven 175°C
Injection Port 200°C
Detector 250°C
Integrator
FID
Delay - off
Stop - 5 min.
Area reject - 100 - (102)
Chart Speed - 1 cm/min
Slope Sens. - 1.00
Attenuation - 64
Range - 10
Single Channel
Atten. set on integrator
Zero - as needed for baseline
A & B side (not Diff.)
B-2
-------
APPENDIX B-l (CONPD)
Sample Size
0.75 u
1. Light detector and wait 15 min for instrument to stabilize. During
this period make up standard and extract the sample and standards.
Standard Preparation
Stock Standards - all of the standards must be extracted before being
injected.
Std. Cone. MeOH. ETOH. & TBA
0.0% -
0.1% 25 y£
0.5% 125 y£
1.0% 250 y£
3.0% 750 y£
5.0% ,1250y£
7.0% 1750 vi
10.0% 2500 yJl
12.0% 3000 yZ
Dilute to 25 m£ with Indolene.
Extraction of Alcohol - for Std.
-------
APPENDIX B-l (CONPD)
Notes
Do not use acetone to clean the syringe between samples - use the next
sample to be injected and rinse the syringe 4-5 times before injecting the
sample.
B-4
-------
APPENDIX B-2
AUTOMATIC RVP INSTRUMENT METHOD
(Excerpts from the Maintenance and Operating Instructions)
DESCRIPTION
The Reid Vapor Pressure Instrument operates automatically - after
sample loading - to determine the Reid Vapor Pressure of gasolines and other
hydrocarbons. The instrument reproduces manual ASTM test data.*
CALIBRATION PROCEDURES, FULL RANGE
This instrument measures the vapor pressure in psia of hydrocarbons at
100°F, expanded to five times its liquid volume. An equation relating absolute
pressure to Reid Vapor Pressure has been developed by computer analysis of
instrument data versus ASTM 0-323 data for a large number of hydrocarbon
samples. The instrument zero and span controls have been adjusted to convert
absolute pressure signals from the pressure transducer to equivalent RVP values
for the direct display of RVP on the meter.
OPERATION
Sample handling, including filling the sample cup, follows the ASTM D-323
procedure - except the cup is kept dry. (No water can be permitted in the
sample or sample system, and the sample need not be air-saturated).
The cup containing the sample is coupled to the instrument inlet fitting,
and a push-button "start" switch is momentarily depressed. The start light wUl
illuminate. At the end of 4 minutes, this light will go out, indicating
completion of the analysis. The RVP value for the sample will be locked on the
digital panel meter and may be read and recorded anytime before starting the
next test.
Depression of the "start" switch provides the impulse to start a ^-minute
cycle. The timer operates to produce the required analysis program.
*ASTM Method D-323, "Test for Reid Vapor Pressure of Petroleum," Part 23 of
ASTM Book of Standards.
B-5
-------
APPENDIX C
Fuel Sample Identification
-------
TABLE C-l. FUEL SAMPLE IDENTIFICATION
Baltimore
Sample
Number
1
2
3
4
5
6
7
8
9
10
Fuel
Type
R
R
R
P
R
R
R
P
R
R
Fuel
Brand
Amoco
ARCO
BP
Exxon
Getty
Gulf
Mobil
Shell
Sunoco .
Texaco
MAJORS
Gas Station Address.
Gallagar's Amoco
5931 Balto National Pike
Reedy Interprise
7001 Liberty Rd.
Corbin Auto Repair
18830 York Rd.
Eastern Ave.
-------
TABLE C-l (CONTD). FUEL SAMPLE IDENTIFICATION
Baltimore
Sample
Number
1*
15
16
17
IS
19
20
21
22
23
24
25
26
27
Fuel
Type
R
R
P
R
R
R
R
P
R
R
R
P
R
R
Fuel
Brand
Crown
Crown
Crown
Citgo
Merit
Crown
Hess
Crown
Crown
Crown
Crown
Merit
BP
Crown
MINORS
Gas Station Address-
Hillendale Crown
6819 Lock Raven Blvd.
Orleans Crown
1920 Orleans St.
Perry Hall Crown
8644 Belair Rd.
Marco Citgo
9301 Liberty Rd.
Merit Reisterstown
5128 Reisterstown Rd.
Charring Cross Crown
5217 Balto National Pike
Ken's Hess
9715 York Rd.
Catonsville Crown
500 Frederick Rd.
Ed's Crown
4500 W. Northern Pkwy.
Merritt Crown
1521 Merritt Blvd.
Towson Crown
935 York Rd.
Charles St. Merit
1801 N. Charles
Calvert's BP Station
8716 Liberty Rd.
Rodgers Forge Crown
7210 York Rd.
C-3
-------
TABLE C-l (CONPD). FUEL SAMPLE IDENTIFICATION
Baltimore
MINORS
Sample
Number
28
29
30
31
32
33
34
35
36
37
38
39
Fuel
Type
R
R
R
R
R
R
R
R
P
R
R
P
Fuel
Brand
Merit
Citgo
Citgo
Citgo
BP
No Brand
Big Red
Crown
BP
Seven-Eleven
Merit
Crown
Gas Station Address
Merit Franklintown
510 Franklintown Rd.
Whiz Milford Car Wash <3c Citgo^
8120 Liberty Rd.
Whiz Dolfield Car Wash <5c Citgo
3321 W. Colespring La
Fell Pt. Auto Repair
1500 Eastern Avenue
Jimen Enterprises
8913 Belair Rd.
Racetrac
8235 Eastern Ave.
Big Red Compass
1 Compass Rd.
Tony's Crown
8623 Lock Raven Blvd.
Weddmpn BP Gas
-------
TABLE C-2. FUEL SAMPLE IDENTIFICATION
Detroit
Sample
Number
40
41
42
43
44
45
46
47
48
49
50
51
52
Fuel
Type
R
R
R
R
R
P
P
R
R
P
R
R
R
Fuel
Brand
Boron
Shell
Union 76
Sunoco
Union 76
Amoco
Mobil
Total
No Brand
Speedway
Martin
No Brand
Total
MAJORS
Gas Station Address-
Gas and Go
Harper at Metro Pkway
Richard Aronki Shell
4000 N. Woodward, Royal Oak
Dallas
10350 Woodward at Harmon
Aranki Service
2931 E. Six Mile
Pat's Service
1102 Nine Mile, Hazel Park
Auto Elec. Center
4399 Highland Rd, Pontiac
Tillard's Mobil
Adams at Maple, Birmingham
MINORS
Total
14900 Gratiot
Frank's Full Service
26701 Gratiot, Roseville
Speedway
31015 Hoover & 13 .Mi. Warren
Blue Island Mini-Mart
5938 Michigan (at Joe St.)
You Save - Rubin Service
6641 Michigan Ave. At Clippert
Total #1187
Plymouth at Southfield
C-5
-------
TABLE C-2 (CONTD). FUEL SAMPLE IDENTIFICATION
Detroit
Sample
Number
53
54
55
56
57
58
59
60
61
62
63
64
65
66
Fuel
Type
P
R
R
P
R
" R
R
P
R
R
R
R
R
R
Fuel
Brand
Total
Total
Speedway
Total
Clark
Citgo
Tulsa
Total
Speedway
Clark
Total
Pennzoil
Clark
No Brand
MAJORS
Gas Station Address
//11601
Wyoming at Plymouth
Total
19018 Woodward at 7 Mile
#2268
22000 Lahser Rd.
Total
27360 Grand River
Clark
27480 W. Seven Mile, Livonia
Phil's Auto Service
29835 W. 8 mi. at Louise
Tulsa
3640 Six Mile, McNichols
Total
15 Mi. <5c Kelly, Fraser
Speedway Service
34977 Groesbeck, Fraser
Clark
30990 Utica Rd., Roseville
Total
12 mi <5c Utica
Pennzoil
DeQuindre at Greig
Clark Super 100
6800 Highland, Pontiac
K&C
3910 Grand River, Avery
C-6
-------
TABLE C-2 (CONPD). FUEL SAMPLE IDENTIFICATION
Detroit
Sample
Number
67
68
69
70
72
73
74
75
Fuel
Type
R
P
R
R
P
R
R
R
Fuel
Brand
Gas & Go
Host
Citgo
Martin
Hi-Fy
Clark
Total
Total
MAJORS
Gas Station Address
Gas & Go
3200 W. Warren
Dearborn Wheels
6425 Telegraph, Dearborn Hgts.
Citgo Enterprises
Telephone Rd.
Martin
26050 Ford Rd.
Hi-Fy
34010 Ford
Clark Super 100
111 Middlebelt, Garden City
Total
Cherry Hill and Venoy
Total
N. Mill and Wilcox, Plymouth
C-7
-------
TABLE A-3. FUEL SAMPLE IDENTIFICATION
Philadelphia
Sample
Number
76
77
78
79
80
SI
82
83
8*
85
86
87
88
Fuel
Type
R
R
R
P
R
R
R
R
R
R
P
R
R
Fuel
Brand
BPOil
Gulf
Amoco
Exxon
Sunoco
Mobil
Texaco
Citgo
Hess
BPOil
Alert
Merit
Hess
MAJORS
Gas Station Address
BP Oil #6896
Delaware Ave <5c Springgarden St.
#00*295*8
*8th
-------
TABLE C-3 (CONPD). FUEL SAMPLE IDENTIFICATION
Philadelphia
MINORS
Sample
Number
89
90
91
92
93
94
95
96
97
98
99
100
101
102
Fuel
Type
R
P
R
R
R
P
R
R
R
P
R
R
R
P
Fuel
Brand
Hess
Citgo
Golden
BPOil
Seven-Eleven
BPOil
Citgo
Merit
Merit
Hess
Merit
T.F.C.O.
Merit
Hess
Gas Station Address
#3821*
Rt. 202 <5c 422, Norristown
Norristown Citgo
Markley St. <5c Spruce, Norristown
Cinelli's Garage
2501 W. Main St. (Ridge Pk), Norristown
6870 BP Oil Inc.
Rt. 309 <5c Broad St., Colmar (Lansdale)
(7-11) - #20*35
Bethlehem Pk. and Butler, Ambler
#6912
Bethlehem Pk. <5c Penn Ave., Ft. Washington
Citgo Quick-Mart
Easton Rd. and Keswick, Glenside
Merit Self-Serve
Broad St. <5c Godfrey Ave.
Merit Bainbridge
Broad St. & Bainbridge
#38211
Torresdale Ave. <5c Harbison Ave.
Lehigh Merit
Lehigh <5c 5th St.
T.F.C.O. Fuel Co.
4201 Aramingo
Merit Self-Serve
Frankford
-------
TABLE C-3 (CONPD). FUEL SAMPLE IDENTIFICATION
Philadelphia
Sample
Number
103
104
105
106
107
108
109
110
111
112
Fuel
Type
R
R
R
P
R
R
R
P
R
R
Fuel
Brand
Hess
BPOil
Hess
BPOil
Citgo
Merit
Alert
Merit
Citgo
Wm. Penn
MINORS
Gas Station Address
#38216
Rt. 132 & 513, Bensalem
#6902
7999 Newfalls Rd., Levittown
#38275
Rd. 1 <$c Woodbourne, Langhorne
#6915
St. Rd.
-------
TABLE C-3 (CONPD). FUEL SAMPLE IDENTIFICATION
Philadelphia
Sample
Number
116
117
118
119
120
121
122
123
Fuel
Type
R
P
R
R
R
P
R
R
Fuel
Brand
ARCO
ARCO
ARCO
ARCO
ARCO
ARCO
ARCO
ARCO
OXINOL
Gas Station Address
A.M.-P.M. Mini-Market
Broad St. <5c Lehigh Ave.
Blvd. ARCO
Rt. 1 Festrvl Trevose
Paul Lopresti A.M.-P.M. Mini-Market
Passyunk Ave.
-------
APPENDIX D
Distillation Data
-------
TABLE D-l. DISTILLATION TEMPERATURES OF CONTROL
IBP 5%
Instrument 1
98 128
95 125
97 131
98 131
95 130
91 129
92 131
O
1 92 129
ho
Instrument 2
86 116
88 113
93 119
90 115
10%
144
142
146
148
146
143
146
146
133
130
138
134
15%
156
153
160
160
160
158
160
160
150
147
152
151
20%
168
167
172
172
171
170
173
172
166
163
166
166
30%
194
196
194
192
194
191
195
198
196
193
193
194
40%
212
214
211
212
211
210
212
214
213
210
209
210
50%
226
227
223
224
223
225
225
227
224
221
221
222
60%
239
239
235
235
238
236
237
238
236
233
234
233
' 70%
254
254
248
250
250
248
250
251
248
244
246
246
80%
279
267
275
274
273
270
278
276
270
267
270
268
90%
322
322
317
319
318
316
321
318
314
314
314
313
95%
349
350
343
343
340
337
351
343
338
338
338
336
FBP
396
394
385
384
385
386
386
388
376
368
374
372
Residue (%)
1.5
1.5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Recoverec
98.5
98.0
99.0
99.0
99.0
99.0
98.0
99.0
98.5
99.0
98.0
99.0
-------
TABLE D-2. DISTILLATION TEMPERATURES OF CONTROL 2
O
lap
5%
10%
15%
20%
30%
40%
50%
60%
70%
80%
90%
95% EP Residue
Instrument 1
99
96
98
95
95
96
97
97
97
97
118
115
120
117
117
115
117
117
117
117
124
123
128
125
124
123
124
124
124
124
132
132
134
132
132
131
131
132
131
131
140
140
141
140
139
138
138
138
139
139
163
161
165
165
163
163
161
163
163
163
195
195
193
196
195
195
195
196
196
196
216
217
216
217
217
218
217
218
217
218
230
230
232
230
230
231
234
233
231
231
243
244
246
244
242
245
246
247
245
245
264
265
268
266
264
267
268
268
267
266
306
307
311
310
311
310
310
311
310
310
335 379 1
333 380 1
335 379 1
338 378 1
337 379 1
335 381 I
337 380 1
338 379 1
337 380 1
337 380 1
Instrument 2
100
100
95
100
118
116
112
114
126
125
122
122
133
131
130
131
141
139
138
138
165
165
163
162
196
197
193
194
218
219
214
215
233
234
228
230
247
248
241
243
270
269
262
266
313
312
309
312
340 -a 1.5
338 376 1
335 374 1
338 380 V
Recovered (%)
99
99
99
99
99
99
99
99
99
99
98.5
99
99
99
a No data
-------
TABLE D-3. DISTILLATION TEMPERATURES OF FUEL EM-6I6-F
IBP _5%. 10% 15% 20% 30% 10% 50% 60% 70% 80% 90% 95% EP_ Residue (%) Recovered (%)
Instrument i
88 114 127 136 It7 165 186 209 236 263 289 324 350 406 1 99
90 115 127 135 146 164 188 210 238 264 291 326 352 398 1.5 98
90 118 130 138 150 172 ~a 207 236 264 296 334 a 414 I 99
90 114 128 137 148 168 186 208 237 263 295 327 355 409 1 99
Instrument 2
90 111 124 132 144 164 186 210 237 262 289 321 346 408 1 99
91 112 125 133 144 165 188 212 237 264 290 328. 348 401 1.5 98
89 110 123 133 143 164 187 210 236 263 296 332 354 405 I 98
91 109 120 130 140 162 186 207 232 261 291 327 350 404 I 99
a No data
------- |