United States
Environmental Protection
Agency
Office of Mobile Source Air Pollution Control
Emission Control Technology Division
2565 Plymouth Road
Ann Arbor, Michigan 48105
EPA 460/3-84-009
September 1984
c/EPA
Ait
Volatility of In-Use Gasoline and
Gasoline/Methanol Blends
-------
EPA 460/3-84-009
Volatility of In-Use Gasoline
and Gasoline/Methanol Blends
by
Charles M. Urban
Southwest Research Institute
6220 Culebra Road
San Antonio, Texas 78284
Contract No. 68-03-3162
Work Assignment No. 14
EPA Project Officers: Robert J. Garbe
Craig A. Harvey
EPA Branch Technical Representative: Robert J. Garbe
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
Office of Mobile Source Air Pollution Control
Emission Control Technology Division
2565 Plymouth Road
Ann Arbor, Michigan 48105
September 1984
-------
This report is issued by the Environmental Protection Agency to report
technical data of interest to a limited number of readers. Copies are available
free of charge to Federal employees, current contractors and grantees, and
nonprofit organizations - in limited quantities - from the Library Services
Office, Environmental Protection Agency, 2565 Plymouth Road, Ann Arbor,
Michigan, 48105.
This report was furnished to the Environmental Protection Agency by/Southwest
Research Institute, 6220 Culebra Road, San Antonio, Texas, in fulfillment of
Work Assignment 14 of Contract No. 68-03-3162. The contents of this report
are reproduced herein as received from Southwest Research Institute. The
opinions, findings, and conclusions expressed are those of the author and not
necessarily those of the Environmental Protection Agency. Mention of
company or product names is not to be considered as an endorsement by the
Environmental Protection Agency.
Publication No. EPA 460/3-84-009
11
-------
FOREWORD
This Work Assignment was initiated by the Control Technology
Assessment and Characterization Branch, Environmental Protection Agency,
2565 Plymouth Road, Ann Arbor, Michigan 48105. The effort on which this
report is based was accomplished by the Department of Emissions Research of
Southwest Research Institute, 6220 Culebra Road, San Antonio, Texas 78284.
This program, authorized by Work Assignment 14 under Contract 68-03-3162,
was initiated February 29, 1984 and was completed September 28, 1984. The
program was identified within Southwest Research Institute as Project 03-7338-
014.
This Work Assignment was conducted by Mr. Charles Urban, Project
Leader, and Mr. Joseph Fisher, Task Leader for the fuels sampling and analyses.
Mr. Charles Hare was Project Manager and was involved in the initial technical
and fiscal negotiations and subsequent major program decisions. The EPA
Project Officers were Mr. Robert J. Garbe and Mr. Craig A. Harvey of the
Technical Support Staff, Environmental Protection Agency.
-------
ABSTRACT
This report provides results of analyses for alcohol content, volatility, and
other properties of forty in-use unleaded gasoline samples. Analyses conducted
on these fuels included: methanol, ethanol, and tertiary butyl alcohol (TBA)
quantitation; Reid vapor pressure; distillation; water and lead content; and the
calculation of FEVI and El volatility indices. Twenty-two of the forty samples
contained between three and five percent methanol. Most of the gasoline
samples, including those not containing methanol, contained several percent
TBA. Data obtained indicated the volatility of fuels containing methanol and
TBA were not significantly different from that of fuels containing only TBA.
The data also showed an average RVP of 13.3 and 13.6 psi respectively for these
fuels, which, is above the maximum ASTM specified RVP of 11.5 psi for the
Houston area at the time these samples were taken.
IV
-------
TABLE OF CONTENTS
Page
FOREWORD iii
ABSTRACT iv
LIST OF FIGURES vi
LIST OF TABLES vii
I. INTRODUCTION 1
II. GASOLINE SAMPLING 2
III. ANALYTICAL PROCEDURES 5
IV. RESULTS OF THE GASOLINE ANALYSES 7
V. ANALYSES AND DISCUSSION OF THE DATA 11
APPENDICES
A. MVMA SAMPLE COLLECTION PROCEDURE (MODIFIED)
B. ANALYTICAL PROCEDURES
C. CALCULATION OF VOLATILITY INDICES
-------
LIST OF FIGURES
Figure Page
1 Relationship of RVP to Percent Methanol
Concentrations 12
2 Relationship of RVP to Percent TBA
C oncent rations 13
3 Plot of the Average Distillation Values for
Methanol- and Nonmethanol-Containing Samples 14
4 Relationship Between El and FEVI 15
5 Relationship Between Water Content and Percent
TBA Concentration 16
VI
-------
LIST OF TABLES
Table Page
1 Location of Seven-Eleven Stores Sampled 3
2 Summary Results of Fuels Analyses 8
3 Distillation Data 9
vii
-------
I. INTRODUCTION
The objective of this Work Assignment was to obtain and analyze forty
samples of in-use gasoline. It was desired that about half of the samples
contain Oxinol, a fuel additive containing methanol and tertiary butyl alcohol.
All gasoline samples were to be obtained, in an essentially random manner,
from Seven-Eleven Stores in and around Houston, Texas.
Analyses of these gasoline samples included: methanol, ethanol, and TBA
content; Reid vapor pressure (RVP); distillation; and water and lead content.
Distillation and RVP data were then utilized to calculate FEVI and El volatility
indices. Graphical presentation and statistical analyses, to the extent
appropriate, were applied to the data to determine trends, especially as regards
comparisons between the base unleaded gasolines and the gasoline/Oxinol
blends.
-------
II. GASOLINE SAMPLING
Contact was made with the Southland Corporation, provider of fuels to
Seven-Eleven Stores in Houston, in an attempt to determine which stores were
distributing base gasoline and which were distributing Oxinol/gasoline blends.
The requirements for obtaining such information were stated to be as follows:
EPA would have to write a letter of request; Southland's attorneys would review
the request; and if approved, SwRI would be provided the information. The EPA
Project Officer decided that time requirements did not allow for this written
approach toward obtaining information. It was confirmed verbally that base
gasolines and gasoline-methanol blends were being provided to the Seven-Eleven
Stores. Based on a very informal sampling, the personnel at the individual
stores did not appear to know whether or not the unleaded gasoline they were
selling contained methanol. A decision was reached by the EPA Project Officer
to initially obtain the total of 40 fuel samples in an essentially random sampling
of the Seven-Eleven Stores in Houston, Texas.
The sample site selections were made on the basis of information on
Seven-Eleven Stores as found in the Houston telephone directory. There were
about 165 stores listed within Houston districts. Therefore, one-fourth of the
stations within each district were designated for samples. Choices were made
for each district by selecting the second store listed in the telephone directory,
followed by each fourth store thereafter. At the request of the EPA Project
Officer, duplicate fuel samples were taken at several of the stations, and those
samples were sent to the EPA for analyses.
Provisions were included to allow substitutions within a district when a
sample could not be obtained from a designated store (e.g., some stores were
closed, some were no longer selling gasoline, etc.). The primary aim was to
obtain forty fuel samples (plus several duplicate samples) in an unbiased manner
from Seven-Eleven Stores in the Houston area, with the selected stores having
reasonable geographic distribution. Sampling and handling procedures used are
described in Appendix A.
All samples were collected during the period of late March through April.
The source locations of the samples are listed in Table 1. Less than ten source
substitutions were required in the original list of forty sources, and several of
these substitutions were to another Seven-Eleven Store a few blocks away on
the same street.
All pumps from which gasoline samples were taken were labeled with an
R + M/2 octane number of 87. There was no indication on any of the pumps
that the gasoline contained alcohols. With few exceptions, in subsequent
analyses it was determined that gasoline samples from the south side of
Houston contained methanol, and those from the north side did not contain
methanol. The reason for the differing methanol content in different areas of
Houston was not determined, but it was possibly due to different terminals
distributing gasoline to different parts of the city.
At the direction of the Project Officer, effort allocated for large-
quantity sampling was redirected toward preparation of two fuel batches for
-------
TABLE 1. LOCATION OF SEVEN-ELEVEN
STORES SAMPLED
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
District
Southwest
Champions3
West
West
West
Northwest
North
North
North
Northwest
Northwest
Champions*5
Northwest
Champions'3
Northwest
North
Northwest
West
North
North
Southeast
South
Southeast
Northwest
Southeast
Pasadena3
Pasadena3
Pasadena3
Pasadena3
Pasadena3
South
Pasadena3
Pasadena3
Pasadena3
South
Southwest
Southwest
West
South
Southwest
Address
6031 Willow Bend
11050 S. Post Oak
6333 San Felipe
1100 W.Alabama
9230 Buffalo Spwy.
6541 W. 43rd
7501 Airline
10301 Shady Lane
2331 Little York
4730 Brinkman
1302 N. Shepherd
5623 Aldine Bender
5718 W. 34th
2950 Greens Road
602 W. Parker Road
5711 Irvington
4401 Irvington
1326 Dairy Ashford
4809 N. Main
2302 White Oak
8637 Glenvista
9602 Telephone
4302 Telephone
2050 Single
6154 Bellfort
5010 Red Bluff
2521 Strawberry
902 Allen Genoa Road
3500 Fairmont Pkwy
6402 Spencer
10855 Telephone
901 W. Harris
502 S. Shaver
3202 Pasadena Frwy
11402 Hughes
8920 Bissonnet
11313 Fondren
5805 Bellair
10602 Fugua
10096 S. Gessner
3Southeast side of Houston
^North side of Houston
-------
use at EPA's Ann Arbor facility. These fuels were an 11.0-11.5 RVP
commercial base gasoline, and a blend of the heavier ends of this gasoline with
9.5% Oxinol to achieve a fuel with a matching Evaporative Index. The effort
was started under Work Assignment No. 1 of Contract 68-03-3192 and
concluded under the subject assignment. A description of the fuel treatment
and blending processes is included as Appendix A-5 to this report. All fuel
drums of each fuel were shipped to EPA.
-------
III. 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 MVMA survey samples, has been
found to be a satisfactory alternate method. This method is
described in Appendix B.
• 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-17W, Karl Fischer Titration
(pyridine free).
•LEAD (Weight Percent) - ASTM D-3237, Atomic Absorption
Spectrometry.
• FEVI AND El VOLATILITY INDICES - These indices were calculated
from the RVP and distillation data using formulas supplied by EPA:
FEVI = RVP + 0.13x(% EVAP @ 158°F)
El = l.lxRVP - 0.32x(% EVAP @ 100°F) + 0.21x(% EVAP @ 200°F
The distillation, water content, and lead content evaluations involve
standard ASTM methods for which repeatabilities have been established,
although it is not known if these repeatabiiities are directly applicable to
gasoline/methanol blends:
• Distillation D-86 - Repeatability varies from about 2 to 5°F
depending on the rate of temperature rise.
•Water Content D-1774 - Repeatability applicable to aviation turbine
fuels is about 0.001 percent for water content between 0.005
and 0.1 percent.
• Lead Content D-3237 - Repeatability is 0.005 g/gal.
-------
For the alcohol content and the RVP evaluations, a control sample was analyzed
periodically . Five individual gallon samples of a single batch of fuel containing
Oxinol were analyzed for alcohol content and RVP; one at the start of the
analysis of the in-use gasoline samples, and one each tenth sample thereafter.
Although of value here only for purposes of comparison, the repeatability and
reproducibility for the standard ASTM D 323 RVP method are 0.25 and 0.55 psi
respectively within the range of 0 to 15 psi.
-------
IV. RESULTS OF THE GASOLINE ANALYSES
Results of the analyses on the forty gasoline samples are summarized in
Tables 2 and 3, and details concerning the El and FEVI volatility index
calculations are given in Appendix C. Relationships between parameters are
discussed in Section V of this report. The following discussion is based on the
data in Table 2.
RVP - The RVPs ranged from 12.4 to 14.3 psi for the samples that
contained methanol (MeOH), and from 13.3 to 14.3 psi for those not containing
methanol. The average RVPs were 13.3 and 13.6 psi, respectively. For the
control samples, the RVP results were as follows:
Analyses RVP, psi
Initial 10.3
Between Samples 10&11 10.2
Between Samples 20&21 10.2
Between Samples 30&31 10.2
Final 10.1
According to ASTM D 439 the specified seasonal RVPs for the Houston area
are:
Volatility
Month Designation Max. RVP, psi
January D 13.5
February C !' 44*5- '-.
March ' C 1K5
April C or-B— 11.5
May B C _IQ&-
June B 10.0
July B 10.0
The forty fuel samples analyzed in the work assignment were all collected
during the period of late March through April.
RVP analyses of four duplicate samples (Numbers 23, 34, 35, 37) were
performed by the EPA, and the results obtained were reported to be 0.4 to 0.7
psi lower than the values obtained under this Work Assignment. These values
obtained by the EPA support those determined by SwRI within reasonable limits
for the four samples, and by extrapolation do so for all forty samples.
Alcohol Content - With one exception, the gasoline samples either
contained 4.5 to 4.9 percent by volume methanol, or no methanol. In general,
samples from the south side of Houston contained methanol, and those from the
north side did not contain methanol. No ethanol was detected in any of the
forty samples. Samples containing 4.5 to 4.9 percent methanol were found to
-------
TABLE 2. SUMMARY RESULTS OF FUELS ANALYSES
Sample
Number , District
/
3
ft
Jl
"~T
|17
i'l 8
9
^JO
11
12
13
rift
'V 15
16
17
18
19
20
— ""
21
22
1, 23
'n 2ft
1 25
,;L?26
n 27
28
29
30
31
32
33
3ft
35
36
37
38
39
ftO
Avg.
Avg.
Avg.
S.D.
S.D.
^m
/Southwest
Champions
West
West
West
Northwest
North
North
North
Northwest
Northwest
Champions
Northwest
Champions
Northwest
North
Northwest
West
North
North
— -^~
Southeast
South
Southeast
Northwest
Southwest
Pasadena
Pasadena
Pasadena
Pasadena
Pasadena
South
Pasadena
Pasadena
Pasadena
South
Southwest
Southwest
West
South
Southwest
with MeOH
w/o MeOHa
, w/o MeOH
with MeOH
w/o MeOHa
% by Volume
MeOH
ft.9
ft.6
ft.6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
ft.6
ft.5
ft.7
0
ft.7
ft.6
ft.7
ft.5
ft.7
ft.5
ft.9
3.3
ft.6
ft.7
ft.7
ft.7
ft.7
ft.6
ft.5
ft.8
ft.7
0
0
0.1
0
TEA
ft.3
ft.2
ft.l
0.3
0.2
3.9
7.0
ft.8
6.9
3.9
ft.6
6.8
5.9
7.0
5.8
5.8
5.3
1.1
0.8
6.1
ft.O
ft.2
ft.2
6.1
ft.2
ft.O
ft.2
ft.O
ft.2
ft.O
ft.ft
2.9
ft.l
ft.l
ft.l
ft.2
ft.l
ft.l
ft.O
ft.3
ft.l
5.7
0.6
0.1
1.1
RVP,
psi
lft.2
lft.3
lft.1
13.5
13.5
13.6
13.3
lft.1
13.5
lft.0
13.6
13.5
lft.3
13.4
13.8
13.4
13.5
13.9
13.8
13.4
13.2
13.7
13.7
13.4
12.9
13.1
13.1
12.7
13.1
12.7
13.1
13.1
13.2
13.1
12.4
lft.3
12.9
12.9
13.1
13.8
13.3
13.6
13.7
0.6
0.3
Water
Content
Percent
0.10
0.12
0.11
0.02
0.01
0.10
0.19
0.13
0.19
0.09
0.12
0.21
0.18
0.20
0.20
0.19
0.17
0.02
0.01
0.18
0.12
0.12
0.11
0.16
0.11
0.11
0.11
0.18
0.11
0.11
0.11
0.09
0.12
O.lft
0.12
0.11
0.11
0.11
0.11
0.11
0.12
0.17
0.02
0.02
0.0ft
Distillation,
Lead,
g/gal
0.002
0.001
0.002
0.001
0.001
0.002
0.00ft
0.001
0.003
0.002
0.001
0.001
0.002
0.001
0.001
0.003
0.001
0.003
0.001
0.025
0.001
0.001
0.001
0.002
0.00ft
0.003
0.002
0.002
0.001
0.001
0.001
0.001
0.001
0.001
0.002
0.002
0.002
0.00ft
0.002
0.001
0.002
0.002
0.002
0.001
0.001
°F at % Evap.
10%
102
103
107
97
95
101
99
100
102
98
101
106
98
102
101
10ft
10ft
96
92
103
106
108
108
103
111
110
108
lift
109
108
110
103
107
102
10ft
105
109
107
109
105
107
101
95
3
2
50%
189
195
203
188
198
183
173
186
181
173
185
185
168
179
185
178
179
187
193
173
193
196
195
18ft
202
202
195
207
197
20ft
199
195
198
19ft
196
195
200
202
199
187
198
179
192
5
6
90%
333
3ftO
3ft5
338
3ft5
339
3ft8
3ft7
3ft8
335
3ft8
352
338
3ft8
3ft7
3ft7
357
331
341
3ft8
336
3ftO
337
3ft5
3ft2
332
339
339
3ft5
339
3ft3
341
341
333
332
3ft5
341
332
335
3ft9
339
3ft6
339
5
6
Calculations
El
23.8
23.7
22.5
22.3
21.4
23.ft
23.3
23.6
23.ft
2ft.O
23.2
23.6
2ft.6
23.5
23.ft
23.8
23.8
2ft.2
23.1
2ft.O
23.1
23.7
23.7
23.3
22.7
22.9
23.1
22.9
23.2
22.ft
23.2
22.5
23.0
22. ft
21.7
23.9
22.8
22.ft
22.9
23.9
23.1
23.6
22.8
0.7
0.4
FEVI
19.4
19.4
18.9
18.7
IS.ft
18.9
18.9
19.3
18.8
19.7
18.9
IS.ft
19.4
18.7
18.9
18.9
18.9
19.3
19.0
19.0
18.2
18.7
18.6
18.6
17.6
17.8
18.1
17.2
18.0
17.4
18.0
18.0
18.2
18.1
17.3
19.3
17.7
17.6
17.9
19.1
18.2
19.0
18.9
0.7
0.3
aExcluding sample numbers ft, 5, 18, and 19
-------
TABLE 3. DISTILLATION DATA
Sample Pet.
Number MeOH
Temperature °F at % Evaporated
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Avg.
Avg.a
Avg.
S.D.
S.D.a
4.9
4.6
4.6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4.6
4.5
4.7
0
4.7
4.6
4.7
4.5
4.7
4.5
4.9
3.3
4.6
4.7
4.7
4.7
4.7
4.6
4.5
4,8
4.7
0
0
4.7
0
IBP
78
81
85
75
72
79
78
80
76
80
77
82
76
80
81
80
90
77
74
81
87
87
84
81
86
84
84
91
86
86
86
80
83
84
85
79
87
88
84
81
85
79
75
3
2
5%
86
89
91
85
81
88
87
86
88
87
87
90
87
90
86
91
91
85
81
91
95
97
95
91
98
98
96
104
98
99
99
91
96
91
90
92
98
96
96
93
95
88
83
4
2
10%
102
103
107
97
95
101
99
100
102
98
101
106
98
102
101
104
104
96
92
103
106
108
108
103
111
110
108
114
109
108
110
103
107
102
104
105
109
107
109
105
107
101
95
3
2
15%
110
111
115
106
104
110
106
111
111
107
110
116
106
112
111
113
113
104
101
112
114
115
116
113
119
117
116
120
116
115
117
110
113
111
112
114
116
116
116
112
115
111
104
3
3
20%
116
118
122
114
113
118
118
119
121
115
118
126
115
122
121
120
121
112
109
120
120
122
123
122
126
124
122
127
122
123
123
117
121
118
119
121
123
124
123
118
122
120
112
3
3
30%
132
134
139
133
136
135
136
137
140
130
135
144
131
139
139
137
137
129
129
136
135
136
139
139
142
140
137
143
137
140
138
137
137
135
137
137
139
141
139
132
138
137
132
3
4
40%
157
160
167
158
164
155
152
158
157
149
156
162
148
156
159
153
154
154
159
151
163
161
163
158
169
169
162
174
164
169
165
164
163
161
164
162
167
169
166
156
164
155
159
4
4
50%
189
195
203
188
198
183
173
186
181
173
185
185
168
179
185
178
179
187
193
173
193
196
195
184
202
202
195
207
197
204
199
195
198
194
196
195
200
202
199
187
198
179
192
5
6
60%
222
233
238
222
234
218
209
223
218
207
222
225
202
217
222
214
216
221
226
208
230
235
230
223
236
232
229
238
228
234
231
225
230
225
228
232
232
235
228
227
231
215
226
4
7
70%
252
265
270
255
271
253
253
261
260
243
261
270
231
261
262
259
260
253
259
256
261
269
262
264
268
258
260
264
255
261
262
254
259
252
256
266
263
265
251
266
261
256
260
6
10
80%
286
299
302
293
307
295
304
302
307
286
303
312
285
305
305
304
306
286
294
305
295
304
298
302
300
288
296
296
290
291
295
293
290
284
287
303
295
296
283
305
294
301
295
7
8
90%
333
340
345
338
345
339
348
347
348
335
348
352
338
348
347
347
357
331
341
348
336
340
337
345
342
332
339
339
345
339
343
341
341
333
332
345
341
332
335
349
339
346
339
5
6
95%
365
374
375
372
375
372
379
380
379
366
381
384
374
381
377
374
384
367
376
381
376
377
376
376
376
373
368
375
384
375
379
376
383
372
363
380
372
370
377
386
375
378
373
6
5
EP
395
415
414
403
413
409
403
415
412
397
414
423
403
405
413
413
416
395
408
409
412
416
416
412
409
416
412
416
415
408
410
413
418
412
400
411
404
408
415
415
411
410
405
6
7
a£xcluding sample numbers 4, 5, 18, and 19
-------
also contain 4.0 to 4.4 percent TBA (an average of 87 percent as much TBA as
methanol). One sample (Number 32) contained 3.3 percent methanol and 2.9
percent TBA (88 percent as much TBA as methanol). For the control samples,
no ethanol was detected, and the methanol (MeOH) and TBA concentrations
were as follows:
Volume Percent
Analyses MeOH TBA
Initial 4.8 4.5
Between Samples 10& 11 4.4 4.1
Between Samples 20&21 4.5 4.2
Between Samples 30&31 4.5 4.1
Final 4.6 4.2
All forty in-use samples contained measurable amounts of TBA. Ten
samples, out of the eighteen with no measurable methanol, contained over five
percent TBA. Only three samples contained less than one percent TBA, and
only five samples had less than three percent TBA.
Water Content - The average water content was 0.12 weight percent for
the samples containing methanol, 0.17 percent for the samples without
methanol that contained over 1.1 percent TBA, and 0.02 percent for the
samples without methanol that contained 1.1 percent TBA or less. The ranges
of the water content were 0.09 to 0.18, 0.10 to 0.21, and 0.01 to 0.02 percent,
respectively. For the samples that did not contain methanol, there appeared to
be some relationship between TBA content and the water content.
Lead Content - With the exception of one sample (Number 20) having a
lead content of 0.025 g/gal, the lead content ranged from 0.001 to 0.004 g/gal.
With the method of analyses having a repeatability of 0.005 g/gal, only the
0.025 g/gal result appears to represent a significant value.
Distillation - Excluding the four samples having less than 1.2 percent
TBA, the methanol-containing samples required higher temperatures for 10%
and 50% distillation and a lower temperature for 90% distillation. Detailed
distillation data are given in Appendix C. For all samples distilled, the residue
was one percent and the losses ranged from one to three percent. The average
losses were 2.0 percent for the samples containing methanol, and 2.4 percent
for the samples with no measurable methanol.
El and FEVI Volatility Indices - The El varied from 21.7 to 23.8, with an
average of 23.1, for the samples containing methanol; and from 21.4 to 24.6,
with an average of 23.4, for the samples having no measurable methanol. The
FEVI varied from 17.2 to 19.4, with an average of 18.2, for the samples with
methanol; and from 18.4 to 19.4, with an average of 19.0, for the samples with
no methanol.
10
-------
V. ANALYSIS AND DISCUSSION OF THE DATA
The data obtained were analyzed for trends, especially as regards
comparisons between the samples without methanol and the Oxinol/gasoline
blends. Initial analyses involved plotting of various parameters; several of
these plots are given in Figures 1 through 5.
With reference to Figures 1 and 2, there is no observable relationship
between the RVP and the methanol concentration, or between the RVP and the
TBA concentration. With reference to Figure 3, there is some difference
between the average distillation curves for samples with and without methanol,
the maximum difference being a temperature of lloc(19OF) at fifty percent
evaporated. With reference to Figure 4, there is an apparent relationship
between the El and the FEVI volatility indices. With reference to Figure 5,
there appears to be some relationship between water content and the
concentration of TBA. The available data, however, do not enable specific
determination of that relationship with a reasonable degree of confidence.
Based on observations of the plotted data, detailed statistical analyses were
considered inappropriate.
There are several observations and conclusions, however, which can be
made concerning the data generated on the forty gasoline samples:
1. Of the 22 samples containing methanol, 21 had methanol
concentrations between 4.5 and 4.9 percent. On the average, these samples
contained about 87 percent as much TBA as methanol. One methanol-
containing sample had 3.3 percent methanol and 2.9 percent TBA (88 percent as
much TBA as methanol). Therefore, it appears that this sample with 3.3
percent methanol may represent a blend of a base unleaded gasoline and a
standard blend of Oxinol/gasoline.
2. All forty samples, including those without measurable methanol,
contained tertiary butyl alcohol (TBA). Of the 18 samples having no methanol,
14 had TBA concentrations between 3.9 and 7.0 percent (with an average of 5.7
percent). The other four samples with no methanol had TBA concentrations
between 0.2 and 1.1 percent (with an average of 0.6 percent).
3. None of the samples contained a measurable amount of ethanol.
4. In general, samples obtained from the south side districts of Houston
contained methanol, and those obtained from the north side districts did not
contain methanol. Three of the four samples containing less than 1.2 percent
TBA were obtained from the west Houston district.
5. There was no observable relationship between RVP and the
concentration of methanoi or TBA. Average RVP for samples containing
methanol was 13.3 psi, and that for samples not containing methanol was 13.6
psi. It appears likely that all samples were blended to a nominal RVP of 13.5
psi.
11
-------
15 r—
A
14
A
w
en
0)
o
0,
(0
T3
•H
0)
13
• Methanol and TBA
A TBA Only
••*•
Note: Pa = 6.895xpsi
12 *- I I
1234
Percent Methanol by Volume
Figure 1. Relationship of RYP to methanol concentration
12
-------
15
• Methanol and TEA
A TEA Only
• A
14 r A
Q.
0)
^
a
*
« 12
A AA
A 44 A
Note: Pa = 6.895xpsi
12
L
4
Percent TEA by Volume
Figure 2. Relationship of RVP to TEA concentration
13
-------
500,-
400
300
0)
H
JJ
-------
25 r
24
w 23
•a
-------
0.2
c
-------
6. The samples were collected during the period of late March through
April.
7. There appears to be some relationship between water content and
TBA concentration. Highest concentration of water in any of the samples was
0.20 percent.
8. With the exception of one sample (Number 20), the lead content was
essentially negligible (i.e., it was less than the repeatability of the procedure).
Sample 20 had a lead content of 0.025 g/gal, indicating some, although not
excessive, contamination of that sample with leaded fuel.
9. In general, the distillation curves for samples containing methanol
differed from the curves for samples containing no methanol, around mid range
of the distillation. That is, the average temperature for 50 percent evaporated
was 198°F for the samples containing methanol, and 179°F for the samples
containing no methanol and over 1.1 percent TBA.
10. There were no major differences in the overall average El or FEVI
volatility indices between samples containing methanol and those containing no
methanol. This result could be expected, since the volatility indices are
primarily a function of the RVP, and the RVP's did not differ by any significant
amount. For these samples, the RVP accounted for about two-thirds of the
total value of the volatility index. There appeared to be some relationship
between El and FEVI; this could also be expected since both indices are
primarily a function of the same parameter, RVP.
17
-------
APPENDICES
A. MVMA SAMPLE COLLECTION PROCEDURE (MODIFIED)
B. ANALYTICAL PROCEDURES
C. CALCULATION OF VOLATILITY INDICES
-------
APPENDIX A
MVMA SAMPLE COLLECTION PROCEDURE (MODIFIED)
A-l GENERAL INSTRUCTIONS
A-2 DRIVER'S INSTRUCTIONS
A-3 PURCHASE-PACK-SHIP SERVICE
A-4 SAMPLE OF ORIGIN REPORT
A-5 PREPARATION OF FUELS FOR EPA
-------
APPENDIX A-l
GENERAL INSTRUCTIONS
A package is sent to the agent two weeks prior to the pick-up date. This
package contains:
a. Attachment Sheets - A list of the gasoline stations and grade of fuel
to be purchased. *No substitutions are made by the agent, without
the consent of Southwest Research Institute.
b. Field Origin Report - Report of the brand and location of each
marketer sampled. These reports are to be completed and returned
in order to be paid.
c. NA & UN Labels - Shipping regulations require these stickers to be
affixed on the top of the boxes for the return shipment.
d. Letter of Instructions - enclosed.
e. Return Address Envelope -61/2x91/2 Manila Envelope. This is a
convenience for the agent to return the field origin reports needed.
Preparations
Tags; Each can is tagged for sample identification indicating the brand name
and grade of fuel to be purchased.
Boxes; A Federal law states that all flammable liquids are to be cargo with the
inscription DOT 12B APP stamped on the side of the box. These boxes are
purchased thru Southwest Research Institute from Mission City, San Antonio,
Texas.
Packing; Place the tagged cans into the shipping cartons with six cans to each
carton. Extra cans are added if for any reason some are damaged during
shipment. A shipment package is included which contains:
a. Seals - to eliminate any leaks.
b. Caution stickers - prevent any danger during shipment.
c. Return address - Address to the Department of Petroleum
Chemistry Laboratory
d. SwRI tape - To seal the boxes before shipping to Southwest
Research Institute
A-2
-------
APPENDIX A-2
DRIVER'S INSTRUCTIONS
Making the Purchase
1. Insert the nozzle of the hose near the bottom of the can.
2. Fill the cans with designated grade of fuel as indicated on the tag.
3. Place the seal in the opening, press down firmly, and screw the cap on
hand tight.
1. Lay the can on its side and check for leaks. If the can leaks, check that
the seal is snapped into place and tighten the cap sufficiently so that the
can does not leak. Extra cans will be supplied so that, if a leak develops
which cannot be corrected, a new sample may be taken.
Packing and Shipping
1. Affix the address and NA or UN labels to the top of shipping cartons.
a. UN 1203 labels are to be affixed on top of shipping cartons
containing gasoline samples.
b. NA 1993 labels are to be affixed on top of shipping cartons
containing diesel samples.
2. Affix the caution labels on the side of the shipping cartons.
3. Check cans once again to be certain that they will not leak in shipment.
Check that the tag is secure on the can.
4. Use Attachment A as a check list to assure that all the designated fuel
samples have been obtained.
5. Insert can in shipping carton with six cans to each carton. Place an empty
can and/or filler in any empty space in the carton. Do not ship partially
filled cartons. There must be 6 cans in each carton shipped. If there is
any reason for not being able to ship samples by the deadline date on the
Attachment A letter, please notify Patsy R. Perez, collect, immediately
at (512) 684-5111, ext. 2868.
6. Seal the cartons with tape. Take cartons to the specified motor or air
freight terminal and ship collect.
A-3
-------
APPENDIX A-3
PURCHASE-PACK-SHIP SERVICE
FOR SOUTHWEST RESEARCH INSTITUTE
GENERAL INSTRUCTIONS
1. All supplies necessary for purchasing, packing and shipping of fuel will be
furnished by Southwest Research Institute. Prior to the specified date for
purchasing fuel, the following materials will be shipped to you:
a. A sufficient number of empty cans for obtaining samples.
b. Sample identification tags attached to each can indicating the brand
name and grade of fuel to be purchased.
c. One or more shipping cartons each accommodating six cans.
d. Caution labels to be affixed to the top of shipping cartons.
e. Labels addressed to Southwest Research Institute for return
shipment.
f. UN and NA labels to be affixed to the top of shipping cartons.
g. Tape for resealing cartons for return shipment.
2. Enclosed with these instructions are the following items:
a. Drivers instructions - instructions for the proper method of sampling
and packing the fuel.
b. Attachment A - A check list of the marketers and grades of fuel to
be purchased. The sampling date is indicated here.
c. Attachment B - A list of marketers and grades of fuel which is to be
returned with the samples.
d. Field origin report - A report of the brand and location of each
marketer sampled. These reports must be completed and returned
in order to be paid for the sample pick-up.
3. Important - Make every effort to obtain each sample listed.
If there is any sample on the list that is not available, call Patsy R. Perez,
collect, (512/684-5111, ext. 2868), for further instructions. Do not make
any deletions or substitutions to the list without approval from Southwest
Research Institute.
4. If any questions arise, please call collect; Patsy R. Perez, Southwest
Research Institute, (512/684-5111, ext. 2868).
A-4
-------
APPENDIX A-4
SAMPLE OF ORIGIN REPORT (Original and 3 Copies)
MVMA
FIELD SAMPLE
ORIGIN REPORT
SOUTHWEST RESEARCH INSTITUTE
FOR LABORATORY
USE ONLY
OtySamoM
Brand Nam*
Nanw at S«vca Scaoon
o*S«vica Station
_ R +• M/2 (S)
G Premium UnlMd«d
Gf«d«NanM
_ R > M/2 (PJ
Q Pramtum Loaded
(3nd>N«TM
CHECK PROPER BOX
_ fl -K M/2 (U)
Q Regular Unleaded
QraoaNanw
_ R +• M/2 (H)
Q Regular Leaded
QMMNOTM
_ R -t- M/2 (G)
D Gasohol
GiadcNanw
Number of Stations of This Brand Visited to Obtain These Samples
Q One ' D Two D Three
PLEASE MAIL IN DUPLICATE TO SOUTHWEST RESEARCH INSTITUTE
Retain gold copy for your records.
A-5
-------
APPENDIX A-5
PREPARATION OF FUELS FOR EPA
MEMORANDUM
DATE: 28 March 1984
TO: C.T. Hare
FROM: J.A. Russell
SUBJECT: EPA OXINOL BLENDING CHRONOLOGY (03-7338-014)
The objective of this job has been to generate approximately 450 gallons each of
(a) a base unleaded gasoline having an RVP of 11.0-11.5, and (b) a blend of the base
gasoline with oxinol with both base and blend fuels having matched Dupont evaporative
index:
El = 1.1 (RVP) -0.32C % EVAP @ lOOop) + 0.21 (% EVAP @ 200QF)
Oxinol 50 (50% methanol, 50% TBA) was obtained from John Tosh's Contra Costa
County fleet for this purpose. The base gasoline was obtained from Division 08 Tank
"L" and originally tested at 12.1 RVP. Since this was in excess of EPA requirements,
it was necessary to nitrogen-strip the light ends from this gasoline in a clean 500-
gailon tank behind Bldg. 63. Five cylinders of nitrogen were required to reduce the
RVP of the base gasoline to 11.4. Since each cylinder contains 255 cubic feet of
nitrogen at stp and it took roughly two hours per tank, flow rate for all nitrogen-
stripping is estimated at 125 cubic feet per hour. Calculated evaporative index for
the base gasoline was 21.75.
The base gasoline was then transferred to nine new 55-gallon drums and picked
up by emissions lab personnel for storage. Approximately 450 gallon (actually
slightly less), of tank "L" gasoline was then transferred to the 500-gallon tank and
nitrogen-stripped for eight hours (four tanks), resulting in an RVP of 10.3 and an
evaporative index of 20.68. One liter samples having 9.5 and 9.0 percent volume
oxinol were also checked. These resulted in an RVP of 12.3 (evap. index 24.43) and
12.2 (evap. index 24.11), respectively. This was obviously too high, so the base
gasoline was further stripped for four hours, resulting in an RVP 9.1 and an El of
19.49. A one liter sample having 9.5 percent oxinol was prepared and tested out at
RVP of 11.4 and and evap. index of 21.64.
A-6
-------
APPENDIX A-5
This seemed adequate, so the 500-gallon tank was "dip sticked" at 383 gallons.
To blend in 9 .5 volume percent oxinol, I set up the equation:
- x 100 s 90.5
X = 40.2 gallons
383.0 gasoline
-t-40.2 oxinol
423.2 gallons blend fuel
After full-scale blending, a sample was sent to the Division 08 lab and tested out
at 11.5 RVP and 23.16 evap. index. After four more hours of nitrogen-stripping the
RVP was down to 11.1 and the evap. index 22.42. The difference of 0.67 was
considered still too high by Bob Garbe and so we stripped for two more hours (one
tank, nine tank total) resulting in a final RVP of 10.7 and Evap. .Index of 22.01
(difference of 0.26). This blend was drummed on March 19th as follows:
Drums 1-4: 53 gallons
Drums 5-8: equal volumes (—49 gal)
Drum 9^15 gallons
The drums were labeled Oxinoi Gasoline Blend and Drum 9 also labeled "retain".
It was understood that Bob Garbe wanted the first four drums shipped first with the
next four at some future date. (ERL to retain 15 gallons of both base and blend).
One quart of the base gasoline and one quart of the blend were sent to Ken Jones
at AFLRL for GC check of the total oxinol content. This turned out to be 8£%, 3.9%
MeoH and 4.4% TBA (47/53 ratio). A subsequent GC check on neat oxinol showed a
49/51 ratio.
Bob Garbe had one further requirement. He wanted three special sub-blends
made up and RVP, Evap. Index measured for each. These were:
Blend No. Blend/Base RVP Evao. Index
1 252/75% 10.9 21.93
2 50%/50% 11.6 22.05
3. 75%/25% 11.7 21.39
Evap. Index does "peak" at 50/50 but, in my opinion, there is no difference within
overall measurement/calculation error.
-------
APPENDIX A-5 (CONPD)
DISTILLATION OF SAMPLES BLENDED FOR EPA
Distillation Temperature, °F
Percent Base Blended
Recovered Gasoline Gasoline
IBP 82 87
5 101 100
10 111 107
15 119 113
20 127 119
30 1** 132
40 165 152
50 194 177
60 229 215
70 273 260
80 315 303
90 343 333
95 367 353
EP 395 382
A-f
-------
APPENDIX B
ANALYTICAL PROCEDURES
B-l Alcohol Content of Unleaded Gasoline
B-2 Automatic RVP Instrument Method
-------
APPENDIX B-l
ALCOHOL CONTENT IN UNLEADED GASOLINE
% Methanol, Ethanol, and T-B in Gasoline
An internal standard, isoproponal, 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 introduced into a gas chromatography column. The eluted alcohols are
detected by a flame ionization detector and recorded on an integrator. The
peak areas are measured and applied to the appropriate calibration curve, from
which the volume percent is obtained.
Method
1. Insert the column for alcohols in side "A" or 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 Sense - 1.00
Attenuation - 6^
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
0.75y£
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, & T-Butyl
0.0%
0.1% 25 y£
0.5% 125 y£
1.0% 250 y£
3.0% 750 y£
5.0% 1250y£
7.0% 1750y£
10.0% 2500y£
12.0% 3000y£
Dilute to 25 m with Indolene.
Extraction of Alcohol - for Std. & Samples
10 m£ of D.I. H20, along with 5 m£ of sample or std. and 50 y£ of
Isopropyl alcohol are added to a 1 oz. jar. The mixture is shaken for 10
min. on a mechanical shaker and then let stand for 30 min. to assure
separation into layers. Part of the lower water layer is then removed for
injection into the G.C.
All standards and samples are run, recording the peak areas for MeOH,
ETOH, T-Butyl, and Isopropyl (Int. Std.)
Calculation
Divide the area of the MeOH peak by the area of the Int. Std. to get a
ratio. Do this for the other two alcohols. The ratio is the number used
for calculating percent alcohol.
Run a linear regression on the standard curve for each of the 3 alcohols.
There will be three answers for each sample - % MeOH, % ETOH, and %
T-Butyl.
B-3
-------
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 D-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 will
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 4-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
CALCULATION OF VOLATILITY INDICES
C-l Calculated El and FEVI Volatility Indices
-------
APPENDIX TABLE C-l. CALCULATED El AND FEVI VOLATILITY INDICES
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
1*
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
RVP,
psi
14.2
14.3
14.1
13.5
13.5
13.6
13.3
14.1
13.5
14.0
13.6
13.5
14.3
13.4
13.8
13.4
13.5
13.9
13.8
13.4
13.2
13.7
13.7
13.4
12.9
13.1
13.1
12.7
13.1
12.7
13.1
13.1
13.2
13.1
12.4
14.3
12.9
12.9
13.1
13.8
% Evaporated at
10QOF
9.4
8.9
10.6
11.7
12.8
9.6
10.7
10.0
9.3
11.1
9.6
8.1
11.3
9.2
9.7
8.5
8.5
7.5
9.4
8.8
7.3
6.4
6.9
8.8
5.8
5.8
6.7
3.5
5.9
5.6
5.5
8.8
6.8
9.1
8.6
9.1
5.9
6.8
6.5
7.9
200°F
53.3
51.3
49.2
53.5
50.6
54.9
57.5
53.8
55.1
57.9
54.1
53.8
59.4
55.5
54.1
56.1
55.7
53.8
52.1
57.7
51.9
51.0
51.4
54.1
49.4
49.4
51.5
47.9
51.0
48.9
50.3
51.7
50.6
51.9
51.3
51.4
50.0
49.4
50.3
53.4
El
23.8
23.7
22.5
22.3
21.4
23.4
23.3
23.6
23.4
24.0
23.2
23.6
24.6
23.5
23.4
23.8
23.8
24.2
23.1
24.0
23.1
23.7
23.7
23.3
22.7
22.9
23.1
22.9
23.2
22.4
23.2
22.5
23.0
22.4
21.7
23.9
22.8
22.4
22.9
23.9
% Evap.
at 158°F
40.3
39.2
36.8
40.0
37.9
41.1
42.9
40.0
40.4
43.8
40.7
37.8
45.0
40.9
39.5
42.0
41.6
41.2
39.7
43.2
38.2
38.8
37.9
40.0
35.9
36.2
38.4
34.8
37.8
36.2
37.4
37.8
38.1
38.8
37.8
38.4
36.8
36.1
37.0
40.6
% by Volume
FEVI
19.4
19.4
18.9
18.7
18.4
18.9
18.9
19.3
18.8
19.7
18.9
18.4
19.4
18.7
18.9
18.9
18.9
19.3
19.0
19.0
18.2
18.7
18.6
18.6
17.6
17.8
18.1
17.2
18.0
17.4
18.0
18.0
18.2
18.1
17.3
19.3
17.7
17.6
17.9
19.1
MeOH
4.9
4.6
4.6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4.6
4.5
4.7
0
4.7
4.6
4.7
4.5
4.7
4.5
4.9
3.3
4.6
4.7
4.7
4.7
4.7
4.6
4.5
4.8
TEA
4.3
4.2
4.1
0.3
0.2
3.9
7.0
4.8
6.9
3.9
4.6
6.8
5.9
7.0
5.8
5.8
5.3
1.1
0.8
6.1
4.0
4.2
4.2
6.1
4.2
4.0
4.2
4.0
4.2
4.0
4.4
2.9
4.1
4.1
4.1
4.2
4.1
4.1
4.0
4.3
El = l.lxRVP - 0.32x(% EVAP @ 100°F) + 0.21x(% EVAP @ 200°F)
FEVI = RVP + 0.13x(% EVAP @ 158°F)
C-2
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA 460/3-84-009
2.
3. RECIPIENT'S ACCESSIOf*NO.
4. TITLE AND SUBTITLE
Volatility of In-Use Gasoline and Gasoline/Methanol
Blends
5. REPORT DATE
September 1984
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S)
Charles M. Urban
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORG-\NIZATION NAME AND ADDRESS
Southwest Research Institute
6220 Culebra Road
San Antonio, Texas 78284
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-3162
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
2565 Plymouth Road
Ann Arbor, Michigan 48105
13. TYPE OF REPORT AND PERIOD COVERED
Final (2/29/84-9/28/84)
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report provides results of analyses for alcohol content, volatility, and
other properties of forty in-use unleaded gasoline samples. Analyses conducted on
these fuels included: methanol, ethanol, and tertiary butyl alcohol (TEA) quanti-
tation; Reid vapor pressure; distillation; water and lead content; and the calculation
of FEVI and El volatility indices. Twenty-two of the forty samples contained between
three and five percent methanol. Most of the gasoline samples, including those not
containing methanol, contained several percent TEA. Data obtained indicated the
volatility of fuels containing methanol and TEA were not significantly different from
that of fuels containing only TEA. The data also showed an average RVP of 13.3 and
13.6 psi respectively for these fuels, which, is above the maximum ASTM specified
RVP of 11.5 psi for the Houston area at the time these samples were taken.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Gasoline
Alternate Fuels
Methanol Blends
Gasoline Volatility
3. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
40
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
-------
SOUTHWEST RESEARCH INSTITUTE
POST OFFICE DRAWER 28510 • 6220 CULEBRA ROAD' SAN ANTONIO, TEXAS, USA 78284 • (512) 684-51 1 1'TELEX 76-7357
December 4, 1984
Mr. Craig A. Harvey
Environmental Protection Agency
2565 Plymouth Road
Ann Arbor, Michigan 48105
Subject: Final Report EPA 460/3-84-009 under Contract No. 68-03-3162
Dear Mr. Harvey:
It has been brought to my attention that the ASTM D439 recommended
volatility values given for Houston on Page 7 of the subject report are in error.
The corrected values are as follows:
Volatility
Month Designation Max. RVP, psi
January D 13.5
February D 13.5
March D/C 13.5
April C 11.5
May C 11.5
June C/B 11.5
July B 10.0
The Abstract has also been modified to reflect the preceding correction to the
ASTM recommended volatility values. In addition, I am providing an additional
information sheet that gives the dates the fuel samples were taken.
I have enclosed twenty-five (25) copies of the errata sheets, which include
the specific changes recommended by you, and of the additional information
sheet for your use in modifying the final report copies previously provided to
the EPA. Should you have any questions please do not hesitate to call me.
Very truly yours,
Charles M. Urban
Senior Research Engineer
Department of Emissions Research
CMU/sat
Enclosures
cc: George Yogis - ARCO - w/attachment
SAN ANTONIO, TEXAS
WITH OFFICES IN HOUSTON, TEXAS, AND WASHINGTON, D.C.
-------
ERRATA
SwRI Technical Report - EPA 460/3-84-009
entitled
VOLATILITY OF IN-USE GASOLINE AND
GASOLINE/METHANOL BLENDS
by
Charles M. Urban
The following corrections are applicable to the above cited report which was
issued under EPA Contract No. 68-03-3162.
Page iv
Remove the entire Abstract and replace with the following:
This report provides results of analyses for alcohol content, volatility, and
other properties of forty in-use unleaded gasoline samples obtained from retail
outlets. Analyses conducted on these fuels included: methanol, ethanol, and
tertiary butyl alcohol (TEA) quantitation; Reid vapor pressure; distillation;
water and lead content; and the calculation of FEVI and El volatility indices.
Twenty-two of the forty samples contained between three and five percent
methanol. Most of the gasoline samples, including those not containing
methanol, contained several percent TBA. Data obtained indicated the
volatility of fuels containing methanol and TBA were not significantly different
from that of fuels containing only TBA; the average RVP was 13.3 and 13.6 psi
respectively for these fuels. The RVP of fuels sampled in late March ranged
from 13.3 to 14.3 psi, and, with one exception, the RVP of fuels sampled around
mid-April ranged from 12.4 to 13.8. ASTM D439 specifications for fuel in the
Houston area are Class D/C for March (RVP 13.5 psi maximum) and Class C for
April (RVP 11.5 psi maximum). Many of the fuel samples (especially for April)
were above the RVP levels in the ASTM specifications.
-------
ERRATA (CONT'D)
SwRI Technical Report - EPA 460/3-84-009
Page?
Text Table
Volatility designations and RVP values should be corrected to read as
follows:
Volatility
Month Designation Max. RVP, psi
January D 13.5
February D 13.5
March D/C 13.5
April C 11.5
May C 11.5
June C/B 11.5
July B 10.0
-------
The following additional information is applicable to Table 2, Page 8 of SwRI
Technical Report - EPA 460/3-84-009, titled "Volatility of In-Use Gasoline and
Gasoline/Methanol Blends" issued under Project No. 03-7338-014, dated
September 1984.
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
District
Southwest
Champions
West
West
West
Northwest
North
North
North
Northwest
Northwest
Champions
Northwest
Champions
Northwest
North
Northwest
West
North
North
Southeast
South
Southeast
Northwest
Southwest
Pasadena
Pasadena
Pasadena
Pasadena
Pasadena
South
Pasadena
Pasadena
Pasadena
South
Southwest
Southwest
West
South
Southwest
Date
Sampled5
3/29
3/29
3/29
3/29
3/29
4/04
4/04
4/04
4/04
4/04
3/27
4/04
3/27
4/04
4/04
3/27
3/27
3/27
3/27
3/27
4/17
4/17
4/17
4/17
4/17
4/25
4/25
4/25
4/25
4/25
4/17
4/25
4/25
4/25
4/17
4/16
4/16
4/16
4/17
4/16
RVP,
psi
14.2
14.3
14.1
13.5
13.5
13.6
13.3
14.1
13.5
14.0
13.6
13.5
14.3
13.4
13.8
13.4
13.5
13.9
13.8
13.4
13.2
13.7
13.7
13.4
12.9
13.1
13.1
12.7
13.1
12.7
13.1
13.1
13.2
13.1
12.4
14.3
12.9
12.9
13.1
13.8
^Sampled in 1984
-------
ERRATA
SwRI Technical Report - EPA 460/3-84-009
entitled
VOLATILITY OF IN-USE GASOLINE AND
GASOLINE/METHANOL BLENDS
by
Charles M. Urban
The following corrections are applicable to the above cited report which was
issued under EPA Contract No. 68-03-3162.
Page iv
Remove the entire Abstract and replace with the following:
This report provides results of analyses for alcohol content, volatility, and
other properties of forty in-use unleaded gasoline samples obtained from retail
outlets. Analyses conducted on these fuels included: methanol, ethanol, and
tertiary butyl alcohol (TBA) quantitation; Reid vapor pressure; distillation;
water and lead content; and the calculation of FEVI and El volatility indices.
Twenty-two of the forty samples contained between three and five percent
methanol. Most of the gasoline samples, including those not containing
methanol, contained several percent TBA. Data obtained indicated the
volatility of fuels containing methanol and TBA were not significantly different
from that of fuels containing only TBA; the average RVP was 13.3 and 13.6 psi
respectively for these fuels. The RVP of fuels sampled in late March ranged
from 13.3 to 14.3 psi, and, with one exception, the RVP of fuels sampled around
mid-April ranged from 12.4 to 13.8. ASTM D439 specifications for fuel in the
Houston area are Class D/C for March (RVP 13.5 psi maximum) and Class C for
April (RVP 11.5 psi maximum). Many of the fuel samples (especially for April)
were above the RVP levels in the ASTM specifications.
-------
ERRATA (CONT'D)
SwRI Technical Report - EPA 460/3-84-009
Page/
Text Table
Volatility designations and RVP values should be corrected to read as
follows:
Volatility
Month Designation Max. RVP, psi
January D 13.5
February D 13.5
March D/C 13.5
April C 11.5
May C 11.5
June C/B 11.5
July B 10.0
-------
The following additional information is applicable to Table 2, Page 8 of SwRI
Technical Report - EPA 460/3-84-009, titled "Volatility of In-Use Gasoline and
Gasoline/Methanol Blends" issued under Project No. 03-7338-014, dated
September 1984.
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
District
Southwest
Champions
West
West
West
Northwest
North
North
North
Northwest
Northwest
Champions
Northwest
Champions
Northwest
North
Northwest
West
North
North
Southeast
South
Southeast
Northwest
Southwest
Pasadena
Pasadena
Pasadena
Pasadena
Pasadena
South
Pasadena
Pasadena
Pasadena
South
Southwest
Southwest
West
South
Southwest
Date
Sampled3
3/29
3/29
3/29
3/29
3/29
4/04
4/04
4/04
4/04
4/04
3/27
4/04
3/27
4/04
4/04
3/27
3/27
3/27
3/27
3/27
4/17
4/17
4/17
4/17
4/17
4/25
4/25
4/25
4/25
4/25
4/17
4/25
4/25
4/25
4/17
4/16
4/16
4/16
4/17
4/16
RVP,
psi
14.2
14.3
14.1
13.5
13.5
13.6
13.3
14.1
13.5
14.0
13.6
13.5
14.3
13.4
13.8
13.4
13.5
13.9
13.8
13.4
13.2
13.7
13.7
13.4
12.9
13.1
13.1
12.7
13.1
12.7
13.1
13.1
13.2
13.1
12.4
14.3
12.9
12.9
13.1
13.8
aSampled in 1984
-------
ERRATA
SwRI Technical Report - EPA 460/3-84-009
entitled
VOLATILITY OF IN-USE GASOLINE AND
GASOLINE/METHANOL BLENDS
by
Charles M. Urban
The following corrections are applicable to the above cited report which was
issued under EPA Contract No. 68-03-3162.
Page iv
Remove the entire Abstract and replace with the following:
This report provides results of analyses for alcohol content, volatility, and
other properties of forty in-use unleaded gasoline samples obtained from retail
outlets. Analyses conducted on these fuels included: methanol, ethanol, and
tertiary butyl alcohol (TBA) quantitation; Reid vapor pressure; distillation;
water and lead content; and the calculation of FEVI and El volatility indices.
Twenty-two of the forty samples contained between three and five percent
methanol. Most of the gasoline samples, including those not containing
methanol, contained several percent TBA. Data obtained indicated the
volatility of fuels containing methanol and TBA were not significantly different
from that of fuels containing only TBA; the average RVP was 13.3 and 13.6 psi
respectively for these fuels. The RVP of fuels sampled in late March ranged
from 13.3 to 14.3 psi, and, with one exception, the RVP of fuels sampled around
mid-April ranged from 12.4 to 13.8. ASTM D439 specifications for fuel in the
Houston area are Class D/C for March (RVP 13.5 psi maximum) and Class C for
April (RVP 11.5 psi maximum). Many of the fuel samples (especially for April)
were above the RVP levels in the ASTM specifications.
-------
ERRATA (CONT'D)
SwRI Technical Report - EPA 460/3-84-009
Page?
Text Table
Volatility designations and RVP values should be corrected to read as
follows:
Volatility
Month Designation Max. RVP, psi
January D 13.5
February D 13.5
March D/C 13.5
April C 11.5
May C 11.5
June C/B 11.5
July B 10.0
-------
The following additional information is applicable to Table 2, Page 8 of SwRI
Technical Report - EPA 460/3-84-009, titled "Volatility of In-Use Gasoline and
Gasoline/Methanol Blends" issued under Project No. 03-7338-014, dated
September 1984.
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
District
Southwest
Champions
West
West
West
Northwest
North
North
North
Northwest
Northwest
Champions
Northwest
Champions
Northwest
North
Northwest
West
North
North
Southeast
South
Southeast
Northwest
Southwest
Pasadena
Pasadena
Pasadena
Pasadena
Pasadena
South
Pasadena
Pasadena
Pasadena
South
Southwest
Southwest
West
South
Southwest
Date
Sampled3
3/29
3/29
3/29
3/29
3/29
4/04
4/04
4/04
4/04
4/04
3/27
4/04
3/27
4/04
4/04
3/27
3/27
3/27
3/27
3/27
4/17
4/17
4/17
4/17
4/17
4/25
4/25
4/25
4/25
4/25*
4/17
4/25
4/25
it/25
4/17
4/16
4/16
4/16
4/17
4/16
RVP,
psi
14.2
14.3
14.1
13.5
13.5
13.6
13.3
14.1
13.5
14.0
13.6
13.5
14.3
13.4
13.8
13.4
13.5
13.9
13.8
13.4
13.2
13.7
13.7
13.4
12.9
13.1
13.1
12.7
13.1
12.7
13.1
13.1
13.2
13.1
12.4
14.3
12.9
12.9
13.1
13.8
^Sampled in 1984
-------
ERRATA
SwRI Technical Report - EPA 460/3-84-009
entitled
VOLATILITY OF IN-USE GASOLINE AND
GASOLINE/METHANOL BLENDS
by
Charles M. Urban
The following corrections are applicable to the above cited report which was
issued under EPA Contract No. 68-03-3162.
Page iv
Remove the entire Abstract and replace with the following:
This report provides results of analyses for alcohol content, volatility, and
other properties of forty in-use unleaded gasoline samples obtained from retail
outlets. Analyses conducted on these fuels included: methanol, ethanol, and
tertiary butyl alcohol (TBA) quantitation; Reid vapor pressure; distillation;
water and lead content; and the calculation of FEVI and El volatility indices.
Twenty-two of the forty samples contained between three and five percent
methanol. Most of the gasoline samples, including those not containing
methanol, contained several percent TBA. Data obtained indicated the
volatility of fuels containing methanol and TBA were not significantly different
from that of fuels containing only TBA; the average RVP was 13.3 and 13.6 psi
respectively for these fuels. The RVP of fuels sampled in late March ranged
from 13.3 to 14.3 psi, and, with one exception, the RVP of fuels sampled around
mid-April ranged from 12.4 to 13.8. ASTM D439 specifications for fuel in the
Houston area are Class D/C for March (RVP 13.5 psi maximum) and Class C for
April (RVP 11.5 psi maximum). Many of the fuel samples (especially for April)
were above the RVP levels in the ASTM specifications.
-------
ERRATA (CONT'D)
SwRI Technical Report - EPA 460/3-84-009
Page 7
Text Table
Volatility designations and RVP values should be corrected to read as
follows:
Volatility
Month Designation Max. RVP, psi
January D 13.5
February D 13.5
March D/C 13.5
April C 11.5
May C 11.5
June C/B 11.5
July B 10.0
-------
The following additional information is applicable to Table 2, Page 8 of SwRI
Technical Report - EPA 460/3-84-009, titled "Volatility of In-Use Gasoline and
Gasoline/Methanol Blends" issued under Project No. 03-7338-014, dated
September 1984.
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
District
Southwest
Champions
West
West
West
Northwest
North
North
North
Northwest
Northwest
Champions
Northwest
Champions
Northwest
North
Northwest
West
North
North
Southeast
South
Southeast
Northwest
Southwest
Pasadena
Pasadena
Pasadena
Pasadena
Pasadena
South
Pasadena
Pasadena
Pasadena
South
Southwest
Southwest
West
South
Southwest
Date
Sampled5
3/29
3/29
3/29
3/29
3/29
4/04
4/04
4/04
4/04
4/04
3/27
4/04
3/27
4/04
4/04
3/27
3/27
3/27
3/27
3/27
4/17
4/17
4/17
4/17
4/17
4/25
4/25
4/25
4/25
4/25
4/17
4/25
4/25
4/25
4/17
4/16
4/16
4/16
4/17
4/16
RVP,
psi
14.2
14.3
14.1
13.5
13.5
13.6
13.3
14.1
13.5
14.0
13.6
13.5
14.3
13.4
13.8
13.4
13.5
13.9
13.8
13.4
13.2
13.7
13.7
13.4
12.9
13.1
13.1
12.7
13.1
12.7
13.1
13.1
13.2
13.1
12.4
14.3
12.9
12.9
13.1
13.8
^Sampled in 1984
------- |