Reid Vapor Pressure, psi

15

14

13

12

@ Methanol and TBA

& TBA Only

4 ee
i; °
4 e
=)
a
L ae °
ee
+ ae
a
r o
e code
oe
oe
r e
r Note: Pa = 6.895xpsi
am L | | |
O 1 2 3 4
Percent Methanol by Volume
Figure 1. Relationship of RVP to methanol concentration

12


APPENDIX TABLE C-1. CALCULATED EI AND FEVI VOLATILITY INDICES

Sample RVP, _% Evaporated at % Evap. % by Volume
Number _ psi 100°0F = 200°F EI at 1580F_ FEVI MeOH TBA
1 14,2 9.4 53.3 23.8 40.3 19.4 4.9 4.3
2 14,3 8.9 51.3 23.7 39.2 19.4 4.6 4.2
3 14,1 10.6 49,2 22.5 36.8 18.9 4.6 41
4 13.5 11.7 53.5 22.3 40.0 18.7 0 0.3
5 13.5 12.8 50.6 21.4 37.9 18.4 0 0.2
6 13.6 9.6 54.9 23.4 41.1 18.9 0 3.9
7 13.3 10.7 57.5 23.3 42.9 18.9 0 7.0
8 14.1 10.0 53.8 23.6 40.0 19.3 0 4.8
9 13.5 9.3 55.1 23.4 40.4 18.8 0 6.9
10 14.0 11.1 57.9 24.0 43.8 19.7 0 3.9
ll 13.6 9.6 54.1 23.2 40.7 18.9 0 4.6
12 13.5 8.1 53.8 23.6 37.8 18.4 0 6.8
13 14.3 11.3 59.4 24.6 45.0 19.4 0 5.9
14 13.4 9.2 55.5 23.5 40.9 18.7 0 7.0
15 13.8 9.7 S41 23.4 39.5 18.9 0 5.8
16 13.4 8.5 56.1 23.8 42.0 18.9 0 5.8
17 13.5 8.5 55.7 23.8 41.6 18.9 0 5.3
18 13.9 7.5 53.8 24.2 41.2 19.3 0 Lt
19 13.8 9.4 52.1 23.1 39.7 19.0 0 0.8
20 13.4 8.8 57.7 24.0 43.2 19.0 0 6.1
21 13.2 7.3 51.9 23.1 38.2 18.2 4.6 4.0
22 13.7 6.4 51.0 23.7 38.8 18.7 4.5 4.2
23 13.7 6.9 51.4 23.7 37.9 18.6 4,7 4.2
24 13.4 8.8 54.1 23.3 40.0 18.6 0 6.1
25 12.9 5.8 49.4 22.7 35.9 17.6 4.7 4.2
26 13.1 5.8 49.4 22.9 36.2 17.8 4.6 4.0
27 13.1 6.7 51.5 23.1 338.4 18.1 4.7 4.2
28 12.7 3.5 47.9 22.9 34.8 17.2 4.5 4.0
29 13.1 5.9 51.0 23.2 37.8 18.0 4.7 4.2
30 12.7 5.6 48.9 22.4 36.2 17.4 4.5 4.0
31 13.1 5.5 50.3 23.2 37.4 18.0 4.9 44
32 13,1 8.3 51.7 22.5 37.8 18.0 3.3 2.9
33 13.2 6.8 50.6 23.0 38.1 18.2 4.6 4
34 13.1 91 51.9 22.4 38.8 18.1 4.7 4.1
35 12.4 8.6 51.3 21.7 37.8 17.3 4.7 4
36 14.3 91 51.4 23.9 38.4 19.3 4.7 4.2
37 12.9 5.9 50.0 22.8 36.8 17.7 4.7 4
38 12.9 6.8 49.4 22.4 36.1 17.6 4.6 4
39 13.1 6.5 50.3 22.9 37.0 17.9 4.5 4.0
40 13.8 7.9 53.4 23.9 40.6 19.1 4.3 43

EI = 1.1xRVP - 0.32x(% EVAP @ 100°F) + 0.21x(% EVAP @ 200°F)
FEVI = RVP + 0.13x(% EVAP @ 158°F)


APPENDIX B-1 (CONT'D)

Sample Size
0.75u2

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. Conc. MeOH, ETOH, & T-Butyl

0.0% -
0.1% 25 wt
0.5% 125 ue
1.0% 250 we
3.0% 750 ue
5.0% 1250u2
7.0% 1750ug

10.0% 25002

12.0% 3000 12

Dilute to25m_ with Indolene.

Extraction of Alcohol - for Std. & Samples

10 m& of D.I. H20, along with 5 m& of sample or std. and 50 UL of
Isopropyl alcohol are added to a | 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 Isopropy! (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.


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"

September 1984,

issued under Project No.

Sample Date RVP,
Number District Sampled@ psi
1 Southwest 3/29 14.2
2 Champions 3/29 14.3
3 West 3/29 14.1
4 West 3/29 13.5
5 West 3/29 13.5
6 Northwest 4/04 13.6
7 North 4/04 13.3
8 North 4/04 14.1
9 North 4/04 13.5
10 Northwest 4/04 14.0
IL Northwest 3/27 13.6
12 Champions 4/04 13.5
13 Northwest 3/27 14.3
14 Champions 4/04 13.4
15 Northwest 4/04 13.8
16 North 3/27 13.4
17 Northwest 3/27 13.5
13 West 3/27 13.9
19 North 3/27 13.8
20 North 3/27 13.4
2i Southeast 4/17 13.2
22 South 4/17 13.7
23 Southeast 4/17 13.7
24 Northwest 4/17 13.4
25 Southwest 4/17 12.9
26 Pasadena 4/25 13.1
27 Pasadena 4/25 13.1
28 Pasadena 4/25 12.7
29 Pasadena 4/25 13.1
30 Pasadena 4/25 12.7
31 South 4/17 13.1
32 Pasadena 4/25 13.1
33 Pasadena 4/25 13.2
34 Pasadena 4/25 13.1
35 South 4/17 12.4
36 Southwest 4/16 14.3
37 Southwest 4/16 12.9
38 West 4/16 12.9
39 South 4/17 13.1
40 Southwest 4/16 13.8

aSampled in 1984

03-7338-014,

dated


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.


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 Cc 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 Date RVP,
Number District Sampled@ psi

1 Southwest 3/29 14.2
2 Champions 3/29 14,3
3 West 3/29 14.1
4 West 3/29 13.5
5 West 3/29 13.5
6 Northwest 4/04 13.6
7 North 4/04 13.3
8 North 4/04 14.1
9 North 4/04 13.5
10 Northwest 4/04 14.0
11 Northwest 3/27 13.6
12 Champions 4/04 13.5
13 Northwest 3/27 14.3
14 Champions 4/04 13.4
15 Northwest 4/04 13.8
16 North 3/27 13.4
17 Northwest 3/27 13.5
18 West 3/27 13.9
19 North 3/27 13.8
20 North 3/27 13.4
21 Southeast 4/17 13.2
22 South 4/17 13.7
23 Southeast 4/17 13.7
24 Northwest 4/17 13.4
25 Southwest 4/\7 12.9
26 Pasadena 4/25 13.1
27 Pasadena 4/25 13.1
28 Pasadena 4/25 12.7
29 Pasadena 4/25, 13.1
30 Pasadena 4/25 12.7
31 South 4/17 13.1
32 Pasadena 4/25 13.1
33 Pasadena 4/25 13.2
34 Pasadena 4/25 13.1
35 South 4/17 12.4
36 Southwest 4/16 14.3
37 Southwest 4/16 12.9
38 West 4/16 12.9
39 South 4l\7 13.1
40 Southwest 4/16 13.8

@sampled in 1984


Water Content, Percent

0.2

O.1

a
A
r e aa
@ Methanol and TBA a
LL A TBA Only a
r e
A
r ome A
<->
r ae
e A
A A
a A
oo L 1 4 1 i 1
0 1 2 3 4 5 6
TBA Content, Percent
Figure 5. Relationship between water content and TBA content

16


TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)

7. REPORT NO. z 3. RECIPIENT'S ACCESSION'NO.
EPA 460/3-84-009
4. TITLE AND SUBTITLE 5. REPORT DATE
e446 = . . September 1984
Volatility of In. Use Gasotine and Gasoline/Methanol Ig, PERFORMING ORGANIZATION CODE

7 AUTHOR(S) Js. PERFORMING ORGANIZATION REPORT NO.

Charles M. Urban

9. PERFORMING ORGANIZATION NAME AND ADORESS 70, PROGRAM ELEMENT NO.

Southwest Research Institute

6220 Culebra Road [77. CONTRACT/GRANT NO.

San Antonio, Texas 78284

° 68-03-3162 .
12. SPONSORING AGENCY NAME AND ADDRESS 13, TYPE OF REPORT AND PERIOD COVERED
Final (2/29/84-9/28/84)
Environmental Protection Agency 14. SPONSORING AGENCY CODE

2565 Plymouth Road
Ann Arbor, Michigan 48105

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 (TBA) quanti-
tation; Reid vapor pressure; distillation; water and lead content; and the calculation
of FEVI and EI 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 i1.5 psi for the Houston area at the time these samples were taken.

H7. KEY WORDS AND DOCUMENT ANALYSIS
ja. DESCRIPTORS lb. |OENTIFIERS/OPEN ENDED TERMS |c, COSATI Field/Group

Gasoline Gasoline Volatility
Alternate Fuels
Methanol Blends

7g, DISTRIBUTION STATEMENT 19, SECURITY CLASS (This Report) 21. NO. OF PAGES
Unclassified 40
Unlimited 20. SECURITY CLASS /This page) 22. PRICE
Unclassified

EPA Form 2220-1 (9-73)



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 EI 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


APPENDIX B
ANALYTICAL PROCEDURES

B-1 Alcohol Content of Unleaded Gasoline
B-2 Automatic RVP Instrument Method


Reid Vapor Pressure, psi

15

14

12

12

@ Methanol and TBA
4 TBA Only

Note: Pa = 6.895xpsi

2 4 6
Percent TBA by Volume

Figure 2. Relationship of RVP to TBA concentration

13


APPENDIX A
MVMA SAMPLE COLLECTION PROCEDURE (MODIFIED)

A-| 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


Calculated EI

25

24

N
w

22

21

@ Methanol and TBA

4 TBA Only
@ No MeOH, but some TBA

Calculated FEVI

Figure 4, Relationship between EI and FEVI

15

r A
e
“a
ee
a
r a
au
4 a
ee a
ee
L e .
ee
e
e
L e e
e e e
2
t
71 1 i 4 1 }
17 18 19 20


APPENDIX B-1
ALCOHOL CONTENT IN UNLEADED GASOLINE

% Methanol, Ethanol, and T-B in Gasoline

Scope

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

Delay - off

Stop - 5 min.

Area reject - 100 - (102)
Chart Speed - 1 cm/min
Slope Sense - 1.00
Attenuation - 64

FID

Range - 10

Single Channel

Atten. set on integrator
Zero - as needed for baseline
A & B side (not Diff.)

B-2


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 45
Between Samples 10&11 44 4
Between Samples 20&21 4.5 4.2
Between Samples 30&31 45 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 al! 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.

EI and FEVI Volatility Indices - The EI 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


Il, 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


APPENDIX A-5 (CONT'D)

This seemed adequate, so the 500-gallon tank was "dip sticked" at 333 gallons.
To blend in 9.5 volume percent oxinol, I set up the equation:

a x 100 = 90.5

X = 40.2 gallons

383.0 gasoline
+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 amd the evap. index 22.42. The difference of 0.67 was
considered still too high by Bob Garde 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 5-3: equal volumes (~49 gal)

Drum 9315 gallons

The drums were labeled Oxinol 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 83%, 3.9%
MeoH and 4.4% TBA (47/53 ratio). A subsequent GC check on neat oxinol showed a
49/51 ratio.

Bob Garde had ome further requirement. He wanted three special sub-dlends
made up and RVP, Evap. Index measured for each. These were:

Blend No. Blend/Base RYP Evap. Index
1 25% |75% 10.9 21.98
2 50 2/50% 11.6 22.05
3. 75%/25% 11.7 21.89

Evap. Index does "peak" at 50/50 but, in my opinion, there is no difference within

overall measurement/calculation error. AT


1.

3.

4,

APPENDIX A-3
PURCHASE-PACK-SHIP SERVICE
FOR SOUTHWEST RESEARCH INSTITUTE
GENERAL INSTRUCTIONS

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:

ae

ge

A sufficient number of empty cans for obtaining samples.

Sample identification tags attached to each can indicating the brand
name and grade of fuel to be purchased.

One or more shipping cartons each accommodating six cans.

Caution labels to be affixed to the top of shipping cartons.

Labels addressed to Southwest Research Institute for return
shipment.

UN and NA labels to be affixed to the top of shipping cartons.

Tape for resealing cartons for return shipment.

Enclosed with these instructions are the following items:

a.

b.

c

d.

Drivers instructions - instructions for the proper method of sampling
and packing the fuel.

Attachment A - A check list of the marketers and grades of fuel to
be purchased. The sampling date is indicated here.

Attachment B - A list of marketers and grades of fuel which is to be
returned with the samples.

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.

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.

If any questions arise, please call collect; Patsy R. Perez, Southwest
Research Institute, (512/684-5111, ext. 2868).


Figure

LIST OF FIGURES

Relationship of RVP to Percent Methanol
Concentrations

Relationship of RVP to Percent TBA
Concentrations

Plot of the Average Distillation Values for
Methanol- and Nonmethanol-Containing Samples

Relationship Between EI and FEVI

Relationship Between Water Content and Percent
TBA Concentration

vi

13

14
15

16


TABLE OF CONTENTS

FOREWORD
ABSTRACT
LIST OF FIGURES
LIST OF TABLES
I, INTRODUCTION
Il GASOLINE SAMPLING
ll ANALYTICAL PROCEDURES
IV. RESULTS OF THE GASOLINE ANALYSES
Vv. ANALYSES AND DISCUSSION OF THE DATA
APPENDICES
A. MVMA SAMPLE COLLECTION PROCEDURE (MODIFIED)
B. ANALYTICAL PROCEDURES
C. CALCULATION OF VOLATILITY INDICES

vi

vii

il


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 | 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 11°C(19°F) at fifty percent
evaporated. With reference to Figure 4, there is an apparent relationship
between the EI 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 methanol 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.

1


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 buty! 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 EI 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.


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 EI 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 EI and FEVI; this could also be expected since both indices are
primarily a function of the same parameter, RVP.

17


United States Office of Mobile Source Air Pollution Control EPA 460/3-84-009
Environmental Protection Emission Control Technology Division September 1984
Agency 2565 Plymouth Road

Ann Arbor, Michigan 48105

SEPA Volatility of In-Use Gasoline and
Gasoline/Methanol Blends


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 Cc 11.5
May Cc 11.5
June c/B 11.5

July B 10.0


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. | 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.


TABLE 1. LOCATION OF SEVEN-ELEVEN

STORES SAMPLED
Sample
Number District Address
1 Southwest 6031 Willow Bend
2 Champions@ 11050 S. Post Oak
3 West 6333 San Felipe
4 West 1100 W. Alabama
5 West 9230 Buffalo Spwy.
6 Northwest 6541 W. 43rd
7 North 7501 Airline
8 North 10301 Shady Lane
9 North 2331 Little York
10 Northwest 4730 Brinkman
1 Northwest 1302 N. Shepherd
12 ChampionsP 5623 Aldine Bender
13 Northwest 5718 W. 34th
14 Champions 2950 Greens Road
15 Northwest 602 W. Parker Road
16 North 5711 Irvington
17 Northwest 4401 Irvington
18 West 1326 Dairy Ashford
19 North 4809 N. Main
20 North 2302 White Oak
21 Southeast 8637 Glenvista
22 South 9602 Telephone
23 Southeast 4302 Telephone
24 Northwest 2050 Bingle
25 Southeast 6154 Bellfort
26 Pasadena® 5010 Red Bluff
27 Pasadena@ 2521 Strawberry
23 Pasadena@ 902 Allen Genoa Road
29 Pasadena® 3500 Fairmont Pkwy
30 Pasadena® 6402 Spencer
31 South 10855 Telephone
32 Pasadena@ 901 W. Harris
33 Pasadena® 502 S. Shaver
34 Pasadena@ 3202 Pasadena Frwy
35 South 11402 Hughes
36 Southwest 8920 Bissonnet
37 Southwest 11313 Fondren
33 West 5805 Bellair
39 South 10602 Fugua
40 Southwest 10096 S. Gessner

aSoutheast side of Houston

bNorth side of Houston


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 EI 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.


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:

EI = 1.1 (RVP) -0.32( % EVAP @ 100°F) + 0.21 (% EVAP @ 2000F)

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-
gallon 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 EI of
19.49. A one liter sample having 9.5 percent oxino! was prepared and tested out at
RVP of 11.4 and and evap. index of 21.64.


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

September 1984.

Blends" issued under Project No.
Sample Date RVP,
Number District Sampled@ psi

1 Southwest 3/29 14.2
2 Champions 3/29 14.3
3 West 3/29 14.1
4 West 3/29 13.5
5 West 3/29 13.5
6 Northwest 4/04 13.6
7 North 4/04 13.3
8 North 4/04 14.1
9 North 4/04 13.5
10 Northwest 4/04 14.0
1 Northwest 3/27 13.6
12 Champions 4/04 13.5
13 Northwest 3/27 14,3
14 Champions 4/04 13.4
15 Northwest 4/04 13.8
16 North 3/27 13.4
17 Northwest 3/27 13.5
13 West 3/27 13.9
19 North 3/27 13.8
20 North 3/27 13.4
21 Southeast 4/17 13.2
22 South 4/17 13.7
23 Southeast 4/17 13.7
24 Northwest 4/17 13.4
25 Southwest 4/17 12.9
26 Pasadena 4/25 13.1
27 Pasadena 4/25 13.1
28 Pasadena 4/25 12.7
29 Pasadena 4/25 13.1
30 Pasadena 4/25 12.7
31 South 4/17 13.1
32 Pasadena 4/25 13.1
33 Pasadena 4/25 13.2
34 Pasadena 4/25 13.1
35 South 4/17 12.4
36 Southwest 4/16 14.3
37 Southwest 4/16 12.9
38 West 4/16 12.9
39 South 4/17 13.1
40 Southwest 4/16 13.8

@Sampled in 1984

03-7338-014,

dated


APPENDIX A-4

SAMPLE OF ORIGIN REPORT (Original and 3 Copies)

MVMA
FIELD SAMPLE FOR LABORATORY
USE ONLY
ORIGIN REPORT
Sempies Recerved
SOUTHWEST RESEARCH INSTITUTE
Reports Received
Cate Sampled
City Sempied
Srend Neme
Name of Service Station
Street Address of Service Stadon
CHECK PROPER BOX
—R+M/2 {S} —R+M/2 (U) —R+M/2 (a)
CO Premium Unieaded © Reguiar Unieaded Cl Gesohoi
Greae Name Grade Name rade Name

—R+ M/Z (PY —R+M/2 (R}
C Premium Leaded Cl Reguiar Leaded
Grade Name Grade Neme

Number of Stations of This Brand Visited to Obtain These Sampies

CQ One

O Two

O Three

Remarks:

——SS OO
PLEASE MAIL IN OUPLICATE TO SOUTHWEST RESEARCH INSTITUTE
Retain gold copy for your records.



Table

nN

i)

LIST OF TABLES

Location of Seven-Eleven Stores Sampled
Summary Results of Fuels Analyses

Distillation Data

vii


Distillation Temperature, °F

500 -

—s- Methanol and TBA
400
r

———— TBA Only (Excluding Samples 4,5, 18 & 19)

300

200

100

Note: °C = (°F - 32)/1.8

“I ! i 1 1 a 1 | i n J
IBP 20 40 60 80 EP

Percent Evaporated

Figure 3. Plot of the average distillation values for methanol-
and non-methanol-containing samples

14


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.


APPENDIX C
CALCULATION OF VOLATILITY INDICES

C-1 Calculated EI and FEVI Volatility Indices


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 Date RVP,
Number District Sampled@ psi

1 Southwest 3/29 14.2
2 Champions 3/29 14.3
3 West 3/29 14,1
4 West 3/29 13.5
5 West 3/29 13.5
6 Northwest 4/04 13.6
7 North 4/04 13.3
8 North 4/04 14,1
9 North 4/04 13.5
10 Northwest 4/04 14.0

iL Northwest 3/27 13.6
12 Champions 4/04 13.5

13 Northwest 3/27 14.3
14 Champions 4/04 13.4
15 Northwest 4/04 13.8
16 North 3/27 13.4
17 Northwest 3/27 13.5
18 West 3/27 13.9
19 North 3/27 13.8
20 North 3/27 13.4
al Southeast 4/17 13.2
22 South 4/17 13.7
23 Southeast 4/17 13.7
24 Northwest 4/17 13.4
25 Southwest 4/17 12.9
26 Pasadena 4/25 13.1
27 Pasadena 4/25 13.1
28 Pasadena 4/25 12.7
29 Pasadena 4/25 13.1
30 Pasadena 4/25 12.7
31 South 4/17 13.1
32 Pasadena 4/25 13.1
33 Pasadena 4/25 13.2
34 Pasadena 4/25 13.1
35 South 4/17 12.4
36 Southwest 4/16 14.3
37 Southwest 4/16 12.9
38 West 4/16 12.9
39 South 4/\7 13.1
40 Southwest 4/16 13.8

aSampled in 1984


APPENDIX A-1
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 - 6 1/2 x 9 1/2 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


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.

aii


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 EI 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 Cc 11.5
May Cc 11.5
June C/B 11.5

July B 10.0


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 EI 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 cH US
March ree 15
April C or-B- 11.5
May BC 10.0-
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 3. DISTILLATION DATA

Sample = Pct. Temperature OF at % Evaporated

Number MeOH IBP 5% 10% 15% 209% 30% 40% 50% 60% 70% 80% 90% 95% EP
1 4.9 78 86 102 110 116 132 157 189 222 252 286 333 365 395

2 4.6 81 89 103 ILL 118 134 160 195 233 265 299 340 374 415
3 4.6 85 91 107 115 122 139 167 203 238 270 302 345 375 414

4 0 75 85 97 106 114 133 158 188 222 255 293 338 372 403
5 0 72, 8 95 104 113 136 164 198 234 271 307 345 375 413
6 0 79° 88 «6101 110 118 135 155 183 218 253 295 339 372 409

7 0 738 87 99 106 118 136 152 173 209 253 304% 348 379 403

8 0 80 86 100 111 119 137 158 186 223 261 302 347 380 415

9 i?) 76 88 102 111 121 140 157 181 218 260 307 348 379 412
10 0 80 987 98 107 115 130 149 173 207 243 286 335 366 397
IL (¢) 77 ~=-87')—S LOLs 110s 118 «135 156 185 222 261 303 348 381 414
12 0 82 90 106 116 126 144 162 185 225 270 312 352 384 423
13 0 76 = 87 98 106 115 131 148 168 202 231 285 338 374 403
14 0 80 90 102 112 122 139 156 179 217 261 305 348 381 405
15 0) 81 86 101 111 121 139 159 185 222 262 305 347 377 413
16 0 80 91 104 113 120 137 153 178 214 259 304 347 374 413
17 0 90 91 104 113 121 137 154 179 216 260 306 357 384 416
18 0 77 85 96 104 112 129 154 187 221 253 286 331 367 395
19 i) 74 81 92 101 109 129 159 193 226 259 294 341 376 408
20 0 81 91 103 112 120 136 151 173 208 256 305 348 381 409
2i 4.6 87 95 106 114 120 135 163 193 230 261 295 336 376 412
22 4.5 87 97 108 115 122 136 161 196 235 269 304 340 377 416
23 4.7 84 95 108 116 123 139 163 195 230 262 298 337 376 416
24 ie) 81 91 103 113 122 139 158 184 223 264 302 345 376 412
25 4.7 86 98 Ill 119 126 142 169 202 236 268 300 342 376 409
26 4.6 84 98 110 117 124 140 169 202 232 258 288 332 373 416
27 4.7 84 96 108 116 122 137 162 195 229 260 296 339 368 412
28 4.5 91 104 114 120 127 143 174 207 238 264 296 339 375 416
29 4.7 86 98 109 116 122 137 164 197 228 255 290 345 384 415
30 4.5 86 99 108 115 123 140 169 204 234 261 291 339 375 408
31 4,9 86 99 110 117 123 138 165 199 231 262 295 343 379 410
32 3.3 80 91 103 110 117 137 164 195 225 254 293 341 376 413
33 4.6 83 96 107 113 121 137 163 198 230 259 290 341 383 418
34 4.7 84 91 102 Lil 118 135 161 194 225 252 284 333 372 412
35 4.7 85 90 104 112 119 137 164 196 228 256 287 332 363 400
36 4.7 79 92 105 114 121 137 162 195 232 266 303 345 380 4iL
37 4.7 87 98 109 116 123 139 167 200 232 263 295 341 372 404
38 4.6 88 96 107 116 124 141 169 202 235 265 296 332 370 408
39 4.5 84 96 109 116 123 139 166 199 228 251 283 335 377 415
40 4 81 93 105 112 118 132 156 187 227 266 305 349 386 415
Avg. 4.7 85 95 107 115 122 138 164 198 231 261 294 339 375 411
Avg.@ 0 79 88 10% Ill 120 137 155 179 215 256 301 346 378 410
Avg. 0 75-83 95 104 112 132 159 192 226 260 295 339 373 405
S.D. 4.7 3 4 3 3 3 3 4 5 4 6 7 5 6 6
S.D.2 0 2 2 2 3 3 4 4 6 7 10 8 6 5 7

aExcluding sample numbers 4, 5, 18, and 19


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

di


APPENDIX B-1 (CONT'D)
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.


APPENDICES

A. MVMA SAMPLE COLLECTION PROCEDURE (MODIFIED)
B. ANALYTICAL PROCEDURES
C. CALCULATION OF VOLATILITY INDICES


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


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 EI 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.


APPENDIX A-5 (CONT'D)

DISTILLATION OF SAMPLES BLENDED FOR EPA

Distillation Temperature, °F

Percent Base Blended
Recovered Gasoline Gasoline

IBP 82 87

5 101 100

10 1 107

15 119 113

20 127 119

30 144 132

40 165 152

50 194 177

60 229 215

70 273 260

80 315 303

90 343 333

95 367 353

EP 395 382


SOUTHWEST RESEARCH INSTITUTE

POST OFFICE DRAWER 28510 * 6220 CULEBRA ROAD * SAN ANTONIO, TEXAS, USA 78284 © (512) 684-5111 °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 Cc 11.5
May Cc 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,

harkea mr, Vober

Charles M. Urban
Senior Research Engineer
Department of Emissions Research
CMU/sat
Enclosures
cc: George Yogis - ARCO - w/attachment

Ss
J TEXAS, ANO WASHINGTON, D.C



APPENDIX A-2
DRIVER'S INSTRUCTIONS

Making the Purchase

1.
2.
3.

4

Insert the nozzle of the hose near the bottom of the can.
Fill the cans with designated grade of fuel as indicated on the tag.

Place the seal in the opening, press down firmly, and screw the cap on
hand tight.

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

b. NA 1993 labels are to be affixed on top of shipping cartons

Affix the caution labels on the side of the shipping cartons.

Check cans once again to be certain that they will not leak in shipment.
Check that the tag is secure on the can.

Use Attachment A as a check list to assure that all the designated fuel
samples have been obtained.

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.

Seal the cartons with tape. Take cartons to the specified motor or air
freight terminal and ship collect.


I, 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-1744, Karl Fischer Titration
(pyridine free).

*LEAD (Weight Percent) - ASTM D-3237, Atomic Absorption
Spectrometry.

+ FEVI AND EI VOLATILITY INDICES - These indices were calculated
from the RVP and distillation data using formulas supplied by EPA:
FEVI = RVP + 0.13x(% EVAP @ 158°F)

EI = 1.1xRVP - 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 repeatabilities 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.


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 b/c 13.5
April c 11.5
May Cc 11.5
June C/B 11.5

July B 10.0


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 EI 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.


TABLE 2, SUMMARY RESULTS OF FUELS ANALYSES

Water Distillation,
Sample % by Volume RVP, Content Lead, OF at % Evap. Calculations

Number _District MeOH TBA psi Percent g/gal 10% 50% 90% EI FEVI
vt _
1 tBawtnwest 49

rad
w&

14,2 0.10 0.002 102 189 333 23.8 19.4

2 Champions 4.6 4.2 14.3 0.12 0.001 103 195 340 23.7 19.4
3 West 4.6 4&1 141 OL) 0.002 107 203 345 22.5 18.9
4 West 0 4.3 13.5 0.02 0.001 97 188 338 22.3 18.7
2. West 0 0.2 13.5 0.01 0.001 95 198 345 21.4 18.4
6 Northwest QO 39 13.6 0.10 0.002 101 183 339 23.4 18.9
iL7 North Oo 7.0 13.3 0.19 0.004 99 173 348 23.3 18.9
«8 North QO 4.8 14,1 0.13 0.001 100 186 347 23.6 19.3
9 North 0 6.9 13.5 0.19 0.003 102 181 348 23.4 18.8
10 Northwest Oo 3.9 14.0 0.09 0.002 98 173 335 24.0 19.7
ll Northwest 0 4.6 13.6 0.12 0.001 101 185 348 23.2 18.9
12 Champions 0 6.8 13.5 0.21 0.001 106 185 352 23.6 18.4
13 Northwest 0 5.9 14.3 0.18 0.002 98 168 338 24.6 19.4
4 4 Champions Oo 7.0 13.4 0.20 0.001 102 179 348 23.5 18.7
"45 Northwest QO 5.8 13.8 0.20 0.001 101 185 347 23.4 18.9
16 North 0 5.8 13.4 0.19 0.003 104 178 347 23.8 18.9
17 Northwest 0 5.3 13.5 0.17 0.001 104 179 357 23.8 18.9
18 West Qo Ll 13.9 0.02 0.003 96 187 331 24.2 19.3
19 North 0 0.8 13.8 0.01 0.001 92 193 341 23.1 19.0
20 North Oo 6.1 13.4 0.18 0.025 103 173 348 24.0 19.0
a
21 Southeast 4.6 4.0 13.2 0.12 0.001 106 193 336 23.1 18.2
22 South 45 4.2 13.7 0.12 0.001 108 196 340 23.7 18.7
23 Southeast 4.7 4.2 13.7 0.11 0.001 108 195 337 23.7 18.6
4l “24 Northwest 0 6.1 13.4 0.16 0.002 103 184 345 23.3 18.6
{ 25 Southwest 4.7 4.2 12.9 O11 0.004 lll 202 342 22.7 17.6
7 ipg26 Pasadena 4.6 4.0 13.1 O.LL 0.003 110 202 332 22.9 17.8
TS 27 Pasadena 4.7 4.2 13.1 0.11 0.002 108 195 339 23.1 18.1
28 Pasadena 4.5 4.0 12.7 0.18 0.002 114 207 339 22.9 17.2
29 Pasadena 4.7 4.2 13.1 0.11 0.001 109 197 345 23.2 18.0
30 Pasadena 4.5 4.0 12.7 0.11 0.001. 108 204 339 22.4 17.4
31 South 4.9 4.4 13.1 0.11 0.001 110 199 343 23.2 18.0
32 Pasadena 3.3 2.9 13.1 0.09 0.001 103 195 341 22.5 18.0
33 Pasadena 4.6 41 13.2 0.12 0.001 107 198 341 23.0 18.2
34 Pasadena 4.7 4.1 13.1 0.14 0.001 102 194 333 22.4 18.1
35 South 4.7 41 12.4 0.12 0.002 104 196 332 21.7 17.3
36 Southwest 4.7 4.2 14.3 0.11 0.002 105 195 345 23.9 19.3
37 Southwest 4.7 4 12.9 0.11 0.002 109 200 341 22.8 17.7
38 West 4.6 41 12.9 0.11 0.004 107 202 332 22.4 17.6
39 South 4.5 4.0 13.1 0.11 0.002 109 199 335 22.9 17.9
40 Southwest 43 4.3 13.8 0.11 0.001 105 187 349 23.9 19.1
Avg. with MeOH 4.7 4t 13.3 0.12 0.002 107 198 339 23.1 18.2
Avg. w/o MeQH4 0 5.7 13.6 0.17 0.002 101 179 346 23.6 19.0
Avg. w/o MeOH 0 0.6 13.7 0.02 0.002 95 192 339 22.8 18.9
S.D. with MeOH Ol OL 0.6 0.02 0.001 3 5 5 0.7 0.7
S.D. w/o MeOQH4 QO Lk 0.3 0.04 0.001 2 6 6 0.4 0.3

aExcluding sample numbers 4, 5, 18, and 19