Designation: D 5191 – 99 An American National Standard

Standard Test Method for

Vapor Pressure of Petroleum Products (Mini Method)1
This standard is issued under the fixed designation D 5191; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

This standard has been approved for use by agencies of the Department of Defense.

1. Scope D 2892 Test Method for Distillation of Crude Petroleum

1.1 This test method covers the use of automated vapor (15-Theoretical Plate Column)2
pressure instruments to determine the total vapor pressure D 4057 Practice for Manual Sampling of Petroleum and
exerted in vacuum by air-containing, volatile, liquid petroleum Petroleum Products2
products. This test method is suitable for testing samples with D 4953 Test Method for Vapor Pressure of Gasoline and
boiling points above 0°C (32°F) that exert a vapor pressure Gasoline-Oxygenate Blends (Dry Method)3
between 7 and 130 kPa (1.0 and 18.6 psi) at 37.8°C (100°F) at D 5190 Test Method for Vapor Pressure of Petroleum Prod-
a vapor-to-liquid ratio of 4:1. Measurements are made on liquid ucts (Automatic Method)3
sample sizes in the range from 1 to 10 mL. No account is made 3. Terminology
for dissolved water in the sample.
3.1 Definition of Terms Specific to This Standard:
NOTE 1—Samples can also be tested at other vapor-to-liquid ratios, 3.1.1 absolute pressure—the pressure of the air-free sample.
temperatures, and pressures, but the precision and bias statements need not
It is calculated from the total pressure of the sample by
apply.
subtracting out the partial pressure of the dissolved air.
1.1.1 Some gasoline-oxygenate blends may show a haze 3.1.2 dry vapor pressure equivalent (DVPE)—a value cal-
when cooled to 0 to 1°C. If a haze is observed in 8.5, it shall culated by a correlation equation (see 13.2) from the total
be indicated in the reporting of results. The precision and bias pressure.
statements for hazy samples have not been determined (see 3.1.2.1 Discussion—The DVPE is expected to be equivalent
Note 12). to the value obtained on the sample by Test Method D 4953,
1.2 This test method is suitable for calculation of the dry Procedure A.
vapor pressure equivalent (DVPE) of gasoline and gasoline- 3.1.3 total pressure—the observed pressure measured in the
oxygenate blends by means of a correlation equation (see experiment that is the sum of the partial pressure of the sample
13.2). The calculated DVPE very closely approximates the dry and the partial pressure of the dissolved air.
vapor pressure that would be obtained on the same material
when tested by Test Method D 4953. 4. Summary of Test Method
1.3 The values stated in SI units are regarded as standard. 4.1 A known volume of chilled, air-saturated sample is
The inch-pound units given in parentheses are provided for introduced into an evacuated, thermostatically controlled test
information only. chamber, the internal volume of which is five times that of the
1.4 This standard does not purport to address all of the total test specimen introduced into the chamber. After injection
safety concerns, if any, associated with its use. It is the into the test chamber, the test specimen is allowed to reach
responsibility of the user of this standard to establish appro- thermal equilibrium at the test temperature, 37.8°C (100°F).
priate safety and health practices and determine the applica- The resulting rise in pressure in the chamber is measured using
bility of regulatory limitations prior to use. For specific a pressure transducer sensor and indicator. Only total pressure
warning statements, see Note 5. measurements (sum of the partial pressure of the sample and
the partial pressure of the dissolved air) are used in this test
2. Referenced Documents
method, although some instruments can measure the absolute
2.1 ASTM Standards: pressure of the sample as well.
4.2 The measured total vapor pressure is converted to a dry
1
This test method is under the jurisdiction of ASTM Committee D-2 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.08 on Volatility.
2
Current edition approved Dec. 10, 1998 and Jan. 10, 1999. Published March Annual Book of ASTM Standards, Vol 05.02.
3
1999. Originally published as D 5191 – 91. Last previous edition D 5191 – 96. Annual Book of ASTM Standards, Vol 05.03.

Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.

1
D 5191
vapor pressure equivalent (DVPE) by use of a correlation better, at the same elevation relative to sea level as the
equation (see 13.2). apparatus in the laboratory.
6.5.1 When a mercury manometer is not used as the
5. Significance and Use
pressure measuring device, the calibration of the pressure
5.1 Vapor pressure is a very important physical property of measuring device employed shall be periodically checked
volatile liquids. (with traceability to a nationally recognized standard) to ensure
5.2 The vapor pressure of gasoline and gasoline-oxygenate that the device remains within the required accuracy specified
blends is regulated by various government agencies. in 6.5.
5.3 Specifications for volatile petroleum products generally 6.6 McLeod Vacuum Gage, to cover at least the range from
include vapor pressure limits to ensure products of suitable 0 to 0.67 kPa (0 to 5 mm Hg). Calibration of the McLeod gage
volatility performance. is checked in accordance with Annex A6 of Test Method
5.4 This test method is more precise than Test Method D 2892.
D 4953, uses a small sample size (1 to 10 mL), and requires
about 7 min to complete the test. 7. Reagents and Materials
6. Apparatus 7.1 Purity of Reagents—Use chemicals of at least 99 %
purity for quality control checks (see Section 10). Unless
6.1 Vapor Pressure Apparatus—The type of apparatus suit- otherwise indicated, it is intended that all reagents conform to
able for use in this test method employs a small volume test the specifications of the Committee on Analytical Reagents of
chamber incorporating a transducer for pressure measurements the American Chemical Society where such specifications are
and associated equipment for thermostatically controlling the available.4 Lower purities can be used, provided it is first
chamber temperature and for evacuating the test chamber prior ascertained that the reagent is of sufficient purity to permit its
to sample introduction. use without lessening the accuracy of the determination.
6.1.1 The test chamber shall be designed to contain between
5 and 50 mL of liquid and vapor and be capable of maintaining NOTE 4—The chemicals in this section are suggested for use in quality
a vapor-to-liquid ratio between 3.95 to 1.00 and 4.05 to 1.00. control procedures (see 11.2) and are not used for instrument calibration.
7.2 Cyclohexane (Warning—See Note 5.)
NOTE 2—The test chamber employed by the instruments used in
generating the precision and bias statements were constructed of stainless 7.3 Cyclopentane (Warning—See Note 5.)
steel or aluminum. 7.4 2,2-Dimethylbutane (Warning—See Note 5.)
NOTE 3—Test chambers exceeding a 15 mL capacity can be used, but 7.5 2,3-Dimethylbutane (Warning—See Note 5.)
the precision and bias statements (see Section 14) are not known to apply. 7.6 2-Methylpentane (Warning—See Note 5.)
6.1.2 The pressure transducer shall have a minimum opera- 7.7 Toluene (Warning—See Note 5.)
tional range from 0 to 177 kPa (0 to 25.7 psi) with a minimum N OTE 5—Warning: Cyclohexane, toluene, cyclopentane, 2,2-
resolution of 0.1 kPa (0.01 psi) and a minimum accuracy of dimethylbutane, 2,3-dimethylbutane, and 3-methylpentane are flammable.
60.8 kPa (60.12 psi). The pressure measurement system shall Health Hazard.
include associated electronics and readout devices to display
the resulting pressure reading. 8. Sampling
6.1.3 A thermostatically controlled heater shall be used to 8.1 General Requirements:
maintain the test chamber at 37.8 6 0.1°C (100 6 0.2°F) for 8.1.1 The extreme sensitivity of vapor pressure measure-
the duration of the test. ments to losses through evaporation and the resulting changes
6.1.4 A platinum resistance thermometer shall be used for in composition is such as to require the utmost precaution and
measuring the temperature of the test chamber. The minimum the most meticulous care in the drawing and handling of
temperature range of the measuring device shall be from samples.
ambient to 75°C (167°F) with a resolution of 0.1°C (0.2°F) and 8.1.2 Obtain a sample and test specimen in accordance with
an accuracy of 0.1°C (0.2°F). Practice D 4057, except do not use the “Sampling by Water
6.1.5 The vapor pressure apparatus shall have provisions for Displacement” section for fuels containing oxygenates. Use a 1
introduction of the test specimen into an evacuated test L (1 qt) sized container filled between 70 and 80 with sample.
chamber and for the cleaning or purging of the chamber NOTE 6—The present precision statement was derived using samples in
following the test. 1 L (1 qt) containers. However, samples in containers of other sizes, as
6.2 Vacuum Pump, capable of reducing the pressure in the prescribed in Practice D 4057, can be used, with the same ullage
test chamber to less than 0.01 kPa (0.001 psi) absolute. requirement, if it is recognized that the precision can be affected.
6.3 Syringe, (optional, depending on sample introduction 8.1.3 In the case of referee testing, the 1 L (1 qt) sample
mechanism employed with each instrument) gas-tight, 1 to 20 container is mandatory.
mL capacity with a 61 % or better accuracy and a 61 % or
better precision. The capacity of the syringe should not exceed
two times the volume of the test specimen being dispensed. 4
Reagent Chemicals, American Chemical Society Specifications, American
6.4 Iced Water Bath or Air Bath, for chilling the samples Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
and syringe to temperatures between 0 to 1°C (32 to 34°F). Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
6.5 Pressure Measuring Device, capable of measuring local and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
station pressure with an accuracy of 0.20 kPa (0.03 psi), or MD.

2
D 5191
8.1.4 Perform the vapor pressure determination on the first test specimen and injecting it into the instrument for analysis,
test specimen withdrawn from a sample container. Do not use check the remaining sample for phase separation. If the sample
the remaining sample in the container for a second vapor is contained in a transparent container, this observation can be
pressure determination. If a second determination is necessary, made prior to sample transfer. If the sample is contained in a
obtain a new sample. non-transparent container, mix the sample thoroughly and
8.1.5 Protect samples from excessive temperatures prior to immediately pour a portion of the remaining sample into a
testing. This can be accomplished by storage in an appropriate clear glass container and observe for evidence of phase
ice bath or refrigerator. separation. A hazy appearance is to be carefully distinguished
8.1.6 Do not test samples stored in leaky containers. Discard from separation into two distinct phases. The hazy appearance
and obtain a new sample if leaks are detected. shall not be considered grounds for rejection of the fuel. If a
8.2 Sampling Handling Temperature— Cool the sample second phase is observed, discard the test and the sample. Hazy
container and contents in an ice bath or refrigerator to the 0 to samples may be analyzed (see Report section ).
1°C (32 to 34°F) range prior to opening the sample container.
Allow sufficient time to reach this temperature. Verify the 9. Preparation of Apparatus
sample temperature by direct measurement of the temperature 9.1 Prepare the instrument for operation in accordance with
of a similar liquid in a similar container placed in the cooling the manufacturer’s instructions.
bath or refrigerator at the same time as the sample. 9.2 Clean and dry the test chamber as required to avoid
8.3 Verification of Sample Container Filling—With the contamination of the test specimen. Prior to sample introduc-
sample at a temperature of 0 to 1°C, take the container from the tion, visually determine from the instrument display that the
cooling bath or refrigerator, and wipe dry with absorbent test chamber pressure is stable and does not exceed 0.1 kPa
material. If the container is not transparent, unseal it and using (0.01 psi). When the pressure is not stable or exceeds this
a suitable gage, confirm that the sample volume equals 70 to value, check that the chamber is clean of volatile materials
80 % of the container capacity (see Note 7). If the sample is remaining in the chamber from a previous sample or check the
contained in a transparent glass container, verify that the calibration of the transducer.
container is 70 to 80 % full by suitable means (see Note 7). 9.3 If a syringe is used for introduction of the sample
8.3.1 Discard the sample if the container is filled to less than specimen, chill it to between 0 and 4.5°C (32 and 40°F) in a
70 %, by volume, of the container capacity. refrigerator or ice bath before drawing in the sample. Avoid
8.3.2 If the container is more than 80 % by volume full, water contamination of the syringe reservoir by sealing the
pour out enough sample to bring the container contents within outlet of the syringe during the cooling process.
the 70 to 80 % by volume range. Do not return any sample to 9.4 Prior to introduction of the test specimen, check that the
the container once it has been withdrawn. temperature of the test chamber is within the required range of
8.3.3 Reseal the container if necessary, and return the 37.86 0.1°C (100 6 0.2°F).
sample container the cooling bath or refrigerator.
10. Calibration
NOTE 7—For non-transparent containers, one way to confirm that the 10.1 Pressure Transducer:
sample volume equals 70 to 80 % of the container capacity is to use a
10.1.1 Check the calibration of the transducer on a monthly
dipstick that has been pre-marked to indicate the 70 and 80 % container
capacities. The dipstick should be of such material that it shows wetting basis or when needed as indicated from the quality control
after being immersed and withdrawn from the sample. To confirm the checks (see Section 11). The calibration of the transducer is
sample volume, insert the dipstick into the sample container so that it checked using two reference points, zero pressure (<0.1 kPa)
touches the bottom of the container at a perpendicular angle, before and the ambient barometric pressure.
removing the dipstick. For transparent containers, using a marked ruler or 10.1.2 Connect a McLeod gage to the vacuum source in line
by comparing the sample container to a like container which has the 70 with the test chamber. Apply vacuum to the test chamber.
and 80 % levels clearly marked, has been found suitable.
When the McLeod gage registers a pressure less than 0.1 kPa
8.4 Air Saturation of the Sample in the Sample Container: (0.8 mm Hg), adjust the transducer control to zero or to the
8.4.1 Transparent Containers Only—Since 8.3 does not actual reading on the McLeod gage as dictated by the instru-
require that the sample container be opened to verify the ment design and manufacturer’s instructions.
sample capacity, it is necessary to unseal the cap momentarily
NOTE 8—Refer to Annex A6 of Test Method D 2892 for further details
before resealing it, so that samples in transparent containers are concerning the calibration of pressure sensors and McLeod gages.
treated the same as samples in non-transparent containers.
8.4.2 With the sample again at a temperature of 0 to 1°C, 10.1.3 Open the test chamber of the apparatus to atmosphere
take the container from the cooling bath or refrigerator, wipe it and observe the corresponding pressure value of the transducer.
dry with an absorbent material, remove the cap momentarily, Ensure that the apparatus is set to display the total pressure and
taking care that no water enters, reseal and shake vigorously. not a calculated or corrected value. Compare this pressure
Return it to the cooling bath or refrigerator for a minimum of value against the value obtained from the pressure measuring
2 min. device, as the pressure reference standard. The pressure mea-
8.4.3 Repeat 8.4.2 twice more. Return the sample to the suring device shall measure the local station pressure at the
cooling bath or refrigerator until the beginning of the proce- same elevation as the apparatus in the laboratory, at the time of
dure. pressure comparison.
8.5 Verification of Single Phase Samples—After drawing a NOTE 9—Caution: Many aneroid barometers, such as those used at

3
D 5191
weather stations and airports, are pre-corrected to give sea level readings; transfer tube, and deliver this test specimen to the test chamber
these must not be used for calibration of the apparatus. as rapidly as possible. The total time between opening the
10.1.3.1 For mercury barometers used as the pressure mea- chilled sample container and inserting/securing the syringe into
suring device, the barometric pressure reading shall be cor- the sealed test chamber shall not exceed 1 min.
rected for the change in the density of the mercury column 12.2 Follow the manufacturer’s instructions for injection of
between 0°C and the operating temperature and converted to the test specimen into the test chamber, and for operation of the
the same units of pressure as the vapor pressure apparatus instrument to obtain a total vapor pressure result for the test
display. After making the density correction, the conversion for specimen.
the height of a mercury column at 0°C to kPa or psia is made 12.3 Set the instrument to read the result in terms of total
as follows: 1 in. (25 mm) Hg at 0°C 5 3.3865 kPa vapor pressure. If the instrument is capable of calculating a dry
or 5 0.49116 psia. vapor pressure equivalent value, make sure that only the
10.1.4 Repeat 10.1.2 and 10.1.3 until the zero and baromet- parameters in 13.2 are used.
ric pressures read correctly without further adjustments. 13. Calculation
10.2 Thermometer—Check the calibration of the platinum
13.1 Record the total vapor pressure reading from the
resistance thermometer used to monitor the temperature of the
instrument to the nearest 0.1 kPa (0.01 psi). For instruments
test chamber at least every six months against a National
that do not automatically record a stable pressure value,
Institute of Standards and Technology (NIST) traceable ther-
manually record the pressure indicator reading every minute to
mometer.
the nearest 0.1 kPa. When three successive readings agree to
11. Quality Control Checks within 0.1 kPa, record the result to the nearest 0.1 kPa (0.01
psi).
11.1 Use a verification fluid with known volatility as an
13.2 Calculate the DVPE using Eq 1. Ensure that the
independent check against the instrument calibration each day
instrument reading used in this equation corresponds to the
the instrument is in use. For pure compounds (see 7.1),
total pressure and has not been corrected by an automatically
multiple test specimens may be taken from the same container
programmed correction factor:
over time, provided the pure compound test specimen is air
saturated according to the procedure given in 8.4, and the spent DVPE, kPa ~psi! 5 ~0.965 X! 2 A (1)
test specimens are not re-used, in whole or in part.. Record the
where:
dry vapor pressure equivalent value, and compare this to the X 5 measured total vapor pressure in kPa (psi), and
statistical value of the control sample from your laboratory. If A 5 3.78 kPa (or 0.548 psi)
the difference exceeds your control limits, check the calibration
of the instrument. NOTE 11—The correlation equation was derived from a statistical
11.2 Some possible materials and their corresponding vapor evaluation of the 1988 cooperative program.5 The equation corrects for the
bias between the measured total vapor pressure and the dry vapor pressure
pressures, as found in ASTM DS4B,5 include: cyclopentane, obtained in accordance with Test Method D 4953.
68.3 kPa (9.91 psi); 2,2-dimethylbutane 68.0 kPa (9.86 psi);
13.3 The calculation described by Eq 1 can be accomplished
2,3-dimethylbutane 51.1 kPa (7.41 psi); 2-methylpentane 46.7
automatically by the instrument, if so equipped, and in such
kPa (6.77 psi); cyclohexane 22.5 kPa (3.26 psi); and toluene
cases the user shall not apply any further corrections.
7.1 kPa (1.03 psi).6
14. Report
NOTE 10—It is recommended that at least one type of control sample
used in 11.1 be representative of the fuel(s) regularly tested by the 14.1 Report the dry vapor pressure equivalent to the nearest
laboratory. The total vapor pressure measurement process (including 0.1 kPa (0.01 psi) without reference to temperature.
operator technique) can be checked periodically by performing this test 14.2 If the sample was observed to be hazy in 8.5, report the
method on previously prepared samples from one batch of product, as per test result as in 14.1, followed by the letter H.
procedure described in 8.1.2. Samples should be stored in an environment
suitable for long term storage without sample degradation. Analysis of NOTE 12—The precision and bias statements have not been determined
result(s) from these quality control samples can be carried out using for hazy samples since these types of samples have not been evaluated as
control chart techniques.7 part of a interlaboratory study.
NOTE 13—The inclusion of the letter H in 14.2 is intended to alert the
12. Procedure data recipient that the sample analyzed was hazy. In the event that a
12.1 Remove the sample from the cooling bath or refrigera- laboratory has a computer system that is incapable of reporting alphanu-
meric results in accordance with the requirements in 14.2, it is permissible
tor, dry the exterior of the container with absorbent material, for the laboratory to report the result obtained as in 14.1, along with a
uncap, and insert a chilled transfer tube or syringe (see 9.3). statement or annotation that clearly conveys to the data recipient that the
Draw a bubble-free aliquot of sample into a gas tight syringe or analyzed sample was hazy.
15. Precision and Bias 8
5
“Physical Constants of Hydrocarbon and Non-Hydrocarbon Materials,” avail- 15.1 Precision—The precision of this test method as deter-
able from ASTM Headquarters. Order PCN 28-003092-12.
6
mined by the statistical examination of interlaboratory test
The vapor pressure values cited were obtained from Phillips Petroleum
Company, Bartlesville, Oklahoma or ASTM DS 4B Physical Constants of Hydro-
results is as follows:
carbon and Non–Hydrocarbon Compounds.
7 8
Reference ASTM MNL 7, Manual on Presentation of Data Control Chart The results of this test program are filed at ASTM Headquarters. Request
Analysis, 6th Edition, Section 3: Control Charts for Individuals. RR:D02-1286.

4
D 5191
NOTE 14—The following precision data were developed in a 1991 working in different laboratories on identical test material
interlaboratory cooperative test program. Participants analyzed sample would, in the long run, in the normal and correct operation of
sets comprised of blind duplicates of 14 types of hydrocarbons and the test method, exceed the value calculated as per the
hydrocarbon-oxygenate blends. The oxygenate content (MTBE, ethanol,
and methanol) ranged from 0 to 15 by volume nominal and the vapor
following equation only in one case in twenty:
pressure ranged from 14 to 100 kPa (2 to 15 psi) nominal. A total of 60 reproducibility 5 0.0161 ~DVPE 1 B! (3)
laboratories participated. Some participants performed more than one test
method, using separate sample sets for each. Twenty-six sample sets were where:
tested by Test Method D 5190 and 27 by this test method. In addition, six B 5 124 kPa (or 18.0 psi).
sets were tested by modified Test Method D 5190, and 13 were modified 15.2 Bias—Since there is no accepted reference material
by this test method. suitable for determining the bias for the procedures in this test
15.1.1 Repeatability—The difference between successive method, bias cannot be determined.
test results obtained by the same operator with the same 15.3 Relative Bias—A statistically significant relative bias
apparatus under constant operating conditions on identical test was observed in the 1991 interlaboratory cooperative test
material would, in the long run, in the normal and correct program between the total pressure obtained using this test
operation of the test method, exceed the value calculated as per method and the dry vapor pressure obtained using Test Method
(Eq 2) only in one case in twenty: D 4953, procedure A. This bias is corrected by the use of Eq 1
(see 13.2), which calculates a DVPE value from the observed
repeatability 5 0.00807 ~DVPE 1 B! (2)
total pressure.
where:
B 5 124 kPa (or 18.0 psi). 16. Keywords
15.1.2 Reproduciblity—The difference between two single 16.1 dry vapor pressure; gasoline; hydrocarbon-oxygenate
and independent test results obtained by different operators blends; mini method; petroleum products; vapor pressure

SUMMARY OF CHANGES

Committee D 02.08 has identified the location of selected changes to this standard since the last issue
(D 5191-96) that may impact the use of this standard.

(1) Revisions were made to allow the testing of hazy samples transparent contianer is filled from 70 to 80 % by volume of the
that have not phase separated. Revisions include changes to the sample container capacity.
scope (1.1.1); verification of a single phase sample (8.5); and (5) In section 8.3.3, it has been explicitly stated to reseal the
reporting (14.2, and Notes 12 and 13). sample container, if necessary.
(2) Footnote 4 reference in 6.1 (which provided a listing of (6) A new 8.4.1 has been added (and subsequent sections
two instrument suppliers that have been found suitable to use renumbered) to ensure that transparent and non-transparent
in this test method) was deleted to align with ASTM bylaws to containers are opened the same number of times prior to
remove footnote references if more than one supplier exists. analysis.
(3) Specifying a pressure measuring device in place of the (7) Updated 10.1.3 to remove specific reference to a Fortin-
required use of a Mercury Barometer in 6.5, along with an type mercurial barometer.
accuracy requirement that needs to be satisfied by the pressure (8) Updated 10.1.3.1 to specify it a mercury barometer is used,
measuring device. Paragraph 6.5.1 has been added to require that it must be corrected for the change in the density of the
pressure measuring devices that are not mercury manometers mercury column.
to have their calibrations periodically checked (with traceabil- (9) Paragraph 11.1 has been updated to allow more than one
ity to a nationally recognized standard). test specimen to be taken from the same container if they are
(4) A new Note 7 has been added after 8.3, to provide pure compounds so that the same material can be used for
guidance as to how to verify whether a transparent or non- control chart purposes.

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