ASTM D6596-00(2005)
(Practice)Standard Practice for Ampulization and Storage of Gasoline and Related Hydrocarbon Materials
Standard Practice for Ampulization and Storage of Gasoline and Related Hydrocarbon Materials
SIGNIFICANCE AND USE
Ampulization is desirable in order to minimize variability and maximize the integrity of calibration standards or RMs, or both, being used in calibration of analytical instruments and in validation of analytical test methods in round-robin or interlaboratory cross-check programs. This practice is intended to be used when the highest degree of confidence in integrity of a material is desired.
This practice is intended to be used when it is desirable to maintain the long term storage of gasoline and related liquid hydrocarbon RMs, controls, or calibration standards for retain or repository purposes.
This practice may not be applicable to materials that contain high percentages of dissolved gases, or to highly viscous materials, due to the difficulty involved in transferring such materials without encountering losses of components or ensuring sample homogeneity.
SCOPE
1.1 This practice covers a general guide for the ampulization and storage of gasoline and related hydrocarbon mixtures that are to be used as calibration standards or reference materials. This practice addresses materials, solutions, or mixtures, which may contain volatile components. This practice is not intended to address the ampulization of highly viscous liquids, materials that are solid at room temperature, or materials that have high percentages of dissolved gases that cannot be handled under reasonable cooling temperatures and at normal atmospheric pressure without losses of these volatile components.
1.2 This practice is applicable to automated ampule filling and sealing machines as well as to manual ampule filling devices, such as pipettes and hand-operated liquid dispensers.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
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Designation:D6596–00 (Reapproved 2005)
Standard Practice for
Ampulization and Storage of Gasoline and Related
Hydrocarbon Materials
This standard is issued under the fixed designation D6596; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
1.1 This practice covers a general guide for the ampuliza-
bility of regulatory limitations prior to use.
tion and storage of gasoline and related hydrocarbon mixtures
that are to be used as calibration standards or reference
2. Referenced Documents
materials. This practice addresses materials, solutions, or
2.1 ASTM Standards:
mixtures, which may contain volatile components. This prac-
D6362 Practice for Certificates of Reference Materials for
tice is not intended to address the ampulization of highly
Water Analysis
viscous liquids, materials that are solid at room temperature, or
E826 Practice for Testing Homogeneity of a Metal Lot or
materials that have high percentages of dissolved gases that
Batch in Solid Form by SparkAtomic Emission Spectrom-
cannot be handled under reasonable cooling temperatures and
etry
at normal atmospheric pressure without losses of these volatile
2.2 ISO Standards:
components.
ISO Guide 30 Terms and Definitions Used in Connection
1.2 This practice is applicable to automated ampule filling
with Reference Materials
and sealing machines as well as to manual ampule filling
ISO Guide 31 Contents of Certificates of Reference Mate-
devices, such as pipettes and hand-operated liquid dispensers.
rials
1.3 The values stated in SI units are to be regarded as
ISO Guide 35 Certification of Reference Materials – Gen-
standard. No other units of measurement are included in this
eral and Statistical Principles
standard.
ISO/REMCO N280 HomogeneityTesting Procedure for the
1.4 This standard does not purport to address all of the
Evaluation of Interlaboratory Test Samples
safety concerns, if any, associated with its use. It is the
1 2
This practice is under the jurisdiction ofASTM Committee D02 on Petroleum For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Products and Lubricants and is the direct responsibility of Subcommittee D02.04 on contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Hydrocarbon Analysis. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved May 1, 2005. Published June 2005. Originally the ASTM website.
approved in 2000. Last previous edition approved in 2000 as D6596–00. DOI: Available fromAmerican National Standards Institute (ANSI), 25 W. 43rd St.,
10.1520/D6596-00R05. 4th Floor, New York, NY 10036.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D6596–00 (2005)
2.3 Government Standard: 4. Summary of Practice
29 CFR 1910.1200 Hazard Communication
4.1 The physical and chemical characteristics (for example,
volatility,reactivity,flammability,andsoforth)ofagasolineor
3. Terminology
related hydrocarbon mixture is first assessed to determine the
3.1 Definitions:
appropriate procedures for sample handling, sample transfer,
3.1.1 accepted reference value (ARV)—a value that serves
and ampulization. Then a uniform quantity of gasoline or
as an agreed-upon reference for comparison and that is derived
hydrocarbon mixture is dispensed into suitably sized glass
as: (1) a theoretical or established value, based on scientific
ampules (purged with an inert gas), and the ampules are
principles; (2) an assigned value, based on experimental work
flame-sealed with a torch.Anumber of ampules from through-
of some national or international organization, such as the
out the filling and sealing process are selected and tested by
National Institute of Standards and Technology (NIST); or (3)
appropriate test methods to determine homogeneity across the
a consensus value, based on collaborative experimental work
lot. Additional ampules are retained for later testing to deter-
under the auspices of a scientific or engineering group.
mine stability and shelf life.
3.1.2 ampule—a glass vessel for the storage of liquid
4.2 This practice addresses the common difficulties associ-
materials, possessing a long narrow neck for the purpose of
ated with the ampulization and storage of gasoline and similar
providing a flame-sealed closure.
liquid hydrocarbon materials, which may contain volatile
3.1.3 headspace—the unfilled capacity of an ampule that
components. The process of ampulization, whether performed
allows for physical expansion due to temperature and pressure
using manual or automated equipment, involves the same
changesofthefilledmaterialwhilemaintainingtheintegrityof
fundamental issues, namely, assessment of the characteristics
the package.
of the material to be ampulized, sources of contamination,
3.1.4 homogeneity—the uniformity of the characteristics of
sampling of the bulk container, volume dispensing accuracy,
the packaged material across the entire packaging run deter-
inert atmosphere blanketing, flame sealing, sequential ampule
mined for the purpose of demonstrating the suitability of the
labeling, packaging homogeneity sampling, and homogeneity
batch for its intended purpose.
testing. Failure to adequately consider any of the above issues
3.1.4.1 Discussion—There are two homogeneity testing
may negatively impact the quality, consistency, and value of
cases; one in which the material is ampulized as a reference
the ampulized material as an RM.
material at the time of ampulization, and one in which the
4.3 Confidence in the homogeneity of the ampulized prod-
material is not.
uct can only be established through homogeneity testing,
(1) reference material at time of ampulization—The material to be
which involves the sampling, analysis, and statistical treatment
ampulized is a reference material that has accepted true or consensus
of data from randomly selected ampules obtained from the
values. Ampulization of a reference material would require homoge-
beginning, middle, and end of the ampulized lot. Determina-
neity testing in order to assess the variability caused by the ampuliza-
tion of ampulization homogeneity requires that the order in
tion process on the true or consensus values for the reference material.
which the ampules have been filled and sealed be maintained.
(2) not a reference material at time of ampulization—Thematerialto
be ampulized is not a reference material at the time of ampulization but Homogeneity testing reveals the variability of the product
is intended to have characterization and assignment of true or consen-
introduced during the ampulization process. Homogeneity
sus values at some future date. Rigid homogeneity testing is not
results must be within acceptable limits of the ARV or
required on such a material at the time of ampulization since the true or
consensus value for the RM.
consensus values have not yet been determined. However, ampules
4.4 Ampulization does not necessarily guarantee sample
must be retained at the beginning, middle, and end of the ampulization
stability or indefinite shelf life of the RM. Initial homogeneity
process. It is recommended that qualitative testing be done on at least
one sample from each of the beginning, middle, and end of the
data establish reference values for future tests of sample
ampulization process. The remaining ampules should then be retained
stability and determination of shelf life.
for future homogeneity testing to determine quantitative or consensus
values.
5. Significance and Use
3.1.5 reference material (RM)—a material or substance of
5.1 Ampulization is desirable in order to minimize variabil-
which one or more properties are sufficiently well established
ity and maximize the integrity of calibration standards or RMs,
to enable the material to be used for the calibration of an
or both, being used in calibration of analytical instruments and
apparatus, the assessment of a method, or the assignment of
in validation of analytical test methods in round-robin or
values to similar materials.
interlaboratory cross-check programs.This practice is intended
3.1.6 shelf life—the period of time, under specified storage
tobeusedwhenthehighestdegreeofconfidenceinintegrityof
conditions, for which the RM will possess the same properties
a material is desired.
or true values, within established acceptance limits.
5.2 This practice is intended to be used when it is desirable
3.1.7 stability testing—tests required to demonstrate the
to maintain the long term storage of gasoline and related liquid
chemical stability of the ampulized RM for the purpose of
hydrocarbon RMs, controls, or calibration standards for retain
determining the shelf life of the RM.
or repository purposes.
5.3 This practice may not be applicable to materials that
contain high percentages of dissolved gases, or to highly
AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments,
732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401. viscous materials, due to the difficulty involved in transferring
D6596–00 (2005)
such materials without encountering losses of components or 6.1.5.1 After bringing the bulk container temperature down
ensuring sample homogeneity. to the working temperature, withdraw a minimum of three
samplesfromeachbulkcontainer,usingcleanmanualpipettes.
6. Procedure Immediately dispense the material into crimp top chromatog-
raphy vials, seal, and label. These samples will be designated
6.1 Manual Ampule Filling and Sealing:
as representative of the bulk material and will be used to
6.1.1 Apparatus—Devices used for manual filling of am-
establish reference values for the homogeneity testing.
pules include glass pipettes as well as other types of commer-
6.1.5.2 Some vial closures are not suitable for hydrocarbon
cially available hand-operated, mechanical, liquid-dispensing
analyses, such as uncoated silicone rubber. Only TFE-
devices.
fluorocarbon-coated closures should be used. In addition, the
6.1.2 Storage of Bulk Material—Bulk gasoline and similar
vials should be analyzed as soon as is practical, since no
liquid hydrocarbon materials must be adequately sealed and
crimped vial is completely leak free.
stored to prevent loss of volatile components prior to ampuli-
zation. Refrigerated storage in sealed metal drums, barrels, or
6.1.6 Adjusting Dispensing Volume:
amber glass containers is recommended.
6.1.6.1 Typically, it is more important to provide a mini-
6.1.3 Compatibility of Materials/Sources of Contamination:
mum dispensed volume in the ampule rather than to provide an
6.1.3.1 MaterialsthatcomeincontactwiththebulkRMand
accurately determined volume of RM. The minimum dispens-
its vapors during dispensing must be compatible with the
ing volume for packaging the RM must be known ahead of
gasoline or hydrocarbon material. Glass pipettes are recom-
time.
mended. Plastic or rubber materials containing phthalates or
6.1.6.2 Introduce an inert atmosphere into the ampule by
other types of plasticizers must be avoided.
purging the ampule for a few seconds with nitrogen or other
6.1.3.2 Any part of the dispensing device that comes in
inert gas immediately prior to filling. A disposable glass
contact with the material, including glass pipettes, hand dis-
dropperconnectedtoagassourceusingrubbertubingprovides
pensers, and any necessary connection hardware, must be
a convenient way of purging the ampule.
cleaned prior to packaging a different material. Recommended
6.1.6.3 If using graduated pipettes, introduce a sufficient
cleaning procedures involve soaking parts in soapy water,
volume of material to the ampule to meet the minimum
rinsing with clean water, followed by methanol or other
dispensing volume requirements for packaging the RM. Note
suitable solvent, followed by drying under a stream of clean
that the final dispensed volume at room temperature will be
nitrogen.
affected by the bulk material temperature at the time of
6.1.4 Assessment of Material to Be Ampulized:
dispensing. Therefore, for consistent volume dispensing, the
6.1.4.1 Volatility—Prior to packaging, materials containing
temperature of the bulk material must be known and must be
highly volatile components must be cooled sufficiently to
kept constant during the entire dispensing process.
minimize volatile losses during ampulization. Failure to suffi-
6.1.6.4 If other types of nongraduated, manual, filling de-
ciently cool the material also may result in difficulty in
obtaining effective ampule sealing. The material must not be vices are being used, they must be calibrated. Using Class A
glassware or pipettes, measure into an ampule a volume of
cooled to temperatures below which the composition of the
RM would be affected (for example, producing precipitation or room temperature water equal to the volume of RM to be
solidification). Gasoline may be cooled to –20°C without dispensed. Mark the level on the ampule.
incurring compositional changes. The bulk material must be
6.1.6.5 Make adjustments to the manual dispensing device
kept cold during the filling process.
until 50 consecutive ampules are consistently filled to the
6.1.4.2 Reactivity—Consideration should be given to the
predetermined mark on the ampule.
chemical reactivity of the RM being packaged. Gasoline
6.1.6.6 Once volume dispensing adjustments have been
samples containing olefins and diolefins should be packaged
completed,beginfillingampulesfromthebulksupply,keeping
under an inert atmosphere blanket of nitrogen, argon, or other
the filled ampules cold by placing them immediately into a
suitable gas. Ampules should be flushed with inert gas imme-
container that is at a temperature of approximately –20°C.This
diately prior to dispensing of the gasoline. Use of amber glass
may be achieved by using crushed dry ice.
ampules will minimize photo-oxidation.
6.1.6.7 The ampules should be sealed as soon as possible
6.1.4.3 Odors—Odorous materials such as gasoline should
afterfillingtoavoidlossofvolatilecomponents.Ifampulesare
bepackagedinawell-ventilatedarea.Thebulkmaterialshould
being manually sealed, a two person operation, in which one
be kept adequately sealed during the ampulization process to
person dispenses the material and a second person seals the
minimize loss of volatiles.
ampules, is suggested.
6.1.4.4 Flammability—Ampule sealing requires use of a
6.1.6.8 Periodically inspect filled
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