1、Designation: D 6596 00 (Reapproved 2005)An American National StandardStandard Practice forAmpulization and Storage of Gasoline and RelatedHydrocarbon Materials1This standard is issued under the fixed designation D 6596; the number immediately following the designation indicates the year oforiginal a
2、doption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This practice covers a general guide for the ampuliza-tion and stora
3、ge of gasoline and related hydrocarbon mixturesthat are to be used as calibration standards or referencematerials. This practice addresses materials, solutions, ormixtures, which may contain volatile components. This prac-tice is not intended to address the ampulization of highlyviscous liquids, mat
4、erials that are solid at room temperature, ormaterials that have high percentages of dissolved gases thatcannot be handled under reasonable cooling temperatures andat normal atmospheric pressure without losses of these volatilecomponents.1.2 This practice is applicable to automated ampule fillingand
5、 sealing machines as well as to manual ampule fillingdevices, such as pipettes and hand-operated liquid dispensers.1.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to address all of thesafet
6、y concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 6362 Practice for Certificates
7、of Reference Fuels forWater AnalysisE 826 Practice for Testing Homogeneity of Materials forDevelopment of Reference Materials2.2 ISO Standards:3ISO Guide 30 Terms and Definitions Used in Connectionwith Reference MaterialsISO Guide 31 Contents of Certificates of Reference Mate-rialsISO Guide 35 Certi
8、fication of Reference Materials Gen-eral and Statistical PrinciplesISO/REMCO N280 Homogeneity Testing Procedure for theEvaluation of Interlaboratory Test Samples1This practice is under the jurisdiction of ASTM Committee D02 on PetroleumProducts and Lubricants and is the direct responsibility of Subc
9、ommittee D02.04 onHydrocarbon Analysis.Current edition approved May 1, 2005. Published June 2005. Originallyapproved in 2000. Last previous edition approved in 2000 as D 659600.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. F
10、or Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Available from American National Standards Institute (ANSI), 25 W. 43rd St.,4th Floor, New York, NY 10036.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Consh
11、ohocken, PA 19428-2959, United States.2.3 Government Standard:429 CFR 1910.1200 Hazard Communication3. Terminology3.1 Definitions:3.1.1 accepted reference value (ARV)a value that servesas an agreed-upon reference for comparison and that is derivedas: (1) a theoretical or established value, based on
12、scientificprinciples; (2) an assigned value, based on experimental workof some national or international organization, such as theNational Institute of Standards and Technology (NIST); or (3)a consensus value, based on collaborative experimental workunder the auspices of a scientific or engineering
13、group.3.1.2 ampulea glass vessel for the storage of liquidmaterials, possessing a long narrow neck for the purpose ofproviding a flame-sealed closure.3.1.3 headspacethe unfilled capacity of an ampule thatallows for physical expansion due to temperature and pressurechanges of the filled material whil
14、e maintaining the integrity ofthe package.3.1.4 homogeneitythe uniformity of the characteristics ofthe packaged material across the entire packaging run deter-mined for the purpose of demonstrating the suitability of thebatch for its intended purpose.3.1.4.1 DiscussionThere are two homogeneity testi
15、ngcases; one in which the material is ampulized as a referencematerial at the time of ampulization, and one in which thematerial is not.(1) reference material at time of ampulizationThe material to beampulized is a reference material that has accepted true or consensusvalues. Ampulization of a refer
16、ence material would require homoge-neity testing in order to assess the variability caused by the ampuliza-tion process on the true or consensus values for the reference material.(2) not a reference material at time of ampulizationThe material tobe ampulized is not a reference material at the time o
17、f ampulization butis intended to have characterization and assignment of true or consen-sus values at some future date. Rigid homogeneity testing is notrequired on such a material at the time of ampulization since the true orconsensus values have not yet been determined. However, ampulesmust be reta
18、ined at the beginning, middle, and end of the ampulizationprocess. It is recommended that qualitative testing be done on at leastone sample from each of the beginning, middle, and end of theampulization process. The remaining ampules should then be retainedfor future homogeneity testing to determine
19、 quantitative or consensusvalues.3.1.5 reference material (RM)a material or substance ofwhich one or more properties are sufficiently well establishedto enable the material to be used for the calibration of anapparatus, the assessment of a method, or the assignment ofvalues to similar materials.3.1.
20、6 shelf lifethe period of time, under specified storageconditions, for which the RM will possess the same propertiesor true values, within established acceptance limits.3.1.7 stability testingtests required to demonstrate thechemical stability of the ampulized RM for the purpose ofdetermining the sh
21、elf life of the RM.4. Summary of Practice4.1 The physical and chemical characteristics (for example,volatility, reactivity, flammability, and so forth) of a gasoline orrelated hydrocarbon mixture is first assessed to determine theappropriate procedures for sample handling, sample transfer,and ampuli
22、zation. Then a uniform quantity of gasoline orhydrocarbon mixture is dispensed into suitably sized glassampules (purged with an inert gas), and the ampules areflame-sealed with a torch. A number of ampules from through-out the filling and sealing process are selected and tested byappropriate test me
23、thods to determine homogeneity across thelot. Additional ampules are retained for later testing to deter-mine stability and shelf life.4.2 This practice addresses the common difficulties associ-ated with the ampulization and storage of gasoline and similarliquid hydrocarbon materials, which may cont
24、ain volatilecomponents. The process of ampulization, whether performedusing manual or automated equipment, involves the samefundamental issues, namely, assessment of the characteristicsof the material to be ampulized, sources of contamination,sampling of the bulk container, volume dispensing accurac
25、y,inert atmosphere blanketing, flame sealing, sequential ampulelabeling, packaging homogeneity sampling, and homogeneitytesting. Failure to adequately consider any of the above issuesmay negatively impact the quality, consistency, and value ofthe ampulized material as an RM.4.3 Confidence in the hom
26、ogeneity of the ampulized prod-uct can only be established through homogeneity testing,which involves the sampling, analysis, and statistical treatmentof data from randomly selected ampules obtained from thebeginning, middle, and end of the ampulized lot. Determina-tion of ampulization homogeneity r
27、equires that the order inwhich the ampules have been filled and sealed be maintained.Homogeneity testing reveals the variability of the productintroduced during the ampulization process. Homogeneityresults must be within acceptable limits of the ARV orconsensus value for the RM.4.4 Ampulization does
28、 not necessarily guarantee samplestability or indefinite shelf life of the RM. Initial homogeneitydata establish reference values for future tests of samplestability and determination of shelf life.5. Significance and Use5.1 Ampulization is desirable in order to minimize variabil-ity and maximize th
29、e integrity of calibration standards or RMs,or both, being used in calibration of analytical instruments andin validation of analytical test methods in round-robin orinterlaboratory cross-check programs. This practice is intendedto be used when the highest degree of confidence in integrity ofa mater
30、ial is desired.5.2 This practice is intended to be used when it is desirableto maintain the long term storage of gasoline and related liquidhydrocarbon RMs, controls, or calibration standards for retainor repository purposes.5.3 This practice may not be applicable to materials thatcontain high perce
31、ntages of dissolved gases, or to highlyviscous materials, due to the difficulty involved in transferring4Available from U.S. Government Printing Office Superintendent of Documents,732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401.D 6596 00 (2005)2such materials without encountering losses
32、 of components orensuring sample homogeneity.6. Procedure6.1 Manual Ampule Filling and Sealing:6.1.1 ApparatusDevices used for manual filling of am-pules include glass pipettes as well as other types of commer-cially available hand-operated, mechanical, liquid-dispensingdevices.6.1.2 Storage of Bulk
33、 MaterialBulk gasoline and similarliquid hydrocarbon materials must be adequately sealed andstored to prevent loss of volatile components prior to ampuli-zation. Refrigerated storage in sealed metal drums, barrels, oramber glass containers is recommended.6.1.3 Compatibility of Materials/Sources of C
34、ontamination:6.1.3.1 Materials that come in contact with the bulk RM andits vapors during dispensing must be compatible with thegasoline or hydrocarbon material. Glass pipettes are recom-mended. Plastic or rubber materials containing phthalates orother types of plasticizers must be avoided.6.1.3.2 A
35、ny part of the dispensing device that comes incontact with the material, including glass pipettes, hand dis-pensers, and any necessary connection hardware, must becleaned prior to packaging a different material. Recommendedcleaning procedures involve soaking parts in soapy water,rinsing with clean w
36、ater, followed by methanol or othersuitable solvent, followed by drying under a stream of cleannitrogen.6.1.4 Assessment of Material to Be Ampulized:6.1.4.1 VolatilityPrior to packaging, materials containinghighly volatile components must be cooled sufficiently tominimize volatile losses during ampu
37、lization. Failure to suffi-ciently cool the material also may result in difficulty inobtaining effective ampule sealing. The material must not becooled to temperatures below which the composition of theRM would be affected (for example, producing precipitation orsolidification). Gasoline may be cool
38、ed to 20C withoutincurring compositional changes. The bulk material must bekept cold during the filling process.6.1.4.2 ReactivityConsideration should be given to thechemical reactivity of the RM being packaged. Gasolinesamples containing olefins and diolefins should be packagedunder an inert atmosp
39、here blanket of nitrogen, argon, or othersuitable gas. Ampules should be flushed with inert gas imme-diately prior to dispensing of the gasoline. Use of amber glassampules will minimize photo-oxidation.6.1.4.3 OdorsOdorous materials such as gasoline shouldbe packaged in a well-ventilated area. The b
40、ulk material shouldbe kept adequately sealed during the ampulization process tominimize loss of volatiles.6.1.4.4 FlammabilityAmpule sealing requires use of aflame hot enough to melt glass. Care must be taken inampulization of highly flammable materials since ampulecontents could ignite. Ampules mus
41、t be kept cold through thesealing step. However, care should be taken to avoid, as muchas possible, condensation of water inside the ampule. Ampu-lization is best carried out when the room humidity is low.6.1.5 Sampling of the Bulk Container:6.1.5.1 After bringing the bulk container temperature down
42、to the working temperature, withdraw a minimum of threesamples from each bulk container, using clean manual pipettes.Immediately dispense the material into crimp top chromatog-raphy vials, seal, and label. These samples will be designatedas representative of the bulk material and will be used toesta
43、blish reference values for the homogeneity testing.6.1.5.2 Some vial closures are not suitable for hydrocarbonanalyses, such as uncoated silicone rubber. Only TFE-fluorocarbon-coated closures should be used. In addition, thevials should be analyzed as soon as is practical, since nocrimped vial is co
44、mpletely leak free.6.1.6 Adjusting Dispensing Volume:6.1.6.1 Typically, it is more important to provide a mini-mum dispensed volume in the ampule rather than to provide anaccurately determined volume of RM. The minimum dispens-ing volume for packaging the RM must be known ahead oftime.6.1.6.2 Introd
45、uce an inert atmosphere into the ampule bypurging the ampule for a few seconds with nitrogen or otherinert gas immediately prior to filling. A disposable glassdropper connected to a gas source using rubber tubing providesa convenient way of purging the ampule.6.1.6.3 If using graduated pipettes, int
46、roduce a sufficientvolume of material to the ampule to meet the minimumdispensing volume requirements for packaging the RM. Notethat the final dispensed volume at room temperature will beaffected by the bulk material temperature at the time ofdispensing. Therefore, for consistent volume dispensing,
47、thetemperature of the bulk material must be known and must bekept constant during the entire dispensing process.6.1.6.4 If other types of nongraduated, manual, filling de-vices are being used, they must be calibrated. Using Class Aglassware or pipettes, measure into an ampule a volume ofroom tempera
48、ture water equal to the volume of RM to bedispensed. Mark the level on the ampule.6.1.6.5 Make adjustments to the manual dispensing deviceuntil 50 consecutive ampules are consistently filled to thepredetermined mark on the ampule.6.1.6.6 Once volume dispensing adjustments have beencompleted, begin f
49、illing ampules from the bulk supply, keepingthe filled ampules cold by placing them immediately into acontainer that is at a temperature of approximately 20C. Thismay be achieved by using crushed dry ice.6.1.6.7 The ampules should be sealed as soon as possibleafter filling to avoid loss of volatile components. If ampules arebeing manually sealed, a two person operation, in which oneperson dispenses the material and a second person seals theampules, is suggested.6.1.6.8 Periodically inspect filled and sealed ampules toensure that the fill volume is maintained thro
