1、Designation: D 6806 02 (Reapproved 2007)e1Standard Practice forAnalysis of Halogenated Organic Solvents and TheirAdmixtures by Gas Chromatography1This standard is issued under the fixed designation D 6806; the number immediately following the designation indicates the year oforiginal adoption or, in
2、 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.e1NOTEThe spelling of millivolts was corrected in 5.1 in March 2007.1. Scope1.1 This practice
3、covers the determination of impurities,stabilizers and assay of halogenated organic solvents and theiradmixtures by gas chromatography.1.2 It is not the intent of this practice to provide a specificmethod of gas chromatography. The intent of this practice is todefine what is required for a user to d
4、emonstrate that a methodto be used is valid. The reason for this approach, as opposed tostating a method, is that gas chromatography is such a dynamicfield that methods are often obsolete by the time they arevalidated. The use of this practice allows the user to use mosteffective technology and demo
5、nstrate that the method in usecomplies with a standard practice and is valid for the analysisof halogenated organic solvents and their admixtures.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this stan
6、dard 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:2E 180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty Chemicals3.
7、Terminology3.1 Purity and assay are used interchangeably in this stan-dard.3.1.1 Purity or assay are defined as 100 sum(impurities +stabilizer) when impurities and stabilizers are expressed in %;3.1.2 Or 100 sum(impurities + stabilizer)/10 000 whenimpurities are expressed in ppm.3.2 Accuracy is defi
8、ned per A2.2.1 of Practice E 180 or theagreement between an experimentally determined value andthe accepted reference value.3.3 Precision is defined per A2.1.7 of Practice E 180 or thedegree of agreement of repeated measurements of the sameproperty. It is generally expressed in standard deviations o
9、rpercent relative standard deviation (s/X) 100, also known ascoefficient of variation.4. Summary of Practice4.1 This practice will define the requirements for a gaschromatographic (GC) method to be valid for the determina-tion of impurities, stabilizers and assay of halogenated organicsolvents and t
10、heir admixtures.5. Method Requirements5.1 The GC method must give adequate separation of theimpurities and stabilizers common to the product in question sothat the instrument response (area counts, millivolts, etc.) to theindividual impurities or stabilizers can be measured withadequate precision an
11、d accuracy as defined in Section 6.Process knowledge from the supplier or manufacturer of theproduct is a resource of information as to what those impuritiesand stabilizers are. GC-Mass Spectrometry (GC-MS) is an-other resource to initially determine what components arepresent to be measured. See Ta
12、ble 1 for a list of possibleimpurities and stabilizers for each product.5.2 Non polar capillary columns of about 0.32 mm by 30 mgenerally work well. Table 2 provides a list of columns thatmay prove suitable for the analysis of the halogenated organicproducts.5.3 Instrument ConditionsThe following GC
13、 conditionsare often appropriate for the analysis of halogenated organicproducts and their admixtures though actual conditions shouldbe optimized for the analysis being performed.5.4 The separation is determined to be adequate by prepar-ing standards of known amounts of the impurities and stabi-lize
14、rs in concentrations near enough to the expected concen-trations in the sample for the instrument response to be linear1This practice is under the jurisdiction of ASTM Committee D26 on Haloge-nated Organic Solvents and Fire Extinguishing Agents and is the direct responsi-bility of Subcommittee D26.0
15、4 on Test Methods.Current edition approved Feb. 1, 2007. Published March 2007. Originallyapproved in 2002. Last previous edition approved in 2002 as D 6806 - 02.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book o
16、f ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.over the concentration range of interest. Repeated injections(minimum of three) of th
17、is standard are made and the accuracyand precision of the method for the individual impurities andstabilizers are determined.5.5 Response to components must not be out of range of thedetector and should be sufficiently Gaussian (symmetrical) toallow adequate measurement as defined by Section 6. Out
18、ofrange response can be corrected by changing the range of theinstrument or changing sample size.5.6 Purity or assay of unblended halogenated organic sol-vents will be determined by determining the amounts of theindividual impurities and stabilizers and subtracting the total ofthose impurities and s
19、tabilizers from 100 %. Purity or assaywill, unless otherwise stated, be determined by subtractingfrom 100, the sum of impurities (as determined by gaschromatography) and stabilizers only. The values for water,acidity, non-volatile matter and other such components will notbe subtracted from 100 % to
20、determine the purity or assay ofthe material in question unless the specifications call for theseitems to be included in the total to be subtracted from 100.5.7 Area percent is generally not suitable for halogenatedorganic products as the sensitivity to a flame ionizationdetector varies greatly betw
21、een components, particularly sta-bilizers which do not contain chlorine. Calibration of theinstrument should be done using a standard containing thecomponents of interest in concentrations similar to that ex-pected in the sample being analyzed.5.8 Precision for the assay is determined by performings
22、tatistical analysis of the purity or assay of individual injectionswhich is determined by 100 % sum(stabilizers + impurities).The units for assay or purity will be weight percent unlessotherwise specified.6. Precision and Bias36.1 Adequate precision and bias is defined by the needs ofthe user of the
23、 method.6.2 As a general guideline, the following table showsprecision of a good gas chromatographic method. These valueswere determined experimentally in a round robin betweendifferent laboratories in different companies. Automatic injec-tors were in common use in all participating laboratories and
24、were used in the round robin.6.3 The average and standard deviation of recovery (aver-age of 3 or 4 results) has been determined to be 100.29 68.02 % with 99.7 % falling between 76 and 124 %. Eighty fivepercent were found to fall between 95 and 105 % recovery.6.4 The lower detection limit can be ass
25、umed to be threetimes the noise level of the chromatogram. The lower quanti-fication limit can be assumed to be ten times the noise level.The noise level is determined by starting a run without an3A research report is available from ASTM Headquarters. RequestRR:D261018.TABLE 1 Impurities and Stabili
26、zerProductPossible Impuritiesand StabilizersMethylene Chloride Methyl ChlorideVinyl ChlorideEthyl ChlorideVinylidene ChlorideTrans 1,2-DichloroethyleneCis 1,2-DichloroethyleneChloroformCarbon Tetrachloride2-Methyl-2-ButeneCyclohexaneCyclohexenePropylene OxidePerchloroethylene TrichloroethyleneCarbon
27、 Tetrachloride1,1,2-Trichloroethane1,1,2,2-tetrachloroethane1,1,1,2-tetrachloroethanePenta ChloroethaneHexachloroethaneN-Methyl MorpholinePara Tertiary Amyl PhenolCyclohexene OxideBHTN-Methyl PyrroleEthoxy PropionitrileTrichloroethylene Cis and trans 1,2-dichloroethylene1,1,2-trichloroethaneCarbon t
28、etrachloride1,1,2,2-tetrachloroethane1,1,1,2-tetrachloroethaneEthylene DichloridePropylene DichlorideDiisopropyl AmineButylene OxideThymolN-Methyl PyrroleEthyl AcetateDiisobutyleneTABLE 2 Suggested GC ColumnsDB 624DB 5DB 1701TABLE 3 Instrument ConditionsDetectorFlame ionization detector or other det
29、ectorof sufficient sensitivity to accuratelymeasure components of interestInjector Temperature 200CDetector Temperature 200COven Temperature for Isothermal 80CProgrammed Oven Temperature 50 to 200CCarrier Gas Helium or hydrogenCarrier Gas Flow Rate 1 to 3 mL/minSample Size 0.5 to 1.0 Split Ratio 50:
30、1TABLE 4 Expected PrecisionConcentration% RelativeStandard Deviation1to25ppm 1225 to 100 ppm 2100 to 10 000 11to25% 0.825 to 75 % 0.575 to 100 % Direct MeasurementBy Difference0.50.1D 6806 02 (2007)e12injection and allowing the run to go to completion through thenormal temperature program and time.
31、Take an average of allof the area counts seen in three such blank runs. This averagearea count will be the background noise for the method.7. Keywords7.1 accuracy; gas chromatography; halogenated organic sol-vent; precisionASTM International takes no position respecting the validity of any patent ri
32、ghts asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision at an
33、y time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comments w
34、ill receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by A
35、STM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).D 6806 02 (2007)e13
