1、Designation: E202 09Standard Test Methods forAnalysis of Ethylene Glycols and Propylene Glycols1This standard is issued under the fixed designation E202; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A
2、number in parentheses indicates the year of last reapproval. Asuperscript epsilon () 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*1.1 These test methods cover the chemical and physicalana
3、lysis of the commonly available grades of ethylene glycol,diethylene glycol, triethylene glycol, propylene glycol, anddipropylene glycol. The key sections appear in the followingorder:SectionsPurity of Reagents 4Specific Gravity 6-8Distillation Range 9-11Acidity 12-14Water 15-17Iron 18-20Color 21-23
4、Gas Chromatographic Analysis 24-26Alternative Test Methods AppendixX11.2 Review the current appropriate Material Safety DataSheets (MSDS) for detailed information concerning toxicity,first aid procedures, and safety precautions.1.3 This standard does not purport to address all of thesafety concerns,
5、 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:2D891 Test Methods for Specific Gravity, Appa
6、rent, ofLiquid Industrial ChemicalsD1078 Test Method for Distillation Range of Volatile Or-ganic LiquidsD1193 Specification for Reagent WaterD1209 Test Method for Color of Clear Liquids (Platinum-Cobalt Scale)D1613 Test Method for Acidity in Volatile Solvents andChemical Intermediates Used in Paint,
7、 Varnish, Lacquer,and Related ProductsD4052 Test Method for Density, Relative Density, and APIGravity of Liquids by Digital Density MeterD5386 Test Method for Color of Liquids Using TristimulusColorimetryE180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industria
8、l and Spe-cialty ChemicalsE203 Test Method for Water Using Volumetric Karl FischerTitrationE394 Test Method for Iron in Trace Quantities Using the1,10-Phenanthroline MethodE611 Test Methods for Low Concentrations of DiethlyeneGlycol in Ethylene Glycol by Gas ChromatographyE1064 Test Method for Water
9、 in Organic Liquids by Cou-lometric Karl Fischer TitrationE1615 Test Method for Iron in Trace Quantities Using theFerroZine MethodE2409 Test Method for Glycol Impurities in Mono-, Di-,Tri- and Tetraethylene Glycol (Gas ChromatographicMethod)E2679 Test Method for Acidity in Mono-, Di-, Tri- andTetrae
10、thylene Glycol byNon-Aqueous Potentiometric Ti-tration3. Significance and Use3.1 These test methods measure certain chemical and physi-cal properties of ethylene glycols and propylene glycols andmay be used to determine compliance with specification inwhich limits are established for these propertie
11、s. For those teststhat use the procedure of another ASTM test method, that testmethod should be consulted for additional information on thesignificance and use of that test.3.2 Alternative test methods and technology for several ofthe methods can be found in the Appendix. Use of thesemethods is opti
12、onal and individuals using the alternativemethods should assure themselves that the method is sufficient1These test methods are under the jurisdiction of ASTM Committee E15 onIndustrial and Specialty Chemicals and are the direct responsibility of Subcommit-tee E15.01 on General Standards.Current edi
13、tion approved Oct. 1, 2009. Published December 2009. Originallyapproved in 1962. Last previous edition approved in 2005 as E20205. DOI:10.1520/E0202-09.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMSta
14、ndards volume information, refer to the standards Document Summary page onthe ASTM website.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.and appropriate for the appl
15、ication. Precision data presented inthis standard is only for the original test methods listed.4. Purity of Reagents4.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-t
16、ee on Analytical Reagents of the American Chemical Society,where such specifications are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.4.2 Unless otherwise indic
17、ated, references to water shall beunderstood to mean reagent water conforming to SpecificationD1193, Type II or III.5. Quality Control5.1 It is recommended that a control chart for the concen-tration of the impurities in the glycol quality control sample beestablished and maintained according to com
18、mon guidelines.4Measure the control sample each time a test sample(s) is tested.If the measured value exceeds the action limit of the controlchart, take appropriate action before proceeding with sampletests.SPECIFIC GRAVITY6. Procedure6.1 Determine the relative density of the sample at 20/20Cusing t
19、he pycnometer test method in accordance with TestMethods D891, except determine the water and sample weightsof the pycnometer at 20.0 6 0.1C.7. Report7.1 Report the relative density at 20/20C (in air) to thenearest 0.0001 unit.8. Precision and Bias8.1 The following criteria should be used for judgin
20、g theacceptability of results (see Note 1):8.1.1 Repeatability (Single Analyst)The standard devia-tion for a single determination has been estimated to be0.0000651 unit at 96 dF. The 95 % limit for the differencebetween two such runs is 0.0002 unit.8.1.2 Laboratory Precision (Within-Laboratory, Betw
21、een-Days)The standard deviation of results (each the average ofduplicates), obtained by the same analyst on different days, hasbeen estimated to be 0.0000598 units at 48 df. The 95 % limitfor the difference between two such averages is 0.0002 unit.8.1.3 Reproducibility (Multilaboratory)The standard
22、de-viation of results (each the average of duplicates), obtained byanalysts in different laboratories, has been estimated to be0.000191 unit at 5 dF. The 95 % limit for the differencebetween two such averages is 0.0005 unit.NOTE 1These precision estimates are based on interlaboratory studiesperforme
23、d in 1962 and 1963 on six samples of the five glycols whosespecific gravity values range from approximately 1.0233 to 1.1255.Atotalof ten laboratories cooperated in the studies in which each analystperformed duplicate determinations on each sample on each of two days.5Practice E180 was used in devel
24、oping these precision estimates.8.2 BiasThe bias of this test method has not been deter-mined due to the unavailability of suitable reference materials.DISTILLATION RANGE9. Procedure9.1 Determine the distillation range of the sample in accor-dance with Test Method D1078. Use the conditions as specif
25、iedin Test Method D1078, and the ASTM Solvents DistillationThermometer shown in Table 1 of Test Method D1078. (SeeNote 2 for certain allowable exceptions in applying this testmethod to triethylene glycol.)NOTE 2In the distillation of triethylene glycol, it may not be possibleto collect the first dro
26、p of liquid within 15 min or to maintain theprescribed distillation rate of 4 to 5 mL/min with some sources of gas. Inthis case, up to 30 min can be allowed to collect the first drop, and adistillation rate of 2 to 3 mL/min is satisfactory. Alternatively, the flaskchamber may be covered with a suita
27、ble shield so that only the upper neckand thermometer are exposed to room air to achieve the specified rates.9.2 Use the following values of K in the equation forbarometric correction (Test Method D1078):Chemical KEthylene glycol 0.045Diethylene glycol 0.050Triethylene glycol 0.055Propylene glycol 0
28、.043Dipropylene glycol 0.05110. Report10.1 Report the corrected temperatures to the nearest 0.1Cat each volume required by the specification for the glycolbeing analyzed.11. Precision and Bias11.1 The following criteria should be used for judging theacceptability of results (Note 3):11.1.1 Repeatabi
29、lity (Single Analyst)The standard devia-tion for a single determination has been estimated to be thevalue in Table 2 of Test Method D1078 at the indicated degreesof freedom. The 95 % limit for the difference between two suchruns is the value in the table.11.1.2 Laboratory Precision (Within-Laborator
30、y, Between-Days)The standard deviation of results (each the average ofduplicates), obtained by the same analyst on different days, hasbeen estimated to be the value in Table 1 at the indicated3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For
31、suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, VWR International Ltd., Poole, Dorset, U.K., and the United StatesPharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc.(USPC), Rockville, MD.4ASTM Manua
32、l on Presentation of Data and Control Chart Analysis, 7thEdition, ASTM Manual Series MNL 7A (revision of Special Technical Publication(STP) 15D).5Supporting data have been filed at ASTM Headquarters and my be obtained byrequesting Research Report RR: E15-0013.E202 092degrees of freedom. The 95 % lim
33、it for the difference betweentwo such averages is the value in the table.11.1.3 Reproducibility (Multilaboratory)The standard de-viation of results (each the average of duplicates), obtained byanalysts in different laboratories, has been estimated to be thevalue in Table 1 at the indicated degrees o
34、f freedom. The 95 %limit for the difference between two such averages is the valuein the table.NOTE 3These precision estimates are based on interlaboratory studiesperformed in 1962 and 1963 on eleven samples of the five glycols whosedistillation ranges varied from 1.4 to 9.7C. A total of ten laborat
35、oriescooperated in the studies in which each analyst performed duplicatedeterminations on each sample on each of two days.5Practice E180 wasused in developing these precision estimates.11.2 BiasThe bias of this test method has not beendetermined due to the unavailability of suitable referencemateria
36、ls.ACIDITY12. Procedure12.1 Determine the acidity of the sample in accordance withTest Method E2679.13. Report13.1 Report the acidity as acetic acid to the nearest 0.1mg/kg for the sample.14. Precision and Bias14.1 PrecisionThe following criteria should be used tojudge the acceptability of the resul
37、ts (see Note 4):14.1.1 Repeatability (Single Analyst)The standard devia-tion for a single determination has been estimated to be thevalue given in Table 2 at the indicated degrees of freedom. The95 % limit of difference between two such runs is also given inTable 2.14.1.2 Laboratory Precision (Withi
38、n-Laboratory, Between-Days Variability)The precision of the procedure for measur-ing acidity is being determined.14.1.3 Reproducibility (Multilaboratory)The precision ofthe procedure for measuring acidity is being determined.NOTE 4The precision statements are preliminary based on 5 analysesby one an
39、alyst on two days for samples of MEG, DEG, TEG and TTEGcontaining approximately 1.7 mg/kg, 1.8 mg/kg, 33.0 mg/kg and 4.7mg/kg acidity as acetic acid respectively. An interlaboratory study isplanned for 2009/2010. Practice E180 was used in developing theseprecision estimates.14.2 BiasThe bias of this
40、 test method was determined byspiking samples of MEG with acetic acid in the 5 to 50 mg/kgrange and analyzing the spiked and unspiked samples. Theaccuracy (recovery) was estimated to be the values given inTable 1 based on the titration curves. The bias depends uponthe accuracy of the titration, weig
41、hing of the spike and theextent of any interferences.WATER15. Procedure15.1 Determine the water content of the sample using anysuitable Karl Fischer reagent titration method. Test MethodE1064 is recommended.16. Report16.1 Report the water content to the nearest 0.001 % mass.17. Precision and Bias17.
42、1 In 2007, ASTM International Committee E15 on In-dustrial and Specialty Chemicals conducted and completedInterlaboratory Study No. 52 to determine Precision data forsix test methods used in the analysis of glycols. The precisionof this test method is based on the interlaboratory study of TestMethod
43、 E1064, conducted in 2007. Each of 17 laboratorieswere asked to test three different materials. Fourteen laborato-ries tested MEG, 13 laboratories tested DEG and 13 laborato-ries tested TEG. Every “test result” represents an individualdetermination. Two test results were conducted on each of twodays
44、 for a total of four test results per assay. Note that in thecombined study, 8 laboratories used a single analyst, 7 labo-ratories used 2 analysts (on different days) and 2 laboratoriesdid not record this information. In the event that there weremissing values for one or more laboratories, this info
45、rmationwas noted in the results. See Table 3.17.1.1 Repeatability Two test results obtained within onelaboratory shall be judged not equivalent if they differ by morethan the “r” value for that material; “r” is the intervalrepresenting the critical difference between two test results forthe same mat
46、erial, obtained by the same operator using thesame equipment on the same day in the same laboratory.17.1.2 ReproducibilityTwo test results shall be judged notequivalent if they differ by more than the “R” value for thatmaterial; “R” is the interval representing the difference be-tween two test resul
47、ts for the same material, obtained bydifferent operators using different equipment in different labo-ratories.17.1.3 Intermediate PrecisionThe day-to-day standarddeviation within a laboratory for results produced by the sameoperator, determined through statistical analysis followingPractice E180. Pr
48、actice E180 was used to confrom to thisTABLE 1 Accuracy for Acidity in Glycols Acidity as Acetic Acidin MEGActual Concentration(mg/kg)Found Concentration(mg/kg)Average Recovery(%)6.62 6.04 91.211.91 10.90 91.527.30 25.67 94.051.51 48.72 94.6TABLE 2 Precision for Acidity in GlycolsGlycol IDGrand Avg(
49、mg/kg)Standard Deviation(mg/kg)Degrees of Freedom95 % Rangemg/kg absoluteMEG 1.66 0.100 5 0.280DEG 1.75 0.114 5 0.319TEG 1.370 5 3.836TTEG 4.71 0.277 5 0.777E202 093particular study design which required an estimate of interme-diate precision. The statistical analysis was conducted usingthe SAS statistical analysis software, Version 8.0.17.1.3.1 The E180 analysis considers the two test resultsfrom each day as being run under repeatability, intermediate,and reproducibilty precision for each assay. The repeatabilityprecision would be estimated from the two se
