1、Designation: E202 10Standard 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 The values stated in SI units are to be regarded asstandard. No othe
5、r units of measurement are included in thisstandard with the exception of foot-pound for apparatusdescriptions.1.4 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 standard to establish appro-priate safe
6、ty 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, Apparent, ofLiquid Industrial ChemicalsD1078 Test Method for Distillation Range of Volatile Or-ganic LiquidsD1193 Specifi
7、cation 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, Varnish, Lacquer,and Related ProductsD4052 Test Method for Density, Relative Density, and APIGravity of Liquids by D
8、igital Density MeterD5386 Test Method for Color of Liquids Using TristimulusColorimetryE180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty Chemicals3E203 Test Method for Water Using Volumetric Karl FischerTitrationE394 Test Method for Iron
9、 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 in Organic Liquids by Cou-lometric Karl Fischer TitrationE1615 Test Method for Iron in Trace Quantities Using theFe
10、rroZine MethodE2409 Test Method for Glycol Impurities in Mono-, Di-,Tri- and Tetraethylene Glycol (Gas ChromatographicMethod)E2679 Test Method for Acidity in Mono-, Di-, Tri- andTetraethylene Glycol byNon-Aqueous Potentiometric Ti-tration3. Significance and Use3.1 These test methods measure certain
11、chemical and physi-cal properties of ethylene glycols and propylene glycols andmay be used to determine compliance with specification in1These test methods are under the jurisdiction of ASTM Committee E15 onIndustrial and Specialty Chemicals and are the direct responsibility of Subcommit-tee E15.01
12、on General Standards.Current edition approved Aug. 1, 2010. Published September 2010. Originallyapproved in 1962. Last previous edition approved in 2009 as E20209. DOI:10.1520/E0202-10.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceast
13、m.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Withdrawn. The last approved version of this historical standard is referencedon www.astm.org.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM
14、 International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.which limits are established for these properties. For those teststhat use the procedure of another ASTM test method, that testmethod should be consulted for additional information on thesignificance
15、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 optional and individuals using the alternativemethods should assure themselves that the method is sufficientand appropriate for the application. Precision d
16、ata 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-tee on Analytical Rea
17、gents of the American Chemical Society,where such specifications are available.4Other 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 indicated, references to
18、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 common guidelines.5Meas
19、ure 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 the pycnometer test m
20、ethod 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 judging theacceptability o
21、f 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, Between-Days)The standar
22、d 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 de-viation of result
23、s (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 studiesperformed in 1962 and 1963 o
24、n 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.6Practice E180 was used in developing these precisio
25、n 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 specifiedin Test Method D1
26、078, 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 drop of liquid within 1
27、5 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 suitable shield so that o
28、nly 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 0.043Dipropylene glyc
29、ol 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):4Reagent Chemicals, American Chemica
30、l Society Specifications, AmericanChemical Society, Washington, DC. For 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 Formula
31、ry, U.S. Pharmacopeial Convention, Inc.(USPC), Rockville, MD.5ASTM Manual on Presentation of Data and Control Chart Analysis, 7thEdition, ASTM Manual Series MNL 7A (revision of Special Technical Publication(STP) 15D).6Supporting data have been filed at ASTM Headquarters and my be obtained byrequesti
32、ng Research Report RR: RR:E15-0013.E202 10211.1.1 Repeatability (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
33、 in the table.11.1.2 Laboratory Precision (Within-Laboratory, 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 indicateddegrees of freedom. The 95 % limit for the differ
34、ence 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 of freedom. The 95
35、 %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 laboratoriescooperated i
36、n the studies in which each analyst performed duplicatedeterminations on each sample on each of two days.6Practice E180 wasused in developing these precision estimates.11.2 BiasThe bias of this test method has not beendetermined due to the unavailability of suitable referencematerials.ACIDITY12. Pro
37、cedure12.1 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 results (see Note 4):1
38、4.1.1 Repeatability (Single Analyst)The standard devia-tion for a single determination has been estimated to be thevalue given in Table 1 at the indicated degrees of freedom. The95 % limit of difference between two such runs is also given inTable 1.14.1.2 Laboratory Precision (Within-Laboratory, Bet
39、ween-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 analyst on two days
40、 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 test method was
41、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, weighing of the spike
42、 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 Bias17.1 In 2007, ASTM I
43、nternational 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 E1064, conducted
44、 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 for a total of f
45、our test results per assay. Note that in thecombined study, eight laboratories used a single analyst, sevenlaboratories used two analysts (on different days), and twolaboratories did not record this information. In the event thatthere were missing values for one or more laboratories, thisinformation
46、 was 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 material,
47、 obtained by the same operator using thesame equipment on the same day in the same laboratory.TABLE 1 Precision for Acidity in GlycolsGlycol IDGrand Avg(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 0.2
48、77 5 0.777TABLE 2 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 94.6E202 10317.1.2 ReproducibilityTwo test results shall be judged notequivalent if they dif
49、fer by more than the “R” value for thatmaterial; “R” is the interval representing the difference be-tween two test results 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. Practice E180 was used to conform to thisparticular study design which required an estimate of interme-diate precision. The statistical analysis
