1、Designation: D 7515 09Standard Test Method forPurity of 1,3-Propanediol (Gas Chromatographic Method)1This standard is issued under the fixed designation D 7515; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revis
2、ion. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method describes the gas chromatographicdetermination of purity for 1,3-propanediol (PDO). This testmethod was origina
3、lly developed to determine the purity of1,3-propanediol used for the application as the freeze pointdepressant base fluid in formulated PDO engine coolants. Useof the method for purity of PDO for other applications may beviable.1.2 The values stated in SI units are to be regarded asstandard. No othe
4、r units of measurement are included in thisstandard.1.3 Review the current Material Safety Data Sheets (MSDS)for detailed information concerning toxicity, first aid proce-dures, and safety precautions.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with it
5、s 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:2E 177 Practice for Use of the Terms Precision and Bias inASTM Test Meth
6、odsE 300 Practice for Sampling Industrial ChemicalsE 691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method3. Summary of Test Method3.1 The neat sample is analyzed by a temperature-programmed gas chromatograph, equipped with a capillarycolumn and flame ioniza
7、tion detector (FID), and quantificationis performed by direct area normalization.3.2 Additionally, the use of a reference sample using Eth-ylene, Propylene or Dipropylene Glycol (EG, PG or DPG) in1,3-PDO (minimum purity 99.5 %) should be used as aperformance check (see Section 8).NOTE 1The applicati
8、on of this reference sample is also used todemonstrate the separation of commonly used glycols (EG, PG and DPG)in engine coolants, from PDO. Solutions of EG, PG, or DPG inconcentrations of 0.1 to not more than 1 % may be used.4. Significance and Use4.1 Knowledge of an approved method is required toe
9、stablish whether the product meets the requirements of itsspecifications. The use of glycols in the reference sample is notintended to suggest the presence of glycol (EG, PG and DPG)impurities, but to demonstrate and quantify the separation ofcommonly used Engine Coolant glycols from PDO.5. Apparatu
10、s5.1 Gas Chromatograph(s)provided with a sample split-ter or on-column injection, flame ionization detector andtemperature-programming facilities. The instrument must besuitable for analysis according to the operating instructionsgiven in Table 1. To account for differences among laboratoryequipment
11、, the two most common column choices are listed.NOTE 2Other column suppliers market alternative stationary phases,therefore, it is permissible to use a different column from an alternativesupplier. However, the chromatogram obtained must be identical, withregard to separation of PDO and other glycol
12、 components, to thoseillustrated in Fig. A1.1 and Fig. A1.2.5.1.1 ColumnsThe analytical column used must com-pletely separate EG, PG or DPG from PDO. Fig. A1.1 and Fig.A1.2 show examples of chormatograms conforming to therequirements.5.2 Digital Integration EquipmentA computer with datacollection so
13、ftware.5.3 Analytical Balance, readability 0.1 mg, calibrated. Cali-brate and verify at regular intervals.1This test method is under the jurisdiction of ASTM Committee D15 on EngineCoolants and is the direct responsibility of Subcommittee D15.07 on Specifications.Current edition approved April 1, 20
14、09. Published May 2009.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Bar
15、r Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5.4 Crimp Top Vials,1mLand5mL.5.5 Crimper/De-capper, for capping and de-capping thevials.5.6 Micro Syringes,5Lor10L.5.7 Bottles, 100 mL, with screw cap.6. Reagents and Materials6.1 Purity of ReagentsUnless otherwise indicat
16、ed, it isintended that all reagents shall conform to the specifications ofthe Committee onAnalytical Reagents of theAmerican Chemi-cal Society where such specifications are available.3Othergrades may be used, provided it is first ascertained that thereagent is of sufficiently high purity to permit i
17、ts use withoutlessening the accuracy of the determination.6.2 Reagents:6.2.1 1,3-Propanediol (PDO), minimum purity 99.5 % mass(m/m).6.2.2 Ethylene Glycol (EG), minimum purity 99.5 % mass(m/m).6.2.3 Propylene Glycol (PG), minimum purity 99.5 % mass(m/m).6.2.4 Dipropylene Glycol (DPG), minimum purity
18、99.0 %mass (m/m).6.3 Water, HPLC grade.7. Sampling, Test Specimens and Test Units7.1 Follow the relevant instructions for sampling as given inPractice E 300.8. Preparation of Apparatus8.1 Gas Chromatograph(s) and Column(s)Check the per-formance of the gas chromatograph and column as follows:8.2 Usin
19、g the standard quality reagents (6.2), prepare a1,3-PDO solution containing approximately 0.1 % of EG, PGand DPG respectively. Determine the exact concentration ofthe components. This will be the reference sample.8.2.1 Weigh 0.1 g of each glycol reagent to the nearest 0.1mg, into a 100-mL vial. Add
20、99.7 g of 1,3-PDO weighed to thenearest 0.1 mg. Cap the vials and mix thoroughly.8.2.2 Calculate the exact concentration of each glycol in thereference sample.8.3 Fill a 1-mL GC autosampler vial with the referencesample (8.2) and close the vial.8.4 Analyze the reference sample using the parametersgi
21、ven in Table 1. Inject the solution at least twice. Calculate thearea %.3Reagent Chemicals, American Chemical Society Specifications , AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryC
22、hemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeia Convention, Inc. (USPC), Rockville,MD.TABLE 1 Typical Operating Parameters for the GC Analysis ofPDOColumnAOption A Option BType Capillary CapillaryMaterial Fused Silica PEGLength 3 I
23、.D. 10 m 3 0.1mm 30m3 0.25 mmStationary Phase DB-5 ZB-WaxFilm Thickness 0.17 m 0.25 mDetector SystemType FID FIDSensitivity The ratio of the signal to thenoise level must be at least 2:1 ata concentration of 5 mg/kgglycols in PDOThe ratio of the signal to the noiselevel must be at last 2:1 at aconce
24、ntration of 5 mg/kg glycols inPDOTemperaturesColumn OvenInitialRamp 1Ramp 2Ramp 30.5 min at 35C35 to 85C at 50C/min85 to 325C at 100C/min2 min at 325C0 min at 50C50 to 200C at 15C/min200 to 250C at 40C/min17 min at 250CDetector 325C 250CCarrier Gas Helium HeliumCalibration This method employs straig
25、htarea normalization so nocalibration is requiredThis method employs straight areanormalization so no calibration isrequiredInjected Volume 01. L 0.2 LPressure Program 0.5 min 30 psi30 to 100 psi at 100 psi/min8 min at 100 psiGas saver on at 0.5 minPressure: 13.2 psi at 50CFlow: 1.1 mL/minVelocity:
26、28 cm/sSplit Ratio 1:250 or appropriate split ratio toallow adequate sensitivity asdefined under Detector System1:18 or appropriate split ratio to allowadequate sensitivity as defined underDetector System (only if splitinjection technique is used)AThe columns are available commercially. Some column
27、suppliers marketalternative stationary phases. The chromatogram obtained must be identical, withregard to separation of PDO and other glycol components, to those illustrated inFig. A1.1 and Fig. A1.2.D75150929. Report9.1 Report the purity of the sample to the nearest 0.1 %mass (m/m).10. Precision an
28、d Bias10.1 The following criteria should be used for judging theacceptability of results (see Note 3):10.1.1 Repeatability Limit (r)Two test results obtainedwithin one laboratory shall be judged not equivalent if theydiffer by more than the “r” value for that material; “r”istheinterval representing
29、the critical difference between two testresults for the same material, obtained by the same operatorusing the same equipment on the same day in the samelaboratory.10.1.1.1 Repeatability limits are listed in Table 2.10.1.2 Reproducibility Limit (R)Two test results shall bejudged not equivalent if the
30、y differ by more than the “R” valuefor that material; “R” is the interval representing the criticaldifference between two test results for the same material,obtained by different operators using different equipment indifferent laboratories.10.1.2.1 Repeatability limits are listed in Table 2.10.1.3 T
31、he above terms (repeatability limit and reproduc-ibility limit) are used as specified in Practice E 177.10.1.4 Any judgment in accordance with 10.1.1 and 10.1.2would have an approximate 95 % probability of being correct.NOTE 3The precision of this test method is based on an intralabora-tory study co
32、nducted in 2008. Seven laboratories tested three differentmaterials for PDO concentration.4Every “test result” represents anindividual determination.4The laboratories were asked to report fourreplicate results for each material in order to estimate the repeatability andreproducibility limits of the
33、standard.4Practice E 691 was followed for thedesign and analysis of the repeatability data.10.2 BiasAt the time of this study, the test specimenschosen for analysis were not accepted reference materialssuitable for determining the bias for this test method, thereforeno statement on bias is being mad
34、e.10.3 The precision statement was determined through sta-tistical examination of the results submitted by six laboratories,running one analysis, on three different materials. These threematerials were described as the following:Sample 1: 99.9 % 1,3-propanediolSample 2: 99.7 % 1,3-propanediolSample
35、3: 99.6 % 1,3-propanediol10.4 To judge the equivalency of two test results, it isrecommended to choose the material closest in characteristicsto the test material.NOTE 4An alternative test method was written into a research reportto support this test method. Details of the research report are availa
36、blefrom ASTM Headquarters. Request RR:D15-1023. The alternative testmethod does not have precision data for the application of this method inanalyzing 1,3-propanediol. Use of this method is optional and individualsusing the alternative method should assure themselves that the method issufficiently p
37、recise. Precision data presented is only for the original testmethod listed.11. Keywords11.1 1,3-propanediol; dipropylene glycol; ethylene glycol;gas chromatography; propylene glycolANNEXA1. EXAMPLE CHROMATOGRAMSA1.1 Chromatograms using Option A:A1.1.1 Chromatogram of PDO (see Fig. A1.1).A1.1.2 Chro
38、matogram of PDO, EG, PG and DPG (see Fig.A1.2).A1.2 Chromatograms Using Option B:A1.2.1 Chromatogram of PDO (see Fig. A1.3).A1.2.2 Chromatogram of PDO, EG, PG and DPG (see Fig.A1.4).4Details of the intrlaboratory study are available from ASTM Headquarters.Request RR: D15-1022.TABLE 2 PDO Concentrati
39、on (%)Sample AverageAxSample StandardDeviationS xRepeatabilityStandard DeviationsrReproducibilityStandard DeviationSRRepeatability LimitrReproducibilityLimitRPDO Sample 1 99.958 0.039 0.010 0.039 0.027 0.111PDO Sample 2 99.814 0.047 0.032 0.054 0.090 0.152PDO Sample 3 99.657 0.199 0.030 0.200 0.085
40、0.561AThe average of the laboratorys calculated averages.D7515093FIG. A1.1 Chromatogram of PDOD7515094FIG. A1.2 Chromatogram of PDO, EG, PG and DPGFIG. A1.3 Chromatogram of PDOD7515095ASTM International takes no position respecting the validity of any patent rights asserted in connection with any it
41、em 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 any time by the responsible technical com
42、mittee 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 will receive careful consideration at a
43、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 ASTM International, 100 Barr Harbor Driv
44、e, 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).FIG. A1.4 Chromatogram of PDO, EG, PG and DPGD7515096
