1、Designation:E240908E240913 Standard Test Method for Glycol Impurities in Mono-, Di-, Tri- and Tetraethylene Glycol and in Mono- and Dipropylene Glycol (Gas Chromatographic Method) 1 This standard is issued under the xed designation E2409; the number immediately following the designation indicates th
2、e year of original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A superscript epsilon () indicates an editorial change since the last revision or reapproval. 1. Scope* 1.1 Thistestmethoddescribesthegaschromatographicdete
3、rminationofglycolimpuritiesinMono-,Di-Tri-andTetraethylene Glycol (MEG, DEG, TEG and TeEG) in the range of 5 to 3000 mg/kg.mg/kg, and in Mono- and Dipropylene Glycol (MPG and DPG) in the range 0.01 to 2.5% (m/m). 1.2 The values stated in SI units are to be regarded as standard. No other units of mea
4、surement are included in this standard. 1.3 Review the current Material Safety Data Sheets (MSDS) for detailed information concerning toxicity, rst aid procedures, and safety precautions. 1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is
5、 the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. 2. Referenced Documents 2.1 ASTM Standards: 2 E180Practice for Determining the Precision ofASTM Methods forAnalysis andTesting
6、 of Industrial and Specialty Chemicals (Withdrawn 2009) 3 E300Practice for Sampling Industrial Chemicals E1064Test Method for Water in Organic Liquids by Coulometric Karl Fischer Titration 2.2 Other Document: Manufacturersinstruction manuals of gas chromatograph and digital integration system used.
7、3. Summary of Test Method 3.1 A portion of the test sample is analyzed by temperature-programmed, capillary gas chromatography over a DB-wax polyethylene glycol column, using ame ionization detection. For quantication, the External Standard Technique or the Internal Standard (Marker) Technique, usin
8、g 1,4-butanediol as marker, Technique are applied. When applying the Internal Standard Technique, the standard addition technique is used to eliminate the effect of other impurities present in the glycols. For this purpose, a blank glycol is used, as 100% pure glycol samples are not available. 4. Si
9、gnicance and Use 4.1 Knowledge of the impurities is required to establish whether the product meets the requirements of its specications. 5. Apparatus 5.1 Gas Chromatograph(s), provided with a sample splitter or on-column injection, ame ionization detector and temperature- programming facilities. Op
10、tional are pressure programming and autosampler auto sampler facilities. The instrument must be suitable for analysis according to the operating instructions given in Table 1 or Table 2. 1 This test method is under the jurisdiction ofASTM Committee E15 on Industrial and Specialty Chemicals and is th
11、e direct responsibility of Subcommittee E15.02 on Product Standards. Current edition approved April 1, 2008June 1, 2013. Published May 2008August 2013. Originally approved in 2004. Last previous edition approved in 20042008 as E240904.E240908. DOI: 10.1520/E2409-08.10.1520/E2409-13. 2 ForreferencedA
12、STMstandards,visittheASTMwebsite,www.astm.org,orcontactASTMCustomerServiceatserviceastm.org.ForAnnualBookofASTMStandards volume information, refer to the standards Document Summary page on the ASTM website. 3 The last approved version of this historical standard is referenced on www.astm.org. This d
13、ocument is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because it may not be technically possible to adequately depict all changes accurately,ASTM recommends that users consult prior editions as
14、 appropriate. In all cases only the current version of the standard as published by ASTM is to be considered the official document. *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. Un
15、ited States 15.1.1 ColumnsThe analytical column (chemically bonded cross-linked polyethylene glycol) used must completely separate MEG, DEG, TEG, TeEG, PentaEG (Penta-ethylene Glycol) and 1,4-butanediol, or MPG, DPG, TPG, and TePG The analytical column used must completely separate MEG, DEG, TEG, Te
16、EG, PentaEG (Penta-ethylene Glycol) and 1,4-butanediol. Figs. A1.1, A1.2 and A1.3 Figs. A1.1 through A1.5 show examples of chromatograms conforming to the requirements. 5.2 Digital Integration Equipment:Equipment. 5.3 Analytical Balance, readability 0.1 mg, calibrated. Calibrate andRe-calibrate or v
17、erify at regular intervals. 5.4 Crimp Top Vials, 1 mL and 5 mL. 5.5 Crimper/De-capper, for capping and de-capping the vials. 5.6 Micro Syringes, 10 L. 5.7 Bottles, 50 mL, with screw cap. TABLE 1 Typical Operating Parameters for the GC Analysis of Glycol Impurities in MEG, DEG, TEG or TeEG Column A T
18、ype Capillary wide-bore Material Fused silica Length I.D. 15 m 0.53 mm Stationary Phase Polyethylene glycol, for example, DB- Wax Film Thickness 1 m Detector System Type FID Sensitivity The ratio of the signal to the noise level must be at least 2:1 at a concentration of 5 mg/kg DEG in MEG Temperatu
19、res Column Oven 0.05 min at 70C Programmed from 70 to 230C at 25C/ min 10 min at 230C Detector 250C Carrier Gas Helium or Nitrogen Calibration see Section 9 Injected Volume 0.2 L (on-column injection), or 0.5 L up to 1 L (using split injection technique) Split Ratio 1:10 or appropriate split ratio t
20、o allow adequate sensitivity as dened under Detector System (only if split injection technique is used) A The above-mentionedThe mentioned DB-Wax column is available from J m 4 ) and add HPLC grade water up to a total mass of approximately 5 g. Cap the vials and mix thoroughly. 9.2.3 Prepare a blank
21、 calibration solution by weighing 0.5 g blank sample of the glycol being analyzed (m 5 ), weighed to the nearest 0.1 mg, into a 5-mLvial.Add 0.5 g internal standard solution (see 6.6.1; m 6 ), also weighed to the nearest 0.1 mg, and add HPLC grade water up to a total mass of approximately 5 g. Cap t
22、he vial and mix thoroughly. 9.2.4 Calibrate separately for each impurity in MEG, DEG, TEG or TeEG by using the Internal Standard (Marker) Technique. 9.2.5 Fill a 1-mL sample vial with the calibration solution from the 5-mL vial (see 9.2.2 and 9.2.3). Close the vial by means of an aluminum crimp cap.
23、 9.2.6 Analyze each calibration solution and the blank solution using the operating parameters given in Table 1. Inject each solutionatleasttwiceandcalculatetheaveragepeakareasforeachofthecalibrationsolutions.Applydigitalintegrationequipment for measuring the peak areas. 9.2.7 For each chromatogram,
24、 calculate the system response factor (f) of each of the components as described in 9.2.8 through 9.2.10. 9.2.8 Calculate the amount of internal standard (1,4-butanediol) added to the calibration solution: MassofInternalStandardm 7 !,g5 m 4 3m 1 m 2 (1) where: m 1 = mass of 1,4-butanediol in interna
25、l standard solution (6.6.1), g, m 2 = total mass of internal standard solution (6.6.1), g, and m 4 = mass of internal standard solution added, g. 9.2.9 Calculate the amount of internal standard (1,4-butanediol) added to the blank solution: MassofInternalStandardm 8 !,g5 m 6 3m 1 m 2 (2) where: m 6 =
26、 mass of internal standard solution added (9.2.3), g. 9.2.10 Calculate the response factor of each component of interest in the calibration solutions by means of the following equation: f5 c 1 310 26 S m 7 3A 1 m 3 3A 2 D 2 S m 8 3A 3 m 5 3A 4 D (3) where: c 1 = added concentration of glycol compoun
27、d in the calibration solution, (9.2.1), mg/kg, A 1 = peak area of component in calibration solution, arbitrary units, A 2 = peak area of internal standard in calibration solution, same arbitrary units, E240913 4A 3 = peak area of component in blank solution, same arbitrary units, A 4 = peak area of
28、internal standard in blank solution, same arbitrary units, m 3 = mass of calibration solution (9.2.2), g, m 5 = mass of blank solution (9.2.3), g, m 7 = mass of internal standard in calibration solution, as obtained in 9.2.8, g, and m 8 = mass of internal standard in blank solution, as obtained in 9
29、.2.9, g. 9.2.11 Calculate the mean of the response factors. If the individual factors differ by more than 5% from the mean response factor, repeat the measurement of the respective calibration solution. 9.3 Internal Standard Technique for Propylene Glycols: Calibrate by determining the calibration f
30、actor for each component of interest relative to the internal standard on the basis of peak area versus mass as follows: 9.3.1 Prepare a calibration solution by accurately weighing 0.5 g of each of the components of interest and of the internal standard, to the nearest 0.1 mg into a previously tarre
31、d, 50 mL bottle. Fill the bottle with a suitable solvent (for example, acetone/cyclohexane), close, and reweigh to the nearest 0.1 mg. Homogenize the calibration solution. 9.3.2 Analyze the calibration solution following the operating parameters given in Table 2. Introduce the calibration solution a
32、t least twice. Determine the areas of the components of interest and the reference component. 9.3.3 Calculatethemeanpeakareasofthecomponentsofinterestforthecalibrationsolution.Ifthetwosinglepeakareasdiffer by more than 3% relative, repeat the analysis. If no satisfactory results can be obtained, sta
33、bilize the conditions and repeat 9.3.1 and 9.3.2. 9.3.4 Calculate the calibration factor (f I ) for all individual compounds, relative to the internal standard, by means of the following equation: f i 5 m i 3A m m m 3A i (4) where: m i = mass of component i in calibration solution (9.3.1), g. m m =
34、mass of internal standard in calibration solution (9.3.1), g. A i = peak area of component i (9.3.3), arbitrary units. A m = peak area of internal standard (9.3.3), same arbitrary units. NOTE1Analternativefortheempiricalcalibrationfactorsasdescribedin9.2and9.3istheuseoftheoreticalfactors,basedonthem
35、olecularstructure of the compounds of interest. Theoretical factors calculated are as follows: For MPG 3.045, for all DPG isomers 2.512, for all TPG isomers 2.244, all relative to octane. See Footnote 5. 5 9.4 External Standard Technique: Technique Ethylene Glycols, similar for Propylene Glycols: 9.
36、4.1 Prepare at least three calibration solutions, for example, containing 200, 500 and 1000 mg/kg of each of the glycol componentstobedetermined,byaddingtherelevantcalibrationstandard(see6.2)toablanksampleoftheglycolbeinganalyzed and mix thoroughly. Weigh each glycol component to the nearest 0.1 mg
37、and the blank glycol to the nearest 0.1 g. (See Table 23 for recommended weights.) 9.4.1.1 Calculate the exact concentration of each glycol component (C i ) in the calibration solutions. The calibration range can be adjusted if needed. C i 5 W Comp;i! W Comp;i! 1W Blank;i! 3 10 6 g g (5) where: C i
38、= the concentration of each glycol component in the calibration standard of interest, i = the calibration standard of interest, W (Comp;i) = weight (g) of glycol component added to the calibration standard of interest, and W (Comp;i) = mass (g) of glycol component added to the calibration standard o
39、f interest, and W (Blank;i) = weight (g) of blank glycol added to the calibration standard of interest. 5 Sternberg, J.C. Gas Chromatography, Academic Press, New York, 1962; pp. 231-267. TABLE 23 External Standard Recommended Weights Standard # Target Weight of Glycol Component,0.0001 g Target Weight of High Purity Blank Glycol,0.1 g 200 mg/kg 0.010 50 500 mg/kg 0.025 50 1000 mg/kg 0.050 50 E240913 5
