1、Designation: D 3695 95 (Reapproved 2001)Standard Test Method forVolatile Alcohols in Water by Direct Aqueous-Injection GasChromatography1This standard is issued under the fixed designation D 3695; the number immediately following the designation indicates the year oforiginal adoption or, in the case
2、 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.1. Scope1.1 This test method covers a wide range of alcohols withvarious structures and boiling points
3、that can be separated anddetected quantitatively in water and waste water at a minimumdetection limit of approximately 1 mg/L by aqueous-injectiongas-liquid chromatography.2This test method can also be usedto detect other volatile organic compounds qualitatively. Or-ganic acids, amines, and high boi
4、ling, highly polar compoundsare not readily detectable under this set of conditions. Foranalysis of organics with similar functionalities, refer to othertest methods in Volumes 11.01 and 11.02 of the Annual Bookof ASTM Standards.1.2 This test method utilizes the procedures and precautionsas describe
5、d in Practice D 2908. Utilize the procedures andprecautions as described therein.1.3 This test method has been used successfully withreagent grade Type II and natural chlorinated tap waters. It isthe users responsibility to assure the validity of this testmethod for any untested matrices.1.4 This st
6、andard 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 safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1
7、 ASTM Standards:D 1129 Terminology Relating to Water3D 1193 Specification for Reagent Water3D 2908 Practice for Measuring Volatile Organic Matter inWater by Aqueous-Injection Gas Chromatography4D 3856 Guide for Good Laboratory Practices in Laborato-ries Engaged in Sampling and Analysis of Water3D 42
8、10 Practice for Intralaboratory Quality Control Proce-dures and Discussion on Reporting Low Level Data3E 355 Practice for Gas Chromatography Terms and Rela-tionships53. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Terminology D 1129 and Practice E 355.4. Summa
9、ry of Test Method4.1 An aliquot of an aqueous sample is directly injected intoa gas chromatograph by means of a microlitre syringe. Theorganic compounds in the sample are separated and elutedfrom a chromatographic column into a flame ionization detec-tor. The compounds are identified by relative ret
10、ention time orKovats Index, and measured by direct comparison with corre-sponding standard responses.5. Significance and Use5.1 The major organic constituents in industrial waste waterneed to be identified for support of effective in-plant orpollution control programs. Currently, the most practical
11、meansfor tentatively identifying and measuring a range of volatileorganic compounds is gas-liquid chromatography.6. Interferences6.1 Since the specified column and conditions are applicableto numerous organics, the possibility of one or more compo-nents having identical retention times is always pre
12、sent.Therefore, the analyst must determine the qualitative identityof the components of each peak by spectrometric techniques ora multi-column approach, or both, so that proper quantitationfor those compounds of interest may be made. Refer to Table1 for relative retention data.7. Apparatus7.1 Gas Ch
13、romatograph and Accessory Equipment, de-scribed in Practice D 2908, Sections 7.1 through 7.6, is usedfor this analysis.1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Wat
14、er.Current edition approved July 10, 2001. Published April 1995. Originallypublished as D 3695 78. Last previous edition D 3695 88.2Sugar, J. W., and Conway, R. A., “Gas-Liquid Chromatographic Techniques forPetrochemical Waste Water Analysis, Journal of the Water Pollution ControlFederation, Vol 40,
15、 1968, pp 16221631.3Annual Book of ASTM Standards, Vol 11.01.4Annual Book of ASTM Standards, Vol 11.02.5Annual Book of ASTM Standards, Vol 14.02.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.7.2 Column: Carbowax 20 M6(5%) on 80/100
16、 AcidWashed Chromosorb W,76.1-m (20-ft), 3.2-mm (18-in.) inoutside diameter, 0.508-mm (0.020-in.) wall thickness, stain-less steel.TABLE 1 Kovats Index and Relative Retention Data for TypicalComponentsAComponentKovatsIndex (Ix)RelativeRetentionBDiethyl ether 580 0.17n-Hexane 600 0.19Isopropyl ether
17、600 0.19Ethylene oxide 700 0.20Acetaldehyde 700 0.20Vinyl ethyl ether 700 0.20n-Heptane 700 0.20Propylene oxide 737 0.22Vinyl isobutyl ether 796 0.26Acetone 796 0.26n-Butyl chloride 796 0.26Cyclohexene 808 0.27Acrolein 820 0.28Methyl acetate 820 0.28Vinyl n-butyl ether 833 0.29Octene-1 842 0.30n-But
18、yraldehyde 865 0.32Vinyl acetate 887 0.34Isopropyl acetate 887 0.34Methyl ethyl ketone 908 0.36Ethyl acetate 912 0.37Methanol 916 0.38Isopropanol 935 0.39Dioxolane 943 0.40Benzene 962 0.42Ethyl acrylate 978 0.44Isopropenyl acetate 983 0.45Methyl n-propyl ketone 983 0.45Methyl vinyl acetate 992 0.46E
19、thanol 1000 0.47Acrylonitrile 1007 0.48Propyl acetate 1007 0.482-Methylpentaldehyde 1026 0.51n-Butyl ether 1026 0.51Methyl isobutyl ketone 1035 0.52Isobutyl acetate 1035 0.522-Ethylbutyraldehyde 1042 0.53Acetonitrile 1050 0.541,2-Dichloropropane 1056 0.55sec-Butyl alcohol 1056 0.55Propylene dichlori
20、de 1065 0.572,3-Pentanedione 1080 0.60Toluene 1080 0.60n-Butyl acetate 1080 0.60Ethylene dichloride 1092 0.62n-Propanol 1100 0.63Crotonaldehyde 1110 0.65TABLE 1 ContinuedComponentKovatsIndex (Ix)RelativeRetentionBParaldehyde 1118 0.661,4-Dioxane 1118 0.66Isobutanol 1137 0.70Mesityl oxide 1137 0.70n-
21、Methylmorpholene 1142 0.72Methyl amyl acetate 1150 0.732-Pentanol 1157 0.74primary-Amyl acetate 11571185 0.740.82(Isomers)p-Xylene 1160 0.75Ethyl benzene 1160 0.75Ethylidene acetone 1170 0.77Methyl isoamyl ketone 1173 0.78n-Butanol 1185 0.82n-Butyl acrylate 1190 0.83Methyl amyl alcohol 1190 0.83Diis
22、obutyl ketone 1202 0.852-Ethylhexyl aldehyde 1210 0.87Epichlorohydrin 1216 0.882-Picoline 1222 0.91n-Ethylmorpholine 1226 0.92Styrene monomer 1240 0.951,2-Trichlorethane 1244 0.96Amyl alcohol 1260 1.00Cyclohexanone 1260 1.001,3-Triethoxybutane 1260 1.00Diethyl benzene 1275 1.042-Ethyl-1-butanol 1295
23、 1.103-Picoline 1300 1.124-Picoline 1303 1.14Diisobutyl carbinol 1308 1.151-Hexanol 1312 1.162-Ethylhexyl acetate 1322 1.20n-Hexyl ether 1325 1.21Diacetone alcohol 1330 1.23Ethylene chlorohydrin 1338 1.252-Octanal 1341 1.261,3-Trichloropropane 1352 1.302-Methyl-5-ethyl pyridine 1354 1.31Cyclohexanol
24、 1354 1.31Ethyl acetoacetate 1356 1.32Iso-octanol (Isomers) 13621386 1.351.45Dichloro isopropyl ether 1362 1.352-Ethyl-1-hexanol 1364 1.362-Ethylhexyl acrylate 1376 1.40Dichloroethyl ether 1384 1.44Tetralin 1388 1.45Glycol diacetate 1392 1.46n-Octanol 1402 1.51Isophorone 1420 1.59Styrene oxide 1423
25、1.60Ethylene glycol 1430 1.63Acetophenone 1435 1.65Diethyl succinate 1441 1.67Methyl acetoacetate 1443 1.69Diethyl maleate 1460 1.79n-Decyl alcohol 1483 1.85Methylbenzyl alcohol 1486 1.866Carbowax is a trademark of Union Carbide Corp.7Chromosorb W is a trademark of Johns-Manville Products Co.D 3695
26、95 (2001)2TABLE 1 ContinuedComponentKovatsIndex (Ix)RelativeRetentionB2-(2-Butoxy) ethoxyethyl ace-tate1486 1.86AGas Chromatographic Data Compilation, ASTM AMD 25A-51, ASTM, 1971.BRelative to amyl alcohol.8. Reagents8.1 Purity of ReagentsReagent grade chemicals shall beused. Unless otherwise indicat
27、ed, it is intended that all reagentsshall conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society, wheresuch specifications are available.8Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit
28、its use without lessening the accuracy ofthe determination.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Specification D 1193, Type II.8.3 Calibration and StandardizationPrepare a stock solu-tion of the materials of interest
29、by weighing a known amountof each, 1.00 g or less, diluting with water to 1 L, and mixing.Subsequent dilutions should be prepared as deemed necessary.9. Sampling9.1 Collect the sample in accordance with Section 9 ofPractice D 2908.10. Procedure10.1 Use the procedures described in Practice D 2908.11.
30、 Typical Chromatogram11.1 Instrument Parameters:Column Carbowax 20 M (5 %), 80/100 AW Chromasorb W.,6.1-m (20-ft), 3.2-mm ( 1/8 -in.) in outside diameter,stainless steelDetector flame ionizationTemperatures injection port165 to 260Cdetector250Ccolumn50 to 250C at 8C/minGases carrierHe at 45 mL/minSa
31、mple Size 10 LRecorder chart speed 1.3 cm/min (0.5 in./min); full-scale re-sponse, 1 mV (23.3 cm)11.2 See the chromatogram in Fig. 1 for relative retentiontimes and separation of compounds used in the round-robintesting.12. Precision and Bias912.1 Six laboratories determined the precision and bias o
32、fthe procedure performing triplicate analyses at three levels inboth natural and reagent water (see Table 2 and Table 3).12.2 The precision and bias data presented in 12.1 and 12.2were based on an interlaboratory collaborative study withsamples containing alcohols only. The precision and bias ofthis
33、 procedure for the other compounds covered by theprocedure may vary from these data.13. Quality Assurance/Quality Control (QA/QC)13.1 Before this test method is applied to the analysis ofsamples of unknown alcohol concentrations, the analyst mustestablish quality control by the procedures recommende
34、d inPractice D 4210 and Guide D 3856.13.2 A duplicate sample and known standard must beanalyzed each day that an analysis is performed. The duplicateand standard shall meet the limits as established by the controlchart before a determination is considered satisfactory.13.3 A blank and a spiked sampl
35、e shall be analyzed eachday that an analysis is performed. Spiking shall be in accor-dance with that outlined in 11.11 of Guide D 3856. The blankshall be low enough that it will not unduly influence the data.13.4 One sample must be analyzed in duplicate with eachgroup of 10 or less samples. The resu
36、lts must meet the criteriaestablished in Table 2 and Table 3 of this test method before thedata for that batch or set of 10 samples is acceptable.13.5 Other QA/QC portions of this test method have notbeen completely established at this time. Analysts performingthis test method will be required to me
37、asure their performanceagainst the performance level achieved by the interlaboratorystudies of this test method.13.6 It is the intention of Subcommittee D19.06 to incorpo-rate formal QA/QC procedures into this test method at suchtime as they have passed the consensus process and have beenofficially
38、accepted by the Society.14. Keywords14.1 alcohols; aqueous-injection; gas chromatography;volatile alcohols8Reagent Chemicals, American Chemical Society Specifications , AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, se
39、e Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.9Supporting data are available from ASTM Headquarters. Request ResearchReport RR:D19-1045.D 3695 95 (2001)3FI
40、G. 1 ChromatogramTABLE 2 Determination of BiasCompoundAmountAdded, mg/LAmountFound, mg/L6 % Bias 6 % BiasStatistically Significant(95 % Confidence Level)Reagent Water:Isopropanol 2041024117985.53325.216.48.012.316.019.5yesyesyes2-Pentanol 197983919697371.01.02.00.51.05.0nonono1-Pentanol 197983919594
41、.536.82.03.52.21.03.65.6nonoyes1-Hexanol 19999402019336.8+2.06.03.2+1.06.08.0nonono2-Ethylhexanol 84421785.341.216.1+1.30.80.9+1.51.95.3nononoNatural Water:Isopropanol 204102511889043.516127.57.811.814.7noyesyes2-Pentanol 19698491959547.31.03.01.70.53.03.5nonono1-Pentanol 197984920610348.2+9.3+5.00.
42、8+4.7+6.10.2nonono1-Hexanol 19999502089949.8+8.80.00.2+4.40.00.4nonono2-Ethylhexanol 84422183.640.320.10.41.70.90.54.04.3nononoD 3695 95 (2001)4ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of t
43、his 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 committee and must be reviewed every five y
44、ears 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 meeting of theresponsible technical comm
45、ittee, 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 Drive, PO Box C700, West Conshohocken, PA 19
46、428-2959,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).TABLE 3 PrecisionAReagent Water Natur
47、al WaterIsopropanol ST= 0.16X 0.60SO= 0.06X0.7ST= 0.19X2.4ST= 0.004X1.72-Pentanol ST= 0.04X 0.007SO= 0.009X + 0.25ST=0.011X + 0.48SO= 0.006X 0.111-Pentanol ST= 0.013X + 0.62SO= 0.004X + 0.41ST= 0.031X + 0.26SO= 0.006X 0.0031-Hexanol ST= 0.024X + 0.77SO=0.003+0.62ST= 0.020X + 0.62SO= 0.003X + 0.212-Ethyl hexanol ST= 0.03X + 1.25SO= 0.01X + 0.25ST= 0.028X + 0.39SO= 0.002X + 0.14AST= overall precision, mg/L, SO= single-operator precision, mg/L, and X= concentration of organic determined, mg/L.D 3695 95 (2001)5
