1、Designation: D 3695 95 (Reapproved 2007)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:3D 1129 Terminology Relating to WaterD 1193 Specification for Reagent WaterD 2908 Practice for Measuring Volatile Organic Matter inWater by Aqueous-Injection Gas ChromatographyD 3856 Guide for Good Laboratory Practices in Laborato-ries Engaged in Sampling and Analysis of WaterD 4210
8、Practice for Intralaboratory Quality Control Proce-dures and a Discussion on Reporting Low-Level Data4E 355 Practice for Gas Chromatography Terms and Rela-tionships3. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Terminology D 1129 and Practice E 355.4. Summary
9、 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 reten
10、tion 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 me
11、ansfor 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 prese
12、nt.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.1This test method is und
13、er the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved Dec. 1, 2007. Published January 2008. Originallyapproved in 1978. Last previous edition approved in 2001 as D 3695
14、95 (2001).2Sugar, J. W., and Conway, R. A., “Gas-Liquid Chromatographic Techniques forPetrochemical Waste Water Analysis, Journal of the Water Pollution ControlFederation, Vol 40, 1968, pp. 16221631.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service
15、 at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.4Withdrawn.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.7. Apparatus7.1 Gas Chromatograph an
16、d Accessory Equipment, de-scribed in Practice D 2908, Sections 7.1 through 7.6, is usedfor this analysis.TABLE 1 Kovats Index and Relative Retention Data for TypicalComponentsAComponentKovatsIndex (Ix)RelativeRetentionBDiethyl ether 580 0.17n-Hexane 600 0.19Isopropyl ether 600 0.19Ethylene oxide 700
17、 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-Butyraldehyde 865 0.32Vinyl a
18、cetate 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 0.46Ethanol 1000 0.47Acrylonitr
19、ile 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 dichloride 1065 0.572,3-Pentanedio
20、ne 1080 0.60Toluene 1080 0.60n-Butyl acetate 1080 0.60Ethylene dichloride 1092 0.62n-Propanol 1100 0.63Crotonaldehyde 1110 0.65Paraldehyde 1118 0.661,4-Dioxane 1118 0.66Isobutanol 1137 0.70Mesityl oxide 1137 0.70n-Methylmorpholene 1142 0.72Methyl amyl acetate 1150 0.732-Pentanol 1157 0.74primary-Amy
21、l 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 0.82TABLE 1 ContinuedComponentKovatsIndex (Ix)RelativeRetentionBn-Butyl acrylate 1190 0.83Methyl amyl alcohol 1190 0.83Diisobutyl ketone 1202 0.852-E
22、thylhexyl 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 1.103-Picoline 1300 1.124
23、-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 1354 1.31Ethyl acetoaceta
24、te 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 1.60Ethylene glycol 1430 1
25、.63Acetophenone 1435 1.65Diethyl succinate 1441 1.67Methyl acetoacetate 1443 1.69Diethyl maleate 1460 1.79n-Decyl alcohol 1483 1.85Methylbenzyl alcohol 1486 1.862-(2-Butoxy) ethoxyethyl ace-tate1486 1.86AGas Chromatographic Data Compilation, ASTM AMD 25A-51, ASTM, 1971.BRelative to amyl alcohol.D 36
26、95 95 (2007)27.2 Column, Carbowax 20 M (trademark)5(5%) on 80/100Acid Washed Chromosorb W (trademark),66.1-m (20-ft),3.2-mm (18-in.) in outside diameter, 0.508-mm (0.020-in.) wallthickness, stainless steel.8. Reagents8.1 Purity of ReagentsReagent grade chemicals shall beused. Unless otherwise indica
27、ted, it is intended that all reagentsshall conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society, wheresuch specifications are available.7Other 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 (18-in.) in outside diameter,stainless steelDetector flame ionizationTemperatures injection port165 to 260Cdetector250Ccolumn50 to 250C at 8C/minGases carrierHe at 45 mL/minSampl
31、e 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 Bias812.1 Six laboratories determined the precision and bias ofth
32、e 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 pr
33、ocedure for the other compounds covered by theprocedure may vary from these data.5The sole source of supply of the apparatus known to the committee at this timeis Union Carbide Corp. If you are aware of alternative suppliers, please provide thisinformation to ASTM International Headquarters. Your co
34、mments will receivecareful consideration at a meeting of the responsible technical committee,1whichyou may attend.6The sole source of supply of the apparatus known to the committee at this timeis Johns-Manville Products Co. If you are aware of alternative suppliers, pleaseprovide this information to
35、 ASTM International Headquarters. Your comments willreceive careful consideration at a meeting of the responsible technical committee,1which you may attend.7Reagent Chemicals, American Chemical Society Specifications , AmericanChemical Society, Washington, DC. For suggestions on the testing of reage
36、nts notlisted by the American Chemical Society, see 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.8Supporting data have been filed at ASTM International Head
37、quarters and maybe obtained by requesting Research Report RR: D19-1045.FIG. 1 ChromatogramD 3695 95 (2007)313. 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 th
38、e procedures recommended 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 b
39、lank and a spiked sample 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.TABLE 2 Determination of BiasCompoundAmountAdded, mg/LAmountFound, mg
40、/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 197983919594.536.82.03.52.21.03.65.6nonoyes1-Hexanol 19999402019336.8+2.06.03.2+1.06.08.0nonono2-E
41、thylhexanol 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+5.00.8+4.7+6.10.2nonono1-Hexanol 19999502089949.8+8.80.00.2+4.40.00.4nonono2-Ethylhexanol 8
42、4422183.640.320.10.41.70.90.54.04.3nononoTABLE 3 PrecisionAReagent Water Natural 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 0.00
43、31-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 (2007)413.4 One s
44、ample must be analyzed in duplicate with eachgroup of 10 or less samples. The results 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 es
45、tablished at this time. Analysts performingthis test method will be required to measure 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 met
46、hod at suchtime as they have passed the consensus process and have beenofficially accepted by the Society.14. Keywords14.1 alcohols; aqueous-injection; gas chromatography;volatile alcoholsASTM International takes no position respecting the validity of any patent rights asserted in connection with an
47、y item 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
48、 committee 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 a
49、t a 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 Drive, 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 (
