1、Designation: E 1840 96 (Reapproved 2007)Standard Guide forRaman Shift Standards for Spectrometer Calibration1This standard is issued under the fixed designation E 1840; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of la
2、st 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 guide covers Raman shift values for commonliquid and solid chemicals that can be used for wavenumbercalibration of
3、 Raman spectrometers. The guide does notinclude procedures for calibrating Raman instruments. Instead,this guide provides reliable Raman shift values that can be usedas a complement to low-pressure arc lamp emission lineswhich have been established with a high degree of accuracyand precision.1.2 The
4、 values stated in SI units are to be regarded as thestandard.1.3 Some of the chemicals specified in this guide may behazardous. It is the responsibility of the user of this guide toconsult material safety data sheets and other pertinent infor-mation to establish appropriate safety and health practic
5、es anddetermine the applicability of regulatory limitations prior totheir use.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 safety and health practices and deter
6、mine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2E 131 Terminology Relating to Molecular SpectroscopyE 1683 Practice for Testing the Performance of ScanningRaman Spectrometers3. Terminology3.1 DefinitionsTerminology used in this guide conforms
7、to the definitions set forth in Terminology E 131.4. Significance and Use4.1 Wavenumber calibration is an important part of Ramananalysis.The calibration of a Raman spectrometer is performedor checked frequently in the course of normal operation andeven more often when working at high resolution. To
8、 date, themost common source of wavenumber values is either emissionlines from low-pressure discharge lamps (for example, mer-cury, argon, or neon) or from the non-lasing plasma lines of thelaser. There are several good compilations of these well-established values (1-8).3The disadvantages of using
9、emissionlines are that it can be difficult to align lamps properly in thesample position and the laser wavelength must be knownaccurately.With argon, krypton, and other ion lasers commonlyused for Raman the latter is not a problem because lasingwavelengths are well known. With the advent of diode la
10、sersand other wavelength-tunable lasers, it is now often the casethat the exact laser wavelength is not known and may bedifficult or time-consuming to determine. In these situations itis more convenient to use samples of known relative wave-number shift for calibration. Unfortunately, accurate waven
11、um-ber shifts have been established for only a few chemicals. Thisguide provides the Raman spectroscopist with average shiftvalues determined in seven laboratories for seven pure com-pounds and one liquid mixture.5. Raman Shift Standards5.1 Reagents and MethodologyRaman shifts were mea-sured in seve
12、n laboratories for the following eight materials:Compound SourceNaphthalene Mallinckrodtfvariant41,4-Bis(2-methylstyryl)benzene (a laser dye) Aldrichfvariant5Sulfur Aldrichfvariant550/50 (v/v) toluene/acetonitrile Mallinckrodtfvariant44-Acetamidophenolfvariant6Aldrichfvariant5Benzonitrile Aldrichfva
13、riant5Cyclohexane Mallinckrodtfvariant4Polystyrene Aldrichfvariant51This guide is under the jurisdiction of ASTM Committee E13 on MolecularSpectroscopy and Separation Science and is the direct responsibility of Subcom-mittee E13.08 on Raman Spectroscopy.Current edition approved March 1, 2007. Publis
14、hed March 2007. Originalyapproved in 1996. Last previous edition approved in 2002 as E 1840 96 (2002).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
15、Document Summary page onthe ASTM website.3The boldface numbers in parentheses refer to a list of references at the end ofthe text.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5.1.1 The eight materials were selected to cover a wide
16、wavenumber range (from 85 to 3327 cm1) for both solids andliquids. They have no known polymorphs, and several batcheswere examined. All of the chemicals are readily available athigh purity from commercial sources such as Aldrich.5Six ofthe laboratories in the study used FT-Raman spectrometers;one us
17、ed a scanning Raman system; and one employed amultichannel spectrometer. The shift values were determinedindependently by each laboratory; only an approximate spec-trum without peak frequencies was provided as a guide. Nowavenumber calibration procedure was recommended, buteach laboratory used their
18、 own calibration procedure to obtainthe most accurate data possible.5.2 DataFigs. 1-8 and Tables 1-8 give representativespectra and peak data for the eight standards. Uncorrected,relative peak intensities determined with a SPEX 1403 scan-ning double monochromator (1200- lines/mm gratings) andRCA 310
19、34A photomultiplier tube with 514.5-nm excitationare included to help the user match spectral peaks with thetabulated shift values. Average shifts and standard deviations(sN1) appear in the tables. With the exception of a few valuesat low and high Raman shifts, only values with standarddeviations le
20、ss than 1.0 cm1are reported. Most of theunreported peaks were weak, had poor shape, or overlappedother bands causing unacceptably high uncertainty in the data.6. Keywords6.1 Raman spectroscopy; wavenumber calibration4Available from Mallinckrodt, 16305 Swingley Ridge Dr., Chesterfield, MO63017. If yo
21、u are aware of alternative suppliers, please provide this information toASTM International Headquarters. Your comments will receive careful consider-ation at a meeting of the responsible technical committee,1which you may attend.5Available from Aldrich, 1001 W. St. Paul Ave., Milwaukee, WI 53233. If
22、 youare aware of alternative suppliers, please provide this information to ASTMInternational Headquarters. Your comments will receive careful consideration at ameeting of the responsible technical committee,1which you may attend.6The active ingredient of Tylenol, a registered trademark of McNeil-PPC
23、. If youare aware of alternative suppliers, please provide this information to ASTMInternational Headquarters. Your comments will receive careful consideration at ameeting of the responsible technical committee,1which you may attend.FIG. 1 NaphthaleneE 1840 96 (2007)2FIG. 2 1,4 bis (2-Methylstyryl)
24、BenzeneE 1840 96 (2007)3NOTE 1Lower three frequencies are averages of only 1 to 3 values.FIG. 3 SulfurE 1840 96 (2007)4FIG. 4 50/50 Toluene/AcetonitrileE 1840 96 (2007)5FIG. 5 4-Acetamidophenol (Tylenol)E 1840 96 (2007)6FIG. 6 BenzonitrileE 1840 96 (2007)7FIG. 7 CyclohexaneE 1840 96 (2007)8FIG. 8 Po
25、lystyreneTABLE 1 NaphthaleneAverage (cm-1) 6 Standard Deviation Relative Intensity513.8 6 0.31 29763.8 6 0.31 301021.6 6 0.49 111147.2 6 0.34 61382.2 6 0.31 1001464.5 6 0.29 121576.6 6 0.29 163056.4 6 0.41 32TABLE 2 1,4Bis (2Methyistyryll)BenzeneAverage (cm-1) 6 Standard Deviation Relative Intensity
26、456.0 6 0.56 3642.4 6 0.12 3841.6 6 0.28 4950.1 6 0.13 4978.0 6 0.16 61104.1 6 0.31 51177.7 6 0.56 491290.7 6 0.28 91316.9 6 0.94 101334.5 6 0.16 121555.2 6 0.19 181593.1 6 0.44 1001627.9 6 0.23 56TABLE 3 SulfurAverage (cm-1) 6 Standard Deviation Relative Intensity85.1 6 2.6 17153.8 6 0.50 38219.1 6
27、 0.57 100473.2 6 0.49 36TABLE 4 Toluene/AcetonitrileAverage (cm-1) 6 Standard Deviation Relative IntensityA378.5 6 0.92 4 (A)521.7 6 0.34 10 (T)786.5 6 0.40 39 (T)919.0 6 0.40 11 (A)1003.6 6 0.37 100 (T)1030.6 6 0.36 23 (T)1211.4 6 0.32 16 (T)1605.1 6 0.47 6 (T)2253.7 6 0.42 44 (A)2292.6 6 0.89 5 (A
28、)2940.8 6 0.25 64 (A)3057.1 6 0.63 30 (T)A(T = toluene, A = acetonitrile).E 1840 96 (2007)9TABLE 5 4AcetamidophenolAAverage (cm-1) 6 Standard Deviation Relative Intensity213.3 6 1.77 17329.2 6 0.52 11390.9 6 0.76 25465.1 6 0.30 11504.0 6 0.60 11651.6 6 0.50 33710.8 6 0.68 17797.2 6 0.48 45834.5 6 0.
29、46 14857.9 6 0.50 82968.7 6 0.60 121105.5 6 0.27 71168.5 6 0.65 701236.8 6 0.46 751278.5 6 0.45 421323.9 6 0.46 1001371.5 6 0.11 381515.1 6 0.70 91561.5 6 0.52 371648.4 6 0.50 732931.1 6 0.63 293064.6 6 0.31 263102.4 6 0.95 203326.6 6 2.18 7AActive ingredient of Tylenol (see Footnote 6).TABLE 6 Benz
30、onitrileAverage (cm-1) 6 Standard Deviation Relative Intensity460.9 6 0.73 15548.5 6 0.82 7751.3 6 0.74 10767.1 6 0.59 101000.7 6 0.98 1001026.6 6 0.81 131177.9 6 0.82 201192.6 6 0.56 251598.9 6 0.70 362229.4 6 0.39 673072.3 6 0.41 26TABLE 7 CyclohexaneAverage (cm-1) 6 Standard Deviation Relative In
31、tensity384.1 6 0.78 2426.3 6 0.41 3801.3 6 0.96 951028.3 6 0.45 151157.6 6 0.94 61266.4 6 0.58 141444.4 6 0.30 122664.4 6 0.42 82852.9 6 0.32 1002923.8 6 0.36 582938.3 6 0.51 67E 1840 96 (2007)10REFERENCES(1) Strommen, D. P., and Nakamoto, K., Laboratory Raman Spectroscopy,John Wiley or through the ASTM website(www.astm.org).TABLE 8 PolystyreneAverage (cm-1) 6 Standard Deviation Relative Intensity620.9 6 0.69 16795.8 6 0.78 101001.4 6 0.54 1001031.8 6 0.43 271155.3 6 0.56 131450.5 6 0.56 81583.1 6 0.86 121602.3 6 0.73 282852.4 6 0.89 92904.5 6 1.22 133054.3 6 1.36 32E 1840 96 (2007)11
