ASTM E1840-96(2022)
(Guide)Standard Guide for Raman Shift Standards for Spectrometer Calibration
Standard Guide for Raman Shift Standards for Spectrometer Calibration
SIGNIFICANCE AND USE
4.1 Wavenumber calibration is an important part of Raman analysis. The calibration of a Raman spectrometer is performed or checked frequently in the course of normal operation and even more often when working at high resolution. To date, the most common source of wavenumber values is either emission lines from low-pressure discharge lamps (for example, mercury, argon, or neon) or from the non-lasing plasma lines of the laser. There are several good compilations of these well-established values (1-8).3 The disadvantages of using emission lines are that it can be difficult to align lamps properly in the sample position and the laser wavelength must be known accurately. With argon, krypton, and other ion lasers commonly used for Raman the latter is not a problem because lasing wavelengths are well known. With the advent of diode lasers and other wavelength-tunable lasers, it is now often the case that the exact laser wavelength is not known and may be difficult or time-consuming to determine. In these situations it is more convenient to use samples of known relative wavenumber shift for calibration. Unfortunately, accurate wavenumber shifts have been established for only a few chemicals. This guide provides the Raman spectroscopist with average shift values determined in seven laboratories for seven pure compounds and one liquid mixture.
SCOPE
1.1 This guide covers Raman shift values for common liquid and solid chemicals that can be used for wavenumber calibration of Raman spectrometers. The guide does not include procedures for calibrating Raman instruments. Instead, this guide provides reliable Raman shift values that can be used as a complement to low-pressure arc lamp emission lines which have been established with a high degree of accuracy and precision.
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 Some of the chemicals specified in this guide may be hazardous. It is the responsibility of the user of this guide to consult material safety data sheets and other pertinent information to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to their use.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
1.5 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
General Information
Relations
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: E1840 − 96 (Reapproved 2022)
Standard Guide for
Raman Shift Standards for Spectrometer Calibration
This standard is issued under the fixed designation E1840; the number immediately following the designation indicates the 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 2. Referenced Documents
2.1 ASTM Standards:
1.1 This guide covers Raman shift values for common
liquid and solid chemicals that can be used for wavenumber E131Terminology Relating to Molecular Spectroscopy
E1683Practice for Testing the Performance of Scanning
calibration of Raman spectrometers. The guide does not
includeproceduresforcalibratingRamaninstruments.Instead, Raman Spectrometers
thisguideprovidesreliableRamanshiftvaluesthatcanbeused
3. Terminology
as a complement to low-pressure arc lamp emission lines
which have been established with a high degree of accuracy 3.1 Definitions—Terminology used in this guide conforms
and precision. to the definitions set forth in Terminology E131.
1.2 The values stated in SI units are to be regarded as
4. Significance and Use
standard. No other units of measurement are included in this
4.1 Wavenumber calibration is an important part of Raman
standard.
analysis.ThecalibrationofaRamanspectrometerisperformed
1.3 Some of the chemicals specified in this guide may be
or checked frequently in the course of normal operation and
hazardous. It is the responsibility of the user of this guide to
even more often when working at high resolution.To date, the
consult material safety data sheets and other pertinent infor-
mostcommonsourceofwavenumbervaluesiseitheremission
mation to establish appropriate safety and health practices and
lines from low-pressure discharge lamps (for example,
determine the applicability of regulatory limitations prior to
mercury,argon,orneon)orfromthenon-lasingplasmalinesof
their use.
the laser. There are several good compilations of these well-
1.4 This standard does not purport to address all of the
established values (1-8). The disadvantages of using emission
safety concerns, if any, associated with its use. It is the lines are that it can be difficult to align lamps properly in the
responsibility of the user of this standard to establish appro-
sample position and the laser wavelength must be known
priate safety, health, and environmental practices and deter- accurately.Withargon,krypton,andotherionlaserscommonly
mine the applicability of regulatory limitations prior to use.
used for Raman the latter is not a problem because lasing
1.5 This international standard was developed in accor- wavelengths are well known. With the advent of diode lasers
dance with internationally recognized principles on standard-
and other wavelength-tunable lasers, it is now often the case
ization established in the Decision on Principles for the that the exact laser wavelength is not known and may be
Development of International Standards, Guides and Recom-
difficult or time-consuming to determine. In these situations it
mendations issued by the World Trade Organization Technical is more convenient to use samples of known relative wave-
Barriers to Trade (TBT) Committee.
numbershiftforcalibration.Unfortunately,accuratewavenum-
ber shifts have been established for only a few chemicals.This
1 2
This guide is under the jurisdiction of ASTM Committee E13 on Molecular For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Spectroscopy and Separation Science and is the direct responsibility of Subcom- contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
mittee E13.08 on Raman Spectroscopy. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved Dec. 15, 2022. Published December 2022. Originally the ASTM website.
approved in 1996. Last previous edition approved in 2014 as E1840–96 (2014). The boldface numbers in parentheses refer to a list of references at the end of
DOI: 10.1520/E1840-96R22. the text.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E1840 − 96 (2022)
FIG. 1 Naphthalene
guide provides the Raman spectroscopist with average shift 5.1.1 The eight materials were selected to cover a wide
−1 −1
values determined in seven laboratories for seven pure com-
wavenumber range (from 85cm to 3327 cm ) for both
pounds and one liquid mixture.
solids and liquids. They have no known polymorphs, and
severalbatcheswereexamined.Allofthechemicalsarereadily
5. Raman Shift Standards
available at high purity from commercial sources such as
Aldrich. Six of the laboratories in the study used FT-Raman
5.1 Reagents and Methodology—Raman shifts were mea-
spectrometers; one used a scanning Raman system; and one
sured in seven laboratories for the following eight materials:
employed a multichannel spectrometer. The shift values were
Compound Source
Naphthalene Mallinckrodt
determinedindependentlybyeachlaboratory;onlyanapproxi-
1,4-Bis(2-methylstyryl)benzene (a laser dye) Aldrich
mate spectrum without peak frequencies was provided as a
Sulfur Aldrich
50/50 (v/v) toluene/acetonitrile Mallinckrodt guide. No wavenumber calibration procedure was
6 5
4-Acetamidophenol Aldrich
recommended, but each laboratory used their own calibration
Benzonitrile Aldrich
4 procedure to obtain the most accurate data possible.
Cyclohexane Mallinckrodt
Polystyrene Aldrich
5.2 Data—Figs. 1-8 and Tables 1-8 give representative
spectra and peak data for the eight standards. Uncorrected,
relative peak intensities determined with a SPEX 1403 scan-
Available from Mallinckrodt, 16305 Swingley Ridge Dr., Chesterfield, MO
ning double monochromator (1200 lines/mm gratings) and
63017. If you are aware of alternative suppliers, please provide this information to
RCA 31034A photomultiplier tube with 514.5nm excitation
ASTM International Headquarters. Your comments will receive careful consider-
ation at a meeting of the responsible technical committee, which you may attend.
are included to help the user match spectral peaks with the
Available from Aldrich, 1001 W. St. Paul Ave., Milwaukee, WI 53233. If you
tabulated shift values. Average shifts and standard deviations
are aware of alternative suppliers, please provide this information to ASTM
(σ ) appear in t
...
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