E925 09 2014
E925 09 2014
INTRODUCTION
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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basis and to compare one instrument’s performance with that ISO Guide 34 General Requirements for the Competence of
of other similar units. Refer to Practice E275 to extensively Reference Material Producers
evaluate the performance of an instrument.
3. Terminology
1.3 This practice should be performed on a periodic basis,
the frequency of which depends on the physical environment 3.1 Definitions:
within which the instrumentation is used. Thus, units handled 3.1.1 For the definitions of terms used in this practice, refer
roughly or used under adverse conditions (exposed to dust, to Terminology E131.
chemical vapors, vibrations, or combinations thereof) should 3.1.2 For a description of the instrumental parameters
be tested more frequently than those not exposed to such evaluated in this practice, refer to Practice E275.
conditions. This practice should also be performed after any 3.1.3 For a description of quantitative ultraviolet spectro-
significant repairs are made on a unit, such as those involving photometric techniques, refer to Practice E169.
the optics, detector, or radiant energy source.
4. Significance and Use
1.4 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 4.1 This practice permits an analyst to compare the perfor-
standard. mance of an instrument to the manufacturer’s supplied perfor-
mance specifications and to verify its suitability for continued
1.5 This standard does not purport to address all of the routine use. It also provides generation of calibration monitor-
safety concerns, if any, associated with its use. It is the ing data on a periodic basis, forming a base from which any
responsibility of the user of this standard to establish appro- changes in the performance of the instrument will be evident.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. 5. Reference to this Calibration-Monitoring Procedure
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A purchaser should require certification by the supplier that the 7.2.1 Examine the holmium oxide reference material and
wavelengths of the absorption bands are within 0.2-nm of the remove any surface contamination using a soft brush or
values given in Ref. (2), and reported below. The appropriate lint-free cloth. Measure the temperature of the sample com-
solution standard is 4 % (mass fraction) holmium oxide in partment by placing an appropriate sensor into the cell com-
10 % (volume fraction) perchloric acid, contained in a 10-mm partment of a stabilized instrument and replacing the compart-
path length cuvette. For this material, the transmittance minima ment cover securely. Place the sensor as close as possible to the
of 18 absorption bands have been certified by a multi- actual position that will be occupied by the standard. After a
laboratory inter-comparison, at the highest level, allowing the suitable period of time record the temperature reading, remove
peak value assignments as an intrinsic wavelength standard (3). the sensor, and resume normal operations.
Absorbance maxima or transmittance minima must be located 7.2.2 Record the blank absorbance or transmittance (air
within 61 nm of the wavelengths given below: versus air) spectrum at the desired resolution and at the
Glass FilterA Dilute Acidic SolutionB appropriate wavelength intervals and scan speeds, in order to
241.5 nmC 241.1 nm perform any necessary baseline adjustments. The wavelength
... 249.9 nm
279.3 nm 278.1 nm
intervals should be no greater than the spectral bandwidth used.
287.6 nm 287.2 nm Acquire the appropriate spectrum of the holmium oxide
333.8 nm 333.5 nm reference material with respect to air and baseline correct if
... 345.4 nm
360.8 nm 361.3 nm
necessary using the blank spectrum. Record the wavelengths of
385.8 nm 385.6 nm the positions of the relevant bands, and compare these values to
418.5 nm 416.3 nm the expected values. If large discrepancies (>1 nm) exist
453.4 nm ...D
459.9 nm 467.8 nm
between the true and measured wavelengths, repeat the proce-
... 485.3 nm dure at a slower scan speed and smaller spectral bandwidth, if
536.4 nm 536.6 nm possible, to verify the nonconformity.
637.5 nm 640.5 nm
7.2.3 Report the wavelength calibration data in the manner
A
Wavelengths taken from Ref. (2) for Corning Glass Works Code 3130 glass,
of Table 1, given as an example for the holmium oxide glass
superceded by Corning Glass Works Code 3131 glass and Kopp Glass Code 3131 reference material.
glass, for which the wavelengths are also valid.
B
Wavelengths rounded to 0.1 nm for a 1-nm spectral bandwidth taken from Ref.
(3).
8. Evaluation of Stray Radiant Power Ratio (SRPR)
C
May not be usable, depending on the base glass of the filter. 8.1 Discussion—A portion of the unwanted stray radiant
D
Peak omitted because it resolves into a doublet at spectral bandwidth values
less than 1 nm. power detected by the photodetector can be measured using the
following sharp cut-off solution filters in 1-cm cells:
NOTE 1—‘Self assertion’ may take the form of value assignment and
Solution Wavelength
certification in many forms. Some specific examples are:
KI or NaL, 10.0 g/L in H2O 220 nm
(1) By a national metrology institute (NMI), NaNo2, 50.0 g/L in H2O 370 nm
(2) By an ISO 17025 and ISO Guide 34 accredited Reference Mate-
rial producer, and
(3) By a laboratory claiming ‘traceability’ to an NMI.
In all cases, the user should be satisfied that the quality of the value
assignment data meets the laboratory requirements. TABLE 1 UV-VIS Spectrophotometer Wavelength and Stray
Radiant Power Ratio Calibration
7.1.1 If the observed absorption bands of the holmium oxide
Instrument
glass or solution deviate by more than 61 nm from the values Date
stated, then corrective service must by performed on the Temperature
instrument by qualified personnel. If the user performs this Analyst
Wavelength Calibration: Holmium Oxide Filter
service, the manufacturer’s recommended procedure should be
followed carefully.
True Observed Conformance
7.1.2 The wavelength accuracy is dependent on the spectral Difference
Wavelength Wavelength
(nm) Does Does Not
bandwidth and thus on the physical bandwidth. Spectral (nm) (nm)
241.5 ± 1
bandwidths may be determined from the manufacturer’s speci- 279.3 ± 1
fications. 287.6 ± 1
7.1.3 Computer based peak location algorithms that may be 333.8 ± 1
360.8 ± 1
used to assign absorbance maxima or transmittance minima are 385.8 ± 1
discussed in 7.6 of Guide E1866. It should be noted that peak 418.5 ± 1
453.4 ± 1
asymmetries in the holmium oxide reference materials are such
459.9 ± 1
that digital filter widths should be smaller than the full-width- 536.4 ± 1
half-maximum recommendation of that guide. 637.5 ± 1
7.1.4 In the absence of drift or slippage in the wavelength
drive train, repeatability of the band positions should be on the Stray Radiant Power Ratio
Wavelength Transmittance Does Not
order of 60.1 nm for a given instrument, especially with the Conforms
(nm) or Absorbance Conform
use of a computer based peak location algorithm. 220
340
7.2 Procedure:
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8.1.1 Reagent grade materials should be used for these 9.1.2 An acceptable absorbance range for each standard for
solutions. They are essentially opaque at the indicated wave- any instrument must be determined based on the instrument
lengths; any observed transmittance is equivalent to the effec- manufacturer’s specifications and on the analytical demands of
tive SRPR. the end-use application of the instrument. As a guide to the
8.1.2 An acceptable level of SRPR depends on the spectral acceptability of photometric accuracy data a tolerance of
character and absorbance level of the sample under investiga- 61.0 % relative (0.2 ≤ A ≤ 2.0) is employed in this practice.
tion. However, an upper limit of 4 × 10-4 is consistent with a The user is encouraged to establish tolerance limits more
worst-case absorbance bias of ~1 % at the upper limit of the appropriate to the application in question, and use the tables of
absorbance range (0 < A ≤ 2) covered by this practice, and is this practice as templates for custom tables that reflect the
suggested in the absence of other criteria. appropriate tolerances. One approach often used in defining
8.1.3 While the stray radiant power ratio is equivalent to the these limits is to linearly add the certified expanded uncertainty
transmittance described previously, it is often more convenient budget (k = 2) for a given reference material, to the manufac-
to make the measurement in the absorbance mode and math- turer quoted instrument photometric accuracy specification.
ematically convert absorbance to transmittance. The value 9.1.3 Rigorous treatment of the construction and use of an
quoted in 8.1.2 (4 × 10-4) equates to an absorbance value of absorbance correction curve for high accuracy work is beyond
3.4A. the scope of this practice.
8.1.4 An excessive SRPR usually arises from dust, 9.1.4 Studies by NIST and other ISO 17025 and
scratches, or corrosion on the collimator or disperser, or both. ISO Guide 34 accredited organizations have indicated that
Qualified personnel should correct this problem. Care should solutions of acidic potassium dichromate are stable for at least
be taken to discriminate between SRPR and light leaks. The six months when prepared in the manner described in 9.3.2.1
latter most often originate in the sample compartment and can and stored in the dark in well-stoppered 1-L volumetric flasks,
be detected by blocking the sample beam alternately at the and for at least two years when permanently sealed in
ports on the source and detector sides of the sample compart- ampoules or far UV quartz cuvettes, by heat fusion. Neutral
ment. Any difference in the detected signals indicates a light density glass filters are certified by different sources for periods
leak. of from two to five years, with appropriately adjusted uncer-
tainties.
8.2 Procedure:
8.2.1 Use the visible light source lamp in the 340 nm region 9.2 Visible Region—The absorbance scale in the visible
and the ultraviolet light source lamp in the 220 nm region. region is tested using filters of a proprietary neutral glass. The
8.2.2 Determine the transmittance or absorbance of each construction and certification of such filters is described in
solution at the appropriate wavelength using the indicated some detail in NIST Special Publication 260-116 and
solvents for reference. NIST Special Publication . Traceability of the certified absor-
bance values to the transmittance scale maintained by the
8.2.3 Refer to Test Method E387 if the dynamic range of the
Analytical Chemistry Division (ACD) of NIST is supported by
readout electronics of the instrument is not adequate for the
NIST for commercial participants in the NIST Traceable
direct measurement of SRPR as described here.
Reference Materials (NTRM) program, or by self assertion
8.2.4 In the manner of Table 1, report the transmittance or (Note 1) for other commercial sources. Traceability of these
absorbance of these solutions. Note whether the effective stray filters is normally maintained through NIST SRM 930 filters
radiant power ratio exceeds the suggested tolerance of 4 × 10-4 with nominal absorbances of 0.5, 0.7, and 1.0 and SRM 1930
or the user-defined tolerance. filters with absorbances of 0.3, 1.5, and 2.0. (A letter series
designation for SRM 930 is periodically adjusted without
9. Determination of the Absorbance Scale Accuracy in significant effect for this practice.) The wavelengths for which
the Ultraviolet and Visible Spectral Regions certified absorbance values are reported for individual filters
9.1 Discussion—The accuracy of the absorbance scale is are close to local extrema in the nearly-neutral glass to
determined using reference materials with known absorbances. minimize the effect of wavelength error on the measured
The absorbance scale accuracy in the ultraviolet region (235 to transmittance:
350 nm) is determined using acidic solutions of potassium 440.0 nm
dichromate as described in NIST Special Publication 260-54. 465.0 nm
In the visible region (440 to 635 nm) the absorbance accuracy 546.1 nm
is determined using certified neutral density glass filters as 590.0 nm
described in NIST Special Publication 260-116 and NIST Spe- 635.0 nm
cial Publication 260-140. The certified absorbances should be Neutral density glass filters are also available from the
traceable to the regular transmittance scale maintained by an National Physical Laboratory (NPL) of the UK and from
NMI. commercial sources asserting traceability to the regular trans-
9.1.1 If the blank-corrected absorbances (Acorr) of the stan- mittance scale maintained by NPL.
dards are outside the acceptable range, then corrective service 9.2.1 These filters have individually certified absorbance
must be performed on the instrument by qualified personnel. If values and the precautionary notes stated in the certificate that
the user performs this service, the manufacturer’s recom- accompanies the filters should be followed. In cases where
mended procedure should be followed carefully. recertification of the absorbance values of these filters is
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required (due to expiration or improper storage or handling) NOTE 2—Acidic potassium dichromate solutions specifically prepared
they should be returned to the certifying laboratory for cleaning for spectrophotometric validation are also available commercially in
solution, sealed ampoules, and sealed cuvette formats. Portions of the
and recertification.
procedure below, for the powder form, will not be required for these
9.2.2 Procedure: forms. Certified values and expiration dates that accompany such prepa-
9.2.2.1 Examine the glass filters for surface contamination rations should be observed.
and clean with a bulb-type of air puffer if necessary. Any other
attempt to clean the filters invalidates the certification. Measure 9.3.1 The precautionary notes stated in the certificate and
the temperature of the sample compartment as described in the material safety data sheet (MSDS) for SRM 935a should be
Section 7. observed. These documents are available from the NIST
9.2.2.2 Determine the absorbance blank (air versus air internet site at www.nist.gov under the Standard Reference
absorbance value) at the indicated wavelengths. Record these Materials Program online catalog.
measurements. If large (>0.001A) blank values are observed, 9.3.2 Procedure:
use these to blank-correct measured apparent absorbances by 9.3.2.1 Prepare the absorbance standard solutions of potas-
subtraction. Measure the apparent absorbance of each filter at sium dichromate by transferring 200.0 6 0.3, 300.0 6 0.3,
each wavelength versus air. Each filter should be oriented in 400.0 6 0.3, and 500.0 6 0.3 mg of the powder to four
the same manner in the sample holder. If a corrected absor- separate 100 mL volumetric flasks and dilute to volume with
bance reading is outside the acceptable absorbance range, distilled water (Absorbance Standard Stock Solutions). Stopper
repeat the procedure with a longer integration time and smaller the solutions and mix well. Dilute these solutions by pipetting
spectral bandwidth, if possible, to verify the nonconformity. 20.0 mL of each solution separately to four 1-L volumetric
9.2.3 Report the visible region validation data in the manner flasks, adding 1 mL of 1M HClO4 (8.6 mL of 70 % HClO4/100
of Table 2, constructed for a set of three filters of the nominal mL H2O) and diluting to volume with distilled water (Absor-
absorbances of NIST SRM 930. bance Standard Sample Calibration Solutions). These final
9.3 Ultraviolet Region—The absorbance scale in the ultra- calibration solutions contain 40, 60, 80, and 100 mg of
violet region is tested using acidic solutions of potassium potassium dichromate per litre of solution, respectively. Pre-
dichromate (available from NIST as SRM 935a). The wave- pare a blank solution by diluting 1 mL of 1 M HClO4 to one L
lengths of interest are: with the same distilled water. Stopper the solutions and mix
235 nm well.
257 nm 9.3.2.2 Clean and match the 1-cm solution cells (cuvettes).
313 nm Measure the temperature of the sample compartment as de-
350 nm scribed in Section 7.
Wavelength ConformanceD
Filter No. AnomA AcertA AcorrA BiasB ToleranceC
(nm) Does Does Not
440.0 0.5 0.005
0.7 0.007
1.0 0.010
A
Anom = nominal absorbance; Acert = certified absorbance; Acorr = measured absorbance, blank corrected as necessary.
B
Bias = Acorr − Acert.
C
Tolerance taken for example as 1 % of the nominal. User to assign as appropriate for each application.
D
Measurement conforms for |Bias| # Tolerance; measurement does not conform for |Bias| > Tolerance.
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TABLE 3 UV-VIS Spectrophotometer Absorbance Calibration—Ultraviolet Region (Potassium Dichromate)
Instrument
Date
Temperature
Analyst
A
Acert = certified absorbance, computed from SRM 935a certified specific absorbance values for the given solution and a 10-mm pathlength.
B
Ameas = measured solution absorbance; Ablank = measured blank absorbance; Acorr = Ameas − Ablank.
C
Bias = Acorr − Acert.
D
Tolerance computed for illustrative purposes as 1 % of the certified absorbance. User may substitute appropriate tolerances.
E
Corrected absorbance conforms when |Bias| # Tolerance.
9.3.2.3 Determine the apparent absorbance blank at the solution at the concentration of interest and repeat the absor-
indicated wavelengths using solvent in each cuvette. Record bance measurements. If non-conformities are verified, correc-
these measurements. If large (>0.01A) blank values are tive service must be performed by qualified personnel. If the
observed, re-cleaning the cuvettes may be necessary. Measure user performs this service, the manufacturer’s recommended
the apparent absorbance of each Absorbance Standard Sample procedure should be followed carefully.
Calibration Solution of potassium dichromate in the sample 9.3.3 Report the ultraviolet region calibration data in the
cuvette at each wavelength and record. Rinse the cuvettes manner of Table 3.
several times with the solutions to be measured before they are
placed in the sample compartment and maintain the same 10. Documentation of Data
orientation of a cuvette throughout the procedure. If a corrected 10.1 Spectral charts and tables should be retained for
apparent absorbance value (Acorr) of an Absorbance Standard reference.
Sample Calibration is outside the acceptable range, repeat the
reading with a longer integration time and smaller spectral 11. Keywords
bandwidth, if possible. If the absorbance readings at all 11.1 absorbance; molecular spectroscopy; reference materi-
wavelengths for a solution are unacceptable, prepare a fresh als; spectrophotometers; UV/visible; wavelength
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REFERENCES
(1) McNeirney, J., and Slavin, W., Applied Optics, Vol 1, 1962, p. 365. Chunnilall, C.J., Crossona, S.C., et al, “Intrinsic Wavelength Standard
(2) Keegan, H.J, Schleter, J.C., and Weidner, V.R., Journal of the Optical Absorption Bands in Holmium Oxide Solution for UV/visible Mo-
Society of America, Vol 51, 1961, p. 1470. lecular Absorption Spectrophotometry,” Journal of Physical
(3) Travis, J.C., Acostab, J.C., Andorc, G., Bastied, J., Blattnere, P., Chemistry, Reference Data, Vol 34, No. 1, 2005.
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