Standard Practice for Measuring Practical Spectral Bandwidth of Ultraviolet-Visible Spectrophotometers

SCOPE
1.1 This practice describes a procedure for measuring the practical spectral bandwidth of a spectrophotometer in the wavelength region of 185 to 820 nm. Practical spectral bandwidth is the spectral bandwidth of an instrument operated at a given integration period and a given signal-to-noise ratio.  
1.2 This practice is applicable to instruments that utilize servo-operated slits and maintain a constant period and a constant signal-to-noise ratio as the wavelength is automatically scanned. It is also applicable to instruments that utilize fixed slits and maintain a constant servo loop gain by automatically varying gain or dynode voltage. In this latter case, the signal-to-noise ratio varies with wavelength. It can also be used on instruments that utilize some combination of the two designs, as well as on those that vary the period during the scan. For digitized instruments, refer to the manufacturer's manual.  
1.3 This practice does not cover the measurement of limiting spectral bandwidth, defined as the minimum spectral bandwidth achievable under optimum experimental conditions.  
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 and health practices and determine the applicability of regulatory limitations prior to use.

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ASTM E958-93(1999) - Standard Practice for Measuring Practical Spectral Bandwidth of Ultraviolet-Visible Spectrophotometers
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Designation:E958–93 (Reapproved 1999)
Standard Practice for
Measuring Practical Spectral Bandwidth of Ultraviolet-
Visible Spectrophotometers
This standard is issued under the fixed designation E 958; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope 3. Terminology
1.1 This practice describes a procedure for measuring the 3.1 Definitions:
practical spectral bandwidth of a spectrophotometer in the 3.1.1 integration period—the time, in seconds, required for
wavelength region of 185 to 820 nm. Practical spectral the pen or other indicator to move 98.6 % of its maximum
bandwidth is the spectral bandwidth of an instrument operated travel in response to a step function.
at a given integration period and a given signal-to-noise ratio. 3.1.2 practical spectral bandwidth, designated by the sym-
1.2 This practice is applicable to instruments that utilize bol:
servo-operated slits and maintain a constant period and a
p
~Dl! (1)
S/N
constant signal-to-noise ratio as the wavelength is automati-
cally scanned. It is also applicable to instruments that utilize
where:
fixed slits and maintain a constant servo loop gain by auto- Dl = spectral bandwidth,
maticallyvaryinggainordynodevoltage.Inthislattercase,the p = integration period, and
S/N = signal-to-noise ratio measured at or near 100 % T.
signal-to-noiseratiovarieswithwavelength.Itcanalsobeused
3.1.3 signal-to-noise ratio—the ratio of the signal, S,tothe
on instruments that utilize some combination of the two
noise, N, as indicated by the readout indicator. The recom-
designs, as well as on those that vary the period during the
mended measure of noise is the maximum peak-to-peak
scan. For digitized instruments, refer to the manufacturer’s
excursion of the indicator averaged over a series of five
manual.
successive intervals, each of duration ten times the integration
1.3 This practice does not cover the measurement of limit-
period. (This measure of noise is about five times the root-
ing spectral bandwidth, defined as the minimum spectral
mean-square noise.)
bandwidthachievableunderoptimumexperimentalconditions.
3.1.4 spectral bandwidth—the wavelength interval of radia-
1.4 This standard does not purport to address all of the
tion leaving the exit slit of a monochromator measured at half
safety concerns, if any, associated with its use. It is the
the peak detected radiant power. It is not synonymous with
responsibility of the user of this standard to establish appro-
spectral slit width, which is the product of the mechanical slit
priate safety and health practices and determine the applica-
width and the reciprocal linear dispersion of the spectropho-
bility of regulatory limitations prior to use.
tometer.
2. Referenced Documents
4. Summary of Practice
2.1 ASTM Standards:
4.1 The pen period and signal-to-noise ratio are set at the
E 131 Terminology Relating to Molecular Spectroscopy
desired values when the instrument is operated with its normal
E 275 Practice for Describing and Measuring Performance
light source and adjusted to read close to 100 % T. The
of Ultraviolet, Visible, and Near Infrared Spectrophotom-
mechanical slit width, or the indicated spectral bandwidth,
eters
required to give the desired signal-to-noise ratio is recorded.
The continuum source is replaced with a line emission source,
such as a mercury lamp, and the apparent half-intensity
This practice is under the jurisdiction ofASTM Committee E-13 on Molecular
Spectroscopy and is the direct responsibility of Subcommittee E13.01on Ultraviolet
bandwidth of an emission line occurring in the wavelength
and Visible Spectroscopy.
region of interest is measured using the same slit width, or
Current edition approved Dec. 15, 1993. Published February 1994. Originally
indicated spectral bandwidth, as was used to establish the
published as E 958 – 83. Last previous edition E 958 – 83 (1989).
Annual Book of ASTM Standards, Vol 03.06. signal-to-noise ratio with the continuum source.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
E958
5. Significance and Use for measuring the spectral bandwidth of ultraviolet/visible
instruments at the levels of resolution encountered in most
5.1 This practice should be used by a person who develops
commercial instruments.All of the lines listed have widths less
an analytical method to ensure that the spectral bandwidths
than 0.02 nm, suitable for measuring spectral bandwidths of
cited in the practice are actually the ones used.
greater than 0.2 nm. The wavelengths of these lines in
NOTE 1—The method developer should establish the spectral band-
nanometres are listed in the first column. Values refer to
widths that can be used to obtain satisfactory results.
measurements in standard air (760 nm, 15°C) except for the
5.2 This practice should be used to determine whether a
two lines below 200 nm. The wavelength for these lines refer
spectral bandwidth specified in a method can be realized with
to a nitrogen atmosphere at 760 nm and 15°C.
a given spectrophotometer and thus whether the instrument is
6.1.1 The second column in Table 1 lists the emitter gas of
suitable for use in this application.
six sources. Only sources operating at low pressure should be
5.3 This practice allows the user of a spectrophotometer to
used, as line broadening can introduce errors. The hydrogen,
determine the actual spectral bandwidth of the instrument
deuterium, and mercury lamps used to obtain these data were
under a given set of conditions and to compare the result to the
Beckman lamps operated on Beckman spectrophotometer
spectral bandwidth calculated from data given in the manufac-
power supplies. The other lamps are all of the “pencil-lamp”
3 4
turer’s literature or indicated by the instrument.
type. A mercury vapor Pen-Ray lamp was used to obtain the
5.4 Instrument manufacturers can use this practice to mea-
data shown in Fig. 1. In many applications the mercury and
sure and describe the practical spectral bandwidth of an
hydrogen (or deuterium) lines suffice.
instrument over its entire wavelength operating range. This
practice is highly prefered to the general practice of stating the
Suitable lamps are available from laboratory supply houses as well as
limiting or the theoretical spectral bandwidth at a single
manufacturers, which include UVP, Inc., 5100 Walnut Grove Ave., P.O. Box 1501,
wavelength.
San Gabriel, CA 91778-1501; Spectronics Corp., 956 Brush Hollow Rd., P.O. Box
483, Westbury, NY 11590-0483; Jelight Co., Inc., 23052Alcalde, Unit E, P.O. Box
2632, Laguna Hills, CA 92653-2632; and BHK, Inc., 2885 Metropolitan Place,
6. Test Materials and Apparatus
Pomona, CA 91767.
6.1 Table 1 lists reference emission lines that may be used Available from UVP, Inc.
TABLE 1 Emission Lines Useful for Measuring Spectral Bandwidth
Reference Line,
Emitter Intensity Nearest Neighbor, nm Separation, nm I /I Weak Neighbor, nm
Neighbor Reference
nm
184.91 Hg 8 194.17 9.26 0.13
194.17 Hg 8 184.91 9.26 0.13 197.33
205.29 Hg 4 202.70 2.59 0.08
226.22 Hg 5 237.83 11.61 0.06 226.03
253.65 Hg 10 . . . 253.48
275.28 Hg 5 280.35 5.07 0.08
289.36 Hg 6 296.73 7.37 0.42
296.73 Hg 8 302.15 5.42 0.04
318.77 He 5 294.51 24.26 0.06
334.15 Hg 7 313.18 20.97 0.70
341.79 Ne 5 344.77 2.98 0.20
359.35 Ne 5 352.05 7.30 0.14 360.02
388.87 He 7 447.15 58.28 0.04
404.66 Hg 8 407.78 3.12 0.04
427.40 Kr 5 431.96 4.56 0.28 428.30
435.95 Hg 9 407.78 28.17 0.02 435.75
447.15 He 5 471.31 24.16 0.04
471.31 He 4 492.19 20.88 0.25
486.0 D . . . .
486.13 H 6 492.87 6.74 0.03 485.66
501.57 He 5 492.19 9.38 0.06
546.07 Hg 8 577.12 31.05 0.04
557.03 Kr 3 587.09 30.06 0.30 556.22
587.56 He 7 706.52 118.96 0.03 667.82
603.00 Ne 5 607.43 4.43 0.54
614.31 Ne 7 616.36 2.05 0.04
626.65 Ne 6 630.48 3.83 0.07
640.23 Ne 7 638.30 1.93 0.11
656.1 D . . . .
656.28 H 7 . . . 656.99
667.82 He 5 706.52 38.70 0.50
692.95 Ne 6 703.24 10.29 0.45
703.24 Ne 7 692.95 10.29 0.06 702.41
724.52 Ne 5 703.24 21.28 0.02 717.39
743.89 Ne 4 724.52 19.37 1.4 748.89
785.48 Kr 3 769.45 16.03 0.7
819.01 Kr 2 811.29 7.72 3.1
E958
signal-to-noise at a given integration period. This is best
accomplished by first establishing the desired period. Next
determine the slit widths required to yield a given signal-to-
noise ratio throughout the region of interest using the standard
continuum source of the instrument. Then use appropriate line
sources to illuminate the monochromator, and record the
spectral bandwidths obtained at the appropriate mechanical slit
widths for the wavelengths in question.
7.1.1 Although the integration period may be indicated on
the instrument or in the manufacturer’s literature, check the
value as follows:
FIG. 1 Comparison of Measured and Calculated Spectral
7.1.1.1 For recording instruments, set the wavelength at any
Bandwidths
convenient position and adjust the 0 and 100 % T controls for
normal recorder presentation. Using 100 % T as the base line,
block the sample beam and measure the time required for the
6.1.2 Relativeintensitydataforthereferencelinesaregiven
pen to reach the 2 % T level (Note 2).
in the third column of Table 1. The data refer to measurements
NOTE 2—The time may be measured with a stopwatch or from the
made with a double prism-grating spectrophotometer equipped
distance the chart moves, if a fast chart speed recorder is being used.
with a silica window S-20 photomultiplier (RCA-C70109E).
Integrationperiodsof1sorlesscanonlybeestimatedbyeithertechnique,
These intensities will be different when using detectors of
but generally this estimate is adequate to determine if the indicated period
different spectral sensitivity. They may also vary somewhat
is approximately correct.
amongsources.Allofthelinesareintenseones,butallmaynot
7.1.1.2 For instruments that can be operated only in the
alwaysbesufficientlyintensetoallowthespectrophotometerto
absorbance mode, follow the same procedure, with the excep-
be operated with very narrow slit widths.
tion that 0 A replaces 100 % T and 1.7 A replaces 2 % T.
6.1.3 Informationonnearestneighborsofappreciableinten-
sity is needed in order to set an upper limit on the measurable 7.1.2 The signal-to-noise ratio is measured as follows:
spectral bandwidth. If the resolution of the instrument in 7.1.2.1 Set the instrument at a convenient wavelength and
question is so poor that two lines or bands of the test source or adjust the pen to read either 100 % T or 0 A. For low-noise
sample overlap, the measured half bandwidth will not indicate levels use an expanded scale, if available.
the spectral bandwidth of the instrument. Very few of the lines
7.1.2.2 Adjust the slit width either to its normal value or to
listed in Table 1 are so well isolated from other lines of a value that gives the desired signal-to-noise ratio.
appreciable intensity that they could always be used without
7.1.2.3 Disengage the wavelength drive, start the chart
interference or overlap. The atomic hydrogen (deuterium) line
drive, and allow the pen to record for at least 2 min or 50
at 656 nm and the very intense mercury resonance line at 253
integration periods, whichever is longer.
nm fall in a category of “isolation,” but in all other cases
7.1.2.4 Divide the recording into five approximately equal
interfering lines are nearby. The nearest neighboring lines
segments and determine the maximum peak-to-peak excursion
having an intensity more than 15 % of the reference lines are
in each segment (Note 3).
given in the fourth column of Table 1. The separation in
NOTE 3—Care should be taken that the noise level is not partially
nanometers between the reference and nearest neighbor lines is
obscured by a detectable recorder dead zone.
listed in the fifth column. In general, lines cannot be used for
a spectral bandwidth test when the spectral bandwidth exceeds
7.1.2.5 Average the five readings to obtain the noise, N.
one half the separation between reference and nearest neighbor
7.1.2.6 If a % T recording is being used, divide 100 by N to
lines.
obtain the signal-to-noise ratio, S/N. If an absorbance record-
6.1.4 To some extent this rule can be modified by the
ing is being used, divide 0.43 by N to determine S/N.
relative intensities of neighbor to reference lines. This ratio,
7.1.2.7 The signal-to-noise ratio should be independent of
I /I , is listed in column 6. Neighboring lines
neighbor reference wavelength for a given source and detector combination, but it
having an intensity less than 15 % of the reference lines will
is advisable to check this point experimentally. For example,
not seriously distort bandwidth measurements. However, to
many instruments are operated with different slit programs in
accommodate the possible situation of sources with intensity
the ultraviolet and visible regions and thus exhibit different
relationships different from that encountered in this study,
signal-to-noise ratios in the two regions.
neighboring lines weaker than 15 % are tabulated in the
7.1.3 Set the period and signal-to-noise ratio to the values
seventh column under the heading “weak neighbor.”
used in 7.1.1 and 7.1.2, scan to the wavelength of interest (see
Table 1), and record the resulting mechanical slit widths or
7. Procedure
spectral bandwidth (Note 4).
7.1 Instruments with Servo-Operated Slits—These instru-
NOTE 4—It may be desirable to scan the entire wavelength range of the
ments maintain a constant period and signal-to-noise ratio as
instrument and record the slit width at suitable intervals so that a curve of
wavelength is automatically scanned. The determination of
slit width versus wavelength may be constructed (usually 25- and 50-nm
practical spectral bandwidth requires a preliminary determina-
intervals are satisfactory for the ultraviolet and visible regions, respec-
tion of the mechanical slit width necessary to yield a given tively).
E958
emitted by this lamp in this region. As slits are widened the continuum
7.1.4 Measure the spectral bandwidth of the instrument as
signalincreaseswiththesquareoftheslitwidth,whilethepeaklinesignal
follows:
increases linearly with slit width.
7.1.4.1 Position the appropriate line source so that it illumi-
The neighboring 302-nm line is clearly evident. It introduces a small
nates the entrance slit of the monochromator (Note 5). The
error into the measured spectral bandwidth when the spectral slit width
positioning
...

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