Describing and Specifying The Spectrometer of An Optical Emission Direct-Reading Instrument
Describing and Specifying The Spectrometer of An Optical Emission Direct-Reading Instrument
1. Scope
Terminology 3
1.1 This guide covers features of a spectrometer or poly- Background Equivalent Concentration (BEC) 3.2.1
chromator used for optical emission, direct-reading, spectro- Channel 3.2.2
chemical analysis. A polychromator in this sense consists of a Readability 3.2.3
Scattered Radiation 3.2.4
spectrometer with an extended and fixed wavelength range and Shot Noise 3.2.5
an array of fixed exit slits to isolate the spectral lines of the White Light Precision 3.2.6
elements to be measured. Working Resolution 3.2.7
Fundamental Spectrochemical Objectives 5
1.1.1 This guide does not apply to direct-reading systems Accuracy 5.2
that employ echelle spectrometers and vidicon or other detec- Precise Photometry 5.2.1
tors where the design parameters are quite different. Bias in Photometry 5.2.2
Detection and Determination Limits 5.3
1.2 This guide covers only the optical portion of the Minimization of Interference 5.4
instrument, from excitation stand to photomultipliers. Parameters of Spectrometer and Associated Components 6
1.2.1 Only general statements are made about source units. Dispersion, Reciprocal Linear 6.2
Working Resolution 6.3
1.2.2 Photomultipliers are included to the extent that they Speed or Radiation Throughput 6.4
are mounted within the spectrometer to convert optical inten- White Light Precision 6.5
sities to electrical signals, and establish the instrumental Scattered Light 6.6
Slits 6.7
precision of each channel as a light measuring device. Readout Accuracy of Positioning Exit Slits 6.7.3
systems are not included. Wavelength Coverage and Focal Curve Length 6.8
1.3 It is not the purpose of this guide to establish binding Secondary Optics 6.9
Optical Stability 6.10
specifications or tolerances, but rather, to call attention to Spectrometer Illumination 6.11
important parameters that manufacturers should include in Astigmatic Image 6.12
their literature, to provide methods for measuring those param- Excitation Stands 6.13
Vacuum Systems 6.14
eters, and to assign values that are indicative of acceptably Flushing With Transparent Gas (Nitrogen) 6.15
good performance. Because of the great variety of demands Other, Including Maintenance Features 6.16-6.18
imposed by spectrochemical techniques, rigid performance Measuring Specified Polychromator Parameters 7
Working Resolution 7.1-7.4
criteria are not feasible. Line Interference 7.5
1.4 The values stated in SI units are to be regarded as the White Light Precision 7.6
Scattered Light 7.7
standard. Optical Alignment and Focus 7.8
1.5 This standard does not purport to address all of the Optical Stability 7.9
safety problems, if any, associated with its use. It is the Precision and Accuracy 7.10
Describing the Spectrometer in Analytical Methods 8
responsibility of the user of this standard to establish appro- Wavelength Coverage and Reciprocal Dispersion 8.2.1
priate safety and health practices and determine the applica- Working Resolution 8.2.2
bility of regulatory limitations prior to use. Entrance and Exit Slit Widths 8.2.3
Low Concentrations 8.2.4
1.6 A partial listing of the information in this guide includes High Concentrations 8.2.5
the following: Varying Parameters on Working Resolution and Throughput Appendix X1
Section Dispersion X1.2
Size of Spectrometer X1.3
Effects of Slit Widths X1.4
Recommended Spectral Lines for Measuring Working Reso- Appendix X2
1
This guide is under the jurisdiction of ASTM Committee E01 on Analytical ution
Chemistry for Metals, Ores, and Related Materials and is the direct responsibility of Photographic Speed Versus Photoelectric Throughput Appendix X3
Subcommittee E01.20 on Fundamental Practices. Photographic Speed X3.1
Current edition approved June 10, 2003. Published September 2003. Originally Polychromator Radiation Throughput X3.2
Calculation of Radiation Throughput X3.3
approved in 1993. Last previous edition approved in 1998 as E 1507 - 98.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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E 1507 – 98 (2003)
Typical Radiation Throughputs X3.4 measured with sharp spectral lines and may be finer than the
practical resolution imposed by the source conditions required
2. Referenced Documents for actual determinations.
2.1 ASTM Standards:
E 135 Terminology Relating to Analytical Chemistry for 4. Significance and Use
Metals, Ores, and Related Materials2 4.1 Direct-reading polychromators are instruments com-
E 172 Practice for Describing and Specifying the Excitation monly used for multi-element spectrochemical analysis. This
Source in Emission Spectrochemical Analysis3 guide seeks to describe those aspects of such instruments that
E 356 Practices for Describing and Specifying the Spec- are of significance in achieving useful spectrochemical perfor-
trograph4 mance. Awareness of parameters described in this practice will
E 380 Practice for Use of the International System of Units make manufacturers cognizant of factors they should consider
(SI) (The Modernized Metric System)5 in designing instruments, assist purchasers of instruments in
E 520 Practice for Describing Photomultiplier Detectors in making intelligent comparisons of competing designs, and
Emission and Absorption Spectroscopy2 make users aware of the compromises they must make in
E 876 Practice for Use of Statistics in the Evaluation of performing particular determinations.
Spectrometric Data2
4.2 Adequate description of spectrometers permits forming
3. Terminology qualified appraisals on three important performance character-
istics: accuracy of analysis, detection limits, and freedom from
3.1 Definitions—For definitions of terms used in this guide,
line interferences.
refer to Terminology E 135.
3.2 Definitions of Terms Specific to This Standard:
5. Fundamental Spectrochemical Objectives
3.2.1 background equivalent concentration (BEC)—the
concentration of an element at which the signal due to the 5.1 The analyst is interested in three important performance
analytical line is equal to the signal from a specimen with zero characteristics of an overall direct-reading system: precision,
concentration of that element. particularly in how it affects the accuracy of a signal; detection;
3.2.2 channel—the combination of exit slit and photomul- and freedom from or minimization of interferences.
tiplier positioned to receive the radiation of a specific spectral 5.2 Accuracy depends on precision and the absence of bias.
line. It includes any mirror, refractor plate, filter, or other items In a spectrometer, accuracy depends on the precision of
in the exit optical path. photometric measurement with minimal bias introduced by
3.2.3 readability—the minimum difference between signals scattered radiation or line interference.
that can be perceived or distinguished. 5.2.1 Precise photometry is the ability to closely repeat
NOTE 1—Readability is of concern for earlier direct-reading spectrom- readings from the excitation of a homogeneous specimen on
eters that use analog or digital voltmeter displays. For direct-reading both short term and long term applications.
spectrometers that are interfaced with a computer, readability is replaced 5.2.1.1 Short term, and particularly long term, precision are
by standard deviation. improved by the use of wide slits and with a marked difference
3.2.4 scattered radiation—that portion of the reading result- between the widths of the entrance and exit slits. These
ing from radiation at wavelengths different from the wave- conditions conflict with the requirements for sensitivity and
length being measured, as a result of scatter by the dispersing freedom from interference.
medium or by surfaces within the spectrometer. 5.2.1.2 Precision is improved by a compact, rugged spec-
3.2.5 shot noise—the minimum deviation in the measure- trometer construction that remains stable despite severe me-
ment of a signal due to the discreteness of the events being chanical vibration. Long term precision may require either a
observed. In an optical emission spectrometer, the “events” are temperature-controlled spectrometer, a closely regulated tem-
photons hitting a photomultiplier. Since the minimum standard perature in the laboratory, or a spectrometer construction that
deviation of the detection of photons is the square root of the adjusts or compensates for shifts in the spectrum that occur as
total available photons, relative standard deviation is reduced a result of changes in ambient temperature. In an air spectrom-
as the signal intensity increases. eter, atmospheric pressure can have a small effect on stability
3.2.6 white light precision—the relative standard deviation and precision.
of at least ten readings from a channel, either as an absolute 5.2.1.3 An important factor in short term stability is the
intensity or as a ratio to an internal standard channel, when “white light precision” for each of the channels. See descrip-
exposed to a stable radiation source. tion of white light in 6.5 and its precision measurement in 7.6.
3.2.7 working resolution—the ability of an exit slit to isolate This precision is limited by the stability of the photomultipli-
the spectral line being measured from possible nearby inter- ers. Frequently the most stable tubes are the least sensitive.
fering lines of other elements. Working resolution can only be 5.2.1.4 Analytical precision depends on excitation condi-
tions and specimen homogeneity, which are outside the scope
of this practice. Practice E 172 describes applicable excitation
2
Annual Book of ASTM Standards, Vol 03.05. source units. See also 5.4.1 on spectral interference.
3
Discontinued. See 2000 Annual Book of ASTM Standards, Vol 03.05.
4
Discontinued. See 2000 Annual Book of ASTM Standards, Vol 03.06. 5.2.2 Bias in photometry signals can be minimized by
5
Replaced by IEEE/ASTM SI - 10, developed by Subcommittee E43.10. spectrometer design and selection of spectral lines.
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E 1507 – 98 (2003)
5.2.2.1 Scattered radiation can be reduced by having fewer dispersion at a wavelength critical to an application. For
components in the optical paths of radiation passing through example: Reciprocal linear dispersion at 3000 Å: in the first
exit slits by dulling neutral surfaces or by masking. order, 4.1 Å/mm; in the second order, 2.0 A/mm.
5.2.2.2 Bias is minimized when a selected analytical line NOTE 2—The angstrom is a depreciated unit according to Practice
shows an optimum response to changes in a concentration of E 380, but is used throughout this guide because the most common
the element of interest, with little effect from other elements. wavelength tables employ angstroms. One Å = 0.1 nanometre.
5.3 Detection and determination limits, which are discussed
in Practice E 876, are favored by: 6.3 Working Resolution—The resolving power of the spec-
5.3.1 Improvement in the precision with which the overall trometer has little bearing on the ability of the instrument to
signal plus background can be measured and distinguished separate an analytical line from a nearby interfering line.
from the background alone. Frequently it will seem to indicate a performance as much as
5.3.2 A higher signal-to-background ratio. Although im- ten times better than can be achieved in practice. The more
provement in the ratio may be realized by the use of narrow appropriate term is working resolution, expressed as the
slits, this may adversely affect precision and stability. half-width of a line, as described and illustrated in 7.1. If there
5.3.3 Use of the most sensitive analytical line for each is a significant difference, the half-width should be specified at
element. the center and ends of the focal curve. Parameters that affect
5.3.3.1 In some cases, the most sensitive line of an element working resolution are discussed in X1.2.2 and X1.3, and X1.4.
may have an interference from a strong line of another element. Recommended spectral lines for measuring working resolution
In these cases, the best practical detection may be obtained by are given in Appendix X2.
using weaker emission lines that do not suffer from interfer- 6.3.1 A specification for working resolution might be: the
ence. half-widths listed below were obtained with a flat specimen of
5.3.3.2 For some sets of elements, access to all the desirable low alloy steel, excited by a 5 A, dc arc in air, with entrance
emission lines may require an extended wavelength range, and exit slits of 25 and 50 µm, respectively:
which involves either reduced dispersion, a broader focal Wavelength: 1930 Å 3110 Å 4358 Å
Half-Width: 0.20 Å 0.35 Å 0.45 Å
plane, or auxiliary monochromators, or spectrometers. Re-
duced dispersion may impair detection. 6.4 Speed or Radiation Throughput—It is a common mis-
5.4 Minimization of Interference—Interference in the signal conception that a spectrometer with a high aperture ratio or
of a particular element may occur due to neighboring lines of radiation throughput will yield improved detection. Measure-
other elements or molecular species. Interference may be ment precision, however, which does affect detection, requires
reduced by the use of narrow slits or higher dispersion. Narrow an adequate radiation throughput. The various factors that
slits, however, may affect photometric precision and detection. determine the radiation throughput of a polychromator are
5.4.1 Different types of excitation sources can enhance or described in Appendix X3. An interrelation of working reso-
suppress certain spectral interferences on identical spectrom- lution and throughput is discussed in Appendix X1.
eters. A practical evaluation of a direct-reading instrument 6.4.1 Radiation throughput varies from channel to channel,
must consider excitation conditions. See also 5.2.1.4 on ana- due primarily to the combination of entrance and exit slit
lytical precision. widths and the blaze of the grating, but the signal that is
5.5 Analytical Compromises—The individual parameters of obtained from a channel depends more on the characteristics of
a spectrometer are closely interrelated, and there is no one best an individual photomultiplier than on the optical system. For
general solution. The characteristics may be modified to suit optimum detection, the selection of a photomultiplier and the
the intended application. voltage used to drive it must produce a signal of sufficient
magnitude that the standard deviation of the background can be
6. Parameters of Spectrometers and Associated measured. See Note 1 on readability.
Components That Affect Spectrochemical Performance 6.5 White Light Precision—The manufacturer should
6.1 Parameters Manufacturers Should Specify—Since specify the guaranteed relative standard deviation in the
many parameters are difficult for a user to determine, but are measurement of ten or more exposures to “white light”
well-known to the manufacturer, manufacturers should include consisting of a stabilized source of undispersed radiation or
them in their instrument specifications. Most of the specifica- dispersed continuous radiation for all channels. In measuring
tions listed in Practice E 356 are germane to direct reading these exposures, there must be sufficient signal averaging that
spectrometers. These include type of mounting, type of dis- shot noise in the source does not contribute significant varia-
persing element, dispersion, resolution, speed, slits, wave- tion. For example: The white light precision for all channels
length coverage, illumination, and astigmatism. Some specific will be equal to or better than 0.3 % RSD.
details on these follow: 6.6 Scattered Light—Radiation scattered within the spec-
6.2 Dispersion—Reciprocal linear dispersion, expressed as trometer will increase an apparent reading. This will have two
angstroms per millimetre (Å/mm), is an important characteris- effects: (1) It will reduce the signal to background ratio and (2)
tic that determines the analytical performance of a polychro- it will give false readings for the sought element when
mator, and should be specified in all analytical methods. All specimens are analyzed that produce strong emission at the
gratings display small changes of dispersion for different scattering wavelengths.
wavelengths. The calculation of dispersion is described in 6.6.1 Scattered light may be classified as being near, from
X1.2. Specify diffraction order as well as the reciprocal linear wavelengths within 100 times the working resolution, or far,
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from wavelengths removed from the wavelength being mea- Profiles will agree within 0.02 Å when the top half, bottom
sured by more than 100 times the working resolution. half, or full slit are separately profiled.
6.6.2 Far scattered light tends to be most severe in the 6.7.3.3 State the mechanism provided to center the exit slits
extreme ultraviolet, while near scatter may be significant at all on the spectral lines. If applicable, state the mechanism
wavelengths. The far scatter usually can be measured easily, provided to align the exit slits parallel to the spectral lines.
whereas near scatter is difficult to distinguish from true spectral 6.8 Wavelength Coverage and Focal Curve Length—The
background. total wavelength range in angstroms and the useful focal curve
6.6.3 Scattered light is difficult to measure without elaborate length in millimetres in any fixed setting should be stated. For
equipment such as tuneable lasers and detectors with very wide example:
dynamic range. Therefore, it is recommended that the specifi- Wavelength Range: 1600–5000 Å, first order, over 810 mm at 4.1 Å/mm;
cation of scattered light be based on measurements of specific 1680–2500 Å, second order, over 410 mm at 2.0 Å/mm.
chemical mixtures, in which one element is present in large 6.8.1 The relationship between the size of a spectrometer
excess such that its emission lines give rise to detectable (diameter of the focal circle) and the reciprocal linear disper-
scattered light at the analytical wavelengths of other elements. sion, and the effect on throughput is discussed in X1.3.
In a practical sense, scattered light acts like a line interference, 6.9 Secondary Optics from Exit Slits to Photomultipliers:
and can be defined and treated as such if it has a significant
6.9.1 Specify any cylindrical or plane splitting mirrors,
effect on the determination of an element.
focusing mirrors, diffusers or filters, and physical placement of
6.6.3.1 For elements that exhibit a linear calibration, a a photomultiplier in the focal plane.
simple statement of the limit of the effect of scattered light will
6.9.2 State the maximum number of detectors and exit
be independent of the actual concentration. For example, with
optical assemblies that can be installed on the focal curve.
a linear calibration of arsenic, it might be stated that the
scattered light at arsenic 1971 Å will not exceed the equivalent 6.9.3 List the type of photomultipliers used for specific
of 3 ppm arsenic when a sample containing 1000 ppm calcium wavelength ranges. (See Practice E 520.)
is burned in a dc arc. 6.9.4 Describe how the photomultiplier sockets divide the
6.6.3.2 When scattered light affects an element which has a voltage between the dynode stages. State if the gain change is
non-linear calibration, the effect must be stated for a specific continuous, and over what range.
concentration of the element being measured. For example, for 6.9.5 Describe any provision to measure the total radiation
the analysis of copper in a ferrous material which can contain from the analytical gap, through a second entrance slit, by
up to 5 % chromium, it could be stated that the effect of observing the zero order reflection from the grating, or by other
scattered light at copper 2136 Å will not exceed the equivalent means.
of 0.05 % copper when the chromium is at 5 % and the 6.10 Optical Stability:
concentration of copper is 0.8 %. The higher amount would 6.10.1 Design Features—Describe the mechanism for com-
have to be acknowledged even though a specimen with no pensating for overall shift of the spectrum, and for changes in
copper may appear to not exceed the equivalent of 0.02 % dispersion caused by changes in ambient temperature and
copper for the same concentration of chromium. The difference pressure (in an air spectrometer). For example: The design and
is due to the change in the calibration slope at a higher copper mechanism for compensation of temperature changes consist
concentration. of alignment servos, using a slit scan, or refractor plate in
6.7 Slits—The combined effect of entrance slits and exit tilt/normal configuration.
slits affects resolution and output as described in X1.4. 6.10.2 Temperature Limits—Specify the temperature limits
6.7.1 Entrance Slit—Specify whether it is fixed or adjust- and rate of temperature change which must not be exceeded if
able, and the width or widths available. For example: A fixed the polychromator is to retain 95 % of its normal response at
slit, 20 µm wide, is standard. the extremes of the wavelength range. For example, in Fig. 1
6.7.2 Exit Slits—Specify the following: the response drops from 910 to 865 arbitrary intensity units
(95 %) for a displacement of 13 µm. If the coefficient of
6.7.2.1 Whether the slit directly faces the grating or is
thermal expansion of the spectrometer is 4 3 10−6 m/°C and
tangential to the focus circle,
the focal curve diameter is 1 m, a 1° temperature change will
6.7.2.2 Normal slit widths and special widths available, and lengthen or shorten the focal curve by 4 3 10−6 m or 4 µm;
6.7.2.3 Limitation on the spacing between exit slits: that is, then a temperature drift of 13 µm/(4 µm/°C) or '3°C is
the minimum wavelength spacing, in angstroms. allowable.
6.7.3 Accuracy of Positioning Exit Slits: 6.10.3 Profiling Mechanism—State the means for moving
6.7.3.1 Concentricity—Specify the accuracy, in angstroms, the spectrum across the array of exit slits, such as by movement
with which spectral lines will be centered on their exit slits of the entrance slit at right angles to the optical path or along
relative to a mercury or other monitor line. For example: Exit the focal curve, by rotation of a refractor plate, or by rotation
slits will be aligned with their respective lines to within 0.03 Å of the grating. In some early direct-reading spectrometers,
of their peak obtainable setting when the mercury 4358 Å sections of slit frames were able to be shifted.
monitor line is in peak alignment. 6.11 Spectrometer Illumination—The condensing system
6.7.3.2 Parallelism—If applicable, state the degree to which normally supplied by the manufacturer for routine quantitative
exit slits will be held parallel to spectral lines. For example: work shall be specified with respect to:
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6.12.1 Lower detection limits may be achieved by looking
at a specific level in the analytical gap. This may be done with
a stigmatic polychromator by focusing the light source on the
entrance slit and using an aperture at the appropriate exit slit.
This is awkward to do in an astigmatic instrument, because the
Sirk’s focus, that is, that position in front of the entrance slit
where an aperture must be located to be in focus at the exit
slits, is usually some distance in front of the entrance slit and
changes with wavelength.
NOTE 3—Even though it may not be practical to work at the Sirk’s
focus, enhancement of line to background may be achieved in an
astigmatic mount by setting the analytical gap either above or below the
central optical plane.
6.12.2 If a spectrometer design achieves a stigmatic image,
or if the condensing system permits a spatial resolution in the
analytical gap, the arrangement should be described.
6.13 Excitation Stands—Describe the types of stands that
are available for holding and exciting specimens, such as the
following:
6.13.1 Flat specimen stand, for air operation,
6.13.2 Gas-flushed, flat specimen stand,
6.13.3 Gas-tight, gas-flushed, flat specimen stand,
FIG. 1 Typical Line Profiles and Overlaps, Illustrating Working
Resolution 6.13.4 Pin specimen stand, for air operation,
6.13.5 Gas-flushed, pin specimen stand, and
6.11.1 Omni Illumination—Accepting radiation from all 6.13.6 Rotating disk, liquid sample stand.
areas of the analytical discharge. 6.14 Type of Vacuum System for Wavelength Coverage
6.11.2 Selective Illumination—Accepting radiation only Below 1900 Å Only (See 6.15 for an alternate way to work
from selected areas of the analytical discharge. below 1900 Å.):
6.11.3 Exclusive Illumination—Accepting radiation from all 6.14.1 Type of pump: diffusion, mechanical, or turbomo-
parts of the analytical gap except selected areas, such as hot lecular.
electrode tips. 6.14.2 Type of vacuum gages supplied and where located.
6.11.4 Optical Material—Quartz or fluorite. State if there 6.14.3 Protection against back-streaming.
are any coatings on optics. 6.14.4 Provision for shutting off high voltage on photomul-
6.11.5 Types of Lenses or Mirrors—Spherical, parabolic, tipliers when the spectrometer is under partial vacuum. This
ellipsoidal, cylindrical, or crossed cylindrical. State apertures safety provision is not needed if photomultiplier receptacles are
and focal lengths at specified wavelengths. State where a lens not in the evacuated chamber.
is placed. 6.14.5 Pump down time required.
6.11.6 Analytical Gap: 6.14.6 Ultimate vacuum expected if no gas is bled into the
6.11.6.1 State where the analytical gap is focused: on the vacuum chamber. Provision, if any, to allow argon or nitrogen
grating, on the slit, or if there is no focus (without lens). to bleed into the chamber to keep a focusing lens clear.
Specify the dimensions of the illuminated area at the dispersing 6.14.7 Provisions for isolating the evacuated chamber from
element. Specify the dimensions of the analytical gap sampled: the pump either by choice or automatically in the event of a
at the extreme wavelength of the polychromator; and at the pump failure. This may include provision for bleeding air to
wavelength at which the ideal focusing is achieved, which is the pump.
the smallest area of the analytical gap that can be sampled. 6.14.8 Safety features.
Indicate the extent of optical aberrations and their wavelength 6.15 If the spectrometer can be flushed with a transparent
dependence. gas, such as nitrogen, which permits an alternate way of
6.11.6.2 Indicate the axis of the analytical gap with respect working in the far ultra-violet region, specify how the gas
to grooves of the grating. flushing is controlled and how long it takes to displace air from
6.11.6.3 Indicate the effect on signal of offsetting the ana- the spectrometer.
lytical gap from the optical center line by 2 mm or other 6.16 Physical Size and Weight—Include overall size and
specified distance in both horizontal and vertical planes. weight, and distribution of weight on each foot of spectrometer.
6.12 Astigmatic Image—Most direct-reading polychroma- 6.17 Service Requirements—Electrical power, water cool-
tors employ concave gratings in some form of Rowland circle ing, gas supplies, and so forth.
mounting, which means that the images are astigmatic. The 6.18 Other Features:
line images are considerably longer than the entrance slit. 6.18.1 Specify whether a fatigue light is needed or supplied.
However, this normally is compensated for by the use of tall 6.18.2 Photographic capability (if any).
exit slits and photocathodes, so that little light is lost. 6.18.3 Maintenance Features:
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6.18.3.1 Cleaning of Entrance Optics—In a vacuum spec- 7.1.3.5 Continue the process for at least the following
trometer, either specify that the entrance optics can be cleaned settings in multiplies of the slit width:
without breaking the working vacuum, or indicate the pump- −2.0, −1.0, −0.6, −0.4, −0.2, 0, 0.2, 0.4, 0.6, 1.0, 2.0
down time required to return to a working vacuum.
6.18.3.2 Cleaning of excitation stand. 7.1.3.6 Plot the readings on linear graph paper, similarly as
NOTE 4—The frequency of cleaning is obviously of great interest to the shown for Curve A in Fig. 1.
user, but depends on the specific application: oil analysis with a rotating 7.1.3.7 Draw a smooth, symmetrical curve that best fits the
disk, analysis of zinc die castings for residual elements with an ignited arc points, even though the curve may not go through several
in air, analysis of steel in an argon-flushed Petrey stand, and so forth. The points.
entrance lens in a vacuum spectrometer may be vulnerable to becoming 7.1.3.8 Draw a baseline between the −2.0 and +2.0 points.
coated with polymerized oil from vacuum pump vapors.
For a line used to specify working resolution, this baseline
6.18.3.3 Ease of access to, and adjustment of components. should be approximately horizontal.
6.18.3.4 Protection, if any, to prevent exposure of photo- NOTE 6—Interfering lines may lead to distortion in the baseline.
multipliers to room light while they are powered with high
voltage. 7.1.3.9 Halfway between the peak and base line reading
under the peak, draw a horizontal line, intersecting the profile
7. Measuring Specified Polychromator Parameters curve.
7.1.3.10 The length of this line between the intercepts,
7.1 Measuring Working Resolution—Curve A of Fig. 1 converted to angstroms, is the half-width that is used to specify
illustrates how to interpret the plot of a dynamic profile of a the working resolution. In Fig. 1, the half-width measures 60
spectral line of an element to obtain the line half-width that is µm at a reciprocal linear dispersion of 5.6 Å/mm; therefore,
used as a measure of working resolution. The data are easy to after converting the half-width to millimetres, the working
obtain on most direct-reading spectrometers. resolution is 0.06 mm multiplied by 5.6 Å/mm or 0.34 Å.
7.1.1 Suitable spectral lines and the approximate concentra- 7.2 Improving Working Resolution—Working resolution is
tions appropriate for several sources are listed in Table X2.1 of enhanced by the following factors:
Appendix X2. 7.2.1 Increased linear dispersion (a lower number for the
7.1.2 Possible specimen-source combinations are as fol- reciprocal linear dispersion),
lows: 7.2.2 A narrower entrance slit. This will have little effect if
7.1.2.1 A pin or Petrey stand with low alloy steel, alumi- the entrance slit is narrower than the exit slit,
num, brass, or other convenient specimen, which may contain 7.2.3 A narrower exit slit. This will have a marked effect if
several of the elements for which the spectrometer has exit the entrance slit is narrower than the exit slit. See X1.4 for a
slits. To avoid broadened lines, the specimen may be excited discussion of the effect of slit widths on working resolution,
with a unidirectional-capacitor discharge, using currents that 7.2.4 Better focus for the line,
are less than 5 r-f A, with the highest inductance and capaci- 7.2.5 Reduced optical aberration for the line, and
tance available on the source unit. 7.2.6 Improved alignment of the exit slit with the line, both
7.1.2.2 A rotating-disk, vacuum cup or porous cup solution for concentricity and for parallelism.
stand, with spark or arc excitation.
7.1.2.3 A pin stand with 6 mm (0.25 in.) diameter low-alloy NOTE 7—Excitation conditions will affect the determination of working
steel rods, excited with a stabilized dc arc of less than 2 A, after resolution. For example, the lithium 6707 Å line, when excited in a high
current dc arc, may have a Doppler width even greater than 1 Å; and due
establishing a bead on the lower, anode rod. to Lorentz broadening, the calcium 3933 Å has a large width that
7.1.2.4 Hollow-cathode lamps, which typically give line contributes to stray light and background far from the line center.
widths of 0.05 Å or less, are recommended for determining However, most iron lines in a dc arc below 3 A will have line half-widths
working resolution that is expected to be better than 0.2 Å. less than 0.1 Å. The latter will give a more accurate measurement of the
7.1.3 Procedure: potential working resolution.
7.1.3.1 Make a conventional burn, at the setting of the 7.3 Importance of Working Resolution—In general, a state-
adjusting mechanism at which the line is in profile. ment of working resolution will help to predict other element
7.1.3.2 Adjust the photomultiplier dynode or other gain interferences. The greatest uncertainty will be due to unreli-
adjustment or the exposure time, to keep the absolute intensity ability in the tabulated relative intensities for lines of different
reading on scale, but at least five times what the background elements, obtained with various types of excitation sources.
reading is expected to be. 7.4 Applying Working Resolution—Curve B of Fig. 1 shows
7.1.3.3 Offset the adjusting mechanism to the minus side of the profile reading that would be obtained at Slit A if there were
the peak setting by two times the exit slit width (or the entrance a line from some other element, B, with the same intensity,
slit width if it is wider). displaced by the half-width of 60 µm or 0.34 Å. If there were
7.1.3.4 Make a normal burn and note the absolute intensity no signal from Element A, the signal produced by Element B
reading for the line. If several lines are to be measured, note the at the peak position for A would be about 68 counts, compared
readings for all the slits involved. to 910 counts for A alone, or approximately 7.5 %. Although
NOTE 5—Absolute intensities, rather than intensities ratioed to an there remains a small contribution of signal from B observable
internal standard, should be used in profiling to avoid changing two on A, the lines may be considered to be resolved from each
variables simultaneously. other. If Element B were 90 µm from A (that is, 1.5 times the
6
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half-width), its contribution would be about 16 counts, or less the copper line is separated from the phosphorus line by only
than 2 %. The actual interference from a nearby line will 0.14 Å and from the nickel line by only 0.08 Å, there is
depend on: potential for interference from both lines. See Table 1 for
7.4.1 The difference in wavelength, which usually can be relative intensities.
determined from wavelength tables. 7.5.1.1 For a capacitor discharge, the spark relative intensi-
ties are more significant. The phosphorus lines in a spark-like
source have greater sensitivity than the tables indicate. The
rated intensities in the MIT Tables (8) indicate that the copper
line is going to present a problem, but since the nickel is
unlisted, it would appear that it should be insignificant at low
nickel concentration. However, in stainless steel, where nickel
may run from 7 to 25 %, it may have a measurable effect.
Experimentally, 1 % nickel has been found to be equivalent to
0.0020 % phosphorus.
NOTE 8—Tungsten has lines at 2149.85 Å, which make phosphorus
2149.11 A useless in tungsten tool steels.
7.5.2 Interference from Broad Line “Wings”—Wide lines,
usually identified by h, R, r, W, or w in tables, can have wings
that extend to several angstroms on either side, producing
interference or an unexpectedly high background. Such an
effect is illustrated in Fig. 3, showing a profile for zinc I 2138
Å. In terms of the zinc profile contour, the background looks
insignificant. However, if the tellurium 2142 Å line is profiled
with a specimen of 0.2 % tellurium in a brass matrix, using a
NOTE—Phosphorus 2149.11 Å is a barely perceptible shoulder on top of
the copper and nickel line wings.
capacitor discharge in argon, the background rises continually
FIG. 2 Example of Line Interferences toward lower wavelengths, which is due to the zinc 2138 Å
line.
7.6 Determining White Light Precision:
7.4.2 The relative intensities of the analytical and interfer- 7.6.1 To measure the white light precision of a channel, it is
ing lines under the excitation conditions used. Some idea of the necessary to have either a line source, such as a mercury lamp,
basic intensity of the interfering line can be obtained from the which is not dispersed by the grating, or a continuous source,
intensity rating of the line in the wavelength tables and an such as a deuterium or tungsten filament lamp or a
appraisal of how much the excitation conditions being em- radioisotope-activated phosphor. Frequently the fatigue lamp,
ployed are arc-like (neutral species) or spark-like (ionic spe- which illuminates the photomultiplier tubes between expo-
cies). These listings do not reflect the wide variations of sures, will provide a suitable light source. The source should be
excitation conditions employed and the wide variations in operated from a regulated power supply, so that it is stable to
sample matrices encountered in practical analyses. At least for 0.05 %. The readout system must be wired to permit integrated
a controlled 10 A dc arc and for a 0.1 atomic percent of an exposures when the light source is substituted for a normal
element in either copper or silver, the NBS (now NIST) values specimen burn. If absolute intensities are employed in the
have consistency (1).6 For intensity measurements for select analytical procedure, they should also be used in determining
lines of the rare earths, methodology is included in Boumans the white light precision, which then is limited by the stability
(2,3) and applications are in Boumans (4-6). Formulae for of the light source (and of the high-voltage supply for the
calculating departures from Maxwell-Boltzman equilibrium photomultipliers). If intensity ratios are employed analytically,
for inductively-coupled plasmas and direct-current plasmas intensity ratios may be used in this test for the analytical
appear in Burton and Blades (7). channels. This will compensate for any slight fluctuations in
7.4.3 The concentration of the interfering element, which lamp output.
normally can be predicted from the nature of the unknown 7.6.2 Run ten or more repeat exposures, and calculate
samples. standard deviation and relative standard deviation. (See Prac-
7.5 Line Interference: tice E 876.)
7.5.1 Fig. 2 shows profiles obtained for phosphorus 2149.11
Å, the element to be analyzed, and two interfering lines, copper TABLE 1 Listed Intensities for an Analytical Line and Potential
2148.97 Å and nickel 2149.03 Å, produced using a triggered- Interfering Lines
capacitor discharge and a low alloy steel specimen. The Wavelength, MIT TablesA NBS TablesB
Element
half-width of the phosphorus line in the second order at 2.7 Å Arc Spark Arc
Phosphorus 2149.11 15 2600
Å/mm, measured with a slit width of 65 µm, is 0.18 Å. Since Copper 2148.97 15 25 unlisted
Nickel 2149.03C unlisted unlisted
A
See Ref (8).
6 B
The boldface numbers given in parentheses refer to a list of references at the See Ref (1).
C
end of the text. See Ref (9).
7
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position of 3946 Å), only the calcium 3968 Å line could be
considered as being far scatter, since the calcium 3934 Å line
could now exhibit near scatter. See 7.7.5. (The photomultiplier
will be directly sensing the background in the second order, as
well as scattered light.)
7.7.4 Scattered light becomes a significant factor only when
the spectral background level becomes extremely weak. With
spectral background levels normally encountered with a spark
or even a dc arc or plasma, it may be difficult to detect scattered
light.
7.7.5 Near scattered light is difficult to distinguish from a
true increase in the spectral background due to a change in the
matrix. If aluminum is being measured at 3961 Å and Speci-
men A, with negligible amounts of aluminum and calcium,
produces a reading of 75, while Specimen B, with 1000 ppm
calcium and negligible aluminum, produces a reading of 300,
FIG. 3 Far Wing Interference of Zinc on Tellurium
the increase might be due either to near scattered light or to a
true increase in background at wavelengths near the calcium
7.6.3 The white light test is a powerful diagnostic tool since ion lines at 3934 Å and 3968 Å.
it checks the precision of each channel as a light measuring 7.7.5.1 If available, the output from a monochromator,
device. If the white light results are favorable, but the analyti- preferably a double monochromator with a bandpass narrower
cal results are poor, the problem could be: inhomogeneity of than 5 Å, can be used to irradiate the spectrometer being tested.
the specimens, erratic excitation by the source unit, an optical By directing the radiation of the specimens through the
system which produces erratic illumination, or vibration in the monochromator set to pass 3961 Å, the signal for aluminum
spectrometer which affects the stability of alignment of the will certainly be reduced, but the new measurements of
spectral lines with slits. Specimens A and B will show show whether the signal for B
NOTE 9—A white light test is not affected by alignment of slits on has been reduced relative to A. To the extent that it has not, it
analytical lines. must be assumed that the calcium may have introduced a true
increase in background, even at some distance from the
7.7 Measuring Scattered Light:
interfering calcium lines.
7.7.1 Scattered light can be the result of defects in the
dispersing and focusing elements. With a grating, minute 7.7.5.2 In a given polychromator, once the best available
irregularities in the spacing of the grooves will result in dispersing element has been used and the greatest care has been
scattered light. taken to shield the photomultiplier from any light that has not
7.7.2 Light can be scattered from various surfaces within the passed through the exit slit, there is no other way to reduce the
spectrometer, or there may be cracks in the spectrometer reading for a blank. If a specimen free of the analyte element
housing which permit some room light to enter the spectrom- but otherwise composed of high concentrations of typical
eter. matrix elements produces higher readings than a less complex
7.7.3 Far scattered light can be measured by employing a reagent blank, it may be irrelevant whether the offset is due to
filter that will transmit at the wavelength suspected of contrib- true background or scattered light. Corrections as if the shift
uting scatter but will not transmit at the wavelength of the were due to an interfering line from a matrix element are
analytical line. Any signal that is measured must then be due to required in such instances.
far scatter. Alternately, a photomultiplier can be used which 7.8 Optical Alignment and Focus—Optimum analytical re-
will respond to the suspected scattering wavelengths but will sults will be achieved only if the optics are well aligned and
not respond at the analytical wavelength. For example, if a focused. All exit slits must be aligned parallel to their respec-
glass filter is placed in the optical path of the photomultiplier tive lines, and centered on them. The entrance slit must be
used as the detector for the arsenic 1972 Å line, the difference aligned parallel to the grating rulings. Any serious departure
in the arsenic reading obtained for a specimen with 1000 ppm from good focus or alignment will affect working resolution.
of calcium and a specimen with calcium below 0.1 ppm would 7.9 Optical Stability—Determine the time required for op-
be due to far scatter from calcium lines and background above tical readjustment, if any, after a temperature change in the
3000 Å. Conversely, if a solar-blind photomultiplier, sensitive laboratory of 63°C. The time required for the observed
to 1650 Å, with no response above 3200 Å, shows a difference intensity of a mercury pen lamp to stabilize at the new
in reading the calcium 3934 Å line between specimens with temperature is an adequate indication of adjustment time.
calcium at 1000 ppm and 0.1 ppm, this indicates a true rise in 7.10 Precision and Accuracy—Test under simulated day-to-
spectral background due to unquantized recombinations be- day operating conditions to determine precision and accuracy
tween free electrons and Ca+ ions. In the case of calcium over a two day period. Standardize the instrument with
interference, scatter could also occur from the calcium 3968 Å homogeneous standardants, as in routine operation, except that
line. In fact, if the arsenic 1972 Å line were being measured as at least four burns should be employed. Rerun these same
a second order line (at the equivalent first order wavelength standardants in quadruplicate at irregular intervals during the
8
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day. A plot of the average concentrations as a function of the provides a means for judging whether other spectrometers will
time will measure the long-term variation in readings, as provide equivalent detection limits and freedom from interfer-
contrasted to the short-term precision. This will define the ences from other elements.
frequency at which standardization should be performed to 8.2.3 Since the combination of entrance and exit slit widths,
maintain a desired accuracy of analysis. For many materials, at a specified reciprocal linear dispersion, affects working
the required accuracy can be realized with standardization once resolution, signal to background ratio, and radiation through-
a day. More critical specimens may require standardization put, the slit widths should be specified.
every 4 or 2 h, or perhaps each hour. For very critical 8.2.4 At low concentrations, for those channels where it is
specimens, reference material may have to be run with each important to achieve detection, the table that shows analytical
unknown. lines and concentration ranges should be supplemented with
NOTE 10—Continual running of a source can cause thermal drift. In columns showing background equivalents, signal to back-
testing for drift, the interval between burns should not be any shorter than ground ratios, and achievable repeatability of measurements.
the intervals that will be used in routine analysis. 8.2.5 At high concentrations, if the precision and accuracy
8. Describing the Spectrometer in Analytical Methods achieved by the method are essential, for some or all channels,
8.1 Each analytical method should contain the minimum the white light precision should be specified. The table of
characteristics required for the spectrometer, as listed in 8.2. analytical lines and concentrations ranges should include a
Other information should be included which will help users to column that lists the relative standard deviations of measure-
decide whether they should be able to obtain comparable ments, at a specified level. If specific calibrations have been
results with their equipment. Performance characteristics for established, the white light precision may be replaced by the
the spectrometer that are essential to the analytical perfor- relative standard deviations of determined concentrations at a
mance described should be specified. specified concentration.
8.2 Essential Information:
8.2.1 Wavelength coverage and reciprocal linear dispersion 9. Keywords
are the most significant features affecting analytical perfor- 9.1 astigmatism; detection; diffraction grating; direct-
mance and should be specified in all analytical methods. reading spectrometer; line interference; optical emission spec-
8.2.2 The working resolution provides an indication of the trometer (OES); optical working resolution; radiation through-
quality of design and adjustment of the spectrometer, and put; scattered light
APPENDIXES
(Nonmandatory Information)
X1.1 The physical size of the spectrometer and fineness of TABLE X1.1 Values of (dQ/dl) for Gratings
its grating obviously affect resolution by establishing the Grooves/mm 600 960 1200 2400
reciprocal linear dispersion. A finer, more closely ruled grating b, in Å 16 666 10 410 8333 4167
Order Radians per Angstrom
provides a greater angular dispersion. n=1 6.0 3 10−5 9.6 3 10−5 1.2 3 10−4 2.4 3 10−4
n=2 1.2 3 10−4 1.9 3 10−4 2.4 3 10−4 4.8 3 10−4
X1.2 Dispersion—Calculate the angular dispersion for a
grating as follows:
~dQ/dl! 5 n/~b cos Q! (X1.1)
having a 1 m diameter focal curve. With a grating of 1200
where: grooves/mm, the reciprocal linear dispersion will be approxi-
Q = the angle of diffraction, mately 8.3 Å/mm, and a combination of a 25 µm entrance slit
l = the wavelength of the radiation being dispersed, and a 50 µm exit slit will produce a working resolution of about
n = the order number, and 0.5 to 0.6 Å. If a grating of 2400 grooves/mm and the same
b = a grating constant, the groove spacing in angstroms: effective aperture is substituted, the reciprocal linear dispersion
b 5 107/g (X1.2)
becomes approximately 4.2 Å/mm. For the same combination
of slits, the working resolution improves to about 0.25 to 0.3 Å,
where: while the radiation throughput for the signals remains the
g = the grooves per millimetre in the grating. same. The instrument designer or the spectroscopist who
X1.2.1 Optical design usually keeps Q close to zero, so that specifies the channel parameters has two contrasting options.
cos Q remains near 1.0, and dQ/dl reduces to n / b. Typical The improved working resolution can be utilized to reduce
values are given in Table X1.1. potential interelement interferences, and to improve signal-to-
X1.2.2 The effect of increased angular dispersion on radia- background ratios in order to obtain better detection. Alter-
tion output can be illustrated by considering a spectrometer nately, the entrance and exit slit widths can be increased to
9
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double the radiation throughput while retaining the original 0.5
to 0.6 Å working resolution.
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50 and 10 µm, show a little more flatness for the greater widths, as in the 10 to 100 µm combination of Case H shown
disparity between slit widths in Case H. Although Case F, with in Fig. X1.1. Such a combination produces a flat-topped line
both slits wide, shows a very flat top which will make the contour which will show relatively little change if there is a
spectrometer insensitive to profile shifts, the wide half-width slight drift in the spectrum with respect to the exit slits.
will show a relatively poor working resolution. X1.4.3.3 The two conditions described above are mutually
X1.4.3 Effects of Slit Widths on Analyses: incompatible for a single analytical line. However, it is
X1.4.3.1 To improve detection by means of better signal to possible in a single polychromator to use an intermediate
background ratios, and to reduce the possibility of interelement entrance slit width, with narrow exit slits for spectral lines of
interferences, it is desirable to employ the narrowest practical elements where the optimum detection limit is desired, and
entrance and exit slits. wider exit slits for lines employed to measure high concentra-
X1.4.3.2 To improve stability and long term repeatability, so tions with optimum precision. The channel gains will need to
far as the spectrometer is concerned, it is desirable to have the be adjusted to maintain adequate electrical performance as the
greatest possible difference between entrance and exit slit slit widths are changed.
X2. RECOMMENDED SPECTRAL LINES AND CONCENTRATION RANGES FOR MEASURING WORKING RESOLUTION
X2.1 Table X2.1 lists 42 lines commonly employed either X2.2 Concentrations should not be too high, to avoid line
as analytical or internal standard lines in many direct-reading broadening and self absorption. Too low a concentration,
spectrometers. These may be used to find lines for measuring however, will not give adequate signal above background.
working resolution from 1900 Å in the extreme ultra-violet Suggested concentration ranges are listed.
region at the limit of transmission of air, to 5200 Å in the green.
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TABLE X2.1 Recommended Spectral Lines and Concentration Ranges for Measuring Working Resolution
Concentration Range, %
Element Wavelength, Å
Spark DC Arc Solution Spark
Tin 1899.9 0.05–0.5 0.05–0.5 0.05–0.5
Carbon 1930.9 0.02–2 ... ...
Arsenic 1937.0 0.02–2 0.05–0.5 0.05–0.5
Arsenic 1972.0 0.02–2 0.05–0.5 0.05–0.5
Antimony 2068.4 0.02–2 0.05–0.5 0.05–0.5
X3.1 Photographic Speed—In a photographic spec- total light flux that passes through the exit slit and falls on the
trograph, the blackness in the developed image depends on the cathode of a photomultiplier. If the entrance slit is opened
level of illumination at the focal curve. The light flux has to be wider than the critical slit width for an equivalent spectrograph,
concentrated in the image to be effective. If the slit is opened the photoelectric signal is increased proportionally, until the
beyond the critical slit width, the line on the emulsion is image begins to exceed the exit slit width. If the height of the
broadened without a significant increase in density. If the slit entrance slit is increased, the signal increases proportionally if
height is increased, the image merely becomes longer. all of the light that passes through an appropriately high exit
X3.2 Polychromator Radiation Throughput—In a poly- slit falls on the photocathode. The level of illumination at the
chromator, the signal from the photomultiplier depends on the focal curve, however, is only one of several significant factors.
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For a direct-reading spectrometer, the theoretical speed must be to = the transmission through oxygen in an air path, and
defined by the radiation throughput. ib = the grating efficiency, that is, that proportion of the
total light (of a particular wavelength) incident on the
X3.3 Calculation of Radiation Throughput (L)—The radia- grating that is diffracted into the image being mea-
tion throughput is calculated as follows: sured. (The remainder of the light is diffracted into
L 5 ITka (X3.1) other orders, into the central image, or is lost in
scattering from the grooves.)
where:
I = the illumination of the grating by a specific radiation All four factors in Eq X3.5 are expressed as decimals, and are
or narrow band of wavelengths, multiplied to show the total transmission, as a decimal.
T = an overall factor affecting the transmission of radia-
tion, and NOTE X3.2—Taking into account cathode sensitivity and window
ka = a factor to account for loss of radiation in an astig- transparency, variation in the response of photomultipliers with wave-
length contributes to spectral response. Even though it is a function of an
matic system if the exit slit is not long enough to individual tube, not a property of the spectrometer, it must be associated
subtend the total focused radiation coming from the with the channel. See X3.3.2.2.
grating.
X3.3.2.1 The reflection and transmission values (r and t)
X3.3.1 Illumination (I)—The flux of radiation passing
remain high throughout the visible and ultra-violet regions.
through the entrance slit is defined by the product of the area
Below 2100 Å, the reflectivity of aluminum oxide (Al2O3),
of the slit and the apparent area of the ruled portion of the
which forms the reflecting surface of an aluminized mirror,
grating as viewed by the slit. It is calculated as follows:
begins to fall off rapidly unless the aluminization was per-
I 5 ~whWH cos a!/f 2 (X3.2) formed with high-purity aluminum, under a high vacuum, with
very rapid deposition, followed by overcoating with magne-
where: sium fluoride (MgF2). The transmission of quartz lenses and
w = the width of the entrance slit, mm (see Note X3.1),
windows also drops rapidly, unless highest-quality fused quartz
h = the height of the entrance slit, mm,
W = the width of the ruled area of the grating, mm, is employed.
H = the height of the ruled area of the grating, mm, X3.3.2.2 Transmission (t) is also affected by optical mate-
a = the angle of incidence, the angle between the normal rials that can be used in front of a photomultiplier to filter out
to the first surface of the dispersing element and the unwanted wavelengths far from the analytical line, or to block
central ray from the entrance slit, and radiation from overlapping orders. Typical transmission curves
f = the focal distance from the center of the dispersing for several optical materials are shown in Fig. X3.1. Also
element to the entrance slit. included is a response curve for a special case of a solar-blind
photomultiplier with a quartz window and a cesium telluride
NOTE X3.1—If the exit slit is narrower than the entrance slit, it becomes (CsTe) cathode which can be used to screen out long wave-
the limiting horizontal aperture, and the narrower width should be used to
calculate I. In that case, if the exit slit is tangential to the focal circle, the
lengths. For practical applications, transmission depends on the
slit width should be reduced by multiplying by the cosine of the angle of combination of the cathode surface of the photomultiplier and
emergence from the dispersing element. the photomultiplier window material as well as on any optical
material positioned in the radiation path. Three examples of the
X3.3.1.1 In a grating polychromator, with a Rowland circle percent of peak sensitivity that can be expected at a specific
mounting: wavelength for three different photomultipliers are shown in
f 5 R cos a (X3.3) Fig. X3.2. Example A is for an R166 photomultiplier, a
solar-blind photomultiplier. Example B is for a 1P28 photo-
where:
multiplier which has a UV glass window and is commonly
R = the radius of curvature of the grating, that is also the
used for measuring signals in the near ultra-violet. When a
diameter of the Rowland circle.
where:
r = the overall reflectivity, due to the individual reflectivi-
ties of each reflecting surface,
t = the overall transmission, due to the individual trans-
missions of each lens, prism, refractor plate or optical
surface,
FIG. X3.1 Filter Transmission
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TABLE X3.1 Wavelength Windows in Air Polychromators, and
Some of the Useful Analytical Lines
Window, Å in air Element Wavelength, Å in air
1890–1902 Tin 1899.26
1915–1923 ... ...
1930–1945 Carbon 1930.30
Arsenic 1936.96
Above 1953 Bismuth 1953.89
Selenium 1960.26
Arsenic 1971.97
Germanium 1998.24
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for ruled gratings. The measured intensity distribution may be X3.3.3.2 In a similar way in which Eq X3.3 established the
available from the manufacturer. distance from the entrance slit to the grating, the distance from
X3.3.3 Astigmatism (ka)—The factor ka accounts for astig- the grating to an exit slit is R cos b, where b is the angle of
matism and becomes 1.0 in relatively stigmatic systems, such diffraction.
as the Wadsworth mount for concave gratings or the Ebert or X3.3.3.3 The distance from the grating to the focus of a
Czerny-Turner mounts for plane gratings, if the exit slit is horizontal aperture, as discussed by Beutler (10), is:
made high enough to accommodate any magnification of the R/~cos b 2 sin a tan a! (X3.7)
image. Since a line image diverges after passing through an
This focus is shown in Fig. X3.5 by the points A2, C2, and B2.
exit slit, it should be intercepted by the cathode of the
X3.3.3.4 Using the height notations of Eq X3.2, the dis-
photomultiplier before it has grown too tall or too wide, unless
tances of the three points, S0, S1, and S2, from the center line
it is refocused on the photomultiplier.
along the exit slit may be calculated as follows:
X3.3.3.1 Fig. X3.5 shows a vertical diagram of rays in an
astigmatic grating polychromator, with vertical heights greatly S0 5 ½h ~cos b!/~cos a! (X3.8)
exaggerated. Points A1, C1, and B1 define an entrance slit S1 5 ½H ~1 2 F cos b! 1 S0 (X3.9)
having a height of h. These points are shown focused at A2, C2, S2 5 ½H ~1 2 F cos b! 2 S0 (X3.10)
and B2 beyond the exit slit. The exit slit is defined by the points
going to S1 in the section of the figure which shows the upper where:
half of the grating of height H, marked as OG. The maximum F 5 cos b 2 sin a tan a (X3.11)
illumination of the grating would be such that all points in the Using Sx equal to half of the height of the exit slit, and
entrance slit would fan out to fill the grating. In fact, the usual comparing Sx to the other S values, ka factors are determined as
optical arrangement is to form an image of the electrode system follows:
at the top and bottom of the grating, or just beyond those X3.3.3.5 If Sx is $S1, there will be no loss in output and ka
points. For simplicity, rays from Points A1 and B1 are shown will equal 1.0.
filling only the upper half of the grating. If the exit slit is tall X3.3.3.6 If Sx is <S1 but $S0, the reduction factor becomes:
enough, each focus point will receive all the radiation it
ka 5 1 2 ~S1 2 Sx!2/@4S0~S1 2 S0!# (X3.12)
possibly can from the grating. By determining the intersection
Points S0, S1, and S2, the limits imposed on throughput by the X3.3.3.7 If Sx is <S0, but >S2, the reduction factor becomes:
exit slit can be determined. ka 5 @1/~2S0!#$Sx 1 ~2SxS0 2 Sx 2 2 S2 2!/[2~S0 1 S2!#%
(X3.13)
X3.3.3.8 If Sx is #| S2 |, the reduction factor becomes:
ka 5 Sx/S0, if S2 is negative, (X3.14)
or:
ka 5 Sx/~S0 1 S2!, if S2 is positive (X3.15)
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TABLE X3.2 Typical Radiation Throughputs
Example 1 Example 2 Example 3
Element
Carbon Aluminum Iron
Channel
Wavelength, Å 1930.9 2568.0 2714.7
Diffraction order, n 2 1 1
Grating
Radius of curvature (R), mm 3000 1500 750
Grooves/mm 960 1200 2400
Groove spacing (b), Å 10416.7 8333.3 4166.7
Blaze wavelength (lm), Å 3000 3000 3000
Width (W), mm 60 60 40
Height (H), mm 30 40 30
Path
Incident angle (a) 27.02° 20.66° 42.07°
Wavelength at grating 4732.3 2940.2 2791.8
normal, Å
Emergent angle (b) 4.79° 2.56° 1.06°
Entrance Slit
Width (w), mmA 0.020 0.025 0.025
Height (h), mm 16 2 2
Exit Slit
Width, mm 0.075 0.075 0.050
Height, mm 20 10 15
Calculations
Illumination (I), mm2 7.18 3 10−5 1.42 3 10−5 8.98 3 10−6
Transmission
Reflectivity (r) 0.85 0.91 0.93
Transmission (t) 0.87 0.90 0.93
Transmission through 0.43 0.99 0.99
(to)
Grating efficiency (ib)B 0.61 0.90 0.96
Overall T 0.19 0.73 0.82
Astigmatism
F 0.7648 0.8660 0.3950
S0 8.95 1.07 1.35
S1 12.52 3.77 10.42
S2 −5.38 1.63 7.73
Sx 10 5 7.5
ka 0.95 1.0 0.83
Overall throughput (L), 1.32 3 10−5 1.04 3 10−5 6.09 3 10−6
2
mm
A
0.020 mm = 20 µm.
B
Relative intensities read from Fig. X3.4.
REFERENCES
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