NOTICE: This standard has either been superseded and replaced by a new version or discontinued.

Contact ASTM International (www.astm.org) for the latest information.

Designation: E 356 – 78 (Reapproved 1996)

Standard Practices for

Describing and Specifying the Spectrograph1
This standard is issued under the fixed designation E 356; 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 5. Description of Pertinent Spectrograph Components

1.1 These practices list and cover those features of the and Associated Equipment
spectrograph that are of importance to spectrochemical analy- 5.1 The following are pertinent to spectrochemical analyses:
sis. They are intended thus to aid in evaluating and comparing 5.1.1 Type of Dispersing Element—A prism, grating,
spectrographs. It is not the purpose of these practices to echelle, or a combination of these shall be used. For a prism,
establish binding specifications or tolerances, but rather to call consider material, type of prism, prism angle, width of base,
attention to important parameters, suggest methods to measure and height (Note 1). For a grating or echelle include the
those parameters, and, in some cases, assign values which are number of grooves per millimetre (or inch), size of ruled area,
indicative of acceptably good performance. Because of the blaze, method of fabrication (original or replica), blank mate-
great variety of demands imposed by spectrochemical tech- rial and configuration, and coating (Note 2).
niques, rigid performance criteria are not feasible. These NOTE 1— Example—Crystal quartz, Cornu, 60° prism, 100-mm base,
practices shall be used to guide authors of analytical proce- 45 mm high.
dures in adequately defining their methods.1 NOTE 2—Example—A 1200 grooves/mm replica grating with ruled
1.2 This standard does not purport to address all of the area 42 mm high by 92 mm wide, blazed for 3000 A first order, and ruled
safety concerns, if any, associated with its use. It is the on an aluminized borosilicate blank ground to a radius of 3 m.
responsibility of the user of this standard to establish appro- 5.1.2 Type of Mounting, whether stigmatic or astigmatic, the
priate safety and health practices and determine the applica- focal length of the collimator, and of the camera, if different.
bility of regulatory limitations prior to use.
NOTE 3— Example—Wadsworth, 3.4 m stigmatic.
2. Referenced Documents 5.1.3 Dispersion—Linear reciprocal dispersion is given in
2.1 ASTM Standards: angstroms per millimetre. If it is a function of wavelength as in
E 115 Practice for Photographic Processing in Optical the case of a prism instrument, specify the dispersion at 500-Å
Emission Spectrographic Analysis2 intervals over the usable wavelength region or at a wavelength
E 116 Practice for Photographic Photometry in Spectro- critical to the application.
chemical Analysis2
NOTE 4—Example—Linear reciprocal dispersion in first order is 4
E 135 Terminology Relating to Analytical Chemistry for Å/mm.
Metals, Ores, and Related Materials2
5.1.4 Resolving Power—As distinct from the working reso-
3. Terminology lution of a spectrograph discussed in 6.1.4, the resolving
3.1 For definitions of terms used in these practices refer to power, R, is a theoretical limit which can only be approached
Terminology E 135. in practice. It is defined as follows for a grating instrument:
R 5 l/Dl 5 nM (1)
4. Summary of Practice
4.1 Certain features and components of the spectrograph where:
l = wavelength,
that must be considered in spectrochemical analysis are dis-
Dl = wavelength differences between two lines just re-
cussed (Section 5). Those features which must be specified
solved,
fully to determine the performance of a spectrograph are n = grating order, and
discussed and methods of specification are given (Section 6). M = number of lines ruled on grating.

1 For the first order of a spectrograph with a grating of 1200

This practice is under the jurisdiction of ASTM Committee E-1 on Analytical
Chemistry for Metals, Ores and Related Materials and is the direct responsibility of grooves/mm and 100 mm wide ruled area at 3000 Å,
Subcommittee E01.20 on Fundamental Practices. R = 120 000 and Dl = 0.025 Å.
Approved Feb. 24, 1978. Published May 1978. Originally published as 5.1.5 Slit, fixed or adjustable, uni- or bilateral, and the width
E 356 – 68. Last previous edition E 356 – 68.
2
Annual Book of ASTM Standards, Vol 03.05. or widths available to be specified; also the maximum and

Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.

1
 E 356
minimum slit heights to be specified. any additional Rowland ghosts are present, their intensity shall
not exceed 0.01 % of the parent line. Ghost lines may be
NOTE 5— Example—Bilateral slit width continuously adjustable from 0
to 0.1 mm; height continuously adjustable from 0 to 15 mm. readily recognized and their relative intensity estimated by
photographing a simple, strong line spectrum such as obtain-
5.1.6 Wavelength Coverage—The total wavelength range able with a mercury vapor lamp. In order to obtain uniform
for which the instrument can be used and the wavelength range illumination of the spectrographic slit,6 mount the lamp in front
which can be photographed at a single setting. of the slit in such a way that irregularities of the filament and
NOTE 6— Example—The entire region from 2000 to 10 000 Å can be markings on the envelope do not interfere. Use a step sector or
photographed. Up to 2400 Å may be photographed at a single setting of step filter, and a 10-µm slit width but no other external optics.
the instrument (first order). A spectral range setting to include the Hg 4358 Å line is quite
5.1.7 Camera—The size of plates or film, or both, that can suitable, but other strong mercury lines could be used as well.
be accommodated should be specified. Make preliminary tests to check stability of the lamp and
uniformity of illumination. Adjust the exposure time to record
NOTE 7— Example—Camera will accommodate two 100 by 250-mm
(4 by 10-in.) or two 50 by 250-mm (2 by 10-in.) plates.
a strong mercury line such as Hg 4358 Å to a transmittance
value between 1 and 10 %. Take two exposures for the actual
5.1.8 Illuminating System (External Optics)—Consider test, one at the exposure time determined above and the other
each component of the illuminating system and note its 1000 times longer, such as 3 s and 3000 s. Note ghost intensity
function. by comparing the two exposures. Steps at the 10003 exposure
NOTE 8— Example—A quartz relay lens ( FD = 60 mm) is used to for the ghost lines should be weaker than their counterparts of
image the source at unit magnification on an aperture 8 mm wide and the parent line in the 13 exposure if the ghost intensity is to be
adjustable in height from 1 to 6 mm. This aperture is imaged on the less than 0.1 %. Because of the reciprocity effect this test
collimator at 113 magnification by a quartz lens (F D = 180 mm) located cannot be more than a coarse guide. For more precise mea-
at the slit. surements, photomultipliers commonly are used.
NOTE 9—It is quite essential to describe fully all external optics. Wide
variations in performance can be brought about by changing the method
6.1.2 Speed—Express the theoretical optical speed of a
of illumination. spectrograph as the effective F number, which is given as
follows:
5.1.9 Accessory Equipment—Shutter, plate racking mecha-
nism, and any other devices which contribute to the perfor- Effective F number 5 f/2=wh/p cos u (2)
mance of the instrument.
where:
5.1.10 Size—Over-all size, weight, and distribution of f = focal length of the camera lens or mirror,
weight on each of the supports. w = width of dispersing element,
h = height of dispersing element, and
6. Specification of Performance u = angle between the normal to the dispersing element
6.1 Adequate performance for a specific problem cannot be and the direction of the radiation leaving that element.
ensured by a set of general specifications. It is possible,
however, to describe some of the design parameters and
performance criteria which primarily determine the quality of The actual optical speed attainable will depend also upon the
performance to be expected from a spectrograph. In addition, number of reflecting and absorbing elements in the optical
for versatility the instrument shall meet or exceed certain train, the illumination employed, the plate tilt angle, and in the
minimum specifications which will be given. For more detailed case of a grating, its blaze. For the latter, the relative speed of
information the literature should be consulted.3,4 ,5 the spectrograph should be specified at 500-Å intervals
6.1.1 Dispersing Element—To specify a prism for spectro- throughout the available wavelength in range in each usable
chemical analysis, include only the information listed in 5.1.1. order. A practical test for the comparative speed of a spec-
Any serious defects will be reflected in the over-all perfor- trograph under conditions in use may be performed by record-
mance of the spectrograph and will be detected by failure to ing the iron spectrum using a controlled set of conditions, and
meet one or more of the subsequent specifications in this estimating the time required for selected lines to produce lines
section. The same remarks apply to gratings and echelles with of 50 % transmittance. An intensity distribution curve is thus
one exception, the specifications of the maximum permissible obtained which is particularly useful in comparing the speed of
intensities of ghosts and satellites. The intensities of Rowland an individual spectrograph using, say, two different gratings or
ghosts in the first order of a grating having 600 grooves/mm two different illuminating systems. The test is less useful in
(15 000 grooves/in.) shall not exceed 0.1 % level. There shall comparing two or more spectrographs because of uncontrol-
be no more than three ghosts at either side of a parent line. If lable variations in illuminating systems, source parameters,
peculiarities of the optical elements, etc. A typical test is
outlined as follows:
3
Sawyer, R. A., Experimental Spectroscopy, Prentice-Hall, New York, NY, 6.1.2.1 Source—A d-c arc between an upper negative graph-
Second Edition, 1951. ite rod and a lower iron bead in a graphite electrode (iron
4
Harrison, G. R., Lord, R. C., and Loofbourow, J. R., Practical Spectroscopy, globule arc) as described in Practice E 116.
McGraw-Hill, New York, NY, 1948.
5
Grove, E. L., Analytical Emission Spectroscopy, Marcel Dekker, Inc., New
6
York, NY, 1971. A type R.S. sunlamp available at drug stores is suitable.

2
 E 356
6.1.2.2 Spectrograph Slit Width, 50-µm. TABLE 1 Exposure Factors
6.1.2.3 Spectrograph Illumination—The condensing system First Order Factor Second OrderA Factor
Third
Factor
normally supplied by the manufacturer for routine quantitative OrderA

work shall be employed using the standard conditions. 2178.09 ⁄

1 14 2374.52 3⁄8 2815.02 21⁄10
2374.52 ⁄
38 2556.86 1 3106.56 ⁄
34
6.1.2.4 Emulsion—Eastman SA No. 1, or equivalent. 2556.86 1 2815.02 3⁄4 ... ...
6.1.2.5 Wavelengths, as indicated in Fig. 1. 2815.02 3⁄4 3106.56 3⁄4 ... ...
6.1.2.6 Exposure—Any set of individual exposures; a two- 3106.56 3⁄4 3376.50 1⁄2 ... ...
3376.50 1⁄2 3626.17 3⁄4 ... ...
step sector or a two-step filter exposure. Make exposures of 1, 3627.17 3⁄4 3979.64 7⁄10 ... ...
3, 9, 27, 81, and 243 s. 3979.64 7⁄10 ... ... ... ...
6.1.2.7 Photographic Processing—Process the emulsion in 4525.15 1⁄3 .. ... ... ...
accordance with Practice E 115. The procedure consists of A
Since Eastman SA No. 1 emulsion is specified, wavelengths above 4500 Å are
not recorded. In their place second and third order lines are used. Thus the relative
taking a sample plate or film under the conditions indicated, speed of a grating at 2400 Å second order equals that at 4800 Å in the first order.
identifying the lines either from a marked sample plate or by
referring to an iron arc enlargement, and estimating visually the technique, it is desirable to measure with a microphotometer several
the exposure which would be required to produce a transmis- lines which have a transmission of approximately 50 %, and to use these
sion of 50 % (Note 10). Where the background is relatively as references.
high, as at 3626 and 3979 A, an effort should be made to
6.1.3 Dispersion—Dispersion requirements vary widely
estimate the exposure in which the line has a transmission
with the material to be analyzed. Increased dispersion reduces
50 % less than that of the immediately surrounding back-
the wavelength coverage per unit length of plate or film. On the
ground. Multiply the exposure determined for each individual
other hand, increased dispersion results in a more favorable
line by the appropriate factor given in Table 1. Plot the final
line-to-background ratio, an important factor in trace analysis.
resultant exposures as in Fig. 1. This technique is only
6.1.4 Resolution—The working resolution of a spectrograph
semiquantitative. However, if all of the steps are followed with
may be stated in terms of its ability to separate given spectral
care, it is possible for two observers to agree to within better
lines. This, however, is highly subjective; it depends on when
than 50 % in determining the actual performance of an indi-
the observer feels that he just sees a space between two lines or
vidual grating in an individual spectrograph under the condi-
when he can just detect a dip in a microphotometer trace. A
tions of the test, that is, illumination, etc.
more objective means of determining resolution is to measure
NOTE 10—For reference purposes, unless one is already familiar with the half-width of a line, the width of the line at half of its

FIG. 1 Work Sheet for Comparative Speed Test

3
 E 356
maximum intensity. Make the half-width measurement with a 500-mm camera, measurements shall be taken about 30 mm
mercury pencil lamp.7 The lamp emits a closely spaced doublet from the ends of the plate to indicate how and if the image is
at 3131.55 Å and 3131.83 A, each of which consists of a very deteriorating. The resolution of a spectrograph is affected by
fine line. Carefully align the illumination system of the many factors. A brief summary of the more important ones is
spectrograph to yield the maximum resolution (see 6.1.6). Use listed below:
a slit of width W such that 6.1.4.1 Focus—Half-width resolution is much more critical
W # fl/d (3) than visual focus. On a large spectrograph (over 2-m focal
length), moving the slit longitudinally by less than 0.5 mm will
where: affect the calculated resolution. Also, measurements should be
f = focal length of collimator, taken at the center as well as both ends of the focal curve to
d = effective width of dispersing element, and check that the focal curve conforms to the Rowland circle.
l = wavelength, A.
6.1.4.2 Coma—As a spectrograph operates off its centrol
optical axis, aberrations such as coma disrupt the shape and
Using either the Hg pencil lamp or a low-current (less than
sharpness of the lines. The half-widths should be smallest at the
3-A) iron globule arc (see 6.1.1 of Practice E 116), take a series
center of the plate.
of spectrograms such that either the Hg 3131 Å doublet or two
lines in the triplet Fe 3100.31 Å and Fe 3100.67 Å are 6.1.4.3 Order—Theoretically, the resolving power of a
photographed with a transmittance of between 20 and 50 % spectrograph is proportional to the order, and resolutions
(Table 2). Spectrum Analysis No. 1, or an equivalent plate of should improve almost equally in the first three or four orders.
low grain size should be used. With a microphotometer slit Again, be sure the instrument is in optimum focus.
width of [frac13] or less that of the width of the line, record the 6.1.4.4 Microphotometer Slit Width—Because of the over-
contour of two adjacent lines on a strip chart. Referencing the all time constant of the measuring system, a good rule of thumb
emulsion calibration curve, find the percentage transmittance is to set the microphotometer slit at a width equal to or less than
of the lines corresponding to one half that of the peak intensity [frac13] of the line being measured. The smallest micropho-
(which can be set at unity on the calculating board, for tometer slit width commensurate with the stability and sensi-
convenience). Referencing the known peak-to-peak distance tivity of the microphotometer amplifier shall be used.
between the lines, measure their half-width in angstroms. At 6.1.4.5 Microphotometer Slit Tilt—Unless the slit is abso-
the center of the plate, the half-width as measured shall not lutely parallel with the line under measurement, false readings
exceed twice theoretical Dl as calculated in 6.1.4. At a distance will result. If the contour of the line is asymmetric, that is, if a
equal to 90 % of that measured from the center to the end of the line drawn from the peak to the base does not divide the area
plate, the ratio shall not exceed 2.5. Shoulders at the base of a in half, the slit is probably not parallel.
line and coma are serious limitations of this technique. Tenth- 6.1.5 Slits—Fixed or adjustable slits are commonly used.
widths can also be measured to avoid this problem. Fig. 2A is There are advantages to both types, but for best reproducibility
a profile of a resolved line, a photoelectric tracing as it should the fixed slits are to be preferred. Slit jaws must be straight,
appear for a grating spectrograph or spectrometer set on-axis free of nicks, accurately parallel, and coplanar. Total variation
and exhibiting no aberrations. Both sides of the curve are in slit width along the full length of the slit must not exceed
symmetrical; the sweep on both sides is without inflection. Fig. 10 % of the nominal slit width. Adjustable slits should be
2B indicates a shoulder on the low wavelength side. Note that, accurate to within 610 % of the actual width at any setting and
although the halfwidths of spectrograph A and B are identical, should be reproducible to within 65 %. Most modern slit jaws
a weak line close to and on the low wavelength side of a strong operate bilaterally so the image remains centered. If inter-
line would remain undetected in B where it would appear in A. changeable fixed slits are provided, positioning must be suffi-
Again, in Fig. 2C the half-width remains the same, but lines on ciently accurate that no change in focus can be detected when
both sides would be obscured.Fig. 2D is an indication of coma slits are interchanged.
or off-axis aberration. The line profile is asymmetrical; the area 6.1.6 Illuminating System—The illuminating system of a
under the curve on the wavelength side away from the optical spectrograph should provide reasonably uniform illumination
center line is greater than on the other side. Coma, increasingly of the slit along its entire usable length. In addition, it should
obvious toward the ends of any spectrographic plate, is seen as be capable of filling (1) the entire width of the dispersing
lines that are sharp toward the center of the plate, fuzzy toward element in order to obtain the maximum resolving power of
the end. In order to account for all of these conditions, two which the instrument is capable, and (2) the exit aperture of the
figures of merit shall be furnished in describing the resolution system (normally the dispersing element) in order to obtain the
of a spectrograph: (1) the half-width; (2) the width of each maximum speed of which the instrument is capable. Other
wing of the intensity distribution curve at a value 1⁄10 of functions such as adjustable masking of certain portions of the
maximum intensity (Table 3). At least three lines, or the same source, intensity controls, etc. are often incorporated into the
line in three positions, shall be measured: (1) in the center of design. Such systems always present problems in both geo-
the plate; (2) and (3) at a distance equal to 90 % of the plate metrical and physical optics with the result that some compro-
width close to the end of the plate. In other words, for a mise is usually necessary. For this reason it is essential that
each component of the optical system be described completely
7
Spectroline 11SC-1, Black Light Eastern, 24 Kindel St., Westbury, NY, Pen Ray with respect to its optical characteristics and its function in the
Quartz Lamp, Ultra Violet Products, San Gabriel, CA, have been found satisfactory. system.

4
 E 356
TABLE 2 Iron Lines for Use in Determining The transmittance of adjacent 2-mm segments of lines in the
Resolving Power range from 40 to 60 % T should not vary more than 61 %
Wavelength, Å Wavelength Difference, Å along the entire length of the line. Transmittance measurements
2486.37} 0.32 must be made with a microphotometer having an effective slit
2486.69
2487.06 J 0.37 width at the plate of not greater than 1⁄2the actual line
half-width at half-height (Note 11), and an effective slit length
2493.18
2493.26 J 0.08 at the plate of not greater than 2 mm. Failure to meet this
specification may be caused by optical defects in the spec-
2749.18} 0.14 trograph as well as defects in the illuminating system (Note
2749.32
2749.48 J 0.16 12).

3099.90
3099.97 JJ 0.07
0.34
TABLE 3 Example of Information Regarding Resolution, First
3100.31
3100.67 J 0.36
OrderA
Center of 25 mm from 25 mm from
low l end high l end
J
Plate
3859.22 0.69
3859.91 Half-width, Å 0.10 0.13 0.15
Width of low l wing at 1⁄10 0.14 0.20 0.15
3956.46
3956.68 J 0.22
max intensity
Width of high l wing at 1⁄10
max intensity
0.14 0.15 0.25

4175.64} 0.93 A

J
Slit set at 10 µm wide by 2 mm high; source low-pressure Hg discharge 3131
4176.57 1.03 Å; grating 1200 grooves/mm.
4177.60

NOTE 11—This may be approximated by taking one fourth of the

geometrical width of the line, that is, (W/4) 3 (f2/f1) sec f, where W is the
spectrograph slit width, f2 is the focal length of the camera lens, f1 is the
focal length of the collimator lens, and f is the angle of plate tilt, that is,
the angle between the plate and the normal to the beam arriving at the
plate.
NOTE 12—Most spectrographs do not employ achromatic lenses in the
illuminating system. To obtain uniform intensity along lines of different
wavelength, it may be necessary to move the condensing lens for the
position of best focus at the region in use.
6.1.7 Racking—The camera should rack vertically so that
the lines are not displaced laterally by more than 0.5 mm in
traveling across a 100-mm plate, or 0.2 mm across a 35-mm
film. Motion in the direction perpendicular to the camera
should be so small that no change in focus can be detected.
6.1.8 Sectors—Step sector ratios should be accurate to
within 2 % of specified values.
6.1.9 Filters—Transmittance of filters and step-filters used
for emulsion calibration should be given to within 62 %
transmittance at 500-Å intervals through the range of intended
use. Variation of transmittance across the filter, or within any
one step of a step-filter, should not exceed 61 %. Filters used
merely to attenuate line intensity need not be calibrated. They
should, of course, be stable under irradiation.
6.1.10 Astigmatism is the phenomenon whereby a point on
the slit is not imaged as a point on the line. The point is
elongated, more or less, in the vertical direction. In astigmatic
grating mounts, the secondary focus substitutes for the en-
FIG. 2 Line Profiles Illustrating Limitations of “Half-Width” trance slit as the proper location for step sectors, step filters,
Specification of Resolution and for an image position for studies in variation along the arc
column. The user should determine the degree of astigmatism
6.1.6.1 In order to determine that the slit is uniformly and the convenience of using the secondary focus. The degree
illuminated, the following test is recommended: of astigmatism is dependent on the angles of incidence and
6.1.6.2 Using a slit height of 12 mm and the slit width, W, diffraction and is, therefore, dependent on both wavelength and
given in 6.1.6, photograph an iron spectrum on a medium- wavelength setting of a particular spectrograph. A nomograph
contrast emulsion. Use a low-current a-c arc or a condensed for calculating astigmatism is given in several texts.3,4 A
spark between 3.2-mm diameter iron rods with a 3.2-mm gap. practical test for determining the degree of astigmatism is to set

5
 E 356
up the spectrograph as recommended and measure the height of is ordinarily accomplished by moving the entrance slit longi-
lines by comparison with that of the height-limiting aperture tudinally; the latter by tilting the camera until it corresponds
between the slit and the source. Of course, any aperture at the with the focal plane.
camera must be opened to a point where it does not interfere.
The lengthening of lines at the center and at each end of the 7. Keywords
camera can be calculated as a percentage of the height of the
aperture. 7.1 optical emission; spectrochemical analysis; spectro-
6.1.11 Focus—Means shall be provided for focusing at the graphic analysis
center of the plate as well as both ends of the plate. The former

The American Society for Testing and Materials takes no position respecting the validity of any patent rights asserted in connection
with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity of any such
patent rights, and the risk of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM Headquarters. Your comments will receive careful consideration at a meeting of the responsible
technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your
views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above address or at
610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website (www.astm.org).