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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
1.1 These practices list and cover those features of the
spectrograph that are of importance to spectrochemical analy-
sis. They are intended thus to aid in evaluating and comparing
spectrographs. It is not the purpose of these practices to
establish binding specifications or tolerances, but rather to call
attention to important parameters, suggest methods to measure
those parameters, and, in some cases, assign values which are
indicative of acceptably good performance. Because of the
great variety of demands imposed by spectrochemical tech-
niques, rigid performance criteria are not feasible. These
practices shall be used to guide authors of analytical proce-
dures in adequately defining their methods.1
1.2 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 appro-
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
E 115 Practice for Photographic Processing in Optical
Emission Spectrographic Analysis2
E 116 Practice for Photographic Photometry in Spectro-
chemical Analysis2
E 135 Terminology Relating to Analytical Chemistry for
Metals, Ores, and Related Materials2
3. Terminology
3.1 For definitions of terms used in these practices refer to
Terminology E 135.
4. Summary of Practice
4.1 Certain features and components of the spectrograph
that must be considered in spectrochemical analysis are dis-
cussed (Section 5). Those features which must be specified
fully to determine the performance of a spectrograph are
discussed and methods of specification are given (Section 6).
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
Subcommittee E01.20 on Fundamental Practices.
Approved Feb. 24, 1978. Published May 1978. Originally published as
E 356 – 68. Last previous edition E 356 – 68.
2
Annual Book of ASTM Standards, Vol 03.05.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
1
5. Description of Pertinent Spectrograph Components
and Associated Equipment
5.1 The following are pertinent to spectrochemical analyses:
5.1.1 Type of Dispersing Element—A prism, grating,
echelle, or a combination of these shall be used. For a prism,
consider material, type of prism, prism angle, width of base,
and height (Note 1). For a grating or echelle include the
number of grooves per millimetre (or inch), size of ruled area,
blaze, method of fabrication (original or replica), blank mate-
rial and configuration, and coating (Note 2).
NOTE 1— Example—Crystal quartz, Cornu, 60° prism, 100-mm base,
45 mm high.
NOTE 2—Example—A 1200 grooves/mm replica grating with ruled
area 42 mm high by 92 mm wide, blazed for 3000 A first order, and ruled
on an aluminized borosilicate blank ground to a radius of 3 m.
5.1.2 Type of Mounting, whether stigmatic or astigmatic, the
focal length of the collimator, and of the camera, if different.
NOTE 3— Example—Wadsworth, 3.4 m stigmatic.
5.1.3 Dispersion—Linear reciprocal dispersion is given in
angstroms per millimetre. If it is a function of wavelength as in
the case of a prism instrument, specify the dispersion at 500-Å
intervals over the usable wavelength region or at a wavelength
critical to the application.
NOTE 4—Example—Linear reciprocal dispersion in first order is 4
Å/mm.
5.1.4 Resolving Power—As distinct from the working reso-
lution of a spectrograph discussed in 6.1.4, the resolving
power, R, is a theoretical limit which can only be approached
in practice. It is defined as follows for a grating instrument:
R 5 l/Dl 5 nM (1)
where:
l = wavelength,
Dl = wavelength differences between two lines just re-
solved,
n = grating order, and
M = number of lines ruled on grating.
grooves/mm and 100 mm wide ruled area at 3000 Å,
R = 120 000 and Dl = 0.025 Å.
5.1.5 Slit, fixed or adjustable, uni- or bilateral, and the width
or widths available to be specified; also the maximum and
 E 356
minimum slit heights to be specified.
NOTE 5— Example—Bilateral slit width continuously adjustable from 0
to 0.1 mm; height continuously adjustable from 0 to 15 mm.
5.1.6 Wavelength Coverage—The total wavelength range
for which the instrument can be used and the wavelength range
which can be photographed at a single setting.
NOTE 6— Example—The entire region from 2000 to 10 000 Å can be
photographed. Up to 2400 Å may be photographed at a single setting of
the instrument (first order).
5.1.7 Camera—The size of plates or film, or both, that can
be accommodated should be specified.
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.
5.1.8 Illuminating System (External Optics)—Consider
each component of the illuminating system and note its
function.
NOTE 8— Example—A quartz relay lens ( FD = 60 mm) is used to
image the source at unit magnification on an aperture 8 mm wide and
adjustable in height from 1 to 6 mm. This aperture is imaged on the
collimator at 113 magnification by a quartz lens (F D = 180 mm) located
at the slit.
NOTE 9—It is quite essential to describe fully all external optics. Wide
variations in performance can be brought about by changing the method
of illumination.
5.1.9 Accessory Equipment—Shutter, plate racking mecha-
nism, and any other devices which contribute to the perfor-
mance of the instrument.
5.1.10 Size—Over-all size, weight, and distribution of
weight on each of the supports.
6. Specification of Performance
6.1 Adequate performance for a specific problem cannot be
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
performance to be expected from a spectrograph. In addition,
for versatility the instrument shall meet or exceed certain
minimum specifications which will be given. For more detailed
information the literature should be consulted.3,4 ,5
6.1.1 Dispersing Element—To specify a prism for spectro-
chemical analysis, include only the information listed in 5.1.1.
Any serious defects will be reflected in the over-all perfor-
mance of the spectrograph and will be detected by failure to
meet one or more of the subsequent specifications in this
section. The same remarks apply to gratings and echelles with
one exception, the specifications of the maximum permissible
intensities of ghosts and satellites. The intensities of Rowland
ghosts in the first order of a grating having 600 grooves/mm
(15 000 grooves/in.) shall not exceed 0.1 % level. There shall
be no more than three ghosts at either side of a parent line. If
3
Sawyer, R. A., Experimental Spectroscopy, Prentice-Hall, New York, NY,
Second Edition, 1951.
4
Harrison, G. R., Lord, R. C., and Loofbourow, J. R., Practical Spectroscopy,
McGraw-Hill, New York, NY, 1948.
5
Grove, E. L., Analytical Emission Spectroscopy, Marcel Dekker, Inc., New
York, NY, 1971.
2
any additional Rowland ghosts are present, their intensity shall
not exceed 0.01 % of the parent line. Ghost lines may be
readily recognized and their relative intensity estimated by
photographing a simple, strong line spectrum such as obtain-
able with a mercury vapor lamp. In order to obtain uniform
illumination of the spectrographic slit,6 mount the lamp in front
of the slit in such a way that irregularities of the filament and
markings on the envelope do not interfere. Use a step sector or
step filter, and a 10-µm slit width but no other external optics.
A spectral range setting to include the Hg 4358 Å line is quite
suitable, but other strong mercury lines could be used as well.
Make preliminary tests to check stability of the lamp and
uniformity of illumination. Adjust the exposure time to record
a strong mercury line such as Hg 4358 Å to a transmittance
value between 1 and 10 %. Take two exposures for the actual
test, one at the exposure time determined above and the other
1000 times longer, such as 3 s and 3000 s. Note ghost intensity
by comparing the two exposures. Steps at the 10003 exposure
for the ghost lines should be weaker than their counterparts of
the parent line in the 13 exposure if the ghost intensity is to be
less than 0.1 %. Because of the reciprocity effect this test
cannot be more than a coarse guide. For more precise mea-
surements, photomultipliers commonly are used.
6.1.2 Speed—Express the theoretical optical speed of a
spectrograph as the effective F number, which is given as
follows:
Effective F number 5 f/2=wh/p cos u (2)
where:
f = focal length of the camera lens or mirror,
w = width of dispersing element,
h = height of dispersing element, and
u = angle between the normal to the dispersing element
and the direction of the radiation leaving that element.
The actual optical speed attainable will depend also upon the
number of reflecting and absorbing elements in the optical
train, the illumination employed, the plate tilt angle, and in the
case of a grating, its blaze. For the latter, the relative speed of
the spectrograph should be specified at 500-Å intervals
throughout the available wavelength in range in each usable
order. A practical test for the comparative speed of a spec-
trograph under conditions in use may be performed by record-
ing the iron spectrum using a controlled set of conditions, and
estimating the time required for selected lines to produce lines
of 50 % transmittance. An intensity distribution curve is thus
obtained which is particularly useful in comparing the speed of
an individual spectrograph using, say, two different gratings or
two different illuminating systems. The test is less useful in
comparing two or more spectrographs because of uncontrol-
lable variations in illuminating systems, source parameters,
peculiarities of the optical elements, etc. A typical test is
outlined as follows:
6.1.2.1 Source—A d-c arc between an upper negative graph-
ite rod and a lower iron bead in a graphite electrode (iron
globule arc) as described in Practice E 116.
6
A type R.S. sunlamp available at drug stores is suitable.
 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

maximum intensity. Make the half-width measurement with a
mercury pencil lamp.7 The lamp emits a closely spaced doublet
at 3131.55 Å and 3131.83 A, each of which consists of a very
fine line. Carefully align the illumination system of the
spectrograph to yield the maximum resolution (see 6.1.6). Use
a slit of width W such that
W # fl/d
where:
f = focal length of collimator,
d = effective width of dispersing element, and
l = wavelength, A.
Using either the Hg pencil lamp or a low-current (less than
3-A) iron globule arc (see 6.1.1 of Practice E 116), take a series
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
photographed with a transmittance of between 20 and 50 %
(Table 2). Spectrum Analysis No. 1, or an equivalent plate of
low grain size should be used. With a microphotometer slit
width of [frac13] or less that of the width of the line, record the
contour of two adjacent lines on a strip chart. Referencing the
emulsion calibration curve, find the percentage transmittance
of the lines corresponding to one half that of the peak intensity
(which can be set at unity on the calculating board, for
convenience). Referencing the known peak-to-peak distance
between the lines, measure their half-width in angstroms. At
the center of the plate, the half-width as measured shall not
exceed twice theoretical Dl as calculated in 6.1.4. At a distance
equal to 90 % of that measured from the center to the end of the
plate, the ratio shall not exceed 2.5. Shoulders at the base of a
line and coma are serious limitations of this technique. Tenth-
widths can also be measured to avoid this problem. Fig. 2A is
a profile of a resolved line, a photoelectric tracing as it should
appear for a grating spectrograph or spectrometer set on-axis
and exhibiting no aberrations. Both sides of the curve are
symmetrical; the sweep on both sides is without inflection. Fig.
2B indicates a shoulder on the low wavelength side. Note that,
although the halfwidths of spectrograph A and B are identical,
a weak line close to and on the low wavelength side of a strong
line would remain undetected in B where it would appear in A.
Again, in Fig. 2C the half-width remains the same, but lines on
both sides would be obscured.Fig. 2D is an indication of coma
or off-axis aberration. The line profile is asymmetrical; the area
under the curve on the wavelength side away from the optical
center line is greater than on the other side. Coma, increasingly
obvious toward the ends of any spectrographic plate, is seen as
lines that are sharp toward the center of the plate, fuzzy toward
the end. In order to account for all of these conditions, two
figures of merit shall be furnished in describing the resolution
of a spectrograph: (1) the half-width; (2) the width of each
wing of the intensity distribution curve at a value 1⁄10 of
maximum intensity (Table 3). At least three lines, or the same
line in three positions, shall be measured: (1) in the center of
the plate; (2) and (3) at a distance equal to 90 % of the plate
width close to the end of the plate. In other words, for a
7
Spectroline 11SC-1, Black Light Eastern, 24 Kindel St., Westbury, NY, Pen Ray
Quartz Lamp, Ultra Violet Products, San Gabriel, CA, have been found satisfactory.
E 356
500-mm camera, measurements shall be taken about 30 mm
from the ends of the plate to indicate how and if the image is
deteriorating. The resolution of a spectrograph is affected by
many factors. A brief summary of the more important ones is
listed below:
6.1.4.1 Focus—Half-width resolution is much more critical
(3) than visual focus. On a large spectrograph (over 2-m focal
length), moving the slit longitudinally by less than 0.5 mm will
affect the calculated resolution. Also, measurements should be
taken at the center as well as both ends of the focal curve to
check that the focal curve conforms to the Rowland circle.
6.1.4.2 Coma—As a spectrograph operates off its centrol
optical axis, aberrations such as coma disrupt the shape and
sharpness of the lines. The half-widths should be smallest at the
center of the plate.
6.1.4.3 Order—Theoretically, the resolving power of a
spectrograph is proportional to the order, and resolutions
should improve almost equally in the first three or four orders.
Again, be sure the instrument is in optimum focus.
6.1.4.4 Microphotometer Slit Width—Because of the over-
all time constant of the measuring system, a good rule of thumb
is to set the microphotometer slit at a width equal to or less than
[frac13] of the line being measured. The smallest micropho-
tometer slit width commensurate with the stability and sensi-
tivity of the microphotometer amplifier shall be used.
6.1.4.5 Microphotometer Slit Tilt—Unless the slit is abso-
lutely parallel with the line under measurement, false readings
will result. If the contour of the line is asymmetric, that is, if a
line drawn from the peak to the base does not divide the area
in half, the slit is probably not parallel.
6.1.5 Slits—Fixed or adjustable slits are commonly used.
There are advantages to both types, but for best reproducibility
the fixed slits are to be preferred. Slit jaws must be straight,
free of nicks, accurately parallel, and coplanar. Total variation
in slit width along the full length of the slit must not exceed
10 % of the nominal slit width. Adjustable slits should be
accurate to within 610 % of the actual width at any setting and
should be reproducible to within 65 %. Most modern slit jaws
operate bilaterally so the image remains centered. If inter-
changeable fixed slits are provided, positioning must be suffi-
ciently accurate that no change in focus can be detected when
slits are interchanged.
6.1.6 Illuminating System—The illuminating system of a
spectrograph should provide reasonably uniform illumination
of the slit along its entire usable length. In addition, it should
be capable of filling (1) the entire width of the dispersing
element in order to obtain the maximum resolving power of
which the instrument is capable, and (2) the exit aperture of the
system (normally the dispersing element) in order to obtain the
maximum speed of which the instrument is capable. Other
functions such as adjustable masking of certain portions of the
source, intensity controls, etc. are often incorporated into the
design. Such systems always present problems in both geo-
metrical and physical optics with the result that some compro-
mise is usually necessary. For this reason it is essential that
each component of the optical system be described completely
with respect to its optical characteristics and its function in the
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

FIG. 2 Line Profiles Illustrating Limitations of “Half-Width”
Specification of Resolution
6.1.6.1 In order to determine that the slit is uniformly
illuminated, the following test is recommended:
6.1.6.2 Using a slit height of 12 mm and the slit width, W,
given in 6.1.6, photograph an iron spectrum on a medium-
contrast emulsion. Use a low-current a-c arc or a condensed
spark between 3.2-mm diameter iron rods with a 3.2-mm gap.
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-
trance slit as the proper location for step sectors, step filters,
and for an image position for studies in variation along the arc
column. The user should determine the degree of astigmatism
and the convenience of using the secondary focus. The degree
of astigmatism is dependent on the angles of incidence and
diffraction and is, therefore, dependent on both wavelength and
wavelength setting of a particular spectrograph. A nomograph
for calculating astigmatism is given in several texts.3,4 A
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

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