Atomic Emission Spectroscopy with Spark or Arc Excitation 1

Fauftritt

Atomic Emission Spectroscopy

with
Spark- or Arc Excitation

Experiments with the DADOS Spectrograph

and Simple Makeshift Tools

Richard Walker

Version 2.0 August 2012

Atomic Emission Spectroscopy with Spark or Arc Excitation 2

Table of Contents

1 Introduction .................................................................................................................. 3

2 Excitation of Emissions Spectra ................................................................................. 4

3 Tests with Spark Excitation ........................................................................................ 5

4 Tests with Arc Excitation ..........................................................................................24

5 The Link between the Stellar- and Laboratory Spectra .........................................28

6 Appendix .....................................................................................................................31

7 Literature and Internet ..............................................................................................33

Atomic Emission Spectroscopy with Spark or Arc Excitation 3

1 Introduction
It may be little known that even amateur astronomers can generate "laboratory spectra"
with very simple means. This document is intended to demonstrate simple ways, how one
can detect chemical elements in certain materials, liquids and gases, with a spectrograph
and easily available electronic and mechanical components.
The strongly simplified procedures, presented in this document, of course do not allow any
kind of real "Analytical Chemistry". However at least qualitatively, for many substances, the
main components of elements or molecules can be shown. For this purpose, the basic prin-
ciple of Optical Emission Spectroscopy (OES) is applied, which is nowadays in use in com-
mercial, chemical analysis equipments. For this, a sample is excited to such an extent, that
it emits a spectroscopically analysable plasma. The wavelength range of professional appli-
cations reaches mostly from about 2,000 – 10,000 Å. With simple amateur means, analo-
gous to the Astro Spectroscopy, some 3,800 – 8,000 Å can be covered.
My personal motivation was to reproduce the link between the stellar and laboratory spec-
tra - quasi on the "traces" of Fraunhofer, Bunsen and Kirchhoff. If amateurs should be en-
couraged to conduct their own experiments, the purpose of this work would be fully met!
Many thanks to Urs Flükiger, who supported me with metallurgical know-how and arc weld-
ing experiments, carried out with equipment and personnel of his company [62].

Richard Walker, CH 8911 Rifferswil © richiwalker@bluewin.ch

Atomic Emission Spectroscopy with Spark or Arc Excitation 4

2 Excitation of Emissions Spectra

Emission lines can not only be generated in stellar atmospheres and gas discharge lamps,
but also under the influence of flames, electrical sparks and arcs. In the following these
three principles are presented, which are very easy to implement with improvised means. In
the professional area numerous other methods exist. Each of these processes is specifically
suited for certain types of samples.

2.1 Flame Excitation

This is certainly the oldest and also sim-
plest method. Generally known is the
“legendary” Bunsen Burner, which is
omnipresent in most of the laboratories
(picture from [20]). Further also the fact
that common table salt, strewed into the
flame, generates the characteristic yel-
low emission of the sodium doublet D1,
D2. Also many gases can be analised
this way. The intense combustion of hy-
drocarbon gases, such as Butane, pro-
duces directly the emission of the fa-
mous molecular Swan bands (C2), as shown in [13].
The disadvantages of this method are the relatively low excitation energy, the latent fire
hazard, and the damage or even destruction of the sample.

2.2 Spark Excitation

This is also a very old method, already applied by Bunsen and Kirchhoff [20]. An electric
spark generates plasma from a tiny fraction of "vaporized" electrode material, as well as
from the struked gas mixture between the electrodes. Thereby temperatures of some 4000
– 5000 K are achieved, corresponding to the stellar atmospheres of the spectral class K.
This excitation energy is sufficient even for non-destructive analysis of metals and alloys.
Performed with improvised means like piezoelectric
push-button gas igniter eg for BBQ grill or spark induc-
tors, this is a relatively harmless procedure.
In current commercial analytical equipment the spark
excitation of the sample material usually takes place
in an inert argon atmosphere. Picture: portable ana-
lyse equipment with pistol grip from Angstrom Inc.
The electrodes consist partly of a special graphite to
minimise unwanted intrinsic lines in the spectrum.

2.3 Arc Excitation

A little more sensitive, but also more complex, is the excitation of spectra with arcs. In addi-
tion, here an impairment or "consumption" of the sample material is an issue. Here mostly
carbon or tungsten electrodes are used and the temperatures reach some 3000 – 4000 K,
as found in the stellar atmospheres of late-K and all M-Class.
Atomic Emission Spectroscopy with Spark or Arc Excitation 5

3 Tests with Spark Excitation

3.1 Equipment
The easiest and cheapest means for first attempts are certainly the
already mentioned piezoelectric push-button gas igniters. I use for
this purpose the „SUPI V01“, from Conrad Electronics, (spare part
for BBQ gas grill). It generates per push of a button a voltage surge
of about 15 kV, which allows a spark length of >1 cm.
Here mounted into a plastic mug, it is important to keep the two
wires at a sufficient distance to avoid an unwanted arcing (short cut). To attenuate the
noise level, the upper part of the cup is finally stuffed with foam.

The spark gap is mounted on the bottom of an upside down positioned plastic box, de-
signed for electrical installations. The whole is interconnected by plugs to stay as versatile
as possible. The top electrode consists of a short piece of graphite pencil lead, which is at-
tached with a lustre terminal to a thick, stiff but still formable copper wire. Such a graphite
electrode is of course only an imperfect substitute for so-called "spectrally pure" graphite.
Anyway relatively "soft" molecular C2 Swan bands are in any case better than sharp narrow
atomic emission lines of Fe I, which for example would be produced by an iron nail! The
lower electrode consists of the sample holder. For the fastening of different types and
shapes of samples I've created a whole set of different versions. In the right picture a
makeshift container for loose material or liquids can be seen (eg salt).
Atomic Emission Spectroscopy with Spark or Arc Excitation 6

Who plans more extensive tests will probably better use a spark inductor. This may be con-
structed for example using a simple car ignition coil and some additional electronics, which
nowadays replaces the former terribly rattling mechanical interruptor. Under these key-
words numerous construction guidances are to find on the Internet.

3.2 Design and Implementation of the Experiment

The DADOS spectrograph with CCD camera is mounted on a tripod. Absolutely necessary is
a focus lens that produces a sharp image of the sample on the slit plate. For this purpose I
use an ancient VIVITAR macro zoom lens. This requirement could also be met using a sim-
ple close-up lens of appropriate focal length. The spectra are recorded here with a mono-
chrome camera Meade DSI III Pro. The line identification was performed using the listed
references, the “elements” or “lineident” tool of the Vspec software [52], as well as the
NIST Atomic Spectra Database [31].

Logically, during the spark discharge the part of the

generated plasma is recorded, which is located just on
the slit of the spectrograph. Therefore, the impact
point of the spark on the sample must be centered on
the slit as precisely as possible. Preferred impact
points are sharp tips, corners or edges.
The necessity of this procedure shows a simple exper-
iment. If the upper graphite electrode is positioned on
the slit, one obtains a spectrum of Swan emission
bands with molecular C2, which is typical for carbon
compounds (Table 1). Aimed on the center of the arc-over between the two electrodes re-
sults in the characteristic spectrum of a lightning strike, with lines of ionised air compo-
nents, ie above all, O II and N II (Table 2). Focused on the sample appears its emission spec-
trum, possibly superimposed by the spark spectrum of the air molecules, because the test
is carried out here without the protection of any argon or another inert gas. In this case, a
previously recorded spark spectrum of the air must be subtracted or be displayed together
with the sample spectrum. Thus, it becomes immediately clear which emissions originate
Atomic Emission Spectroscopy with Spark or Arc Excitation 7

from the sample and which from the air molecules. Should only the spark spectrum of the
air be visible, in most cases, the impact point of the spark was not positioned accurately
enough on the slit of the spectrograph. Therefore, it is always worth to take several shots
with a slightly altered perspective. The spark should hit diagonally from the side onto the
sample and not run in the slit axis – such as it is shown on the picture above.
For the 200L grating in a darkened room, exposure times <15 seconds have been proven.
During this time, the spark was triggered about 10 times. With the 900L grating about 30
seconds, combined with approximately 20 – 30 spark strikes are necessary. Here own ex-
periments are essential. Who is tired of the noise from manually triggerd sparks should
soon change to a sparc inducor. Computer monitors should be turned off during the record-
ings or turned away because they produce itself relatively intense emission lines.
The following experiments were carried out with electrically conductive samples, which
were used directly as electrodes. Non-conductive materials must first be prepared accord-
ingly. In the literature, e.g. the coating of the surface with graphite powder, etc. is recom-
mended. For liquids, [21] for example suggests the impregnation of coal pills, available in
pharmacies.

3.3 Results
Table 1:
Table 1 shows the spectrum of the graphite electrode, i.e. the typical C2 Swan bands, pro-
duced for example by comets and carbon stars [13]. Superimposed is here the spark spec-
trum of the air molecules, which consists of emissions of ionised oxygen O II, -nitrogen N II
and the hydrogen line Hα. The strong sodium emission (Fraunhofer D1 and D2) shows up in
most such material spectra as a dominant byproduct or "contamination" due to the low ex-
citation energy of Na. This was already noticed by Bunsen and Kirchhoff – excerpts from
[20], translated here from German to English:
…Of all the spectral responses the one of sodium is most sensitive. The yellow line, the only
one which sodium exhibits in the spectrum, coincides with the Fraunhofer D line and is
characterized by a particularly sharp boundary and its exceptional brightness. If the flame
temperature is very high and the amount of the applied substance very large a continuous
spectrum in the immediate vicinity of the line becomes evident. Intrinsicly weak
neigbouring lines of other substances appear to be even more weakened and some of them
remain often invisible until the reaction of sodium expires…
…Already Swan has advised to the just small amounts of salt, which are necessary to gen-
erate very intense sodium lines. The following experiment shows that in the field of chemis-
try no other reaction can be compared, not even remotely, with the sensitivity of spectro-
scopic determination of sodium. We deflagrated in the furthermost corner of the observa-
tion room, which holds about 60 cubic meters of air, 3 milligrams sodium chlorate with milk
sugar. After a few minutes a strong sodium line appeared, wich completely disappeared
just after 10 minutes.

To a somewhat lesser extent than the sodium, also calcium lines (Ca I and Ca II) may ap-
pear as a byproduct in such material spectra.
 Atomic Emission Spectroscopy with Spark or Arc Excitation 8

©Richard Walker 2011/02

TABLE 1
Composite Spectrum: Graphite Electrode + Air DADOS 200L/mm

Hα 6562.82
O I 7157

N II 5932/42
Na l 5890/96
Komposit Graphit + Luft

N II 5667/79
C2 5636
C2 5585
C2 5541
C2 5502

C2 5165
C2 5130

N II 5004/6

C2 4737
C2 4715
C2 4698
C2 4685 O II / N II
Green: Byproducts or contaminations
Black: Emission lines Air (N II, O II)

N II 6611 N II 4447
Red: Emission lines Graphite

Hα 6562.85
Legend:

N II 6482
Atomic Emission Spectroscopy with Spark or Arc Excitation 9

Table 2:
Table 2 shows the spark spectrum of the air molecules, recorded in the middle between the
two graphite electrodes. Here just emission lines of the air and no remnants of C2 Swan
bands or any other carbon molecules can be detected.
This profile shows, not surprisingly, striking similarities with a lightning spectrum (see table
2a), which is dominated by the emissions of singly ionised nitrogen (N II) and oxygen (O II).
The most intense lines are the cause for the bluish-white color of the lightning or spark. On-
ly the usually strong hydrogen emissions, typically observed in the lightning spectra, appear
here just weak in this experimental setup. Interestingly, however, they are more or less
intensly visible in most material spectra, even if the assessed samples hardly contain any
hydrogen.
Table 2a:
Table 2 shows a lightning spectrum, which was recorded via cloud reflection. The C8 tele-
scope was set up in the living room at night with DADOS and Atik314L+, aiming through
the closed window on the approaching thunderstorm. Three shots have been processed,
each 180 seconds in 2x2 binning mode. Per exposure the reflected light of about 5-10
lightning strokes has been recorded. Since the cloud base was very low, on all shots the
light pollution had to be subtracted. Striking is the intense CN emission at about 3900A.
Already since the beginning of spectroscopy in the 19 century, it was attempted to gain
spectra of lightning discharges. To the beginning of the 20th century also well known as-
tronomers have been involved like Pickering and Slipher. The lightning research today is
particularly interested in the course of intensity, plotted against time, of the individual
emission lines during a lightning strike. This allows conclusions about the physical pro-
cesses that are active during the various phases of this phenomenon. The following dia-
grams from [15], taken with high-speed cameras, show the intensity profile of a lightning
spectrum in a time span of 0–50 μ sec and plotted in the range of 4,000-5,000 Å.
 Atomic Emission Spectroscopy with Spark or Arc Excitation 10

©Richard Walker 2011/02

TABLE 2

Hα 6562.85

N II 5932/42
DADOS 200L/mm

N II 5667/79

N II 5535
N II 5496

N II / O II 5179

N II 5001 - 07 N II 5045

O II 4943
Hβ 4861 / N II 4859
Spark spectrum of air

N II 4803.3
N II 4780/88
Black: Emission lines Air (N II, O II)

O II 4700/05
N II 4630/43
N II 4601/07

N II 4510/14
N II 4447
O II
O II 4349

N II 4227 - 37
O II 4190
O II 4119 - 53
N II 4097
Legend:

O II 4072/76
N II 4041
N II 3995
 Atomic Emission Spectroscopy with Spark or Arc Excitation 11

©Richard Walker 2012/08

TABLE 2a O I 7157

O II 6721.35
O II 6640.9
Hα 6562.83
N I 6482 - 84
N I 6441 - 57

O I 6156- 58
OI
N I 6008
N II
NI
N I / N II
N II 5670- 90
N I 5616- 23
N I 5560- 64
Atik 314L+ -2°C, 3x180s, 2x2 Binning (ca. 30 Lightning strokes)
C8, DADOS: Grating 200L mm-1, Slit width 25μm 4.8.2012

N II / OI
Lightning Cloud Reflection

N II 5171 -99

N II 5001 - 07
N I 4915
Hβ 4861

N II/O II

N I / O II
Hγ / N I / O II
N I / N II / OI
Hδ /N II / O II
N II 4041 - 44
N II 3995
O II 3910 - 26 OI
CN 3871 ?
Atomic Emission Spectroscopy with Spark or Arc Excitation 12

Table 3 to 7:
The tables 3 to 7 show the spectrum of C15E steel/materialnumber 1.1141 (hereafter
called “C15 E”). Chemical additives in [%] according to [62]:
Chemische Zusammensetzung (in %)
C carbon: 0.12 – 0.18
Si silicium: max. 0.40
Mn manganese: 0.30 – 0.60
P phosphor: max. 0.035
S sulfur: max. 0.035

Besides the main component Fe in the higher-resolution spectra only Mn (0.4%) is detecta-
ble. The numerous Fe lines could theoretically be used to calibrate a spectrum. Since there
are smarter ways however, as to fire up the spark coil each time. The profiles are
unnormalised and uncorrected pseudocontinua.

Table 3: Low-resolution (200L) composite spectrum:

C15E steel + spark spectrum of air.

Table 4: 900L composite spectrum in the range 3900 – 4800 Å of C15E steel + spark
spectrum of air (blue profile). See also Table 20, where this spectrum is compared with the
profile of the sun. Shown here is also the separately recorded air spectrum without iron
lines (red curve).

Table 4a: C15E steel spectrum from Table 4 after subtraction of the air spectrum. Neverthe-
less, here some weaker emission lines of the air can still be seen. The iron lines show up
here more intensive (subtraction with the Vspec function "Subtract Profile by Profile").

Table 5: dito Table 4, here in the range of 4650 – 5550 Å

Table 6: dito Table 4, here in the range of 5550 – 6450 Å and without a superposed air
spectrum, because almost no Fe I lines show up here.

Table 7: dito Table 6, here in the range of 6450 – 7400 Å

.
 Atomic Emission Spectroscopy with Spark or Arc Excitation 13

©Richard Walker 2011/02

TABLE 3
K I 6964 ?

Green: By-products or contaminations

Black: Emission lines Air (N II, O II)
Red: Emission lines steel C15E
Composite Spectrum: C15E Steel + Air DADOS 200L/mm

Hα 6562.82
Legend:

N II 5932/42
Na l 5890/96

N II 5667/79
Fe I 5615
N II 5535
Fe I 5455
Fe I 5406
Fe I 5369-71
Fe I 5328
Fe I 5269-72
Fe I 5227/33
N II / O II 5179
Fe I 5139

N II 5001 - 07
Fe I 4958
Fe I 4920
Fe I 4891
Fe I 4871
N II 4788
O II 4706
O II 4664/76
N II 4630/43
N II 4601
N II 4510/14

N II 4447
Fe I 4404.75
Fe I 4383.54
Fe I 4326
Fe I 4308
Fe I 4271
Ca I/N II/Fe I 4226 - 28
O II 4190
O II 4119 - 53
Fe I 4071
N II 4041 / Fe I 4046
N II 3995
Ca II 3968.47
Ca II 3933.66
Fe I 3878
Fe I 3856
 Atomic Emission Spectroscopy with Spark or Arc Excitation 14

©Richard Walker 2011/02

N II 4788

TABLE 4
O II 4700/05

O II 4676
O II 4662
O II 4649
O II 4642 + N II 4643
Composite Spectrum: C15E Steel + Air DADOS 900L/mm

N I 4630.54
N II 4621
N II 4614
N II 4607
N II 4601

N II 4596
N II 4591
N II 4530
Composite spectrum C15 E + Air

N II 4510/14

O II 4466
Spark Spectrum Air

N II 4447

O II/Fe I 4415
Fe I 4404.75
O II 4396
Fe I 4383.55
O II 4367-68
O II 4349

Fe I 4325.76
O II 4317.14
Fe I 4307.9

Fe I 4271.15
Fe I 4260.47
Fe I 4250.8
Fe I 4236 N II 4237
Ca I/Fe I 4227 N II 4227

Fe I 4199 N II 4200
O II/N II 4190/95
Fe I 4175
O II 4153
Green: By-products or contaminations

O II 4146
Black: Emission lines Air (N II, O II)

O II 4132.8
Red: Emission lines steel C15E

O II 4119.22

O II 4076 N II 4097

Fe I 4071.7 O II 4072/76
Fe I 4062
Mn I 4057.9
N II 4041
Fe I 4045.8
Legend:

Fe I 4005
N II 3995

Ca II 3968.47

Ca II 3933.66
 Atomic Emission Spectroscopy with Spark or Arc Excitation 15

©Richard Walker 2011/02

TABLE 4a
C15E-Steel Spectrum after Subtraction of the Air Spectrum 900L/mm

Fe I 4404.75
Fe I 4383.55

Fe I 4325.76
Fe I 4307.9

Fe I 4271.15
Fe I 4260.47
Fe I 4250.12

Ca I/Fe I 4227

Fe I 4071.7
Fe I 4062
Mn I 4057.9
Fe I 4045.8

N II 3995

Ca II 3968.47

Ca II 3933.66
 Atomic Emission Spectroscopy with Spark or Arc Excitation 16

©Richard Walker 2011/02

TABLE 5
N II 5535

N II 5496
N II 5480

Fe I 5455

Fe I 5406

Fe I 5341
Composite Spectrum: C15E Steel + Air DADOS 900L/mm

Fe I 5369 - 71

Fe I 5341
Fe I 5328
Fe I 5324

Fe I 5269 - 72
Composite spectrum C15 E + Air

Fe I 5233
Fe I 5227
Spark Spectrum Air

Fe I 5192
N II / O II 5179

Fe I 5139

Fe I 5075

N II 5045

N II 5001 - 5007

Fe I 4957.6
O II 4943

Fe I 4920.5

Fe I 4891
Green: By-products or contaminations
Black: Emission lines Air (N II, O II)

Fe I 4871
Hβ 4861 / N II 4859
Red: Emission lines steel C15E

N II 4803.3
N II 4788
N II 4779.71
Legend:

Fe I 4737

O II 4705.36
O II 4699.21
O II 4676.23
 Composite Spectrum: C15E Steel + Air DADOS 900L/mm
Legend:
Composite spectrum C15 E + Air
Black: Emission lines Air (N II, O II)
Red: Emission lines steel C15E
TABLE 6

Na I 5889.95
Green: By-products or contaminations

N II 5679.56
Na I 5895.92

N II 5666.63
Atomic Emission Spectroscopy with Spark or Arc Excitation

N II 5941.65
N II 5931.78

N II 5535
N II 5710.77

Fe I 5616
17

©Richard Walker 2011/02

 Composite Spectrum: C15E Steel + Air DADOS 900L/mm
Legend:
Composite spectrum C15 E + Air
Black: Emission lines Air (N II, O II)
Red: Emission lines steel C15E
Green: By-products or contaminations
TABLE 7

N II 6611
Atomic Emission Spectroscopy with Spark or Arc Excitation

Hα 6562.85

N II 6482
O I 7157
18

©Richard Walker 2011/02

Atomic Emission Spectroscopy with Spark or Arc Excitation 19

Table 8: Low-resolution (200L) composite spectrum:

Galvanized steel + spark spectrum of air.
Striking are here, as expected, the emission lines of zinc. “Front runner” is clearly the line at
4810.53 Å. In this profile it is clearly noticeable that the emission lines of the air show up
relatively modest, particularly the otherwise intense line, N II 5001 – 5007 Å, is missing
here even totally. There is also no strong continuum visible. The reason for this effect re-
mains unclear until now. Perhaps the spectrograph slit was accidentally aligned here very
precisely to the impact site of the spark.

Table 9: Low-resolution (200L) composite spectrum: aluminum + spark spectrum of air.

Here three aluminum emissions in the blue region of the spectrum are dominant. Also in
this profile, it is striking that the emission lines of the air appear relatively modest and a
strong continuum is missing. Two clusters with emission lines in the range of
4600 – 4750 Å and 5100 – 5200 Å, can currently not be clearly identified.

Table 10: Low-resolution (200L) composite spectrum: copper wire + spectrum of air.
At first the insulation varnish was removed from the copper wire. Also here a strong contin-
uum is missing. Striking are here three dominant copper lines in the range of 5100 - 5300
Å. Several others are blended with N II and O II emissions, which appear here relatively in-
tensive. Noteworthy are also the by-products, i.e. Na I and Ca II lines.

Table 11: Low-resolution (200L) composite spectrum, recorded with Urs Flükiger in his
company in Oberburg, Switzerland. Sample: Tool steel coated with titanium oxide (Ti O2).
Well visible are here emission bands of diatomic titanium monox-
ide molecules (TiO) and atomic Ti lines. Titanium dioxide (Ti O2) at
such high temperatures > 3000 K, dissociates to titanium monox-
ide (Ti O) like in the stellar atmospheres, down to late M-Class.
The air spectrum appears here only weak. See also Table 21,
where a section of this spectrum is shown in a montage with the
profile of Ras Algethi (α Her). In the area of 5000 Å, however, the
leading line of the air spectrum, the intense emission of N II, is
blended with the TiO bands.
Because in this experiment the spark had to penetrate the titanium oxide layer, it was cor-
respondingly weaker. Therefore to improve the recognisability of the absorption bands, the
exposure time was increased here to 1 minute and the spark was triggered approximately
150 times. If the spark hits an edge or corner of the sample, there is a risk that the coating
is here too thin or no longer present. Therefore it has proven to be ideal, when the spark
hits the center of the sample at a right angle and the picture is recorded approximately in
the surface plane. So it does not matter if the impact point slightly moves.
Remark: Several attempts failed so far, to generate emission lines of gold. In each case only
the spectrum of the air molecules was obtained. The reason is still unknown.
Composite Spectrum: Galvanised Steel + Air DADOS 200L/mm

Legend:
TABLE 8

Black: Emission lines Air (N II, O II)

Red: Emission lines galvanised steel

Zn I 4810.53
Green: By-products or contaminations

Zn I 4722.15
Atomic Emission Spectroscopy with Spark or Arc Excitation

N II 4041
N II 3995
Zn I 4680.14

Mn I ?
N II 4195
Na l 5890/96

O II/N II ?
Zn I 6362.34

Mn I ?
Mn I ?

N II 4097
20

©Richard Walker 2011/02

 Atomic Emission Spectroscopy with Spark or Arc Excitation 21

©Richard Walker 2011/02

TABLE 9

Green: By-products or contaminations

Black: Emission lines Air (N II, O II)
Red: Emission Aluminum
DADOS 200L/mm

Hα 6562.85
Legend:

Na l 5890/96
Composite Spectrum: Aluminum + Air

N II 5667/79

C2 ?

N II 5001 - 07

N II / Hβ 4859/61

O II ?

Al II 4226.81

Al I 3961.52
Al I 3944.0
 Atomic Emission Spectroscopy with Spark or Arc Excitation 22

©Richard Walker 2011/02

TABLE 10

Hα 6562.85

Green: By-products or contaminations

Black: Emission lines Air (N II, O II)
Red: Emission Copper Wire
DADOS 200L/mm

Cu II 6154.22
Legend:

N II 5932/42
Na l 5890/96

Cu I 5782.13
Cu I 5700.24
N II 5667/79
Composite Spectrum: Copper Wire + Air

Cu I 5292.52
Cu I 5218.2
Cu I 5153.24
Cu I 5105.54

Cu I / N II 5001 - 07

N II 4803.3

O II 4700/05
Cu I 4651.12 / N II 4630/43

N II 4447

Cu I 4062.6 / O II 4349
Cu I 4275.1
Cu I 4230 / N II 4227 – 37 / Ca I
O II 4190
O II 4119 - 53
N II 4041
N II 3995
Ca II 3968.47
Ca II 3933.66
Fe I 3906.48 ?
 Atomic Emission Spectroscopy with Spark or Arc Excitation 23

©Richard Walker 2011/03

TABLE 11 ?
?
?
Hα 6562.82

Green: By-products or contaminations

Black: Emission lines Air (N II, O II)
Red: Emission Titanium Monoxide
Composite Spectrum: Titanium Monoxide (Ti O) Coating + Air

TiO 6268
Legend:

Na I 5889/95
DADOS 200L/mm

TiO 5497
TiO 5448/51

N II / O II 5179
TiO 5167

TiO 5003/5020 N II 5001 - 07

TiO 4804
TiO 4761-63
TiO 4704
TiO 4668
TiO 4626

Ti I/ TiO 4531/36

N II 4447
Ti I 4390/93
Ti I 4300
Ti I 4263
O II 4190
Ti I 4137
Ti I 4055
Ti I 3989.76
Ca II/Ti 3934
Atomic Emission Spectroscopy with Spark or Arc Excitation 24

4 Tests with Arc Excitation

4.1 Design and Implementation of the Experiment
Professionally arc spectra are obtained in an inert protective gas atmosphere with elec-
trodes, made of tungsten or spectrally pure high density graphite. In the factory of Urs
Flükiger in Oberburg Switzerland [61] we have attempted to simulate this rudimentary with
an ordinary electric welding machine and a rutile-acide type electrode (Ti O2). An additional
test was carried out with a TIG electrode, combined with argon gas (TIG: Tungsten-Inert-
Gas).
Picture: Electric welding with rutile coated electrode. DADOS spektrograph and old VIVITAR
macro zoom lens on an AYO mount, distance ca. 3m. Urs Flückiger (left picture in the back-
ground), recording the spectra on the laptop.

TIG welding with Argon protective gas (Mr. Baumgartner)

Atomic Emission Spectroscopy with Spark or Arc Excitation 25

4.2 Results
Table 15: Electric arc, simulated with electric welding machine and rutile-acide type elec-
trode (Ti O2). Low-resolution (200L) composite spectrum: steel 37, materialnumber
1.0037, (herafter called “steel 37”) + spectrum of air. The comparison with the spark spec-
trum shows that the arc spectrum is resolved somewhat higher. In addition to the lines of
Fe I atoms and air molecules here very numerous atomic and molecular emissions of titani-
um appear (Ti / TiO), obviously originating from the mineral rutile (Ti O2) of the welding
electrode. The distinction between Fe I and Ti I has proven to be difficult and uncertain.
These lines are often separated only by a fraction of 1Å. Also striking is the broad Na I
emission with a central self-absorption dip, as can be observed in the spectra of high-
pressure sodium vapor lamps (see [13]).

Table 16: Electric arc, simulated with electric welding machine, TIG electrode, combined
with argon gas. Low-resolution (200L) composite spectrum: steel 37 + spectrum of air.
In older welding systems radioactive thoriumoxide improved the ignition. This tungsten
electrode is free of radioactive thorium here because Flükiger & Co Ltd applies modern
welding equipment and high-voltage ignition with appropriate control system. Consequent-
ly, such emission lines are her absent in the spectrum.
The profile is impressively dominated by intensive emissions of argon protective gas Ar I. To
make the Fe I lines at all visible, a strong zoom in to the intensity axis was necessary. In the
red region of the spectrum, therefore most of the Ar I emission appear cutted. In reality,
they are about two to three times as high! Clearly visible here is the protective effect of ar-
gon gas. The emissions of the air molecules are weak. The "front runner line" N II at 5000 –
5007 Å is here even completely missing!
 Atomic Emission Spectroscopy with Spark or Arc Excitation 26

©Richard Walker 2011/03

TABLE 15 Fe I 6945 ?
Fe I 6917 ?

Fe I 6710 – 13 ?
Green: By-products or contaminations
Black: Emission lines Air (N II, O II)
Red: Emission steel 37/C15E

Hα 6562.82

TiO 6268
Legend:

TiO 6159

Fe I 6015-18
N II 5932/42
Na l 5890/96
Fe I 5800
Spark Spectrum C15E DADOS 200L/mm
Comparison Arc Spectrum Steel 37 versus

N II 5667/79

N II 5535
Fe I 5512-13
Fe I 5455
Fe I 5406
Fe I 5369-71
Arc Spectrum Stahl 37
Spark Spectrum C15E

Fe I 5328
Fe I 5269-72
Fe I 5205 Fe I 5227/33
Fe I 5170 N II / O II 5179

Fe I 5065
Ti I 5038
N II 5001 - 07
Fe I 4958
Fe I 4985-87 Fe I 4920
Fe I 4891
Fe I 4871
Ti I 48251
TiO 4761/63
TiO 4761/63

N II/OII

Ti I 4531
Ti I 4457
Fe I 4405
Fe I 4383.54
Ti I 4300/Fe I 4271 4326
Ca I/N II/Fe I 4226 - 28
O II 4190
O II 4119 - 53

N II 4041 / Fe I 4046/71
N II 3995
Ca II 3968.47
Ca II 3933.66
Fe I 3878
Atomic Emission Spectroscopy with Spark or Arc Excitation 27

Ar I 7384

©Richard Walker 2011/02

TABLE 16 Ar I 7272.94
Ar I 7316

Ar I 7206.98
Ar I 7158.84
Ar I 7067.22
Ar I 7030.25
Ar I 6965.43
Ar I 6937.66
Ar I 6871.3
DADOS 200L/mm

Ar I 6752.83

Hα 6562.82

Fe I 6416 - 19

?
Fe I 6220
?
?
?
Fe I 5914
Steel 37 + Air

Na l 5890/96 ?
Fe I 5860/61
Fe I 5835
Fe I 5740
Ar I 5650
Fe I 5610
Fe I 5563 - 66
Ar I 5496
Fe I 5455
Fe I 5406
Fe I 5369-71
Fe I 5328
Fe I 5269-72
Fe I 5227/33
Composite Arc Spectrum:

N II / O II 5179
Blue: Emission lines protective gas Ar
Green: By-products or contaminations
Black: Emission lines Air (N II, O II)

Fe I 4958
Fe I 4920
Fe I 4891
Red: Emission steel 37

N II 4780/88

Ar I 4628.44
Ar I 4596
Legend:

Ar I 4510 / 22
N II 4447
Fe I 4383.54
Ar I 4333 / 35 / 45
Ar I 4300
Ar I 4259 / 66 /72
Ar I 4198 / 00
?
Ar I 4158 / 64

N II 4041 / Fe I 4046/71
Ca II 3968.47
Ca II 3933.66
Fe I 3856 Fe I 3878
Atomic Emission Spectroscopy with Spark or Arc Excitation 28

5 The Link between the Stellar- and Laboratory Spectra

Table 20:
Shows in the blue range the comparison of the higher resolution (900L) composite spec-
trum of C15E (according to Table 4) and the solar spectrum. All Fe I and Ca II lines of the
sparc spectrum, can be clearly identified in the solar spectrum. Several iron lines in the
spark spectrum are overprinted here by the much more intensive emissions of the air mole-
cules (O II, N II) and therefore not available for a link to the solar spectrum.

Table 21:
Profile comparison, range from 4650 - 5900 Å, titanium oxide bands (TiO) (200L grating):
– Spark spectrum TiO emission bands of a surface coating (according to Table 11)
versus
– Stellar TiO absorption bands of Ras Algethi (α Her).
In this wavelength range in the spectrum of the surface coating appear clearly visible emis-
sions of TiO bands. The intensity runs approximately mirror inverted to the characteristic
absorption bands of the late M-class star α Her. The emissions of air molecules are here
relatively weak. At 5000 Å however, N II forms an intense blend with the TiO bands.
 Atomic Emission Spectroscopy with Spark or Arc Excitation 29

©Richard Walker 2011/02

TABLE 20 Fe I 4415
Fe I 4405

Fe I 4383

O II 4367-68

O II 4349
Sun versus C15E (+ Air) 900L/mm

Hγ 4340.47

Fe I 4326
O II 4317.14

CH 4299 - 4313 Fe I 4308

Composite spectrum C15 E + Air

Fe I 4271
Fe I 4260
Fe I 4250
Spectrum of the Sun

Fe I 4236
Fe I 4227 / Ca I
N II 4227

Fe I 4199 N II 4200
O II/N II 4190/95

Fe I 4175

O II 4153
O II 4146
O II 4132.8

O II 4119.22

Hδ 4101.74
N II 4097

O II 4076
Fe I 4072 O II 4072/76
Comparison of Spectra:

Fe I 4062
Blue: Absorption lines spectrum of the sun

Fe I/Mn I 4058
Fe I 4046
Green: By-products or contaminations
Black: Emission lines Air (N II, O II)

N II 4041
Red: Emission steel C15E

Fe I 4005
N II 3995

Ca II 3968.47
Legend:

Ca II 3933.66
 Atomic Emission Spectroscopy with Spark or Arc Excitation 30

Na l 5889/95

©Richard Walker 2011/03

TABLE 21 TiO 5847
TiO 5814
Comparison TiO2 Coating and Ras Algethi (α Her M5 Ib-Il) 200L/mm

TiO 5760

TiO 5668

TiO 5597/03
Composite spectrum TiO2 Coating + Air

TiO 5497

TiO 5448/51
Spectrum Ras Algethi

TiO 5359

TiO 5308

TiO 5240

N II / O II 5179
TiO 5167

TiO 5003/20 5020

N II 5001 - 07
TiO 4955

TiO 4847 N II 4859

TiO 4804

TiO 4761

TiO 4704
TiO 4668
Atomic Emission Spectroscopy with Spark or Arc Excitation 31

6 Appendix
6.1 Kirchhoff's hand-drawn Spectra [20].
The Fraunhofer absorption lines of the sun (top line) compared to the emission spectra of
the elements Ka (today K), Na, Li, Sr, Ca und Ba.
Atomic Emission Spectroscopy with Spark or Arc Excitation 32

6.2 Vatican Spectral Atlases of Elements and Molecules

The Vatican Observatory in 1930-40 published several fundamental works with spark and
arc spectra, continuing the tradition of the legendary Father Secchi, who wrote in the 19th
century the first stellar spectroscopic atlas. The driving force behind this project was Father
Alois Gatterer. The following pictures are from the antiquarian book J. Ricerche
Spettroscopiche, from J. Junkes and E.W. Saltpeter [1].
Atomic Emission Spectroscopy with Spark or Arc Excitation 33

7 Literature and Internet

Literature:
[1] Ricerche Spettroscopiche, J. Junkes, E.W. Salpeter, 1966, Laboratorio Astrofisico Della Specola
Vaticana. Dreissig Jahre Spektralatlanten des Astrophysikalischen Laboratoriums der Vatikanischen
Sternwarte. Vergriffen, nur noch antiquarisch erhältlich.

Internet Links:
Author:
The following scripts on the subject are downloadable under this link (some of them in german):
http://www.ursusmajor.ch/astrospektroskopie/richard-walkers-page/index.html
[10] Analysis and Interpretation of Astronomical Spectra, Theoretical Background and Practical
Applications for Amateur Astronomers
[11] Das Aufbereiten und Auswerten von Spektralprofilen mit den wichtigsten IRIS und Vspec
Funktionen
[12] Kalibrierung von Spektren mit der Xenon Stroboskoplampe
[12a] Kalibrierung von Spektren mit dem Glimmstarter ST 111 von OSRAM
[13] Spectroscopic Atlas for Amateur Astronomers
[14] Quasar 3C273, Optical Spectrum and Determination of the Redshift
Lightning Spectroscopy:
[15] A High-Speed Time-Resolved Spectroscopic Study of the Lightning Return Stroke: Part I, a Quali-
tative Analysis, Richard E. Orville, Institute of Atmospheric Physics, Tucson Arizona.
http://journals.ametsoc.org/doi/pdf/10.1175/1520-0469(1968)025%3C0827%3AAHSTRS%3E2.0.CO%3B2
[16] The optical spectrum of aircraft St. Elmos fire, E.M. Wescot et al. University of Alasca, 1996.
http://www.uas.alaska.edu/artssciences/naturalsciences/envs/faculty_staff/pubs/wescott96_stelmo.pdf
[17] Lightning Physics and Effects, V. Rakov, M. Uman
[18] The Spectrum of Lightning, L. Wallace, Kit Peak, National Observatory
http://adsabs.harvard.edu/full/1964ApJ...139..994W
[19] Lightning Spectroscopy, T. Walker, H. Christian, D. Sentman
Emission Spectroscopy (German language)
[20] Chemische Analyse durch Spectralbeobachtungen, G. Kirchhoff R. Bunsen, Annalen der Physik
und [20]Chemie 1860, http://www.ub.uni-heidelberg.de/helios/fachinfo/www/physik/erg/spek.pdf
[21] http://www.students.uni-mainz.de/jungc000/uugit/inhaltsv.htm
Inhaltsverzeichnis mit zahlreichen Ideen und Tips zur Funken- und Flammenspektroskopie u.a. unter
der Rubrik „Chemische Analysen“.
[22] Phasenaufgelöste, optische Emissionsspektroskopie an RF Plasmarandschichten, Diplomarbeit
2007, S. Nemschokmichal, Universität Greifswald
http://www1.physik.uni-greifswald.de/download/dissertationen/dip-nemschokmichal.pdf
Database
[31] NIST Atomic Spectra Database:
http://physics.nist.gov/PhysRefData/ASD/lines_form.html
[32] Simulated emissionspectra of all elements,
http://bmauclaire.free.fr/astronomie/spectro/simulation/noblet/index2.htm
Atomic Emission Spectroscopy with Spark or Arc Excitation 34

Metallurgy and Welding Technology (German language)

[61] Flükiger & Co AG - Industrieschmiede, Emmentalstrasse 75, CH 3414 Oberburg
http://www.fluekiger.ch/
[62] Werkstoffdatenblatt Voegelin AG, C15E Stahl/Werkstoffnummer 1.1141
http://www.voegelinag.ch/DE/Dokumente/Werkstoffdatenblatt_C15E.pdf