Atomic Emission Spectroscopy with Spark or Arc Excitation

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

Table of Contents
1 2 3 4 5 6 7 Introduction .................................................................................................................. 3 Excitation of Emissions Spectra ................................................................................. 4 Tests with Spark Excitation ........................................................................................ 5 Tests with Arc Excitation ..........................................................................................24 The Link between the Stellar- and Laboratory Spectra .........................................28 Appendix .....................................................................................................................31 Literature and Internet ..............................................................................................33

Atomic Emission Spectroscopy with Spark or Arc Excitation

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 principle of Optical Emission Spectroscopy (OES) is applied, which is nowadays in use in commercial, 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 applications reaches mostly from about 2,000 10,000 . With simple amateur means, analogous to the Astro Spectroscopy, some 3,800 8,000 can be covered. My personal motivation was to reproduce the link between the stellar and laboratory spectra - quasi on the "traces" of Fraunhofer, Bunsen and Kirchhoff. If amateurs should be encouraged to conduct their own experiments, the purpose of this work would be fully met! Many thanks to Urs Flkiger, who supported me with metallurgical know-how and arc welding 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

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 simplest 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 yellow emission of the sodium doublet D1, D2. Also many gases can be analised this way. The intense combustion of hydrocarbon gases, such as Butane, produces directly the emission of the famous 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 inductors, 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 analyse 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 addition, 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

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, designed 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 attached 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

Who plans more extensive tests will probably better use a spark inductor. This may be constructed for example using a simple car ignition coil and some additional electronics, which nowadays replaces the former terribly rattling mechanical interruptor. Under these keywords 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 simple close-up lens of appropriate focal length. The spectra are recorded here with a monochrome 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 experiment. 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 results in the characteristic spectrum of a lightning strike, with lines of ionised air components, ie above all, O II and N II (Table 2). Focused on the sample appears its emission spectrum, 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 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 experiments 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 recordings 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 accordingly. In the literature, e.g. the coating of the surface with graphite powder, etc. is recommended. 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, produced for example by comets and carbon stars [13]. Superimposed is here the spark spectrum of the air molecules, which consists of emissions of ionised oxygen O II, -nitrogen N II and the hydrogen line H. 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 excitation 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 generate very intense sodium lines. The following experiment shows that in the field of chemistry no other reaction can be compared, not even remotely, with the sensitivity of spectroscopic determination of sodium. We deflagrated in the furthermost corner of the observation 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 appear as a byproduct in such material spectra.

Atomic Emission Spectroscopy with Spark or Arc Excitation

TABLE 1

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

H 6562.82

O I 7157

Komposit Graphit + Luft

Na l 5890/96

N II 5932/42

C2 5636 C2 5585 C2 5541 C2 5502

N II 5667/79

C2 5165

C2 5130
N II 5004/6

C2 4715 C2 4698
Black: Emission lines Air (N II, O II) Red: Emission lines Graphite Green: Byproducts or contaminations

C2 4737

C2 4685

O II / N II N II 6611

N II 4447

H 6562.85

Legend:

N II 6482

Richard Walker 2011/02

Atomic Emission Spectroscopy with Spark or Arc Excitation 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. Only 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 telescope 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 astronomers 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 processes that are active during the various phases of this phenomenon. The following diagrams from [15], taken with high-speed cameras, show the intensity profile of a lightning spectrum in a time span of 050 sec and plotted in the range of 4,000-5,000 .

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TABLE 2

H 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 H 4861 / N II 4859 N II 4803.3 N II 4780/88 O II 4700/05

Spark spectrum of air

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

N II 4630/43

N II 4601/07

N II 4510/14 N II 4447 O II O II 4349 N II 4227 - 37

N II 4097 O II 4072/76 O II 4190

O II 4119 - 53

N II 4041 N II 3995

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TABLE 2a

O I 7157

H 6562.83

O II 6721.35 O II 6640.9 N I 6482 - 84 N I 6441 - 57 O I 6156- 58

C8, DADOS: Grating 200L mm-1, Slit width 25m 4.8.2012 Atik 314L+ -2C, 3x180s, 2x2 Binning (ca. 30 Lightning strokes)

OI N I 6008 N II NI N I / N II N II 5670- 90 N I 5616- 23 N I 5560- 64 N II / OI N II 5171 -99

Lightning Cloud Reflection

N II 5001 - 07 N I 4915 H 4861

N II/O II

N I / O II H / N I / O II N I / N II / OI H /N II / O II O II 3910 - 26 CN 3871 ?
N II 4041 - 44 N II 3995

OI

Richard Walker 2012/08

Atomic Emission Spectroscopy with Spark or Arc Excitation 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 %)

12

C Si Mn P S

carbon: silicium: manganese: phosphor: sulfur:

0.12 0.18 max. 0.40 0.30 0.60 max. 0.035 max. 0.035

Besides the main component Fe in the higher-resolution spectra only Mn (0.4%) is detectable. 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 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. Nevertheless, 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 Table 6: dito Table 4, here in the range of 5550 6450 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

Atomic Emission Spectroscopy with Spark or Arc Excitation

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TABLE 3
Black: Emission lines Air (N II, O II) Red: Emission lines steel C15E Green: By-products or contaminations
K I 6964 ?

Composite Spectrum: C15E Steel + Air DADOS 200L/mm

H 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

Fe I 4383.54 Fe I 4326 Ca I/N II/Fe I 4226 - 28

Fe I 4404.75 Fe I 4308 Fe I 4271

N II 4447

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

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N II 4788

TABLE 4
O II 4700/05 O II 4676 O II 4662

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

O II 4642 + N II 4643 N I 4630.54

O II 4649 N II 4621 N II 4614 N II 4607 N II 4601

N II 4596 N II 4591 N II 4530 N II 4510/14

Composite spectrum C15 E + Air

O II 4466

Spark Spectrum Air

N II 4447 O II/Fe I 4415 Fe I 4404.75 Fe I 4383.55 O II 4367-68 O II 4349 Fe I 4325.76 O II 4317.14 Fe I 4307.9

O II 4396

Fe I 4271.15

Ca I/Fe I 4227

Fe I 4260.47 Fe I 4250.8 Fe I 4236

N II 4237 N II 4227 N II 4200

Fe I 4199 O II/N II 4190/95 Fe I 4175

Black: Emission lines Air (N II, O II) Red: Emission lines steel C15E Green: By-products or contaminations

O II 4153 O II 4146 O II 4132.8 O II 4119.22 O II 4076 N II 4097 O II 4072/76 N II 4041

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

Legend:

Fe I 4005

Richard Walker 2011/02

Atomic Emission Spectroscopy with Spark or Arc Excitation

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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 Fe I 4045.8

Mn I 4057.9

N II 3995

Ca II 3968.47 Ca II 3933.66

Richard Walker 2011/02

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TABLE 5

N II 5535

N II 5496 N II 5480 Fe I 5455

Fe I 5406

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

Fe I 5341 Fe I 5369 - 71 Fe I 5341 Fe I 5328 Fe I 5324

Composite spectrum C15 E + Air

Fe I 5269 - 72 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

Black: Emission lines Air (N II, O II) Red: Emission lines steel C15E Green: By-products or contaminations

Fe I 4891 Fe I 4871 H 4861 / N II 4859

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

Richard Walker 2011/02

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

TABLE 6
Na I 5889.95

Legend:
Composite spectrum C15 E + Air

Black: Emission lines Air (N II, O II) Red: Emission lines steel C15E Green: By-products or contaminations

Atomic Emission Spectroscopy with Spark or Arc Excitation

N II 5679.56 Na I 5895.92 N II 5941.65 N II 5931.78

N II 5666.63

N II 5710.77

N II 5535

Fe I 5616

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

TABLE 7
Composite spectrum C15 E + Air

Legend:

Black: Emission lines Air (N II, O II) Red: Emission lines steel C15E Green: By-products or contaminations

Atomic Emission Spectroscopy with Spark or Arc Excitation

N II 6611

H 6562.85

N II 6482

O I 7157

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Atomic Emission Spectroscopy with Spark or Arc Excitation 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 . 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 , is missing here even totally. There is also no strong continuum visible. The reason for this effect remains 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 and 5100 5200 , 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 continuum is missing. Striking are here three dominant copper lines in the range of 5100 - 5300 . Several others are blended with N II and O II emissions, which appear here relatively intensive. Noteworthy are also the by-products, i.e. Na I and Ca II lines. Table 11: Low-resolution (200L) composite spectrum, recorded with Urs Flkiger in his company in Oberburg, Switzerland. Sample: Tool steel coated with titanium oxide (Ti O2). Well visible are here emission bands of diatomic titanium monoxide molecules (TiO) and atomic Ti lines. Titanium dioxide (Ti O2) at such high temperatures > 3000 K, dissociates to titanium monoxide (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 ( Her). In the area of 5000 , 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 correspondingly 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.

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Composite Spectrum: Galvanised Steel + Air DADOS 200L/mm

TABLE 8
Legend:
Black: Emission lines Air (N II, O II) Red: Emission lines galvanised steel Green: By-products or contaminations

Zn I 4810.53

Atomic Emission Spectroscopy with Spark or Arc Excitation

Zn I 4722.15

N II 4041

Zn I 4680.14

N II 3995

Mn I ?

Na l 5890/96

Zn I 6362.34

N II 4195

O II/N II ?

N II 4097

Mn I ?

Mn I ?

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Atomic Emission Spectroscopy with Spark or Arc Excitation

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TABLE 9
Black: Emission lines Air (N II, O II) Red: Emission Aluminum Green: By-products or contaminations

DADOS 200L/mm

H 6562.85

Na l 5890/96
N II 5667/79

Composite Spectrum: Aluminum + Air

Legend:

C2 ? N II 5001 - 07 N II / H 4859/61

O II ?

Al II 4226.81

Al I 3961.52

Al I 3944.0

Atomic Emission Spectroscopy with Spark or Arc Excitation

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Richard Walker 2011/02

TABLE 10
Black: Emission lines Air (N II, O II) Red: Emission Copper Wire Green: By-products or contaminations

H 6562.85

DADOS 200L/mm

Cu II 6154.22

Legend:

Na l 5890/96
Cu I 5782.13

N II 5932/42

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 Fe I 3906.48 ?

Ca II 3933.66

Ca II 3968.47

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TABLE 11
Black: Emission lines Air (N II, O II) Red: Emission Titanium Monoxide Green: By-products or contaminations
H 6562.82

? ? ?

Composite Spectrum: Titanium Monoxide (Ti O) Coating + Air DADOS 200L/mm

TiO 6268

Legend:

Na I 5889/95

TiO 5497 TiO 5448/51

TiO 5167

N II / O II 5179

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

Richard Walker 2011/03

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Tests with Arc Excitation

4.1 Design and Implementation of the Experiment

Professionally arc spectra are obtained in an inert protective gas atmosphere with electrodes, made of tungsten or spectrally pure high density graphite. In the factory of Urs Flkiger 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-InertGas). Picture: Electric welding with rutile coated electrode. DADOS spektrograph and old VIVITAR macro zoom lens on an AYO mount, distance ca. 3m. Urs Flckiger (left picture in the background), recording the spectra on the laptop.

TIG welding with Argon protective gas (Mr. Baumgartner)

Atomic Emission Spectroscopy with Spark or Arc Excitation

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4.2 Results
Table 15: Electric arc, simulated with electric welding machine and rutile-acide type electrode (Ti O2). Low-resolution (200L) composite spectrum: steel 37, materialnumber 1.0037, (herafter called steel 37) + spectrum of air. The comparison with the spark spectrum 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 titanium 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 1. Also striking is the broad Na I emission with a central self-absorption dip, as can be observed in the spectra of highpressure 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 Flkiger & Co Ltd applies modern welding equipment and high-voltage ignition with appropriate control system. Consequently, 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 argon gas. The emissions of the air molecules are weak. The "front runner line" N II at 5000 5007 is here even completely missing!

Atomic Emission Spectroscopy with Spark or Arc Excitation

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Richard Walker 2011/03
TiO 6159

TABLE 15
Black: Emission lines Air (N II, O II) Red: Emission steel 37/C15E Green: By-products or contaminations

Fe I 6945 ? Fe I 6917 ?

Fe I 6710 13 ?

H 6562.82

TiO 6268

Legend:

Fe I 6015-18

Na l 5890/96

N II 5932/42 Fe I 5800 N II 5667/79 N II 5535 Fe I 5512-13 Fe I 5455 Fe I 5406 Fe I 5369-71 Fe I 5227/33

N II / O II 5179

Comparison Arc Spectrum Steel 37 versus Spark Spectrum C15E DADOS 200L/mm

Arc Spectrum Stahl 37

Spark Spectrum C15E

Fe I 5328 Fe I 5269-72 Fe I 5205 Fe I 5170 Ti I 5038 N II 5001 - 07 Fe I 4985-87 Fe I 5065

Fe I 4958 Fe I 4920

Ti I 48251 TiO 4761/63 TiO 4761/63

Fe I 4891 Fe I 4871

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 3995 Fe I 3878

N II 4041 / Fe I 4046/71 Ca II 3968.47 Ca II 3933.66

Atomic Emission Spectroscopy with Spark or Arc Excitation

Ar I 7384 Ar I 7272.94 Ar I 7158.84 Ar I 7067.22 Ar I 6965.43 Ar I 7030.25 Ar I 6937.66 Ar I 6871.3 Ar I 6752.83 Ar I 7316 Ar I 7206.98

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TABLE 16

DADOS 200L/mm

H 6562.82
Fe I 6416 - 19

?
Fe I 6220

? ?
Na l 5890/96 ?

Steel 37 + Air

Fe I 5914 Fe I 5860/61 Fe I 5835 Fe I 5740

Composite Arc Spectrum:

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 N II / O II 5179

Black: Emission lines Air (N II, O II) Red: Emission steel 37 Green: By-products or contaminations Blue: Emission lines protective gas Ar

Fe I 4958 Fe I 4920 Fe I 4891

N II 4780/88

Ar I 4628.44 Ar I 4596 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

Legend:

Ca II 3933.66

Ca II 3968.47 Fe I 3856 Fe I 3878

Richard Walker 2011/02

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The Link between the Stellar- and Laboratory Spectra

Table 20: Shows in the blue range the comparison of the higher resolution (900L) composite spectrum 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 molecules (O II, N II) and therefore not available for a link to the solar spectrum. Table 21: Profile comparison, range from 4650 - 5900 , 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 ( Her). In this wavelength range in the spectrum of the surface coating appear clearly visible emissions of TiO bands. The intensity runs approximately mirror inverted to the characteristic absorption bands of the late M-class star Her. The emissions of air molecules are here relatively weak. At 5000 however, N II forms an intense blend with the TiO bands.

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TABLE 20

Fe I 4415 Fe I 4405 Fe I 4383

O II 4367-68 O II 4349

Sun versus C15E (+ Air) 900L/mm

H 4340.47 Fe I 4326 CH 4299 - 4313 Fe I 4308

O II 4317.14

Composite spectrum C15 E + Air

Fe I 4271 Fe I 4260 Fe I 4250 Fe I 4236 Fe I 4227 / Ca I Fe I 4199

O II/N II 4190/95 N II 4227

Spectrum of the Sun

N II 4200

Fe I 4175
O II 4153 O II 4146 O II 4132.8 O II 4119.22

H 4101.74

N II 4097 O II 4076

Comparison of Spectra:

Black: Emission lines Air (N II, O II) Red: Emission steel C15E Green: By-products or contaminations Blue: Absorption lines spectrum of the sun

Fe I 4072 Fe I 4062 Fe I/Mn I 4058 Fe I 4046

O II 4072/76

N II 4041

Fe I 4005
N II 3995

Legend:

Ca II 3968.47

Ca II 3933.66

Richard Walker 2011/02

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TABLE 21

TiO 5847 TiO 5814 TiO 5760

Comparison TiO2 Coating and Ras Algethi ( Her M5 Ib-Il) 200L/mm

TiO 5668 TiO 5597/03

Composite spectrum TiO2 Coating + Air

TiO 5497 TiO 5448/51

Spectrum Ras Algethi

TiO 5359 TiO 5308

TiO 5240 TiO 5167

N II / O II 5179

TiO 5003/20 5020 N II 5001 - 07 TiO 4955

TiO 4847 TiO 4804 TiO 4761 TiO 4704 TiO 4668

N II 4859

Richard Walker 2011/03

Na l 5889/95

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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.

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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].

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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 erhltlich.

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 Qualitative 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] Phasenaufgelste, optische Emissionsspektroskopie an RF Plasmarandschichten, Diplomarbeit 2007, S. Nemschokmichal, Universitt 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

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Metallurgy and Welding Technology (German language)

34

[61] Flkiger & 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