Designation: E 172 – 90 (Reapproved 1999)

Standard Practice for

Describing and Specifying the Excitation Source in
Emission Spectrochemical Analysis1
This standard is issued under the fixed designation E 172; 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 3.2.4 plasma—a flowing stream of gaseous charged par-

1.1 This practice provides for the description of the various ticles containing either atomic or molecular ions and free
parameters of sources used to excite the spectra in optical electrons. It is a good conductor of electricity and is affected by
emission spectrochemical analysis. Recent research on sam- magnetic fields. It is differentiated from “gas containing ions”
pling and excitation of metals has shown that the critical in that the motions of charged particles in a plasma must be
parameter to control is the current through the specimen and described collectively, not individually.
circuit although the actual mechanism of sampling is unknown. 3.2.5 self-initiating capacitor discharge—a discharge of
A specific current can be achieved by several combinations of current from a capacitor that occurs at such time as the voltage
capacitance, voltage, resistance, and inductance, depending on on the capacitor is sufficient to break down the analytical or
the values for all four. A practice consisting of component control gap. Discharge may also take place by triggering a
values only is insufficient to properly describe an excitation control device such as a thyratron tube. (This type of discharge
source. has been traditionally known as a spark source).
1.2 This standard does not purport to address all of the 4. Significance and Use
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 4.1 The purpose of this practice is to provide fundamental
priate safety and health practices and determine the applica- information on equipment used to excite the spectrum of the
bility of regulatory limitations prior to use. specimen in optical emission spectrochemical analysis.
4.2 The selection of equipment to analyze the specimen
2. Referenced Documents depends on the nature of the specimen, the elements to be
2.1 ASTM Standards: determined, and the concentration levels expected. In certain
E 135 Terminology Relating to Analytical Chemistry for cases the time required to complete the analysis may be an
Metals, Ores, and Related Materials2 important factor.

3. Terminology 5. Description of Excitation Source Power Supplies

3.1 Definitions: 5.1 Where an analytical gap is an element of the excitation
3.1.1 For definitions of terms used in this practice, refer to system, it is recommended that the circuitry be described in an
Terminology E 135. overall way as producing one of the four types of current forms
3.2 Definitions of Terms Specific to This Standard: described in 5.1.1-5.1.4. Where an analytical gap is not an
3.2.1 capacitor discharge—an electrical discharge of cur- element of the excitation system, it is recommended that the
rent from a capacitor or combination of capacitors, the energy source be described as producing one of the three types of
of which is obtained from either an a-c or d-c electrical supply. excitation described in 5.1.5-5.1.7.
3.2.2 glow discharge—a low pressure, usually 0.01 to 3 5.1.1 Continuous d-c Arc—A self-maintaining d-c electrical
kPa, electrical discharge in an inert gas resulting from the discharge.
passage of current through the gas. 5.1.2 Noncapacitive a-c Arc—A series of electrical dis-
3.2.3 laser—a device that generates coherent electromag- charges in which the individual discharges are either self-
netic radiation in the ultraviolet, visible, or infrared regions of initiating or initiated by separate means. These discharges are
the spectrum. extinguished when the potential across the analytical gap falls
to a value that no longer is sufficient to maintain the discharge.
Each current pulse is in the reverse direction from the previous
1
This practice is under the jurisdiction of ASTM Committee E-1 on Analytical one. The magnitude of peak current in each half-cycle is
Chemistry for Metals, Ores and Related Materials and is the direct responsibility of approximately constant.
Subcommittee E01.20 on Fundamental Practices. 5.1.3 Noncapacitive, Intermittent d-c Arc—A series of elec-
Current edition approved Jan. 26, 1990. Published March 1990. Originally
published as E 172 – 85. Last previous edition E 172 – 85. trical discharges in which d-c pulses are initiated by separate
2
Annual Book of ASTM Standards, Vol 03.05. means, either mechanically or electrically. Each current pulse

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

1
 E 172
has the same polarity as the previous one and lasts for less than 5.1.6.2 IC ( Inductively Coupled)—A plasma in a nonoxi-
0.1 s. dizing atmosphere, argon, nitrogen, or helium produced by a
5.1.4 Capacitor Discharge (Note 1): radio frequency field between 1 MHz and 1 GHz. Only
5.1.4.1 Triggered Capacitor Discharge— A series of elec- frequencies allowed by the appropriate international agree-
trical discharges from capacitors, the energy of which is ments for use in industrial equipment should be employed.
obtained from either an a-c or d-c electrical supply. Each 5.1.6.3 MI ( Microwave Induced)—A plasma in an inert
discharge may have either an oscillatory, bipolar, or unipolar gas, usually helium, produced by a field of frequency greater
character. It is initiated by separate means and is extinguished than 1 GHz, most commonly 2.45 GHz.
when the potential across the analytical gap or the current 5.1.7 Laser:
through the gap falls to a value that no longer is sufficient to 5.1.7.1 A laser consists of an active medium in which
maintain the discharge. population inversion of energy levels and therefore stimulated
5.1.4.2 Self-Initiating Capacitor Discharge—A series of emission of radiation may be obtained by optical pumping or
electrical discharges, each of which may be oscillatory or electrical excitation. Laser action may either be continuous or
directional and has a comparatively high maximum instanta- discontinuous in the form of a laser pulse or a sequence of laser
neous current resulting from the breakdown of the analytical pulses. The medium may be a solid, liquid, or gas. A laser
gap or the auxiliary gap, or both, by electrical energy stored at analytical system may or may not use auxiliary capacitor
high voltage in capacitors. Each discharge is self-initiated and discharge excitation for enhanced light output from the vapor
is extinguished when the potential across the gap, or gaps, or plume.
the current through these gaps is no longer sufficient to
maintain the discharge. A following discharge will occur when 6. Required Electrical Parameters
the voltage on the capacitor has built up to a sufficient level and 6.1 The following parameters, including specimen polarity,
a control gap has been activated. This control gap may be an air should be specified in analytical practices to permit users to
blast gap, a mechanical rotary gap, thyratron, or gated solid match the source characteristics employed by this practice. For
state device. each type source, specify where applicable the current, voltage,
frequency, capacitance, inductance, resistance, pulse duration,
NOTE 1—The self-initiating capacitor discharge (SICD) differs from the
gas, flow rate, pressure, and other significant parameters (Note
triggered capacitor discharge mainly in the range of electrical parameters
available to each and that the triggered capacitor discharge requires 2).
separate means for initiating each discharge. In general, an SICD has NOTE 2—The actual detailed electrical circuits and parts are beyond the
potentials of the order of 5000 to 40 000 V using capacitances between scope of this practice. The reader is referred to specific manufacturer’s
0.001 and 0.02 µF. A triggered capacitor discharge has potential of 200 to literature or to a comprehensive review of sources,3 which contains an
2000 V and uses capacitances of 1 to 250 µF. extensive bibliography.
5.1.5 Glow Discharge: 6.2 Continuous d-c Arc Source—List the current as mea-
5.1.5.1 Hollow Cathode—An electrical discharge in an inert sured during the first 5 s of arcing. For example:
gas at a pressure normally between 10−2 and 10 3 Pa that Current, A, d-c 14.0
vaporizes and excites the sample. The sample-holding device is 6.3 Noncapacitive a-c Arc Source—List the rms current,
frequently a metal or graphite rod with a hole along its axis. output potential of the transformer, and frequency of the power
The discharge occurs within the cavity of the cathode. supply during operation. State whether the discharge is self-
5.1.5.2 Plane Cathode—The specimen, which must have a initiating or separately initiated. If separately initiated, list the
plane surface, is made the cathode of the glow discharge. The parameters of the initiating circuit. For example:
discharge operates in an inert atmosphere at a pressure of Power Circuit
between 10 −2 and 103 Pa. Current, A, rms (root mean square) 2.3
5.1.5.3 Jet-Assisted Glow Discharge—One or more high Potential, V, rms 2400
Frequency, Hz 60
velocity gas jets strike the surface of the sample cathode, Ignitor
increasing the sampling rate and the emission intensities. When Capacitance, µF 0.0025
the observation is made in a direction parallel to the sample Inductance, µF residual
Resistance, V 2.5
surface, the jets are positioned so as to sweep the sputtered Voltage, V 20 000
sample atoms away from the surface into the observation zone.
One configuration spaces six jets around the circumference of 6.4 Noncapacitive Intermittent d-c Arc Source—Describe
a circular sputtering region, and angles the jets towards the the primary power supply and list the rms current. State
center causing a plume of entrained sample atoms and ions to whether the initiating means is mechanical or superimposed
rise in a direction normal to the flat surface of the sample. high frequency. If the latter, list the parameters of the circuit.
5.1.5.4 Pulse Glow Discharge—A glow discharge that is For example: The primary power supply is a half-wave
pulsed intermittently to a high current to improve its spectral rectified, 110-V, 60-Hz power line. It is initiated by a low-
characteristics. Observations are usually synchronized with the power spark synchronized to initiate each half cycle when the
pulses. primary power supply reaches 80 V.
5.1.6 Plasma: Current, A, d-c 6.5
5.1.6.1 d-c ( Direct Current)—A plasma in an inert gas,
argon or helium, produced by a direct current between elec- 3
Emission Spectroscopy, edited by Ramon M. Barnes; Dowden, Hutchinson,
trodes in the gas stream. Ross, Stroudsburg, PA, 1976.

2
 E 172
The parameters of the initiating circuit are as follows: irradiated with ultraviolet rays from a low pressure mercury
Capacitance, µF 0.0012 lamp.
Inductance, µH 8 6.5.2.2 Directional (Unipolar)Discharge—The addition of
Resistance, V 0.3
Potential, V 12 000 a second inductance and diode leg in the discharge circuit can
Number of discharges per sec- 120 change the character of the current waveform from oscillatory
ond (bipolar) to directional (unipolar). The normal current oscilla-
Current, A, rms 2.5
tions occur, however the current remains unipolar. List the
6.5 Capacitor Discharge—List the nominal capacitance, parameters below:
inductance, and resistance values of the discharge circuit Capacitance, µF 0.018
together with the capacitor potential at the moment of break- Inductance, L1, µH 200
Inductance, L2, µH 12
down, the number of discharges per second, and the radio- Resistance, V residual
frequency current. State whether the charging potential is a-c or Potential, V 8000
d-c. Give the values of the current through the specimen in Peak current, A 80
First valley current, A 30
terms of peak current and duration. If the current is not totally Current pulse duration, µs 160
directional, indicate the current and duration of the reverse Number of discharges per second 240
peak (Note 3).
The source may use a rotary gap with tungsten electrodes
NOTE 3—The current is best measured with a calibrated pulse trans- and irradiated with a low pressure mercury lamp or an air gap
former and oscilloscope. The duration of the pulse is that time interval irradiated with a low pressure mercury lamp.
from the start of current until current no longer passes through the 6.6 Glow Discharge:
analytical gap. If the required pulse transformer and oscilloscope are not
6.6.1 Hollow Cathode—List the parameters below:
available, it is suggested that the manufacturer of the equipment be
contacted to obtain a description of the operation parameters. Current, mA 20
Operating voltage, V 550
6.5.1 Triggered Capacitor Discharge— List the parameters Pressure, kPa 1
Gas argon
below (Note 4):
Capacitance, µF (d-c charged) 10 6.6.2 Plane Cathode—List the parameters below:
Inductance, µH 50 Current, mA 160
Resistance, V 2 Operating voltage, V 500
Potential, V 700 Pressure, kPa 1
Peak current, A 150 Gas argon
Current pulse duration, µs 100
Number of discharges per second 60 6.6.3 Jet-Assisted Glow Discharge—List the parameters
Trigger
Capacitance (d-c charged),µ F 0.005
below:
Inductance,µ H residual Current, mA 60
Resistance, V residual Operating voltage, V 300
Potential, V 8000 Pressure, kPa 1
Gas argon
NOTE 4—It is possible to produce similar results in terms of back- Flow rate, L/min 0.5
ground equivalent concentration, precision and accuracy on homogeneous
specimens using triggered capacitor discharges that differ considerably in A description of the jet nozzles should be included. For
capacitor potential, capacitance, inductance, and resistance. example:
Jet nozzle positions On circumference of 0.8 cm circle
6.5.2 Self-Initiating Capacitor Discharge—List the capaci- Jet nozzle distance from sample, cm 0.2
tance, inductance, and resistance of the discharge circuit Jet nozzle angle from the normal to
together with the capacitor potential at moment of breakdown, the ample surface,° 30
Jet nozzle diameter, cm 0.03
the number of discharges per cycle and the radio-frequency
current. If the source is controlled, state whether it is by means 6.6.4 Pulse Glow Discharge—List the parameters below (in
of an auxiliary gap (with or without air blast deionization), a addition to other parameters appropriate to the type of glow
mechanical rotary interrupter, a thyratron, or a gated solid state discharge):
device (Note 5). Pulse current, mA 900
Pulse voltage, V 1000
NOTE 5—If important, further details of the auxiliary gap should be Pulse width, µs 10
given (electrode material and configuration, ultraviolet irradiated or not, Repetition rate, Hz 60
spacing, air blast orifice size, air pressure, etc.). Pulse current rise time, µs 0.5
Pulse current fall time, µs 4
6.5.2.1 Oscillatory (Bipolar)Discharge (Spark Source): Continuous background current, mA 1
Continuous background voltage, V 200
List the parameters below: Duration of observation window, µs 8
Capacitance, µF 0.018 Delay of start of observation window
Inductance, µF 200 after the start of current pulse, µs 2
Resistance, V residual
Potential, V 15 000 6.7 Plasma:
Peak current, A 100 6.7.1 d-c (Direct Current)—List the parameters below:
Current pulse duration, µs 400
Number of discharges per second 240 Current, A 14
Gas argon
The source uses a rotary gap with tungsten electrodes and Flow Rate, L/min 7

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 E 172
6.7.2 IC (Inductively Coupled)—List the parameters below: capacitor discharge circuits use a calibrated pulse transformer
Frequency, MHz 27.12 along with a fast sweep oscilloscope. For currents involved in
Power, kW 1.2 glow discharges and plasmas, use the information provided on
Gas argon
Outer Gas, L/min 14 the manufacturer’s power supply.
Intermediate Gas, L/min 0 8.2 Voltage—For d-c voltage any standard calibrated d-c
Carrier Gas, L/min 1
voltmeter can be used. For a-c voltage below 1000 V any
6.7.3 MI (Microwave Induced)—List the parameters below: standard calibrated a-c voltmeter can be used. For voltages on
Frequency, GHz 2.45 charged capacitors use calibrated high-voltage probes.
Power, W 50
Gas helium 8.3 Capacitance—Measure the capacitance with a high
Pressure, kPa 0.2 quality L-C meter (Note 7).
Flow rate, L/min 0.1
NOTE 7—Due to the method of construction of capacitor discharge
6.8 Laser—List the parameters below: sources, it is acceptable to use the manufacturer’s values for capacitance
Power, KW 4 3 103 and inductance.
Pulse duration at half-max, µs 0.6
8.4 Gas Flow—Measure the gas flow rate with flowmeters
7. Excitation Index (Note 6) calibrated for the gas being used. Mass flow gages are also
7.1 For spectrographic methods list a value or a range of acceptable.
values for the ratio of the radiant powers of two selected 8.5 Pressure—Measure the pressure with calibrated gages
spectral lines of a single element having widely different having at least 10 % resolution for the range being used.
excitation energies. Where possible the lines should be as 8.6 Inductance—Measure the inductance with a high qual-
similar as possible in wavelength and intensity. This suggestion ity L-C meter (Note 7).
is not practical for spectrometers where line selection is
determined by the concentration range covered and interfer-
9. Selection of Excitation
ences.
9.1 The mode of excitation selected will depend on the
NOTE 6—Though the excitation index can be very useful for a method,
it is not a unique measure of excitation. It is an oversimplification of
sample form, matrix, and the concentration of the elements to
complex temperature and electron density functions of excitation and be determined. For many solutions either a d-c or IC plasma
ionization states. The observed excitation index also is affected by the will cover a wide list of elements with minimum sample
optical system, slit width, dispersion, measurement of intensities, etc. The handling. Powder samples may be readily analyzed using a-c
following line pairs have been found useful for this purpose: (Fe I2813.29 or d-c arc excitation especially where trace concentrations are
Å)/(Fe II 2813.61 Å): (Fe I2501.70 Å)/(Fe II 2476.27 Å): (Fe I3016.19 of interest. Solid metal samples will frequently be analyzed
Å)/(Fe III 3013.12 Å): (Ni I2419.31 Å)/(Ni III 2448.35 Å).
using one of the capacitor discharge types of excitation.
8. Devices for Measuring Parameters
10. Keywords
8.1 Current—For d-c current any standard calibrated d-c
ammeter can be used. For a-c current use a calibrated radio- 10.1 emission; excitation source; glow discharge; laser;
frequency ammeter. For the current value and duration in plasma; spectrochemical analysis

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