Pure & App!. C/tern., Vol. 45, pp. 105—123. Pergamon Press, 1976. Printed in Greal Britain.

INTERNATIONAL UNION OF
PURE AND APPLIED CHEMISTRY
ANALYTICAL CHEMISTRY DIVISION

COMMISSION ON SPECTROCHEMICAL AND OTHER

OPTICAL PROCEDURES FOR ANALYSIS

NOMENCLATURE, SYMBOLS, UNITS AND THEIR

USAGE IN SPECTROCHEMICAL ANALYSIS—Ill.
ANALYTICAL FLAME SPECTROSCOPY AND
ASSOCIATED NON-FLAME PROCEDURES

(RULES APPROVED 1975)

PERGAMON PRESS
OXFORD NEW YORK PARIS FRANKFURT
 ANALYTICAL CHEMISTRY DIVISION
COMMISSION ON SPECTROCHEMICAL AND OTHER
OPTICAL PROCEDURES FOR ANALYSISt

NOMENCLATURE, SYMBOLS, UNITS AND THEIR

USAGE IN SPECTROCHEMICAL ANALYSIS—Ill.
ANALYTICAL FLAME SPECTROSCOPY AND
ASSOCIATED NON-FLAME PROCEDURES
(RULES APPROVED 1975)

CONTENTS
1. Introduction
2. Terms and symbols for general quantities and constants
3. Terms, symbols, and units for the description of the analytical apparatus
3.1. Transformation of sample into vapour
3.1.1. Descriptive terms concerning nebulizer-flame systems
[Link]. Nebulization, desolvation, volatilization, and atomization
[Link]. Nebulizers
[Link]. Burners and flames
3.1.2. Terms, symbols, and units for measurable quantities relating to nebulizer-flame systems
3.1.3. Terms concerning special sampling, atomizing, and exciting devices
[Link]. Special sampling devices for flames
[Link]. Electrical flame-like plasmas for atomization and excitation
[Link]. Non-flame atomizing devices
[Link].1. Resistance-heated devices
[Link].2. Hollow-cathode devices
[Link].3. Radiation-heated devices
3.2. Light sources in atomic absorption and atomic fluorescence spectroscopy
3.3. Optical systems
3.4. Photodetectors
3.5. The electrical measuring system
3.6. Survey of terms, symbols, and units for measurable quantities in the optical and measuring systems
4. Terms and symbols relating to the analytical procedure and the performance of an analysis
4.1. General analytical terminology in flame spectroscopy
4.2. Analytical calibration
4.3. Assessment of an analytical procedure
4.3.1. Measurement scatter
4.3.2. Limit of detection, precision, and accuracy
4.4. Interferences by concomitants
4.4.1. General
4.4.2. Classification of interferences
[Link]. Spectral interferences
[Link]. Non-spectral interferences
4.4.3. Reduction of errors due to interferences for given instrumental conditions
5. Terms, symbols, and units relating to radiant energy and its interaction with matter
5.1. Descriptive terms relating to the emission, absorption, and fluorescence of radiation
5.1.1. Emission
5.1.2. Absorption and self-absorption
5.1.3. Fluorescence
5.2. Terms, symbols, and units for measurable quantities
6. Terms, symbols, and units relating to the gaseous state of matter
6.1. Descriptive terms concerning the gaseous state of matter
6.2. Terms, symbols, and units for measurable quantities
7. Index of terms

1. INTRODUCTION
tChairman: V. A. Fassel (USA); Secretary: B. F. Scribner Part III is a sequel to Parts I [Pure App!. Chem. 30 653
(USA); Members: C. Th. J. Alkemade (Netherlands), L. S. Birks (1972)1 and II [Pure App! Chem 45 (2) 99—103 (1976)] of
(deceased)(UK),[Link](Czechos- the Nomenclature for Spectrochemical Analysis. Whereas
lovakia)JP Parts I and II are mainly concerned with some general
Associate Members: R. Jenkins (USA), H. Kaiser (Germany) A.
Kvalheim (Norway), R. Muller (Switzerland), I. Rubeika recommendations, Part III deals specifically with analyti-
(Czechoslovakia), A. Strasheim (South Africa), V. Vukanoviè cal flame spectroscopy and associated procedures.
(Yugoslavia), J. Walters (USA). The purpose of this nomenclature, as well as its
107
108 COMMISSION ON SPECTROCHEMICAL AND OTHER OPTICAL PROCEDURES FOR ANALYSIS

adaptation to the documents developed by IUPAC and terminology in this field and calls for international
IUPAP in more general fields of chemistry and physics, cooperation.
has already been explained in the Foreword of Part I. In Part III is concerned with the analytical application of
the development of Part III, the recommendations of flame spectroscopy by emission, absorption, and fluores-
IUPAC, IUPAP and the International Commission on cence methods. These three branches of analysis have
Illumination (CIE), and of the foregoing Parts I and II many terms in common and a uniform terminology seems
were taken as a starting point. Deviations from these mandatory. In the context of this document, an "ordi-
recommendations occur only in some exceptional cases nary" flame may be defined as a continuously flowing gas
and mainly concern the choice of a consistent set of mixture at atmospheric pressure, which emerges from a
symbols within the restricted field of analytical flame burner and is heated by combustion. Although this
spectroscopy. Deviations may also be found in a few document is primarily concerned with systems that
cases where previous international documents are not in comprise such ordinary flames, burners, and nebulizers,
agreement among themselves. Such deviations are exp- attention is also paid to similar procedures comprising
licitly identified in the Notes added to this document. other sampling, atomizing, and/or exciting devices (see
In those instances of specific usage in flame spectros- Section 3.1.3). These procedures bear some resemblance
copy which are not already established by international to ordinary flame spectroscopy with regard to the
conventions, compromises often had to be made between methods of measuring emission, absorption, or fluores-
the historically developed terminology and nomenclature cence signals, as well as to the rather simple nature of the
and those based on more logical considerations. Some devices involved and the simplicity of the spectra
expressions which have found their way into the language obtained. Arc and spark spectroscopy involving more
of practical analysts, but which could be misleading, have elaborate and expensive instrumentation are not discus-
been abandoned. The use of alternative terms for the sed in this document.
same item was considered undesirable and, as a rule, only As can be seen from the Table of Contents, this
one term has been recommended for each item. Some document is subdivided into several sections correspond-
differences in terminology that developed historically ing to the different aspects of analytical flame spectros-
among the practitioners of emission and atomic absorption copy. A general classification and consistent terminology
methods have been reconciled. of the different branches of flame spectroscopy are
During the period in which this document was in presented in Table 1.1. For some terms, abbreviations are
preparation, several national organizations developed suggested for practical usage. To comply with the
their own nomenclature for atomic absorption spectros- internationally agreed restricted meaning of "photome-
copy. Through mutual deliberations, serious conflicts ter" (see Section 4.5 in Part I), the term "flame
between national documents of restricted scope and the photometry" had to be abandoned, although it was
IUPAC nomenclature were significantly reduced. The realized that many of the older practitioners of flame
simultaneous emergence of these national initiatives emission spectroscopy may have difficulty in giving up
clearly proves the general need for a well defined this long-cherished term. On the other hand, the
Table 1.1. Classification of methods and instruments

Absorption Emission Fluorescence

Methods:
General classification Absorption spectroscopyt Emission spectroscopyt Fluorescence spectroscopyt

Instruments:
General classification Absorption spectrometer Emission spectrometert Fluorescence spectrometert

When atomic lines are Atomic absorption Atomic emission Atomic fluorescence
observed spectroscopy (AAS) spectroscopy (AES) spectroscopy (AFS)
Atomic absorption Atomic emission Atomic fluorescence
spectrometer spectrometer spectrometer

When a flame is used as Flame absorption Flame emission Flame fluorescence

a means for vaporization, spectroscopy (FAS) spectroscopy (FES) spectroscopy (FFS)
atomization and/or Flame absorption Flame emission Flame fluorescence
excitationT spectrometer spectrometer spectrometer

When both a flame is Flame atomic absorption Flame atomic emission Flame atomic fluorescence
used and atomic lines spectroscopy (FAAS) spectroscopy (FAES) spectroscopy (FAFS)
are observed Flame atomic absorption Flame atomic emission Flame atomic fluorescence
spectrometer spectrometer spectrometer

Note: The term flame photometry (flame photometer) has been abandoned (see also Part I, Section 4.5).
tSpectroscopy may be replaced by the more restrictive term spectrometry when quantitative measurements of
intensities at one or more wavelengths are performed with a spectrometer (see below).
tThe term spectrometer as it is used here implies that quantitative measurements of intensities at one or more
wavelengths are performed with a photoelectric detector. Wavelength selection may be accomplished, e.g. with a
monochromator or optical filter.
§When molecular species are observed, "molecular" is substituted for "atomic".
¶Alternative, but presently less common means of vaporization, atomization and/or excitation are, for example,
furnaces, flame-like (electrical) plasmas, and cathodic sputtering tubes (see Section 3.1.3). The appropriate adjective
should replace the term flame.
 Nomenclature, symbols, units and their usage in spectrochemical analysis—Ill 109

abandonment of this term removes the illogical juxtaposi- Table 2.1. Terms and symbols for general quantities and con-
tion of terms such as "emission flame photometry" and stants
"atomic absorption spectroscopy," which are often found
in the literature. The more uniform terminology presented Terms Symbol Note
in Table 1.1 should help to bridge the gap between
Mass m
emission and absorption methods.
Atomic weight (Ar), Ar(X)
Descriptive terms denoting processes or instrumental (A, = 12 for carbon
components and terms for measurable quantities are '2C) of species X
presented separately. The descriptive terms and some of Atomic mass of mx, m(X)
the most important quantitative terms are explained in a species X
narrative form. To facilitate reference, all quantitative Volume V
terms are presented in tables, together with their symbols Solid angle 11,0)
and practical units. Notes have been added to the text as Time
Frequency (in optical ii
well as to the tables in order to provide additional
spectroscopy)
explanation or justification, or to warn against improper
usage of terms. These notes may readily be passed over
Frequency (in
electrotechnics)
f
on first reading, as all specifically recommended terms are Wavelength A
incorporated in the text or the tables themselves. Such Wavenumber (1/A) cT, V
terms, when first met and defined in the text, are printed in Gas pressure p
italics for easy recognition. Total pressure of Pt
This nomenclature is not intended to provide a gas mixture
comprehensive set of terms. Definitions and explanations Partial pressure of Px, p(X)
of specific terms are only given when this is required to species X
make their meaning unambiguous. General physical or
Number of particles N
(Number) density of n
chemical concepts and quantities are presented in most particles (number per
cases without further elucidation. To facilitate the use of unit volume)
this document, terms and symbols employed in flame (Number) density of flx, n(X), [XI
spectroscopy which were presented in the foregoing Parts species X
I and II have been recapitulated. This applies in particular Thermodynamic (or T The unit for T is
to the general quantitative terms listed in Tables 2.1 and absolute) temperature the kelvin (K)
5.1. Important terms such as "concentration," "analytical Velocity of light c
curve," "sensitivity," etc. are briefly explained in Section (in vacuo)
Gas constant R
4 with explicit reference to Parts I and II for a fuller Avogadro constant NA
explanation. Boltzmann constant k
In view of the limited number of letters in the alphabet, Planck constant h
symbols have been selected carefully, while making Elementary charge e The symbol for
allowance for existing international recommendations as "electron" is e
well as for long usage. In some cases, alternative symbols and should not
have been added, which allows the user to select a set of be printed in
symbols that is most consistent in a particular context. italics.
Alternative symbols that are recommended without
preference are listed after each other and separated by
commas. When a particular symbol is preferred, it is listed (c) Amplification and read-out of the electrical signal.
first while the alternative symbols are separated from it by Terms for the description of component parts of a flame
a row of dots. The printing of symbols and indices should spectrometer (and similar systems) and of processes
conform to the general international rules recapitulated in occurring therein are discussed below. Terms for the
Section 2.3 of Part I. description of processes and properties related in
particular to the gaseous state of matter in flames are
discussed in Section 5.
2. TERMS AND SYMBOLS FOR GENERAL
QUANTITIES AND CONSTANTS
Table 2.1 lists terms and symbols for some general
physical and chemical quantities which are commonly 3.1. Transformation of sample into vapour
used in analytical spectroscopy. This Table is partly an 3.1.1. Descriptive terms concerning nebulizer-flame sys-
tems
abstract from, and partly forms a supplement to, Sections
[Link]. Nebulization, desolvation, volatilization, and
3.1 and 7.2 of Part I of the Nomenclature on Spec- atomization. With a pneumatic nebulizer driven under the
trochemical Analysis. action of a compressed gas stream, the solution is
aspirated from the sample container and nebulized into a
3. TERMS, SYMBOLS, AND UNITS FOR THE mist or aerosol of fine droplets. The term sprayer denotes
DESCRIPTION OF THE ANALYTICAL APPARATUS that particular part of a nebulizer where the aspirated
The functions of an analytical flame spectrometer in liquid is disrupted by the gas-jet into a spray.
general are: By desolvation, i.e. evaporation of the solvent from the
(a) Transformation of the solution to be analyzed into a droplets, this mist is converted into a dry aerosol
vapour containing free atoms or molecular compounds of consisting of a suspension of solid or molten particles of
the analyte (see Section 4) in the flame; the solute. In the high-temperature environment of the
(b) Selection and detection of the optical signal (arising flame, volatilization of these particles follows.
from the analyte vapour) which carries information on the In atomic flame spectroscopy, the atomization, i.e. the
kind and concentration of the analyte; conversion of volatilized analyte into free atoms, should
110 COMMISSION ON SPECTROCHEMICAL AND OTHER OPTICAL PROCEDURES FOR ANALYSIS

be as complete as possible in order to obtain a maximum aerodynamically by surrounding the flame with a sheath
signal. Any system which is capable of converting the of inert gas that emerges from openings at the rim of the
analyte into an atomic vapour is called an atomizer (see burner top (shielded flame). Observations can thus be
also Section 3.1.3). made without disturbances from the secondary-
[Link]. Nebulizers. In the chamber-type nebulizer, the combustion zone.
nebulizing gas-jet stream emerges from the sprayer into a To promote the atomization of elements that readily
spray chamber. In such a chamber, the gas-jet stream is form oxides in the vapour phase in the flame, a fuel-rich
homogeneously mixed with the mist droplets. Some of flame is often chosen, where reducing conditions favour
these droplets may evaporate, coalesce, or deposit on the the dissociation of the metal oxides.
chamber walls and subsequently drain as waste.
3.1.2. Terms, symbols and units for measurable quantities
Nebulizers can be described as follows:
According to the source of energy used for nebulization, relating to nebulizer-flame systems
An easily measurable quantity is the rate of liquid
as, for example, pneumatic or ultrasonic nebulizer.
consumption by the nebulizing system, defined as the
According to the way the liquid is taken up, e.g. suction, volume of liquid sample that is consumed per unit of time
gravity -fed, controlled-flow, and reflux-nebulizers. (symbol: F1: see Table 3.1). In the particular, but common
According to the relative position of the capillaries for
case of a pneumatic nebulizer, the term rate of liquid
the nebulizing gas and the aspirated liquid, e.g. angular aspiration is more specific.
and concentric nebulizers.
Often only a fraction of the analyte solution that is
Special devices are the nebulizer with heated spray aspirated passes through the flame cross-section at the
chamber, the twin nebulizer, and the drop generator. observation height (see Table 3.2) in a form that is
accessible for spectroscopic observation. There are losses
Note: Nebulizers by themselves should not be called atomizers.
of different kinds that limit this fraction and consequently
[Link]. Burners and flames. Flames are produced by the sensitivity of the method. Examples of such losses
means of a burner to which fuel and oxidant are supplied, with premix burners are the waste of solution in the spray
usually in the form of gases. With the premix burner, fuel chamber, the burner, and the tubes between them,
and oxidant are thoroughly mixed inside the burner because of deposition of mist droplets on the walls. With
housing before they leave the burner ports and enter the direct-injection burners, there may be losses of droplets
primary-combustion or inner zone of the flame. This type that are ejected from the flame because of the turbulent
of burner usually produces an approximately laminar motion of the gases leaving the burner. Moreover, the
flame, and is commonly combined with a separate unit for residence time of the larger droplets in the flame may be
nebulizing the sample. insufficient for complete desolvation (see Section [Link]).
In contrast, a direct-injection burner combines the Similarly, the particles formed after desolvation may not
functions of nebulizer and burner. Here oxidant and fuel be completely volatilized (see Section [Link]) at the
emerge from separate ports and are mixed above the observation height. Finally, it should be recognized that
burner orifices through their turbulent motion. The flame only part of the vapour produced by the analyte may
produced by such a burner is turbulent. Most commonly, consist of free atoms.
the oxidant is also used for aspirating and nebulizing the To describe these losses quantitatively, the following
sample. However, when the fuel is used for this purpose, terms are recommended. These terms relate to the amount
the term reversed direct-injection burner is applied. In of analyte aspirated per second and entering the flame per
each case, the mist droplets enter the flame directly, second or passing through the total horizontal flame
without passing through a spray chamber. cross-section per second at the observation height in
different states.
Note: The term total-consumption burner, which is often used, is
not recommended. The efficiency of nebulization, En, is the ratio of the
amount of analyte entering the flame to the amount of
Premix burners are distinguished as Bunsen-, Méker-, analyte aspirated.
or slot-burners according to whether they have one large
hole, a number of small holes, or a slot as outlet port(s) for Notes: The quantity n is not related to the amount of solvent but
to the amount of analyte. Its value cannot be determined
the gas mixture, respectively. When several parallel slots unambiguously by simply comparing the volume of solution
are present, they are identified as multislot burners (e.g. a drained per second from the spray chamber with the aspiration
three-slot burner). The small diameter of the holes in the rate. Correction must usually be made for the difference in analyte
Méker burner or the narrowness of the slot in the concentration in the drained and aspirated solution, respectively,
slot-burner usually prevents the unwanted flash -back of due to the partial evaporation of solvent from the mist droplets
the flame into the burner housing. deposited on the walls.
At the edge of the flame where the hot gas comes into The quantity €. is not merely characteristic of the operation of
contact with the surrounding air, secondary combustion the nebulizer, but of the nebulizer-burner system as a whole.
occurs and the secondary combustion or outer zone is The (local) fraction desolvated, f3s, is the ratio of the
formed. The region of the flame confined by the inner and amount of analyte passing in the desolvated state (i.e.
outer zones, where in many instances the conditions for either as adry aerosol or as a vapour) to the total amount
flame analysis are optimum, is called the interzonal region, of analyte passing. When this fraction varies with height,
or, when the combustion zones have the form of a cone, due to progressive evaporation of the aerosol droplets in
the interconal zone. the flame, it is appropriate to speak of the local fraction
Sometimes provision is made to screen the observed desolvated.
portion of the flame gases from direct contact with the
surrounding air. This may be done either mechanically by Notes: Losses due to incomplete volatilization of the dry aerosol
placing a tube on the top of the burner around the flame, (which depend largely on the nature and concentration of the
which produces a zonal separation (separated flame), or solute) are not covered by the definition of Ps but by the definition
 Nomenclature, symbols, units and their usage in spectrochemical analysis—Ill 111

of fL. The quantity j3, will usually depend on the solute whereas f3 In Table 3.1, the above quantitative terms and some
will depend on the solvent. further terms for measurable quantities belonging to this
When this ratio varies markedly with height over the volume of section are listed, together with their symbols and units.
flame observed, the amount of analyte found in this volume in the
considered state is related to the average value of this ratio over
this volume.
3.1.3. Terms concerning special sampling, atomizing and
The (local) fraction volatilized, IL, is the ratio of the exciting devices
amount of analyte passing in the gaseous state to the total [Link]. Special sampling devices for flames. Samples
amount of analyte passing in the desolvated state. The may be introduced into flames by means other than
gaseous state includes free atoms as well as molecules. nebulizers. The samples may be deposited on a sampling
The (local) fraction atomized, a, is the ratio of the ioop, sampling boat, or sampling cup made from
amount of analyte passing as free neutral (or ionized) platinum, tungsten, or other high melting point materials,
atoms to the total amount of analyte passing in the and subsequently thermally vaporized.
gaseous state. Note: These devices are heated only by the flame and not by an
Note: This fraction is determined by chemical reactions in the additional source of energy.
gaseous state. The bond strengths of the molecular compounds In atomic absorption spectroscopy a long tube device is
which the analyte may form in the flame play an important part as sometimes used with a nebulizer-flame system to increase
well as the composition and the temperature of the flame.
the sensitivity. The increase in sensitivity is achieved by
The overall (local) efficiency of atomization, Ca, is "retaining" the combustion gases with the atomized
defined as the ratio of the amount of analyte that passes analyte over an extended path length by means of a tube
coaxial with the optical axis. The tube is made from
through the flame cross-section at the observation height,
as free neutral (or ionized) atoms, to the amount of material capable of withstanding the flame temperature.
analyte aspirated. Therefore, Ca = Enf3s/3v13a. The atomic The flame gases enter the tube at one end and leave at the
signal strength obtained for a given solution concentration other, or when a T-shaped tube arrangement is used, the
is proportional to the product PiCa. It is noted that a may gases enter at the centre and flow toward the two open
depend on F1. ends. T-shaped tubes are called T-tubes.

Table 3.1. Transformation of sample into vapour. Terms, symbols, and units for measurable
quantities

Practical
Terms Symbol unit Note

Rate of liquid consumption F, cm3 s' For definition, see the text of
Section 3.1.2. In the usual
case of a pneumatic
nebulizer F is called the
rate of liquid aspiration.
Efficiency of nebulization 1 For definition, see the
text of Section 3.1.2.
Fraction desolvated IL 1 For definition, see the
text of Section 3.1.2.
Fraction volatilized /L 1 For definition, see the
text of Section 3.1.2.
Fraction atomized I For definition, see the
text of Section 3.1.2.
Efficiency of atomization Ca 1 For definition, see the
text of Section 3.1.2.
Flame temperature Tf K When the temperature varies
locally in the flame, it is
more appropriate to speak
of the local flame
temperature.
Travel time (time needed for ttv
substance to be carried
from base of flame to the
observation volume)
Transit time (time needed for tts
substance to pass through
the observation volume)
(Vertical) rise velocity of yr cms'
flame gas
Burning velocity (of flame vb cm 5'
front)
Flow rate of unburnt gas cm3 s' Measured at atmospheric
mixture pressure and at room
temperature.
Flow rate of X, e.g. Fx cm3 s' Measured at atmospheric
air, 02, etc. pressure and at room
temperature.
112 COMMISSION ON SPECTROCHEMICAL AND OTHER OPTICAL PROCEDURES FOR ANALYSIS

Note : The long tube has often been referred to as an absorption 3.2. Light sources in atomic absorption and atomic
cell. However, the term absorption cell should be reserved for fluorescence spectroscopy
devices closed by optical windows. In AAS and AFS an auxiliary light source is required to
[Link]. Electrical flame-like plasmas for atomization produce the radiation which is to be absorbed (and partly
and excitation. Electrical flame-like plasmas may be re-emitted as fluorescence) by the analyte in the atomizer
current-carrying plasmas or current-free plasmas. Plas- (see Section [Link]).
mas may be formed by an arc discharge in a chamber and Notes : The traditional term "light" here also includes other than
transferred through an appropriate opening to form a visible radiation, although according to the International Commis-
plasma jet. Flame-like plasmas can also be generated by sion on Illumination (C.I.E. Publication No. 17, E-l.1., 1970), this
high-frequency fields with or without the use of elec- term should be restricted to visible radiation (see footnote in
trodes. With the electrodeless plasma, the electromagnetic Section 1 of this Part and Section 4.5 of Part I).
field is usually inductively coupled to the plasma The general term "source" includes not only lamps but also the
(inductively-coupled plasma). The single-electrode use of an auxiliary flame into which a constant amount of analyte
plasma is formed on a metallic tip that is connected to a vapour is introduced to produce the (primary) radiation.
high-frequency generator. Light sources are conveniently distinguished as
Notes : Both chamber-type nebulizer systems and nebulizers (spectral) continuum sources or (spectral) line sources.
which spray the aerosol directly into the plasma are used to Examples of spectral continuum sources used in AAS or
introduce the sample. AFS are the tungsten-filament lamp and the high -
The term "plasma flame," often used for flame-like plasmas, is pressure xenon lamp. These lamps radiate light as a result
not recommended. The term "flame" should be reserved for hot of the high temperature of the filament or as a result of a
gases which are produced by combustion. Similarly, the term gas discharge. They belong to the class of thermal
"plasma burner" is discouraged. As a general descriptive term, radiators (see also the definition of thermal radiation in
"plasma torch" is often used.
Section 5.1.1).
[Link]. Non-flame atomizing devices Notes: Usually a spectral line source is employed containing
[Link].1. Resistance-heated devices. When small atoms of the same element as the analyte. The line spectrum may
amounts of liquid are to be analysed or if the sample is to be often superimposed upon a background that may be both
be atomized directly from the solid state, different types discrete and/or a continuum.
of atomizing devices with electrical resistance heating can The International Commission on Illumination (C.I.E. Publica-
be used. The sample can be introduced on, or into, an tion No. 17, E-l.l., 1970) calls a spectral line source a
"spectroscopic lamp."
electrically conductive support made of a material with Planck's law describes the spectral radiance BAb (see Table 5.1)
high melting point and heated by an electrical current. The of a so-called full radiator (or black body) as a function of
device may be specified according to the material and wavelength A and temperature T. A black body is a thermal
shape, such as a carbon or metal filament, loop, ribbon or radiator having an absorption factor a(A) (see Table 5.1) equal to
braid atomizer. Atomizing devices using heated carbon or unity at all wavelengths. In thermal equilibrium, according to
graphite tubes are called carbon- or graphite-tube Kirchhoff's law, the spectral radiance BA of any radiator with
furnaces. If a rod is used with a hole drilled perpendicu- a(A)1 is given by
larly to its axis, such furnaces are referred to as carbon- BA =
or graphite-rod furnaces. Cup shaped atomizers used
most often in AFS are called carbon- or graphite-cup where BAb is to be taken at the temperature of the radiator.
atomizers. Spectral line sources can be realized by an electrical
Normally an electrical current flowing through the walls discharge through a gas, a metal vapour, or a mixture of
of the support causes the temperature to rise by resistance both at a low total pressure (the so-called low-pressure
heating. Other less often used types have a separate discharge lamps). The following types have found
resistance wire wound around the walls of the tubes or application in AAS and AFS as light sources.
rods. Another type of resistance-heated graphite-tube In the hollow -cathode lamp accelerated electrons
furnace is used with a d.c. arc discharge to accelerate the generate positive ions upon collisions with atoms of the
atomizing process. In this case, the sample is not placed carrier gas (usually a noble gas). These ions gain energy in
directly into the tube but on the tip of an anode electrode the electric field and collide with the cathode which
and evaporated by the arc into the heated tube. usually has a hollow cylindrical form. Atoms of the
Note: The terms "graphite cell" or "graphite cuvette" should be cathode material are released by these collisions (cathodic
reserved for devices with closed ends. sputtering). These atoms are excited in the discharge and
radiate their spectral lines. These lamps can be made
[Link].2. Hollow-cathode devices. In AAS, a hollow- either with the cathode sealed within the same enclosure
cathode discharge can also be used as an atomizer when (sealed lamp) or the cathode element can be changed by
the sample is used either as the cathode or placed in the dismantling the lamp (demountable lamp). The cathode
hollow cathode in a low-pressure discharge chamber. In a material may be composed of pnly one element (single-
cooled hollow cathode the cathode cylinder is cooled by
element lamp) or of several elements (multi-element
water, liquid nitrogen, or other means. Under such lamp).
conditions samples are atomized by cathodic sputtering
even at high current densities. In a hot hollow cathode Note: Carrier gas has also been called fill-gas, but this term is
usually limited to sealed lamps.
samples are atomized primarily by thermal evaporation.
[Link].3. Radiation-heated devices. Solid samples can Another common type of spectral line source is the
be evaporated and atomized by radiation sources, such as metal-vapour lamp operated at low vapour pressures.
pulsed-discharge lamps and lasers. Because a laser beam The lamp is filled with a noble gas while the metal vapour
can be brought to a sharp focal point on the sample is produced from the volatile element by the thermal
surface, a local analysis can be made with this device. effect of the discharge.
 Nomenclature, symbols, units and their usage in spectrochemical analysis—Ill 113

The (high -frequency excited) electrodeless-discharge Table 3.2 contains some further terms and their
lamp contains a noble gas at low pressure and some symbols for measurable quantities connected with the
volatile metal or metal salt (such as an iodide or chloride). optical system.
A discharge produced in the noble gas by high-frequency
fields generates electrons which by collisions excite the Table 3.2. Selection, detection, and readout of the analytical
analyte atoms. signal. Terms, symbols, and u nits for measurable quantities

Practical
Terms Symbol unit Note
3.3. Optical systems
The functions of the optical system are to transfer, to Entrance-slit width 5 mm See Part I of this
of monochromator nomenclature series.
select (spectrally, spatially, and temporally), and, possi-
bly, to encode (by modulation) the radiation flux to be Entrance-slit height h mm See Part I of this
of monochromator nomenclature series.
received by the photodetector. In addition, in AAS and
AFS, the optical system should provide for the efficient
Spectral bandwidth Am nm See Part I, 2.8 and
of monochromator 5.2.2 respectively,
conduction of the light beam through the analyte vapour for the use of A and
contained in the atomizer (e.g. flame). In this Section, choice of symbol.
optical components, special systems, and their properties 10%- or 1%-width of See Part I, 2.8 and
which are of interest in analytical flame spectroscopy will optical filter (measured or 5.2.2 respectively,
be considered. In Section 5 of Part I of this Nomencla- between points of 10% nm for the use of A and
or 1% of maximum choice of symbol.
ture, general terms applicable to optical systems and
spectroscopic instruments were considered. Those defini- transmission factor)
tions will not be repeated here, but some of these terms
Wavelength for Am nm See Part I, 2.8 and
maximum transmission 5.2.2 respectively,
are included in Table 3.2 for convenience, together with of optical filter for the use of A and
the recommended symbols. or monochromator choice of symbol.
The general term spectrometer, as it is used in this Optical conductance G cm2sr For definition, see
document (see Table 1.1), implies that quantitative Part I, 5.3.2.
measurements of intensities at one or more wavelengths Half-intensity width 6A5 nm See Part I, 2.8 and
are performed with a photoelectric detector. Spectral of source line 5.2.2 respectively,
isolation of the desired radiation may be performed by for the use of A and
choice of symbol. See
means of (optical) filters (absorption filter, interference Table 5.1, Part III
filter, etc.) or by a dispersing system. When the for definition of
spectrometer is able to isolate only one narrow half-intensity width.
wavelength region, the instrument is called a mono - Half-intensity width Aa nm
chromator. A polychromator is a multichannel spectrome- of absorption line
ter that allows spectra! isolation of a number of narrow Response time of a T, To. 5
wavelength regions. system (time needed
A resonance spectrometer consists of a "reservoir" of to reach the reading
analyte atoms, which is irradiated by an external radiation that is a specified
fraction, e.g. 99%,
beam containing, among others, the resonance frequen- of the final value)
cies of the analyte atoms. The vapour in the reservoir is cm
Observation height hOb5
excited specifically by this resonance radiation. The (above top of burner)
resulting fluorescence radiation which is related to the Frequency of fmod Hz
intensity of the analyte resonance radiation in the original light-modulation
radiation beam, is measured. Electrical current for A The official symbol
In AAS, the sensitivity (see Section 4.2) may be operating light source I for current may
improved by means of a multipass system, which allows give confusion with
the radiation beam from the light source to pass several I for intensity.
times through the analyte vapour before it reaches the Dark current Id A For definition see
(of photodetector) Section 3.4. The
detector.
official symbol I
Most optical systems in use in flame spectroscopy are for current may give
single-beam systems. For double-beam systems used in confusion with I for
AAS, the radiation from the light source is split into the intensity.
sample beam and the reference beam. Photocurrent A For definition see
The optical signal can be modulated or pulsed by the Section 3.4. The
periodic interruption or intensity variation of the light official symbol I
beam of interest. Light modulation when combined with for current may give
an a.c. measuring system provides some advantages. For confusion with I for
example, in FES, the electrical signal arising from the intensity.
Solid angle over sr
flame emission may thus be distinguished from the d.c. which emission is
dark current (see Section 3.4) of the photodetector. In measured
AAS and AFS, modulation of the primary radiation beam Solid angle over QF sr
(prior to its entrance into the flame), provides for the which fluorescence
discrimination between the absorption or fluorescence is measured
signal and the thermal emission of the flame. Light Solid angle over sr
modulation can, be achieved by means of a mechanical which radiation is
absorbed by flame
chopper, or by modulating the electrjcal current through from light source
the lamp.
114 COMMISSION ON SPECTROCHEMICAL AND OTHER OPTICAL PROCEDURES FOR ANALYSIS

3.4. Photodetectors analyte, i.e. the element sought, and the concomitants, i.e.
The most commonly applied photodetectors are the any species other than the analyte and the solvent. Some
vacuum phototube (without internal amplification), the concomitants may be present in known and constant
photomultiplier tube (with internal amplification by concentrations through having been added during chemi-
secondary emission of electrons) and the photovoltaic cell cal pretreatment of the sample, and are called additives.
(a semiconductor device producing an electromotive Others, which were in the original sample, may have
force upon irradiation). variable and/or unknown concentrations.
The border line between the solvent and the concomit-
Note : The photovoltaic cell is often called a barrier-layer cell or
ant cannot always be sharply drawn. For example, when
photodiode.
alcohol is added to the solution in constant known
There are two components in the output current of a proportions (in order to improve nebulization or to
photodetector. One component, the photocurrent, i, is produce chemiluminescence), it is regarded as a part of
that portion induced by the radiation. The detector is said
the solvent; when present in the original sample, in
to be linear if the photocurrent is proportional to the unknown or varying concentration, it may be regarded as
radiant flux. The other component is called the dark a concomitant.
current, Id, because it continues to exist when the A reference solution is a solution with the same solvent
radiation flux is blocked. as the sample, and contains the analyte, and possibly
The responsivity of a photodetector (or in more general some concomitants, in known concentrations.
terms, the sensitivity) is the chartge in output current per A blank solution is a solution that does not intentionally
unit change in radiant flux. The responsivity is wavelength contain the analyte, but in other respects has, as far as
dependent; the curve describing this dependence is called possible, the same composition as the sample solution. A
the spectral response curve. solvent blank consists only of the solvent.
Table 3.2 lists the quantitative terms and symbols The analytical result is the final value of concentration,
related to photodetectors. c, or quantity, q, of the element sought, after all
subprocedures and evaluations have been performed. For
3.5. The electrical measuring system example, the analytical result may be obtained from a
In the electrical measuring system, the electrical signal meter reading which provides a measure of some physical
delivered by the photodetector (see Section 3.4) is quantity, such as analyte emission intensity, absorbance,
processed and converted to a reading on an appropriate or fluorescence intensity measured at the wavelength of
readout device. The reading provides a measure (see an analytical line. The physical quantity carrying the
Section 4.1) of the radiant flux emitted, absorbed or information on the analyte concentration, is called the
fluoresced in the flame. In the absence of analyte, the (analyte) signal.
signal trace recorded as a function of time or of Note: If the position of the sensitivity knob of the instrument is
wavelength is called the baseline. In order to speed up the changed, the reading, but not the measure, is changed.
evaluation of an analysis, the readout is sometimes
directly calibrated in terms of concentration or amount of The measure obtained when a blank solution is
analyte. A non-linear analytical curve (see Section 4.2) nebulized into the flame. is called the blank measure, XbI.
may be linearized by means of a curve corrector. The The measure, x, obtained when the (reference) solution is
background (see Section 4.1) can be compensated nebulized, can be corrected for the blank measure, Xbl,
electronically by means of a background corrector. either instrumentally or numerically. The difference,
Readings of small differences in two relatively large x — Xbl, is called the net measure. The signal that is
signals may often be made more readily by scale observed when no solution or solvent is nebulized into the
expansion of a segment of the reading range. When zero flame, is called the flame background (emission or
suppression is used, one of the signals is suppressed by absorption). The background observed when a blank
displacing the zero of the meter, usually by electronic solution is nebulized in FES, FAS or FFS, is called the
means, and the difference signal is increased by increasing blank background (emission, absorption, or scattering,
the amplifier gain. respectively).
The response time (see also Table 3.2) is the time Note: See also Part I, Section 6, for a further explanation of some
needed for the readout to reach a specified fraction (which general terms.
must be stated) of its final value if the photodetector is
suddenly exposed to the radiation flux. If this fraction is 4.2. Analytical calibration
chosen to be (1 — l/e) = 063, then the response time is The relationship between the measure, x, of the signal
called the time constant. and the solution concentration, c, of the analyte is given
Scatter and drift will be discussed in Section 4.3.1. by the analytical curve. This curve is generally established
by making measurements on a series of reference
solutions.
3.6. Survey of terms, symbols, and units for measurable The derivative of the function x = g(c), dx/dc, is the
quantities in the optical and measuring systems
sensitivity of the analytical procedure. When the analyti-
(See Table 3.2).
cal curve is non-linear, the sensitivity is a function of
concentration.
4. TERMS AND SYMBOLS RELATING TO THE In AAS, it is often desirable to compare slopes of
ANALYTICAL PROCEDURE AND THE analytical curves at low analyte concentration values for
PERFORMANCE OF AN ANALYSIS different lines and/or elements. This is often done by
4.1. General anal ytical terminology inflame spectroscopy reporting concentration values of the analyte correspond-
In analytical flame spectroscopy, the sample may be a ing to 1% net absorption or 00044 absorbance. The term
solution or is brought into solution. We distinguish characteristic concentration is recommended for this
between the solvent (e.g. an alcohol—water mixture), the particular concentration value.
 Nomenclature, symbols, units and their usage in spectrochemical analysis—Ill 115

Note : In the past the term 'sensitivity' has been incorrectly used where
for this concentration value.
x=
Different techniques may be used for obtaining the
analytical result. When the analytical-curve technique is is the average.
used, the analytical result is read from an analytical curve The scatter in general is a composite quantity produced
covering the concentration range of interest. by random fluctuations from different sources. If these
When the bracketing technique is applied, the analytical random fluctuations in the measure x are independent, the
result is found by graphical or numerical (usually linear) formula for the propagation of variance (square of the
interpolation between measures of two reference solu- standard deviation) can be applied to this case in the
tions, one having a slightly lower, and the other a slightly following symbolic form:
higher analyte concentration than the unknown sample
solution. 5l Si2+5j+ 5j+ ...
When the (analyte) addition technique is applied, Typical sources of scatter in the blank and net measure
successive known quantities of the analyte are added to are the following: (not all independent)
aliquots of the sample solution. The net measures of the
solutions thus obtained are plotted against the added Preparation of solution (accidental differences in weigh-
concentrations. This plot is extrapolated to intercept the ing, adsorption, etc.);
negative concentration axis. The analytical result is found Accidental external contaminations of solution;
from the corresponding concentration value. Variation of impurities in reagents;
Direct methods, i.e. those where the analyte produces Random fluctuations of nebulization and transport;
the measured signal, are generally used in flame spec- Random fluctuations of desolvation, atomization, and
trometry. For some elements, indirect methods have been excitation;
applied. A given amount of another element, whose Random fluctuation in the background;
measured signal depends on the analyte concentration Random fluctuations from the light source;
present, is added to the sample solution. If the change in Uncontrolled variations in the optical system;
the signal of the latter element is measured, a measure of Random fluctuations in the photodetector, such as shot
the analyte concentration is obtained (e.g. the determina- noise in the photocurrent and dark current, and low-
tion of phosphate by the addition and measurement of frequency flicker noise arising from instabilities in a
strontium). In some cases, the added element reacts with photocathode;
the analyte in the solution before nebulization, the Electronic noise in the electrical measuring device, such
resulting compound being separated. The remainder of the as shot noise and thermal or Johnson noise which is due
added element, or the amount of added element that is to the thermal agitation of charge carriers in resistors;
separated because of the compound formation, is then Drift in amplifiers;
measured (e.g. the chloride content may be determined by Reading errors, accumulated rounding errors in calcula-
the addition and measurement of silver). tions, calibration errors, etc.
In a complicated measuring system the contribution of
Note: See also Part II for a further explanation of some general these different sources can rarely be predicted theoreti-
terms.
cally. Blank scatter, Sbl, can only be determined by making
blank analyses and then treating the measures, Xbl,
4.3. Assessment of an analytical procedure statistically. It is therefore highly important that such a
4.3.1. Measurement scatter series of blank analyses be planned carefully. All causes
The measure observed when a sample solution is for random fluctuations involved in the original analytical
analyzed is, in general, composed of two portions: the procedure must play their full part, except those which
blank measure and the net measure (see Section 4.1). The are directly bound to the presence of the analyte.
net measure refers to the (analyte) signal (see Section 4.1)
and is thus the useful, informative portion. The blank 4.3.2. Limit of detection, precision, and accuracy
measure can be isolated and observed when a blank The merits of an analytical procedure may be character-
solution is treated in exactly the same way as the sample ized by its limit of detection, precision, and accuracy.
solution. Because the analyte should not be present in the The limit of detection expressed as concentration, cL,
blank solution, the blank measure contains no information or quantity, qL, is derived from the smallest measure, XL,
about the analyte. that can be accepted with confidence as genuine and is not
When replicate determinations are made on a given suspected to be only an accidentally high value of the
sample or blank, the measured values will not be constant, blank measure. The valueof XL is givenbythe equation:
but will show scatter. If the causes of the scatter are not
known (or considered), they cannot be controlled and XL = Xbl + ksb,
therefore appear accidental. Blank scatter and signal
scatter both contribute to the uncertainty of the analytical where lb is the mean and Sb the standard deviation of the
result. blank measures, and k a numerical factor chosen
The numerical value for the scatter may be taken as the according to the specified confidence level. The limit of
standard deviation, which is determined from a suffi- detection is obtained directly from the analytical curve. A
ciently large series of repeated determinations. For a set value of k = 3 is strongly recommended for the reasons
of n measured values x the standard deviation, s, is, in given in Part II, Section 4.1. Although a value of 2 has
general, defined and calculated by the formula: often been used, this value is not recommended. To avoid
ambiguity, the k-value should be indicated as follows:
n 1/2
XL(k=3). The time constant of the measuring device should
s (x — i)2/(n —
1)] be stated specifically, so that meaningful comparison
116 COMMISSION ON SPECTROCHEMICAL AND OTHER OPTICAL PROCEDURES FOR ANALYSIS

between the limits of detection for different instruments comparing the measures of the analyte-free blank solution
may be made. and the solvent blank (1).
The precision of an analytical procedure can be Spectral interferences are usually strongly dependent
conveniently expressed by the standard deviation, s, or by on the spectral bandwidth of the monochromator.
the relative standard deviation Sr 5/C in the analytical Spectral interference may arise:
result (see Part II, Section 2.4). In FES—from radiation (spectral continuum, molecular
The accuracy relates to the difference between the
bands, or atomic lines, called interfering lines) emitted by
analytical result obtained by a given analytical procedure the concomitants. Spectral interference may also arise
and the (known or assumed) true analyte concentration in
from stray or scattered light or spectral ghosts that reach
the sample.
The bias characterizes the systematic error in a given the detector;
—by the indirect effect of the concomitants on flame
analytical procedure and is the (positive or negative) background (which is sometimes difficult to distinguish
deviation of the mean analytical result from the (known or
from their direct contribution to the background).
assumed) true value.
In FAS and/or FFS—by absorption or fluorescence of
If materials with certified analyte concentration values
radiation by overlapping molecular or atomic lines of
(i.e. the best estimates of the true values) are not
available, and the results cannot be compared with those concomitants;
—by thermal emission of concomitants transmitted by the
obtained by other reliable methods, several test experi-
monochromator, or received by the photodetector as
ments may be used to check the accuracy of the stray light, when the light source is not modulated;
procedure. The recovery test is based on the addition of a
—by scattering of source radiation by nonvolatilized
known amount of the analyte to the sample at an early
stage of the analytical procedure. This amount should be particles formed by the concomitants;
—by the indirect effect of the concomitants on the blank
found when the analytical result for the sample solution
without addition is subtracted from the result for the background absorption or scattering in the flame;
sample solution with addition. In the dilution test, —by foreign line absorption and/or fluorescence if the
corresponding radiation happens to be emitted by the light
different known dilutions of the sample are made and the
source, in addition to the analysis line, within the spectral
results obtained are compared.
bandwidth of the monochromator, particularly when a
The correct outcome of these tests is a necessary but
continuum source is used.
not sufficient proof of the absence of systematic errors in
a given analytical procedure. Note 1: The spectral interference found when a blank solution is
nebulized need not be identical with the true spectral interference,
Note: For a further explanation, see also Part II and Pure App!.
since the presence of analyte in the sample might, in turn,
Chem. 18 (3), 439 (1969).
influence the emission or absorption of the concomitants through
one of the effects to be discussed in this Section.
4.4. Interferences by concomitants [Link]. Non -spectral interferences. For interferences
4.4.1. General other than spectral, the analyte signal itself is directly
The presence of concomitants in the sample can cause affected. The non -spectral interferences may be classified
interferences, i.e. systematic errors in the measure of the according to the following viewpoints:
signal. An interference may be due to a particular (a) To the place or stage at which the particular
concomitant or to the combined effect of several interference occurs, i.e. transport, solute-volatilization,
concomitants. A concomitant causing an interference is vapour-phase and spatial-distribution interferences;
called an interferent. When C is an interferent and A the (b) To the effects on different elements, i.e. specific
analyte, there is an interference of C on A. When an and non -specific interferences;
element X acts as an interferent on an analysis element Y, (c) To the properties which are decisive for the
and Y acts as an interferent on the analysis element X, a mechanism of the interference, i.e. physical and chemical
mutual interference is said to exist. interferences.
Note: The influence of the solvent or of the flame background Note: The latter classification is discouraged since it can easily
(without nebulization) on the measure is not called an interfer- lead to confusion. Some physical processes (e.g. volatilization)
ence. This is logical, because the sample and the reference determined by physical properties of the particles formed by the
solutions presumably contain the same solvent (see Section 4.1). analyte in the presence of an interferent depend on the chemical
An interference will cause an error in the analytical properties of the analyte and interferent.
result only if the interference is not adequately accounted These different classifications do not exclude one
for in the evaluation procedure. The analyte concentra- another. If the interference cannot be specified, the term
tion determined when the interference is not accounted effect may be used. Thus the matrix effect is a composite
for is called the apparent concentration. If the apparent interference due to all of the concomitants, except for the
concentration is larger than the true concentration, an additives (see Part I, Section 6.1); the anion, cation or
enhancement occurs or, if smaller, a depression. The organic effect includes all interferences caused by the
interference curve relates the measure, or apparent presence of different anions, cations or organic con-
concentration of the analyte, to the concentration of stituents of the sample. When a particular solvent other
interferent, at fixed analyte concentration. than water is used, its effect on the signal (as compared
with an aqueous solution) is not to be considered as an
4.4.2. Classification of interferences interference (see Note in Section 4.4.1).
[Link]. Spectral interferences. Spectral interferences Transport interferences affect the amount of desolvated
are due to incomplete isolation of the radiation emitted or sample passing through the horizontal flame cross-section
absorbed by the analyte from other radiation detected by per unit time at the observation height. They include
the instrument. Their occurrence may be established by factors affecting the rate of liquid consumption, F1, the
 Nomenclature, symbols, units and their usage in spectrochemical analysis—Ill 117

efficiency of nebulization, €,,, and the fraction desolvated, In the (analyte) addition technique (see Section 4.2),
PS. They may be classified as non-specific (and physical). errors arising from both specific and non-specific interfer-
Solute-volatilization interferences are due to changes in ences but not from spectral interferences are minimized.
the volatilization rate of the dry aerosol particles in the In the simulation technique, reference solutions suffi-
case when volatilization of the analyte is incomplete in the ciently similar in quantitative composition to the sample
presence and/or absence of the concomitant. These solutions to be analyzed are used so that the interferences
interferences can be either specific, if the analyte and in the reference and sample solution are equivalent.
interferent form a new phase of different thermostability, In the buffer-addition technique, an additive (called a
as when Mg and Al form MgA12O4 in an air-acetylene spectrochemical buffer) is added to both the sample and
flame, or non-specific, if the analyte is simply dispersed in reference solutions for the purpose of making the
a large excess of the interferent, as when Ag is dispersed measure of the analyte less sensitive to variations in
in Th02. If the interferent has a high boiling point, this interferent concentration. Additives that may serve as
latter case is sometimes referred to as blocking interfer- spectrochemical buffers are:
ence. It is often difficult •to make sharp distinctions
between the specific and non-specific solute-volatilization Suppressors reduce emission, absorption or light scatter-
interferences. ing by an interferent, thus removing or lowering spectral
interference.
Note: Solute-volatilization interferences do not necessarily Releasers reduce solute-volatilization interferences by
depress the signal. Effects due to compounds causing explosive forming a compound preferentially with the interferent,
disintegration of the solid aerosol particles and consequent thus preventing the analyte from entering a thermally
enhancement also belong to this group.
stable compound.
Vapour-phase interferences are caused by a change in Protective agents combine chemically with the analyte or
the fraction of analyte dissociated,t ionized, or excited in the interferent in such a way as to reduce the type of
the gaseous phase. These interferences may be called interferences discussed under [Link].
dissociation, ionization, and excitation interferences re- Ionization buffers are added to increase the free-electron
spectively. An excitation interference may occur when concentration in the flame gases thus repressing and
the concomitant alters the flame temperature. Experimen- stabilizing the degree of ionization (see Section 6.2).
tally these interferences may be easily recognized Volatilizers increase the fraction volatilized (see Section
because they take place even when twin nebulizers are 3.1.2) either by forming more volatile compounds or by
used for aspirating the analyte and the interferent increasing the total surface area of all analyte particles
separately. All interferences of this type are specific. (e.g. by explosive disintegration or by dispersal of the
Spatial-distribution interference may occur when analyte in a highly volatile matrix).
changes in concentration of concomitants affect the mass Saturators are interferents added in sufficiently high
flow rates or mass flow patterns of the analyte species in concentration to the sample solution to reach the
the flame. If they are caused by changes in the volume and saturation (plateau) of the interference curve (see
rise velocity of the gases formed by combustion, in Section 4.4.1).
extreme cases manifesting themselves by changes in the
size and/or shape of the flame, they are non-specific and 5. TERMS, SYMBOLS, AND UNITS RELATING TO
are called flame-geometry interferences. However if RADIANT ENERGY AND ITS INTERACTION WITH MATTER
caused by changes in diffusion processes they may be
specific. Thus the lateral diffusion interferences arise Relevant descriptive terms relating to the emission,
when the presence of concomitants delays the vaporiza- absorption, and fluorescence of optical radiation are
discussed in this section. Terms for measurable quantities
tion of spray droplets or solid particles thereby shortening
the time available for lateral diffusion of the analyte are listed separately in a table, together with their
gaseous species before they reach the viewing field of the recommended symbols and practical units.
spectrometer.
4.4.3. Reduction of errors due to interferences for given 5.1. Descriptive terms relating to the emission, absorption,
instrumental conditions and fluorescence of radiation
Several techniques may be used to reduce or eliminate 5.1.1. Emission
analytical errors resulting from various types of interfer- The emission spectrum of a light source may consist of
ences. Apart from changing the instrumental conditions, separate spectral lines (see Section 7.6.1 in Part I) and/or
the following techniques represent some of those in a spectral continuum with a continuous distribution of
current use: frequencies or wavelengths. Spectral lines emitted by free
neutral atoms and ions are called atomic lines and ionic
In the baseline technique (see Section 3.5), background
spectral interference is corrected. The background is lines, respectively (see Section 7.6.1 in Part I). The
interpolated from background readings on both sides of spectral lines emitted by free molecules are grouped
the analytical line and the value thus found is subtracted together in spectral bands. When the resolution of the
from the reading at the peak of the line. monochromator (see Section 5.2.2 in Part I) is insufficient,
In the reference-element technique, the measure of the some bands may appear as a (quasi-)continuum in the
analyte is compared with the measure of a reference recorded spectrum.
element (see Part I, 6.2.2). This technique is used mainly
The emission of an atomic line is the result of a
transition of the atom from a state of higher excitation to a
for minimizing non-specific interferences.
state of lower excitation. When the lower state of the
tHere "dissociation" means the formation of free neutral atoms transition is the ground state, the line is called a resonance
from free molecules in the gaseous phase (see also Section 6.1). line. When the ground state is a multiplet, only transitions
The term atomization is here not appropriate because the latter to the lowest multiplet component should be called a
also covers the formation of free atomic ions (see Section [Link]). resonance line.
118 COMMISSION ON SPECTROCHEMICAL AND OTHER OPTICAL PROCEDURES FOR ANALYSIS

Note : Some handbooks define a resonance line as the line that ity of the atoms in a flame are normally in the ground
originates from the lowest excitation state for which an optical state, absorption of photons (whether followed by
transition to the ground state is allowed. Other handbooks adopt conversion into heat or by fluorescence), is usually
the wider definition presented in the text (compare, e.g. Lexicon detectable only with resonance lines (see Section 5.1.1) or
der Physik, edited by H. Franke, Stuttgart, with the Handbook of
with lines absorbed by atoms or ions in low-lying excited
the American Institute of Physics). The broader definition
conforms to common usage in analytical flame spectroscopy. If
states.
desired, the resonance line (or doublet) originating from the lowest For a similar reason, self-absorption (see Part I,
excited level(s) may be specifically called the first resonance line Section 7.6.2) is usually found with the resonance lines
(or doublet). emitted by the flame or spectral line source. There is a
certain probability that the photons of the resonance line
The radiation originating from a source where all
which are generated inside the light source, e.g. a flame or
particles are in a state of thermal equilibrium (see Section
a hollow-cathode lamp, may be absorbed on their way out
6.1), is called thermal radiation. This term applies for the
by ground-state atoms and of being partly converted into
radiation of a spectral continuum as well as of isolated
heat. This results in aloss of intensity of the total outgoing
spectral lines or bands.
radiation. The loss will be larger, the thicker the cloud of
When the excited state from which the transition
atoms and/or the higher their concentration (4).
originates is mainly populated as a direct result of a
Self-reversal of emission lines is a special case of
chemical reaction, the radiation process is called self-absorption which occurs when the radiating core
chemiluminescence.
inside the light source (flame, hollow-cathode lamp) is
Note : The adjective "thermal" as such does not indicate the kind surrounded by a mantle of atomic vapour in which little or
of process (collisional, chemical or radiative) that is responsible no excitation takes place (see also Part I, Section 7.6.3).
for the excitation of the radiating substance. Note, however, that With a flame, this situation occurs when the temperature
the term chemiluminescence specifies the kind of excitation in the mantle is appreciably lower than at the centre. The
process. These two concepts therefore do not necessarily exclude
each other. In flames, "thermal chemiluminescence" can exist, if
absorption, in the mantle, of the line radiation from the
the chemical species involved in the chemiluminescent reaction core is then no longer (fully) compensated by the emission
are in chemical equilibrium. Suprathermal chemiluminescence of the mantle itself. Since the absorption factor (see Table
results if the concentrations of the chemical species taking part in 5.1) has a peak value at the centre of the line, the
the excitation reaction are above the equilibrium value. uncompensated loss of radiation will here be more
pronounced than in the line wings. This may result in the
5.1.2. Absorption and self-absorption appearance of a minimum or reversal dip in the centre of
When a light beam traverses a flame or other hot gases the line profile. In the extreme case, when practically only
into which a sample is nebulized, its intensity (in the beam the line wings remain, the line may appear as two diffuse
direction) may be attenuated by several processes (1). lines.
First, radiation may be lost due to (real) absorption,
Note (4): At high concentrations, where self-absorption becomes
whereby photon energy is indirectly converted into heat noticeable, the intensity of a resonance emission line will
(2). Furthermore, scattering by particles in the condensed therefore increase less than proportionately with increasing atom
(1) or gaseous phase (3), may change the direction (but not concentration in the flame. If the emitting species occurs in a zone
the energy or frequency) of the incident photons. of the flame with a homogeneous radial temperature distribution,
Resonance fluorescence (see Section 5.1.3) is a special the relation between line intensity and atom concentration is
case of scattering by free atoms or molecules. Finally, described by the curve-of-growth. This curve has a linear branch
photons may be removed from the original beam when in the range of low concentrations where self-absorption is still
they are transformed into photons of different frequency negligible. At high concentrations, the intensity increases as the
and direction as a result of non-resonance fluorescence square-root of the concentration (square-root-branch).
(see Section 5.1.3).
5.1.3. Fluorescence
Note (1): In atomizers (see Section 3.1.1) which incorporate
optical windows, trivial reflection losses may also occur. Random The absorption of photons from a primary beam to
reflections of the light beam by unevaporated droplets in the flame raise an atom to a higher excited state may be followed
are for practical reasons not distinguished here from scattering directly or indirectly by (secondary) photon emission; this
effects. process is called atomic fluorescence. When the
Note (2): Conversion of radiation into heat occurs when an atom wavelengths of the absorbed radiation in the exciting
that has been excited by photon absorption subsequently loses its beam and of the re-emitted radiation are identical,
excitation energy through collisional processes. The energy lost is resonance fluorescence is said to occur. Resonance
converted to kinetic energy (see also Section 5.1.3). Note that the fluorescence may be considered to be a special case of
expression: "absorption of a radiation beam in a medium" means
the indirect conversion of radiant energy into heat, whereas the scattering (see Section 5.1.2). When the wavelengths of
expression: "absorption of a photon by an atom" only means the the two radiations are different, several cases can be
transition of the atom to a higher excited level. When the excited distinguished. Direct line fluorescence exists when the
atom returns to the lower level by re-emission of a photon of the transitions in the absorption and fluorescence process
same energy, no conversion of photon energy into heat results. have a common upper level. When the upper levels are
Note (3): Scattering by free atomic or molecular species is not different, stepwise line fluorescence occurs. Stokes and
important in flames when the frequency of the photon does not anti-Stokes fluorescence apply when the wavelength of
correspond to any of the optically allowed transitions in the atom the fluorescence radiation is longer or shorter, respec-
or molecule. tively, than that of the absorbed radiation.
The absorption of a photon, by which the atom is raised
Notes: In resonance fluorescence the line need not be a resonance
from a lower level to a higher one, is the reverse process line (see Section 5.1.1), although this will most often be the case.
of photon emission. Each atomic line appearing as an In stepwise line fluorescence, atoms excited to an upper level by
emission line, can thus in principle also occur as an the primary beam are transferred, usually by collisions, to another
absorption line. However, since the overwhelming major- excited level from which the fluorescent line is emitted.
 Nomenclature, symbols, units and their usage in spectrochemical analysis—Ill 119

Table 5.1 Radiant energy and its interaction with matter. Terms, symbols, and units for measurable quantities

Terms Symbol Practical unit Note

(Radiant) energy Q J See also Section IV, Part I.

Spectral (radiant) energy QA J nm' When a quantity is considered per unit of wavelength (or
frequency) at a given wavelength (or frequency), it is
preceded by the adjective 'spectral' (see Part I, 4.2).
The appropriate symbol is obtained by adding A (or v)
as a suffix, e.g. QA. Note that the units for Q(J) and QA
(J nm') are different. The radiant energy contained in
a small wavelength interval, dA, is given by QA dA.
Intensity (of radiation) I 1 The general term "intensity" may be used as a loose,
relative expression referring to any radiant quantity
without specification (see also Part I, 6.3.1). Note,
however, that "radiant intensity" has a well-defined
meaning.
Radiant intensity I W sr1 All of above notes apply to this term.
Radiant flux 'I, W See also Section IV, Part I. When this quantity is
considered per unit of wavelength (or frequency) at a
given wavelength (or frequency), it is preceded by the
adjective "spectral" (see Part I, 4.2). The appropriate
symbol is obtained by adding A (or v) as a suffix, e.g.
&. Note that the units for '1(W) and A (W nm) are
different. The radiant flux contained in a small
wavelength interval, dA, is given by dA.
Radiant flux incident on (absorbing) medium W See also Section V, Part I.
Radiant flux transmitted by (absorbing) medium cP W See also Section V, Part I.
Radiant flux absorbed by medium cPa W See also Section V, Part I.
Transmission factor (4?,I4?) T 1 See also Section V, Part I. This quantity also includes
the transmission properties of the apparatus (cell
windows, etc.). The value of this quantity, for strictly
monochromatic radiation with wavelength A, is
denoted by T(A) (not: TA).
Internal transmission factor 1 The value of this quantity, for strictly monochromatic
radiation with wavelength A, is denoted by r(A). This
quantity refers to the transmission properties of the
sample alone.
Absorption factor (ckJI'0) a 1 See also Section V, Part I. The value of this quantity, for
strictly monochromatic radiation with wavelength A,
is denoted by a(A) (not: aA). When the absorption
properties of the apparatus, e.g. cell windows, are
excluded, the adjective "internal" is added. "Ab-
sorptance" is not recommended in this context
because of confusion with "absorbance."
(Internal) absorbance (—log10 r) A 1 This quantity refers to the transmission properties of the
sample alone. In AAS, however, the adjective
"internal" is usually dropped.
Peak value of A (at absorption line centre A0) A (A0)
Absorption path length 1... b cm
Integral absorption (of spectral line) [fa(A) dA] A1 nm For the use of A, see Part I, Section 2.8. This quantity
describes the energy absorbed from a continuum
within the wavelength profile of a spectral line.
(Radiant) energy density u, w J cm3 See also Section IV, Part I. When this quantity is
considered per unit of wavelength (or frequency) at a
given wavelength (or frequency), it is preceded by the
adjective "spectral" (see Part I, 4.2). The appropriate
symbol is obtained by adding A (or v) as a suffix, e.g.
UA.
Radiance B.. . L W sr1 cm2 See also Section IV, Part I. When this quantity is
considered per unit of wavelength (or frequency) at a
given wavelength (or frequency), it is preceded by the
adjective "spectral" (see Part I, 4.2). The appropriate
symbol is obtained by adding A (or v) as a suffix, e.g.
BA.
(Einstein) transition probability for A, A1 s' Also called (Einstein) coefficient for spontaneous
spontaneous photon emission (by optical emission.
transition from upper state u to lower
state 1)
Oscillator strength for absorption (by optical f,flu
transition from lower state 1 to upper state
u) (f—value)
Intensity of spectral line due to transition from Ii
upper state u to lower state 1

P.A.C., Vol. 45, No. 2—E

120 COMMISSION ON SPECTROCHEMICAL AND OTHER OPTICAL PROCEDURES FOR ANALYSIS

Table 5.1 (Contd)

Terms Symbol Practical unit Note

Wavelength at (atomic) line centre A0 nm For the use of A, see Part I, Section 2.8.
Quantum efficiency of fluorescence (number Y, Yq I
of photons re-emitted per second/number of
primary photons absorbed per second)
Power efficiency of fluorescence (radiant flux Y, 1
re-emitted/primary radiant flux absorbed)
Total quantum efficiency of fluorescence [= Y Yt 1
for the case when the upper level of the
fluorescence transition is populated directly
or indirectly (by 2-step process) by absorp-
tion of more than I spectral line].
Half-intensity width (full width at half peak ÔÀ nm The term half-width is sometimes used instead of
height of a spectral line profile) half-intensity width, but may readily be misunder-
stood as half of the full width. For the use of A, see
Part I, Section 2.8.
Doppler half-intensity width (of spectral 5AD nm The term half-width is sometimes used instead of
line due to Doppler broadening) half-intensity width, but may readily be misunder-
stood as half of the full width. For the use of A, see
Part I, Section 2.8.
Collisional half-intensity width (of spectral 5A nm The term half-width is sometimes used instead of
line due to collisional broadening) half-intensity width, but may readily be misunder-
stood as half of the full width. For the use of A, see
Part I, Section 2.8.
a-parameter [\/i(&tc/ôAD)] a I Also called: line-broadening parameter or damping
constant. In this definition of a, the natural line-
broadening is disregarded. When natural line-
broadening is important, it should be included in the
numerator.

Collisions of fluorescing atoms with other atoms or the state of excitation, ionization, and dissociation in
molecules are said to quench the fluorescence when they which the analyte is found in the gaseous phase.
destroy the state of excitation brought about by absorption Note: The Maxwell—Boltzmann law describes the distribution
of the primary photons. The number of secondary photons over the translational and internal energies of the particles.
will then be smaller than the number of primary photons Planck's law describes the distribution of the radiant energy over
absorbed. The extent of quenching is determined by the the spectrum. Saha's law describes the distribution of the particles
competition between the rates of radiative and collisional over their different states of ionization, while the mass action law
de-excitation of the excited atoms, and quantitatively determines the fraction of element that is bound in molecular form.
expressed by the efficiency of fluorescence (for definition In atomic spectroscopy, the term "dissociation" usually
see Table 5.1). refers to the splitting of a free molecule into fragments,
one or more of which is a free neutral analyte atom, and is
5.2. Terms, symbols, and units for measurable quantities
Table 5.1 presents terms with their symbols and thus important in connection with the atomization (see
practical units for some measurable quantities belonging Section [Link]).
to this Section. Section IV of Part I lists additional terms. Strictly speaking, thermodynamic equilibrium implies
that the spectral energy density obeys Planck's law (see
Although practical units generally conform, alternative Note in Section 3.2). In flames of analytical interest, this
symbols that differ from those in Part I are occasionally
recommended.
condition is not met except at the centre of strongly
self-absorbed resonance lines. However, radiative proces-
6. TERMS, SYMBOLS, AND UNITS RELATING TO ses usually play a minor part in the population of the
THE GASEOUS STATE OF MA11ER excited states, at least if the flame is not irradiated by an
Analytical flame spectroscopy and similar techniques external light beam. The distribution of the particles over
are based on the interaction of radiation with the analyte. their various energy states and over the various forms in
The strength of this interaction depends on the properties which they may occur (as neutral or ionized atoms, or as
and state of the analyte in the vapour phase. In the molecules) is then hardly affected by deviation from
following, we restrict ourselves to this phase (the Planck's law. The system is then said to be in thermal
transformation of the analyte from the condensed phase equilibrium. This implies that there is chemical equilib-
into the vapour "phase has already been discussed in rium between all chemical species (including ions and
Section 3.1). A few descriptive terms will be mentioned, electrons) in the system, as well as physical equilibrium
followed by a list of terms for measurable quantities with for the translational and internal energies of the particles.
their symbols and practical units. However, there need then be no radiative equilibrium.
Note: In the absence of radiative equilibrium, it is still meaningful
6.1. Descriptive terms concerning the gaseous state of to define thermal radiation as it has been done in Section 5.1.1.
matter
In (thermodynamic) equilibrium, the state of a system is 6.2. Terms, symbols, and units for measurable quantities
generally described by the thermodynamic or absolute Many of the terms listed in Table 6.1 are also found in
temperature (Table 2.1) which occurs as a univeral Part I, Section 7.3, where the terms are discussed in more
parameter in the distribution laws. These laws determine detail.
 Nomenclature, symbols, units and their usage in spectrochemical analysis—Ill 121

Table 6.1. Properties and state of matte r. Terms, symbols, and units for measurable quantities

Terms Symbol Practical unit Note

Excitation energy J. . . eV See Part 1,7.4. The electron volt (eV), as a practical unit
for energy on an atomic scale, is still in common use.
When several excited states are to be distinguished,
the excitation energy of state q may be written as Eq.
When several kinds of particles are also considered,
the excitation energy of state q of a particle X may be
written as Eq(X).
Excitation potential Vexc V See Part I, 7.4.
Ionization energy E0, E J...eV See Part I, 7.4.
Ionization potential vion, vi V See Part I, 7.4.
Dissociation energy Ed1, D0, D, J...eV This is the minimum energy required to dissociate one
molecule of XY at zero K in perfect gas state. The
fragments must be specified when the molecule
contains more than 2 atoms. The molar dissociation
energy refers to one mole of substance XY. In
chemistry, the symbol D, is customarily used.
Dissociation potential Vd V
Degree of ionization [Mi)] M denotes an atom; [M] denotes number density of M in
the flame (see also Table 2.1).
Degree of dissociation I + [MX])] /3d . . a 1 M denotes an atom; [M] denotes number density of M in
the flame (see also Table 2.1).
Statistical weight of particle in state q gq 1 When several kinds of particles are considered, the
symbol may be extended by adding the chemical
symbol X as in: gq(X).
Statistical weight of particle in ground state g0 1 When several kinds of particles are considered, the
symbol may be extended by adding the chemical
symbol X as in: g0(X).
Partition function Z, Q 1 When several kinds of particles are considered, the
symbol may be extended by adding the chemical
symbol X as in: Z(X).
(Number) density of particles in state q flq cm3 When several kinds of particles are considered, the
(see also Table 2.1) symbol may be extended by adding the chemical
symbol X as in: flq(X).
(Number) density of particles in ground state n0 cm3 When several kinds of particles are considered, the
symbol may be extended by adding the chemical
symbol X as in: nq(X).
(Number) density of free atoms (M) nat, fla, nM cm3
n (M), [M]
(Number) density of free ions (M) n10, n, nM cm3
n(M), [M]
(Number) density of free electrons ne, [e] cm3
(Number) denisty of molecules MX flMX, [MXI cm3
Total (number) density of element flt, (nt)M, cm3
M(nM+nM++nMx) [MIt
Ionization constant (n1njn in K1, K(T) cm3
equilibrium at T)
Dissociationconstant (flMflX/flMX in Kd, Kd(T) cm3
equilibrium at T)

7. INDEX OF TERMSt anti-Stokes fluorescence (Section 5.1.3)

absolute temperature (Table 2.1, Section 6.1) apparent concentration (Section 4.4.1)
absorption (Section 5.1.2) aspiration (Section [Link])
accuracy (Section 4.3.2) atomic fluorescence (Section 5.1.3)
additive (Section 4.1) atomic line (Section 5.1.3)
aerosol (Section [Link]) atomization (Section [Link])
analyte (Section 4.1) atomizer (Section [Link])
(analyte) addition technique (Sections 4.2, 4.4.3)
(analyte) signal (Section 4.1) background corrector (Section 3.5)
analytical curve (Section 4.1) baseline technique (Section 4.4.3)
analytical-curve technique (Section 4.2) bias (Section 4.3.2)
analytical result (Section 4.1) blank background (Section 4.1)
angular nebulizer (Section [Link]) blank measure (Section 4.1)
anion effect (Section [Link]) blank scatter (Section 4.3.1)
blank solution (Section 5.1)
— bracketing technique (Section 4.2)
tQuantitative terms and some qualitative terms that are defined buffer-addition technique (Section 4.4.3)
only in the tables are not included in this index. They are easily Bunsen-burner (Section [Link])
found in the tables under the appropriate headings. burner (Section [Link])
122 COMMISSION ON SPECTROCHEMICAL AND OTHER OPTICAL PROCEDURES FOR ANALYSIS

carbon atomizer (Section [Link].1) hollow-cathode lamp (Section 3.2)

carbon-cup atomizer (Section [Link]. 1) hot hollow cathode (Section [Link].2)
carbon-tube furnace (Section [Link].1)
carrier gas (Section 3.2) indirect methods (Section 4.2)
cathodic sputtering (Sections [Link].2 and 3.2) inductively-coupled plasma (Section [Link])
cation effect (Section [Link]) inner zone (Section [Link])
chamber-type nebulizer (Section [Link]) interconal zone (Section [Link])
characteristic concentration (Section 4.2) interference curve (Section 4.4.1)
chemical equilibrium (Section 6.1) interference (Section 4.4.1)
chemical interference (Section [Link]) interferent (Section 4.4.1)
chopper (Section 3.3) interfering line (Section [Link])
concentration (Section 4.1) interzonal region (Section [Link])
concentric nebulizer (Section [Link]) ionic line (Section 5.1.1)
concomitant (Section 4.1) ionization (Section 6.1)
controlled-flow nebulizer (Section [Link]) ionization buffer (Section 4.4.3)
cooled hollow cathode (Section [Link].2) ionization interference (Section [Link])
current-carrying plasma (Section [Link])
current-free plasma (Section [Link]) laminar (flame) (Section [Link])
curve corrector (Section 3.5) laser (Section [Link].3)
curve-of-growth (Section 5.1.2) lateral diffusion interference (Section [Link])
light modulation (Section 3.3)
dark current (Section 3.4) light source (Section 3.2)
demountable lamp (Section 3.2) limit of detection (Section 4.3.2)
depression (Section 4.4.1) linear (detector) (Section 3.4)
desolvation (Section [Link]) local analysis (Section [Link].3)
dilution test (Section 4.3.2) long tube device (Section [Link])
direct-injection burner (Section [Link]) low-pressure discharge lamp (Section 3.2)
direct line fluorescence (Section 5.1.3)
direct methods (Section 4.2) matrix effect (Section [Link])
dissociation (Section 6.1) measure (Section 4.1)
dissociation interference (Section [Link]) Méker-burner (Section [Link])
double-beam system (Section 3.3) metal-vapour lamp (Section 3.2)
drop generator (Section [Link]) mist (Section [Link])
dry aerosol (Section [Link]) monochromator (Section 3.3)
multi-element lamp (Section 3.2)
effect (Section [Link]) multipass system (Section 3.3)
efficiency of atomization (Section 3.1.2) multislot burner (Section [Link])
efficiency of fluorescence (Table 5.1, Section 5.1.3) mutual interference (Section 4.4.1)
efficiency of nebulization (Section 3.1.2)
electrical flame-like plasma (Section [Link])
nebulization (Section [Link])
electrical measuring system (Section 3.5)
electrodeless-discharge lamp (Section 3.2) nebulizer (Section [Link])
nebulizer with heated spray chamber (Section [Link])
electrodeless plasma (Section [Link])
net measure (Section 4.1)
emission (Section 5.1.1)
non-specific interference (Section [Link])
enhancement (Section 4.4.1)
non-spectral interference (Section [Link])
excitation (Section 6.1)
excitation interference (Section [Link])
organic effect (Section [Link])
fill-gas (Section 3.2) outer zone (Section [Link])
filter (Section 3.3) oxidant (Section [Link])
flame (Section 1)
flame background (Section 4.1) photocurrent (Section 3.4)
flame-geometry interference (Section [Link]) photodetector (Section 3.4)
flash-back (Section [Link]) photomultiplier tube (Section 3.4)
fluorescence (Section 5.1.3) photovoltaic cell (Section 3.4)
fraction atomized (Section 3.1.2) physical equilibrium (Section 6.1)
fraction desolvated (Section 3.1.2) physical interference (Section [Link])
fraction volatilized (Section 3.1.2) plasma jet (Section [Link])
fuel (Section [Link]) pneumatic nebulizer (Sections [Link], [Link])
fuel-rich flame (Section [Link]) precision (Section 4.3.2)
premix burner (Section [Link])
graphite-cup atomizer (Section [Link].1) polychromator (Section 3.3)
graphite-rod furnace (Section [Link].1) primary-combustion zone (Section [Link])
graphite-tube furnace (Section [Link].1) protective agent (Section 4.4.3)
gravity-fed nebulizer (Section [Link]) pulsed-discharge lamp (Section [Link].3)

high-pressure xenon lamp (Section 3.2) quantity (Section 4.1)

hollow-cathode discharge (Section [Link].2) quenching (Section 5.1.3)
 Nomenclature, symbols, units and their usage in spectrochemical analysis—Ill 123

radiative equilibrium (Section 6.1) solvent blank (Section 3.5)

rate of liquid aspiration (Section 3.1.2) spatial-distribution interference (Section [Link])
rate of liquid consumption (Section 3.1.2) specific interference (Section [Link])
reading (Section 3.5) spectral band (Section 5.1.1)
recovery test (Section 4.3.2) spectral continuum (Section 5.1.1)
reference beam (Section 3.3) (spectral) continuum source (Section 3.2)
reference element (Section 4.4.3) spectral interference (Section [Link])
reference-element technique (Section 4.4.3) (spectral) line source (Section 3.2)
reference solution (Section 5.1) spectral line (Section 5.1.1)
reflux nebulizer (Section [Link]) spectral response curve (Section 3.4)
relative standard deviation (Section 4.3.2) spectrochemical buffer (Section 4.4.3)
releaser (Section 4.4.3) spectrometer (Table 1.1, Section 3.3)
resistance-heated device (Section [Link].1) spectrometry (Table 1.1)
resonance fluorescence (Section 5.1.3) spray chamber (Section [Link])
resonance line (Section 5.1.1) sprayer (Section [Link])
resonance spectrometer (Section 3.3) standard deviation (Section 4.3.1)
response time (Section 3.5) stepwise line fluorescence (Section 5.1.3)
responsivity (Section 3.4) Stokes fluorescence (Section 5.1.3)
reversal dip (Section 5.1.2) suction nebulizer (Section [Link])
reversed direct-injection burner (Section [Link]) suppressor (Section 4.4.3)
suprathermal chemiluminescence (Section 5.1.1)
sample (Section 4.1)
sample beam (Section 3.3) T-tubes (Section [Link])
sampling boat (Section [Link]) thermal equilibrium (Section 6.1)
sampling cup (Section [Link]) thermal radiation (Section 5.1.1)
sampling ioop (Section [Link]) (thermodynamic) equilibrium (Section 6.1)
saturation (plateau) (Section 4.4.3) thermodynamic temperature (Table 2.1, Section 6.1)
saturator (Section 4.4.3) three-slot burner (Section [Link])
scale expansion (Section 3.5) time constant (Section 3.5)
scatter (Section 4.3.1) transport interference (Section [Link])
scattering (Section 5.1.2) tungsten-filament lamp (Section 3.2)
sealed lamp (Section 3.2) turbulent (flame) (Section [Link])
secondary-combustion zone (Section [Link]) twin nebulizer (Section [Link])
self-absorption (Section 5.1.2)
self-reversal (Section 5.1.2) ultrasonic nebulizer (Section [Link])
sensitivity (Section 4.2)
separated flame (Section [Link])
vacuum phototube (Section 3.4)
shielded flame (Section [Link])
yapour-phase interference (Section [Link])
simulation technique (Section 4.4.3)
variance (Section 4.3.1)
single-beam system (Section 3.3) volatilization (Section [Link])
single-electrode plasma (Section [Link])
volatilizer (Section 4.4.3)
single-element lamp (Section 3.2)
slot burner (Section [Link])
solute-volatilization interference (Section [Link]) zero suppression (Section 3.5)