“ EMISSION SPECTROSCOPY”

GOALS:

 GENERAL: Know the basic concepts of emission spectroscopy.

 INDIVIDUALS:
 Analyze and adequately describe what emission spectrometry consists of and its most
used techniques.
 Obtain the necessary information for the recognition and conceptualization of emission
spectrometry techniques for their future application, both theoretical and practical.

SUMMARY:

This research reviews the concepts that lead to the study of emission spectroscopy, showing both
definitions and the variants contained in this type of spectroscopy and its methods, as well as examples of
situations or practices in which it is carried out. cape. In this way, emission spectroscopy can be defined as
an analytical method that is based on the emission of light experienced by excited atoms in a flame, a
furnace or an inductively coupled plasma or an electric arc or a spark in which applies a thermal or
electrical stimulus.

INTRODUCTION

Atoms or molecules that are excited at high energy levels can fall to lower levels by emitting radiation
(emission or luminescence). For atoms excited by a high temperature energy source this light emission is
commonly called atomic or optical emission (atomic emission spectroscopy) and for atoms excited with
light it is called atomic fluorescence (atomic fluorescence spectroscopy).

Atomic emission spectroscopy (AES) uses the quantitative measurement of optical emission from excited
atoms to determine the concentration of the analyzable substance. The analyte atoms in the solution are
drawn into the excitation region where they are dissolved, vaporized and atomized by a flame, discharge
or plasma. These high temperature atomization sources provide sufficient energy to promote atoms to high
energy levels. The atoms return to lower levels emitting light.

The use of flame emission spectroscopy (FES) is of great application in elemental analysis. It can be used
for quantitative and qualitative analysis and is a single element method. Its most important uses are the
determination of sodium, potassium, lithium and calcium in biological fluids and tissues.

Emissions Spectrometry - Instrumental

The sample must be converted to free atoms, commonly in a high temperature excitation source, for
example, a flame. The liquid samples are nebulized and carried to the flame by the gas flow. The
excitation source must dissolve, atomize and excite the atoms of the substance to be analyzed. The flame
provides enough energy to promote atoms to high energy levels.

As the atoms return to the stable state, the

emitted radiation passes through the
monochromator which isolates the
wavelength specified for the required
analysis. A photodetector measures the
strength of the selected radiation which is
then amplified and sent to a reading device.1 .

DEVELOPMENT:

1
http://hiq.aga.com.co/International/Web/LG/CO/likelgspgco.nsf/DocByAlias/anal_emis

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Spectroscopy is the measurement and interpretation of electromagnetic radiation absorbed, scattered or
emitted by atoms, molecules or other chemical species. These phenomena are associated with changes in
the energy states of different species. Therefore, since each species has characteristic energy states,
spectroscopy can be used to identify them.

Spectroscopy forms the basis of spectrochemical analysis, in which the interaction of electromagnetic
radiation with matter is used to obtain qualitative and quantitative information about the composition of a
sample. Within spectrochemical analysis, atomic spectroscopy studies the absorption and emission of
radiation by free atomic, ionic and molecular species. These species are generated and examined in a
high-energy gaseous medium, which constitutes a source of vaporization-atomization-ionization-excitation.

The term emission spectroscopy is usually applied to methods in which a thermal or electrical stimulus is
applied. The radiant energy emitted when the analyte returns to its basal state can provide information
about its nature and its concentration. The results of this analysis are usually represented in the form of a
spectrum, that is, a graph of the radiation emitted as a function of frequency or wavelength.

When the sample is stimulated with an external electromagnetic radiation source, several processes can
take place. For example, radiation can be scattered or reflected. To obtain information about the analyte,
the electromagnetic radiation emitted when it returns to its basal state is measured, or the amount of
radiation absorbed as a consequence of excitation can be measured.

Types of emission spectroscopy:

TYPE OF RADIATION
ATOMIZATION METHOD
SPECTROSCOPY SOURCES
BOW BY HEATING THE SAMPLE BY ELECTRIC ARC SAMPLE
SAMPLE EXCITED BY HIGH VOLTAGE ELECTRICAL
SPARK SAMPLE
SPARK
ARGON PLASMA SAMPLE HEATED BY ARGON PLASMA SAMPLE
SAMPLE Aspirated AND INTRODUCED INTO THE
ATOMIC OR FLAME SAMPLE
FLAME, IT IS ATOMIZED INSIDE THE FLAME
NO NEED THE SAMPLES ARE BOMBARDED WITH
X-RAYS SAMPLE
ELECTRONS

Arc spectroscopy:

The most used sources in emission spectrography are the DC arc, the Ca arc, and the Ca spark. Its
mission is to evaporate the sample and cause the passage of electrons to higher energy levels.
Temperatures of 8.00°K are reached.

The CC arc is normally used when high sensitivity is desired, such as in the identification of trace elements
in samples; the oscillation of the arc constitutes a difficulty for quantitative work; the Ca arc is more stable
and reproducible. The Ca spark provides higher excitation energies, is more stable and reproducible, and
is generally the preferred source for quantitative analysis.

Metal elements can be used as electrodes. The pulverized solids are placed in a small depression made at
the end of a carbon or graphite rod that normally constitutes the opposite pole of the arc. The solutions can
be evaporated to dryness on the carbon or graphite electrode, forming a bottom approximately 1mm thick
through which the solution passes and evaporates by the action of the arc or the spark.

The main components of a spectrograph, in addition to the radiation source, are a prism or a diffraction
grating to disperse the radiation from the source, a camera or other detection and measurement device,
auxiliary devices, slits, lenses or mirrors to conduct the energy beam

Most photographic emulsions are sensitive to small wavelength, blue, violet and ultraviolet radiation; The
use of various colorants allows the emulsion to be sensitized for application at longer wavelengths.

For qualitative work, an iron spectrum is recorded along with that of the unknown element. The spectrum
of any element whose existence in the sample is suspected is also recorded. The finished film is studied in
a comparator, using the spectrum of iron or the known element to locate the wavelengths; most
comparators have a standardized plate indicating the main lines of many elements. Scales are available
for the exact measurement of spectral lines and tables of wavelengths and relative intensities of the
spectral lines of an element. To give the identification of an element as positive, at least three of its
sensitive lines must be observed.

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Quantitative emission spectrography requires control of all variables such as: excitation conditions,
exposure time, film work. In order to eliminate small variations in these factors as much as possible, it is
customary to add an internal standard by measuring the intensities of a pair of homologous lines formed
by a line from the problem element and another from the internal standard. The pairs of homologous lines
must have very close wavelengths and both elements must present the same vaporization characteristics
and ionization potential analogues; Small variations in the excitation or working conditions of the film will
affect both lines with the same intensity and the relationship between their intensities will be constant. The
resulting spectral line is measured with a densitometer by comparing the transmittance of the line with that
of the unexposed film area adjacent to the line.

Atomic emission spectroscopy (AS)

It is used in the quantitative measurement of the optical emission of excited atoms to determine the
concentration of the analyzable substance. The analyte atoms in the solution are drawn into the excitation
region where they are dissolved, vaporized and atomized by a flame, discharge or plasma. These high
temperature atomization sources provide sufficient energy to promote atoms to high energy levels. The
atoms return to lower levels emitting light.

It allows carrying out a quantitative and qualitative analysis of between 70 to 80 elements. The detection
limits for many of these elements is one part per billion. It is necessary to bring the sample to a state of
atomic vapor. This process, known as atomization, consists of volatilizing the sample and breaking it down
into its atoms and perhaps some gaseous ions. Flame atomization (flame photometry) and oven
atomization are mainly used to atomize the samples to be analyzed.

The main factors that determine the magnitude of the emission are:

· The energy distribution of excited levels

· The transition probabilities for emission and absorption
· The atomic absorption coefficient
· The characteristics of the atomizing cell2

flame photometry

It is an emission technique that uses a flame as an excitation source and an electronic photodetector as a
measurement device. It is mainly a quantitative analysis method and is one of the simplest and most
accurate methods for the analysis of alkali metals, most alkaline earth metals and some other metallic
elements. It is also possible to perform a qualitative analysis by examining all wavelengths of the emission
spectrum (flame spectrophotometry or flame photometry). Its application is limited when compared to
ordinary emission spectroscopy, since the energy of the flame allows only 30 to 50 elements to be excited,
this number being a function of the type of flame used; Flames are characteristic colorations produced by
the compounds sodium (yellow), strontium (red), and barium (green) and constitute common qualitative
tests of these elements. The sample must be dissolved.

The radiation of the element of interest, whose light source is usually a hollow cathode lamp, is directed
through the flame containing the atomic gas. The analyte solution is nebulized by means of an atomizer or
nebulizer in fine droplets and brought to the flame. The solvent in the droplets evaporates immediately and
the salt particles break down into atoms, ions and electrons. The atoms in the sample will absorb the
radiation emitted by the same atom in the hollow cathode lamp, thereby attenuating the energy of the
source. Using a monochromator, the spectral line of the element of interest is separated from any other
radiation coming from the source or the flame. The radiant energy from the source is transformed into
electric current through a photomultiplier tube.

The radiation source that causes the activation of atoms is a flame. The monochromator will be
interference filters in complex devices and low-resolving power networks in simple devices. The detectors
may be photovoltaic cells or phototubes; they can measure relatively high intensities.

Like all instrumental techniques, flame spectrometry is a relative technique. Consequently, it is necessary
to experimentally establish a curve (or mathematical function) that relates the analytical signal obtained
with the concentration of the analyte element in the solutions to be analyzed. In the most direct case, the
concentration of an unknown solution is obtained by graphical interpolation from a signal (A or IE) vs.
curve. c, obtained with several standards (patterns) adequately spaced, covering the required range of
concentrations; In most cases it is necessary that the composition of the standard solutions be similar to
that of the sample to be analyzed. In the case of very complex sample solutions, in which the presence of
concomitant elements can affect the response obtained for the analyte, there are other calibration
procedures, such as the analyte standard addition method (single or multiple).
2
http://www.q1.fcen.uba.ar/materias/ai/aa_ea1.pdf

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Since the processes that the analyte undergoes in the atomization cell are essentially common to both
techniques, the selection of the type and conditions of the flame (oxidant/fuel ratio) and the observation
region are critical for numerous elements. It is also necessary to optimize the spectral bandpass of the
monochromator used for the selection of the wavelength, the solution aspiration speed, the parameters of
the detection and reading system and in the case of atomic absorption, the current intensity of the hollow
cathode lamp.

Interference is the effect of a concomitant present in the sample on the signal generated by the analyte.
The presence of an interferent leads in all cases to a systematic error. An interference exists when the
measurement result on a given sample solution differs from that obtained with the same concentration of
analyte in the same chemical and solvent combination, but in the absence of the interferent.

Essentially the same interferences occur in EEA and EAA with flame, although with different magnitudes.
They can be classified into four groups:

1. Spectral, including background emission or absorption effects.

2. Physical, associated with the transport and dispersion of the sample in the flame.
3. Chemicals, related to the vaporization of the solute.
4. Ionization, related to the variation in the concentration of neutral emitting or absorbing atoms in the
flame caused by the phenomenon of thermal ionization.

The following figure compares a flame emission spectrophotometer scheme (a) and an atomic absorption
spectrophotometer scheme (b).

The
fundamental advantages of using the flame as an excitation source are that the spectra are very simple
and that the quantitative results tend to be more reproducible. The spectra are simple due to the low
excitation energy of the flame which gives rise to few emission lines. This fact reduces the problem of
spectral interference from lines and bands of other elements and also does not imply the need for a high
resolution monochromator. The greater reproducibility of these methods is due to the better control of the
variables in a flame excitation.

The two most important disadvantages of flame emission methods are that the excitation energy is too low
for most elements and that the sample must be dissolved. In atomic absorption, low energy is not such an
important disadvantage since the mission of the flame, in that case, is only to atomize the sample and form
a vapor of unexcited atoms; For this reason it is applicable to a greater number of elements than flame
photometry.

Other types of atomic spectroscopy:

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Oven, or electrothermal, atomization is used with an electrothermal atomizer; Small volumes of sample are
taken, usually a few microliters, and placed in the oven. With a progressive heating program, the solvent
evaporates from the sample, the organic matter is reduced to ash or carbon, and atomic vapor is
produced. It is one to two orders of magnitude more sensitive than flame atomization.

Some EA methods use flames for excited atoms, which emit a characteristic radiation when they return to
their ground state. Other AE methods use more powerful atomizers such as plasma inductively coupled
(PIC) and arc and spark atomizers. Unlike atomic absorption, atomic emission can be applied to qualitative
analysis. With this method, complete spectra can be recorded, where elements are identified by the
wavelengths of the emission lines.

Flame emission was once widely used in clinical laboratories to determine sodium and potassium. These
techniques have now been replaced by methods using ion-selective electrodes. In fact, inductively coupled
plasma emission spectrometry is now more important than flame emission spectrometry, and is also an
important source of ions for mass spectrometry analysis.3 .

DEFINITIONS:

 Analyte: Species present in a sample from which analytical information is sought.

 Spectroscopy: General term used to describe techniques that are based on the measurement of
absorption, emission or fluorescence of electromagnetic radiation.
 Atomic emission spectroscopy: Analytical method that relies on the emission of light experienced by
atoms excited in a flame, a furnace or an inductively coupled plasma or an electric arc or a spark.
 Flame emission spectroscopy: One of the methods that uses a flame to cause an atomized analyte to
emit its characteristic emission spectrum. It is also known as flame photometry.
 Photometer: Instrument for measuring absorbance that is equipped with a filter to select the
wavelength of a photon detector.
 Hollow cathode lamp: Source used in atomic absorption or emission spectrophotometry that emits
clear lines of one or more elements.
 Monochromator: Mechanism to identify polychromatic radiation at the wavelengths that compose it.
 Nebulize: Transformation of a liquid into a myriad of very fine droplets 4 .

BIBLIOGRAPHY:

 Skoog, D. TO.; West, D. M.; Holler, F. J. and Crouch, S. A.: Analytical Chemistry. Mc Graw
Hill, 7th ed, Mexico, 2004. pp 572, 573, 648, 651; G-4.
 Harris, C. d. Quantitative Chemical Analysis. Iberoamericana Group, Mexico, 1992

WEB REFERENCES:

 http://hiq.aga.com.co: consulted on February 13, 2007 (6:15 p.m.)

 http://www.q1.fcen.uba.ar: consulted on February 13, 2007 (6:30 p.m.)
 http://www.elergonomista.com/tecnicas/emision.htm

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Skoog, D. TO.; West, D. M.; Holler, F. J. and Crouch, S. A.: Analytical Chemistry. Mc Graw Hill, 7th
ed, Mexico, 2004. pp 572, 573, 648, 651.
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Skoog, D. TO.; West, D. M.; Holler, F. J. and Crouch, S. A.: Analytical Chemistry. Glossary. Mc Graw
Hill, 7th ed, Mexico, 2004. G-4