Atomic Emission

Spectroscopy
Yongsik Lee
May 14, 2004

Introduction to AES

Atomization Emission Sources

Flame still used for metal atoms

Electric Spark and Arc
Direct current Plasmas
Microwave Induced Plasma
Inductively Coupled Plasma the most important
technique

Advantages of plasma

Simultaneous multi-element Analysis saves

sample amount
Some non-metal determination (Cl, Br, I, and S)
Concentration range of several decades (10 5 106)

Disadvantages of plasma

very complex Spectra - hundreds to thousands of

lines
High resolution and expensive optical components
Expensive instruments, highly trained personnel
required

10A Plasam Source AES

Plasma

an electrically conducting gaseous mixture

containing significant concentrations of cations
and electrons.
Three

main types

Inductively Coupled Plasma (ICP)

Direct Current Plasma (DCP)
Microwave Induced Plasma (MIP)

ICP

Inductively Coupled Plasma (ICP)

Plasma generated in a device called a

Torch
Torch up to 1" diameter
Ar cools outer tube, defines plasma shape
Rapid tangential flow of argon cools outer
quartz and centers plasma
Rate of Argon Consumption 5 - 20 L/Min
Radio frequency (RF) generator 27 or 41
MHz up to 2 kW
Telsa coil produces initiation spark

Ions and e- interact with magnetic field and

begin to flow in a circular motion.
Resistance to movement (collisions of eand cations with ambient gas) leads to
ohmic heating.
Sample introduction is analogous to
atomic absorption.

Sample introduction
Nebulizer
Electrothermal
Table

vaporizer

8-2 methods of sample introducton

Nebulizer
convert

solution to fine
spray or aerosol
Ultrasonic nebulizer
uses ultrasound waves
to "boil" solution
flowing across disc
Pneumatic

nebulizer

uses high pressure gas

to entrain solution

Electro-thermal vaporizer ETV

Electrothermal

vaporizer (ETV)
electric current rapidly
heats crucible
containing sample
sample carried to
atomizer by gas (Ar, He)
only for introduction, not
atomization

Plasma structure
Brilliant

white core

Ar continuum and lines

Flame-like

tail

up to 2 cm
Transparent

region

where measurements are

made (no continuum)

Plasma characteristics

Hotter than flame (10,000 K) more complete atomization/

excitation
Atomized in "inert" atmosphere
Ionization interference small due to
high density of eSample atoms reside in plasma for
~2 msec and
Plasma chemically inert, little oxide
formation
Temperature profile quite stable
and uniform.

DC plasma

First reported in 1920s

DC current (10-15 A) flows
between C anodes and W
cathode
Plasma core at 10,000 K,
viewing region at ~5,000 K
Simpler, less Ar than ICP less expensive
Less sensitive than ICP
Should replace the carbon
anodes in several hours

Atomic Emission Spectrometer

May be >1,000 visible lines (<1 ) on continuum

Need

higher resolution (<0.1 )

higher throughput
low stray light
wide dynamic range (>1,000,000)
precise and accurate wavelength calibration/intensities
stability
computer controlled

Three instrument types:

sequential (scanning and slew-scanning)

Multichannel - Measure intensities of a large number of elements
(50-60) simultaneously
Fourier transform FT-AES

Desirable properties of an AE
spectrometer

Sequential vs. multichannel

Sequential instrument

PMT moved behind aperture plate,

or grating + prism moved to focus new l on exit slit
Pre-configured exit slits to detect up to 20 lines, slew scan

characteristics
Cheaper
Slower

Multichannel instrument

Polychromators (not monochromator) - multiple PMT's

Array-based system
charge-injection

characteristics

device/charge coupled device

Expensive ( > $80,000)

Faster

Sequential vs. multichannel

Sequential monochromator
Slew-scan

spectrometers

even with many lines, much spectrum contains

no information
rapidly scanned (slewed) across blank regions
(between atomic emission lines)
From

165 nm to 800 nm in 20 msec

slowly scanned across lines

0.01

to 0.001 nm increment

computer control/pre-selected lines to scan

Slew scan spectrometer

Two

slew-scan
gratings
Two PMTs for
VIS and UV
Most use
holographic
grating

Scanning echelle spectrometer

PMT is moved to monitor signal from slotted aperture.

About 300 photo-etched slits
1 second for moving one slit

Can be used as multi channel spectrometer

Mostly with DC plasma source

AES instrument types

Three

instrument types:

sequential (scanning and slew-scanning)

Multichannel - Measure intensities of a large
number of elements (50-60) simultaneously
Fourier transform FT-AES

Multichannel polychromator AES

Rowland circle
Quantitative det.
20 more elements
Within 5 minutes

In 10 minutes

Applications of AES
AES

relatively insensitive

AAS

still used more than AES

small excited state population at moderate temperature

less expensive/less complex instrumentation
lower operating costs
greater precision

In

practice ~60 elements detectable

10 ppb range most metals

Li, K, Rb, Cs strongest lines in IR
Large # of lines, increase chance of overlap

Detection power of ICP-AES

ICP/OES INTERFERENCES

Spectral interferences:

caused by background emission from continuous or recombination

phenomena,
stray light from the line emission of high concentration elements,
overlap of a spectral line from another element,
or unresolved overlap of molecular band spectra.

Corrections

Background emission and stray light compensated for by subtracting

background emission determined by measurements adjacent to the analyte
wavelength peak.
Correction factors can be applied if interference is well characterized
Inter-element corrections will vary for the same emission line among
instruments because of differences in resolution, as determined by the
grating, the entrance and exit slit widths, and by the order of dispersion.

Physical interferences of ICP

cause

effects associated with the sample nebulization and transport

processes.
Changes in viscosity and surface tension can cause significant
inaccuracies,
especially

in samples containing high dissolved solids

or high acid concentrations.

Salt buildup at the tip of the nebulizer, affecting aerosol flow rate
and nebulization.

Reduction

by diluting the sample

or by using a peristaltic pump,
by using an internal standard
or by using a high solids nebulizer.

Interferences of ICP
Chemical

interferences:

include molecular compound formation,

ionization effects, and solute vaporization
effects.
Normally, these effects are not significant with
the ICP technique.
Chemical interferences are highly dependent on
matrix type and the specific analyte element.

Memory interferences:

When analytes in a previous sample contribute to the

signals measured in a new sample.
Memory effects can result
from sample deposition on the uptake tubing to the nebulizer
from the build up of sample material in the plasma torch and spray
chamber.

The site where these effects occur is dependent on the

element and can be minimized
by flushing the system with a rinse blank between samples.

High salt concentrations can cause analyte signal

suppressions and confuse interference tests.

Typical Calibration ICP curves

Calibration curves of ICP-AES

10B. Arc and Spark AES

Arc

and Spark Excitation Sources:

Limited to semi-quantitative/qualitative analysis

(arc flicker)
Usually performed on solids
Largely displaced by plasma-AES
Electric

current flowing between two C

electrodes

Carbon electrodes

Sample pressed into

electrode or mixed with Cu
powder and pressed Briquetting (pelleting)
Cyanogen bands (CN) 350420 nm occur with C
electrodes in air -He, Ar
atmosphere
Arc/spark unstable
each line measured >20 s
needs multichannel
detection

Arc and Spark spectrograph

spectrograph
Beginning

1930s
photographic film

Cheap
Long integration times
Difficult to develop/analyze
Non-linearity of line "darkness
Gamma

function
Plate calibration

Multichannel photoelectric
spectrometer
multichannel

PMT instruments

for rapid determinations (<20 lines) but not

versatile
For routine analysis of solids
metals,

alloys, ores, rocks, soils

portable instruments
Multichannel

charge transfer devices

Recently on the market

Orignally developed for plasma sources

Homework
10-1,

10-2, 10-5, 10-7