Optical Atomic Spectroscopy

 Optical Spectrometry
 Absorption
 Emission
 Fluorescence
 Mass Spectrometry
 X-Ray Spectrometry
Optical Atomic Spectroscopy
 Atomic spectra: single external electron

Slightly
different
in energy
 Atomic spectrum Mg
Spins are paired Spins are unpaired
No split Energy splitting

Single ground state Single excited state Triple excited state

 Atomic spectroscopy
 Emission

 Absorption

 Fluorescence
 Line Broadening
 Uncertainty Effects
 Heisenberg uncertainty principle:
The nature of the matter places limits on the
precision with which certain pairs of physical
measurements can be made.
One of the important forms Heisenberg
uncertainty principle:

t ≥ 1 p156
To determine  with negligibly small uncertainty, a huge measurement time is
required.

 Natural line width

 Line Broadening

 Doppler broadening
 Doppler shift:
The wavelength of radiation emitted or
absorbed by a rapidly moving atom decreases
if the motion is toward a transducer, and
increases if the motion is receding from the
transducer.

In flame, Doppler broadening is much

larger than natural line width
 Line Broadening
 Doppler broadening
 Line Broadening

 Pressure broadening

Caused by collisions of the emitting or

absorbing species with other ions or atoms

High pressure Hg and xenon lamps,

continuum spectra
 Temperature Effects

 Bolzmann equation
 Effects on AAS, AFS, and AES
 Atomic spectroscopy
 Interaction of an atom in the gas phase
with EMR

 Samples are solids, liquids and gases but

usually not ATOMS!
Atomic Spectroscopy
Sample Introduction
Flame

Furnace

ICP

Sources for Atomic Absorption/Fluorescence

Hollow Cathode Lams
Sources for Atomic Emission
Flames

Plasmas

Wavelength Separators + Slits +Detectors

How to get things to atomize?
How to get samples into the
instruments?
What is atomization?

??
What happens inside the flame?
 FLAMES

Rich in
free atoms
FLAMES

TE
 Boltzmann Equation: Relates Excited State
Population/Ground State Population Ratios to
Energy, Temperature and Degeneracy

N* g*
 ( )  e -(E/RT)
No go
GOOD AND BAD THINGS

oxidation
 Sample Introduction

 Pneumatic Nebulizers
 Break the sample solution into small droplets.
 Solvent evaporates from many of the droplets.

 Most (>99%) are collected as waste

 The small fraction that reach the plasma have

been de-solvated to a great extent.
What is a nebulizer?

SAMPLE
AEROSOL
Concentric Tube
Cross-flow
Fritted-disk
Babington
 Flame AAS/AES Spray Chamber/Burner
Configurations

Samples are nebulized (broken into small droplets)

as they enter the spray chamber via a wire capillary
Only about 5% reach the flame
Larger droplets are collected
Some of the solvent evaporates
–Flow spoilers
»Cheaper, somewhat more rugged
–Impact beads
»Generally greater sensitivity
ElectroThermal AAS (ETAAS or GFAAS)

 The sample is contained in a heated, graphite

furnace.

 The furnace is heated by passing an electrical

current through it (thus, it is electro thermal).

 To prevent oxidation of the furnace, it is sheathed in

gas (Ar usually)

 There is no nebulziation, etc. The sample is

introduced as a drop (usually 5-20 uL), slurry or
solid particle (rare)
ElectroThermal AAS (ETAAS or GFAAS)

 The furnace goes through several steps…

 Drying (usually just above 110 deg. C.)

 Ashing (up to 1000 deg. C)
 Atomization (Up to 2000-3000 C)
 Cleanout (quick ramp up to 3500 C or so). Waste is blown
out with a blast of Ar.

 The light from the source (HCL) passes through the

furnace and absorption during the atomization step
is recorded over several seconds. This makes
ETAAS more sensitive than FAAS for most
elements.
 Radiation Sources for AAS
Hollow Cathode Lamp

Conventional HCL
Ne or Ar at
1-5 Torr
 Hollow Cathode Lamp (Cont’d)

a tungsten anode and a

Ionize the inert gas at a potential of ~ 300 V
Generate a current of ~ 5 to 15 mA as ions
and electrons migrate to the electrodes.
cylindrical cathode
neon or argon at a pressure of 1
to 5 torr
The cathode is constructed of
the metal whose spectrum is
desired or served to support a
layer of that metal

The gaseous cations acquire enough kinetic energy to dislodge some of the
metal atoms from the cathode surface and produce an atomic cloud.
A portion of sputtered metal atoms is in excited states and thus emits their
characteristic radiation as they return to the ground sate
Eventually, the metal atoms diffuse back to the cathode surface or to the glass
walls of the tube and are re-deposited
Hollow Cathode Lamp (Cont’d)

 High potential, and thus high currents lead to

greater intensities
 Doppler broadening of the emission lines from the
lamp
 Self-absorption: the greater currents produce an
increased number of unexcited atoms in the cloud.
The unexcited atoms, in turn, are capable of
absorbing the radiation emitted by the excited
ones. This self-absorption leads to lowered
intensities, particular at the center of the emission
band

Doppler broadening ?
 Improvement…….
 Most direct method of obtaining improved lamps
for the emission of more intense atomic resonance
lines is to separate the two functions involving the
production and excitation of atomic vapor
 Boosted discharge hollow-cathode lamp (BDHCL)
is introduced as an AFS excitation source by
Sullivan and Walsh.
 It has received a great deal of attention and a
number of modifications to this type of source
have been conducted.
Boosted discharge hollow-cathode lamp (BDHCL)
Operation principle of BDHCL

 A secondary discharge (boost) is struck

between an efficient electron emitter and the
anode, passing through the primary atom cloud.
 The second discharge does not produce too
much extra atom vapor by sputtering the walls
of the hollow cathode, but does increase
significantly the efficiency in the excitation of
sputtered atom vapor.
 This greatly reduces the self-absorption
resulting from simply increasing the operating
potential (increase Doppler broadening and
self-absorption) to the primary anode and
cylindrical cathode.
Electrodeless Discharge Lamps (EDL)
 Electrodeless discharge lamps (EDL)

 Constructed from a sealed quartz tube containing a few torr

of an inert gas such as argon and a small quantity of the
metal of interest (or its salt).
 The lamp does not contain an electrode but instead is
energized by an intense field of radio-frequency or
microwave radiation.
 Radiant intensities usually one or two orders of magnitude
greater than the normal HCLs.
 The main drawbacks: their performance does not appear to
be as reliable as that of the HCL lamps (signal instability
with time) and they are only commercially available for some
elements.
 DOUBLE BEAM FAA
SPECTROMETER
Note: the Ref bean does not pass
through the flame thus does not correct for the
interferences from the flame!

synchronized
Interferences in AAS and AFS
 Spectral Interferences
 Overlapping
 Broadening absorption for air/fuel mixture
 Scattering or absorption by sample matrix
 Background Correction
 Two-line Correction (like Internal Standard)
 Continuum-Source Correction
 Zeeman Effect
 Source Self-Reversal (Smith –Hieftje)
Continuum-Source Correction
Continuum-Source Correction
 (The draw is not to scale)

A B
0.04 nm

The light from the HCL is absorbed by both the sample and the background, but
the light from the D2 lamp is absorbed almost entirely by the background

A: HCL lamp, the shaded portion shows the light absorbed from the HCL. The emission
has a much narrower line width than the absorption line.

B: D2 lamp, the shaded portion shows the light absorbed by D2 lamp. The lamp
emission is much broader than the sample absorption, and an averaged absorbance taken
over the whole band pass of the monochromator.
 Zeeman Effect Background
Correction:

Analyte absorption is cancelled out in a strong magnetic field. When the field is
on, the instrument measures background absorption. When the field is off, the
instrument measures analyte absorption. The difference is the corrected
absorption.
Source Self-Reversal (Smith –Hieftje)

Self-absorption
Line broadening

A relative new technique

Source Self-Reversal (Smith –Hieftje)
Absorbed by sample reduced, not complete eliminate!
But the background absorbs the same portion of light.

Absorbed by sample and background

Vandecasteele and Block, 1997, p126

 Interferences in AAS and AFS
 Chemical Interferences
 Formation of compounds of low volatility
Calcium analysis in the presence of Sulfate or phosphate

Solutions
 Higher temperature
 Releasing agents: cations that react preferntially with the
interference ions.
 Protection agents: form stable but volatile species with
the analytes (i.e. EDTA,APDC….)
 Chemical Interferences
 Atom ionization

M ↔ M+ + e
 Atomic Fluorescence Spectrometry

Commercial AFS instruments are

on the market!

Learn more in CHM 6157