Optical Atomic

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

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

Singlet ground state Singlet excited state Triplet excited sta

 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

 n Should be 

Superposition of tw sinusoidal wave of different frequencies but identical

amplitudes.

Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007 7

 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

Nj gj  Ej
 exp( )
N0 g0 Nj
N0

gj
g0 kT
exp(
 Ej
kT
)

 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?
 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
What happens inside the
flame?
 FLAMES

Rich in
free
atoms
FLAMES

TE
GOOD AND BAD
THINGS

oxidation
 Boltzmann Equation: Relates
Excited State Population/Ground
State Population Ratios to Energy,
Temperature and Degeneracy
N* g* -(E/RT)
( ) e
No go
 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.
Single-beam design
 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 D 2

lamp. The lamp emission is much broader than the sample
Zeeman Effect Background
Correction:
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 backg

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