Afssajjad 190127101514

Atomic Fluorescence Spectroscopy
Dr. Sajjad Ullah

Institute of Chemical Sciences,
University of Peshawar
Atomic Fluorescence Spectroscopy
line Source (low resolution monochromator)
Continuous source (high resolution monochromator)
P • Same apparatus as for AAS

M
T • Radiative source is generally
Pulsed and the detector is tuned
To respond only to radiation that oscillates
at the pulse frequency
• IF = KI0C (low DL when using high I source)

(both line & continuous
High intensity sources)
AFS
Atomic Fluorescence occurs when neutral atomic

Species emit radiation after being excited by a line
or continuous source.
Photoexcitation is the same as in AAS but we

measure the emitted (rather than absorbed)
radiation in AFS
Four Major Categories of AF
A = log Po/P = k C
Radiation Sources for AFS

Important Considerations!!!
Atomic Spectral lines are very narrow (0.001-0.01 nm)
So Source Intensity, I, must be very high within this

narrow absorptive bands.
Why?
Sufficient radiation to permit accurate measurement at the detector

can be achieved only if I of the EMR is high.
This requirement is not that critical for molecular electronic

spectroscopy as Molecule absorb in broader range and even broad
EMR band (= band pass of monochromator) can be absorbed.
Radiation Sources for AFS
Line Sources
Hollow Cathode Lamp
High Intensity HCL
Electrodeless Dischage Lamp (EDL): More common
LASER
Continuous Source:
Xenon-arc lamp
LASER (Light Amplification by Simulated Emission of Radiation)
Laser are devices that emit high-intensity coherent
(in-phase) radiation over a narrow (0.001-0.01 nm)
bandwidth
Metastable
Cr(III) dope Al2O3 state
Population inversion occurs when more Cr ions are in the excited (2E) state Excitation of Cr(III) ions the ruby rod by radiation from
than in the ground state The flash lamp
DC Argon Plasma
 It relies on application of less than a

kilowatt of a DC between two carbon
anodes and a tungsten cathode.
 The high Temperature in a DC

plasma can excite atomic/ionic
species
 More and intense line than in Flames

Xenon short-arc lamp
Xe gas
Electric arc between two electrode causes
excitation of Xe filled in a quartz tube at
high pressure and Xe atoms/ions upon
de-excitation give continuous spectrum
 Continuous source used for AAS

 λ-range 200-700 nm
 Requires a monochromator for λ
selection
 Advantage?
 Disadvantage?
http://www.enlitechnology.com/show/xe-lamp-light-generation-mechanism.htm
Luminescence of Solids, Editor D.R. Vij
Photobiology: The Science of Life and Light, Editor: Lars Olof Björn
Line Sources (AAS)
 Hollow Cathode Lamp (HCL)
• Multielement HCL
• Demountable HCL
• High Intensity HCL
 Electrodeless Discharge Lamp (EDL)
 Temperature Gradient Lamp

Hollow Cathode Lamp
(Most popular)
Quartz window
Pyrex body
Anode
Cathode
Why Low P?
Sputtering?
100-200 V Disadvantage?
(1-25 mA) Ar+
Filler Gas 1 torr = 0.0013158 atm

Made up of (Ne or Ar)
element of W, Zr, Ni
at 1-2 Torr
interest or its
alloy
Ar+ ions strike the cathode to cause Sputtering.
Multi-element HCL (2-7 elements)/Suffer Demountable HCL. Replaceable cathode,

Composition change/More volatile but time/effort involved.
elements distills first and more, Caution!
HOW Hollow Cathode Lamp works?
a tungsten anode and a

cylindrical cathode
neon or argon at a pressure of 1
to 5 torr
The cathode is constructed of
Ionize the inert gas at a potential of ~ 300 V the metal whose spectrum is
Generate a current of ~ 5 to 15 mA as ions desired or served to support a
and electrons migrate to the electrodes. 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 (Operators’ control) as more
sputtering occurs, BUT also leads to self-absorption
and resonant broading.
 Self-absorption or Self-reversal: 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
 Resonanat Broading: Pressure broadening caused by
collision between identical atoms
Improvement…….High Intensity HCL
 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)
or High Intensity HCL 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.
*rarely used for AAS

Photomultiplier Detector
• The type is commonly used especially for low
radiant powers.
• The detector consists of a photoemissive cathode
(coated with cesium oxide) coupled with a series
of electron-multiplying dynode stages.
• The primary electrons ejected from the photo-
cathode are accelerated by an electric field so as to
strike onto the first dynode and then the e emitted
from 1st dynodes are directed onto the 2nd dynodes
and so on.
• Amplification = nd where d is the number of dynodes and n is the
no of electrode emitted per dynode. Usually 106 to107 e are emitted per photon
Photomultiplier Detector
Analysis with AFS
Quantitaive Analys: Working-curve method (or standard addition technique (if curves show linearity). Around 58
elements can be assayed.
Interferences in Atomic Spectroscopy
1- Chemical Interferences
2- Ionization interferences
3- Spectral interferences
4- Matrix interferences
 Chemical Interferences
 Chemical reaction in cell (removal of atoms)
 Formation of compounds of low volatility
Calcium analysis in the presence of Sulfate (CaO.SO3) or
phosphate(CaO.P2O5)
Formations of refractory oxides (Al2O3, Fe2O3) of unusual stability
in flames
Formation of carbides or cyanogen (CN)2 in furnaces
Solution!
 Higher temperature or deceases O2 concentration (fuel rich
flame), e.g., changing air-C2H2 flame to N2O-C2H2 flame
 Releasing agents: Cations (e.g LaCl3 used for Ca, Mg, Sr) that
react preferentially with the interference ions.
(Ca2+ (analyte) + PO43- (interfering) + La3+  LaPO4 + Ca2 (free) )
 Protection agents: form stable but volatile species with the
analytes (i.e. EDTA)
 Ionization Interferences
 Atom ionization (usually due to high T)
M ↔ M+ + e (group IA and IIA have low IE)

 Spectral lines of ions occur at different λ than atomic lines
-decrease in Atomic signal
 Ionization decreases at high concentration
- competition B/W atom for available E
Solutions
 Use low temperature flame (air-propane)
 Add large amount of easily ionizing element
(500-5000 µg/mL of Li, Na, K) element
 Use high concentration of analyte
 Matrix interferences
 These are caused by the physical nature of the matrix enhancing
or depressing sensitivity
 Example: Viscosity difference b/w sample and standards
(different nebulzation/aspiration/atomization)
Solutions!
 Standard addition technique
 Matching the matrix of sample
with that of standards
 Solvent extraction or so to
isolate the analyte
 Spectral Interferences
 Overlapping (spectra of analyte and another atomic/molecular
species)
 Background (non-specific) Interferences :
-Spectral interferences resulting from emission of EMR
from elements in cell
-Scattering or absorption by sample matrix or polyatomic
species
 Positive error (analyte and matrix absorb the same λ)
 Negative error: Interfering species emits same λ as used for AA
measurement
Examples:
Tb/Mg = 285.2 nm
Cr/Os = 290.0 nm
Ca/Ge = 422.7 nm
Spectral Interferences…
Solutions
 Chemical Separation prior to the assay
 Modulation of the detector
 Background correction
Modulation of the detector:

The detector is tuned to the frequency of oscillation of the
EMR source, it doesn’t respond to the steady-state emissions
from the cell. Therefore, interference owing to emission from
the cell is eliminated
Background Correction
Background (non-specific) Interferences:
-Spectral interferences resulting from emission of EMR
from elements in cell
-absorption by polyatomic species or scattering within the
cell
- More severe in furnaces than flames
- Greater at shorter λs (more scattering)
Background Correction
Continuum-Source Correction
AHCL = Aanalyte + Abackground

AD2 = Abackground
Continuum-Source Correction

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Atomic Fluorescence Spectroscopy

Dr. Sajjad Ullah

P • Same apparatus as for AAS

• IF = KI0C (low DL when using high I source)

Atomic Fluorescence occurs when neutral atomic

Photoexcitation is the same as in AAS but we

Radiation Sources for AFS

Atomic Spectral lines are very narrow (0.001-0.01 nm)

So Source Intensity, I, must be very high within this

Sufficient radiation to permit accurate measurement at the detector

This requirement is not that critical for molecular electronic

 It relies on application of less than a

 The high Temperature in a DC

 More and intense line than in Flames

 Continuous source used for AAS

 Electrodeless Discharge Lamp (EDL)

 Temperature Gradient Lamp

Filler Gas 1 torr = 0.0013158 atm

Ar+ ions strike the cathode to cause Sputtering.

Multi-element HCL (2-7 elements)/Suffer Demountable HCL. Replaceable cathode,

a tungsten anode and a

 High potential, and thus high currents lead to

 Self-absorption or Self-reversal: the greater currents

*rarely used for AAS

M ↔ M+ + e (group IA and IIA have low IE)

 Example: Viscosity difference b/w sample and standards

Modulation of the detector:

AHCL = Aanalyte + Abackground

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