Atomic Absorption

and
Atomic Fluorescence
Spectroscopy
 Emission Flame Photometer

P Signal Processor
Source Wavelength Selector Detector Readout

Sample
 Flame Atomic Absorption
Spectrometer

Po P Signal Processor
Source Wavelength Selector Detector Readout

Chopper

Sample
 Fluorescence Spectrometer

Po P Signal Processor
Wavelength Selector Detector Readout
per
hop
C
90o

Source

Sample
 Atomization Techniques

Processes
occurring
during
atomization.
 Emission
Type Method of Atomization Radiation Source
arc sample heated in an sample
electric arc
spark sample excited in a sample
high voltage spark
argon sample heated in an sample
plasma argon plasma
flame sample solution sample
aspirated into a flame
x-ray emission none required; sample
sample bombarded w/
emission
 Absorption
Type Method of Atomization Radiation Source
atomic sample solution aspirated HCL
(flame) into a flame
atomic sample solution evaporated HCL
(non-flame) & ignited
x-ray absorption none required x-ray tube
 Fluorescence
Type Method of Atomization Radiation Source
atomic sample solution aspirated sample
(flame) into a flame
atomic sample solution evaporated sample
(non-flame) & ignited
x-ray fluorescence none required sample
 Flame Characteristics
Flame Temperature
Properties of Flames
Flame Characteristics
Regions in a flame
 Flame Characteristics

Temperature profiles

Temperature
profiles for a
natural gas/air
flame
 Flame Characteristics

Effect of Temperature

Flame absorbance
profile for three
elements
 Flame Characteristics
"Flame profile for calcium line in a
cyanogen/oxygen flame for different
sample flow rates."
 Flame Atomizers
"A turbulent flow burner."
Flame Atomizers

A laminar flow burner

 Electro-thermal Atomizers

Non-flame atom
cells. (a) Cross
section of heated
graphite furnace.
(b) Carbon rod
and cup furnace
Hollow Cathode Lamps (HCL)
Schematic cross section of a hollow
cathode lamp
Electrode-less Discharge Lamp

Cutaway of electrode-less discharge lamp

 Instruments for Atomic
Absorption Spectroscopy
Typical flame spectrophotometers: (a) single-beam
design
 Instruments for Atomic
Absorption Spectroscopy
Typical flame spectrophotometers: (b) double-beam
design
Buck 210VGP
 Buck 210VGP
Buck Scientifics' Stable Beam System
creates an optimum optical alignment. We
have the lowest number of energy reducing
optics (no energy wasting beam splitters)
for the greatest throughput of sample
energy.
Buck 210VGP
 Buck 210VGP
Background Correction
The Model 210VGP offers two exceptional
background correction systems; a unique,
in-line D2 system and Variable Giant Pulse
(VGP) correction.
 Buck 210VGP: Deuterium (D2)
Continuum Lamp Correction
A D2 lamp emits radiation from the far-UV
region (<190nm through approximately
350nm). With our proprietary in-line system,
the D2 emission corresponds precisely with the
spectrum of the analyte. Using modulated
signals, the absorbance of analyte and
background interferences are rationed resulting
in a clean, unbiased absorbance signal.
 Buck 210VGP: Variable Giant
Pulse (VGP) Correction
Hollow cathode lamps normally operate at
currents of 3-15 mA. If the applied power is
raised to several hundred mA, they exhibit a
phenomenon called self-reversal. This giant
pulse of current changes the nature of the
analyte absorption line so it will only
measure the background absorbance.
 Buck 210VGP: Variable Giant
Pulse (VGP) Correction
Like D2 correction, the background
absorbance is subtracted from the total
signal to give the corrected sample reading.
The VGP system removes interferences for
elements outside the normal D2-UV region.
 Buck 210VGP
Background Correction
Bucks unique internal software allows the
user to vary both modes of the background
correction to optimize the analysis for
selected elements.
Buck 210VGP
 Analytical Techniques for
Atomic Absorption Spectroscopy
Sample Preparation
Calibration Standards
Organic Solvents
Calibration Curves
Standard Addition Method
 Analytical Techniques for
Atomic Absorption Spectroscopy
Standard Addition Method
Ax = k cx or Ax = b cx (Vx/Vt)

AT = k(cs + cx)
or
AT = b cs (Vx/Vt) + b cx (Vx/Vt)
 Analytical Techniques for
Atomic Absorption Spectroscopy
Standard Addition Method
cx = cs (Ax/(AT - Ax))

or

cx = (Ax cs Vs)/((AT - Ax)Vx)

Atomic Emission
Spectroscopy
 ICP
Inductively Coupled Plasma
much higher temperatures than AA
thus higher number of atoms in excited state
thus stronger signal
 Maxwell-Boltzman Distribution
Nj/No = Pj/Po exp (-Ej/kT)
where Nj = particles in excited state
No = total particles
Pj/Po = factor for type of orbital
Ej = excitation energy
k = Boltzman constant
T = absolute temperature
ICP: Inductively Coupled Plasma

A typical
inductively
coupled plasma
source
ICP: Inductively Coupled Plasma

A typical nebulizer
for sample injection
into a plasma source
ICP: Inductively Coupled Plasma

Temperatures in a
typical inductively
coupled plasma
source
 ICP
Inductively Coupled Plasma
"A sequential spectrometer for ICP
emission and atomic absorption
spectroscopy."
 ICP: Inductively Coupled Plasma

A plasma multi-
channel
spectrometer
based upon
Rowland circle
optics