ATOMIC

ABSORPTION
SPECTROSCOPY

2
Atomic Spectroscopy
Types:
1. Atomic Absorption Spectrometry (AAS)
2. Atomic Fluorescence Spectrometry (AFS)
3. Atomic Emission Spectrometry (AES)
4. Atomic Mass Spectrometry (many types)*
Inductively coupled plasma mass spectrometry (ICP-MS)
Thermal Ionization Mass Spectrometry (TIMS)
Secondary Ion Mass Spectrometry (SIMS)
Laser Microprobe Mass Spectrometry (LMMS)
5. Atomic X-Ray Spectrometry*
Absorption, fluorescence, and emission forms

3
Characteristics of Atomic
Spectroscopy
Involves EMR in the UV and visible
regions of the EMR spectrum
Based on excitation of a (valence) electron
to an excited state
Involves atoms or ions in the gaseous
state
Involves a process called atomization
Capable of analyzing ~ 70 elements
5
Atomization
A process by which molecular constituents
(analyte) of a sample are simultaneously
decomposed and converted to atoms (and
ions) in the gaseous state
Atomic spectroscopy methods are
categorized based on the type of
atomization
The atomization process is the signal
generator
6
Atomization
From Skoog et al. (2004); Table 28-1, p.840
7
The Atomization Process
[M
+
,X
-
]
aq
[M
+
,X
-
]
aq
nebulization
solution mist
[MX]
solid
vaporization desolvation
[X
0
]
gas
[M
0
]
gas
[MX]
gas
[M
+
]
gas
[X
+
]
gas
a
t
o
m
i
z
a
t
i
o
n

[M*]
gas
[M
0
]
gas
emission
excitation
or
absorption
(via heat or
light)
ground state excited state
8
Atomization and Excitation
The excitation step involves promotion of an
electron to a higher energy state
Excitation can occur several ways, including
Flame
Electrical discharge
Inductively coupled plasma
Absorption of EMR
Involves outer bonding electrons
Several transitions are possible
Excitation involves discrete spectral lines
9
Atomization and Excitation
Atomic Emission Spectroscopy
The heat from a flame or an
electrical discharge promotes
an electron to a higher energy
level
As the electron falls back to
ground state, it emits a
wavelength characteristic of the
excited atom or ion
From Skoog et al. (2004); Figure 28-1, p.840
10
Atomic Line Spectra
Each spectral line
is characteristic of
an individual
energy transition

E = hv =

|
.
|

\
|
n
c
h
11
Atomizers
Atomization
occurs in an
electrically
heated graphite
tube
The graphite
tube is flushed
with an inert
gas (Ar) to
prevent the
formation of
(non-absorbing)
metal oxides

Electrothermal or Graphite Furnace Atomizer
graphite
tube
FORMATION OF ATOMIC VAPOR
Four methods used to vaporize sample from solution:
Ovens: Sample placed in an oven; after evaporating
solvent, sample vaporized into irradiation area by rapidly
increasing temperature.
Electric arc or spark: Sample subjected to high current or
high potential A.C. spark.
Ion bombardment: Sample placed on cathode and
bombarded with + ions (Ar
+
). Sputtering process
dislodges them from cathode and directs them to
irradiation region.
Flame atomization: Sample sprayed into flame where it
undergoes atomization and irradiation.
FLAME ATOMIZERS
Total consumption burner:
Separate channels bring sample,
fuel, and oxidant to combustion
area. All of the sample, that is
carried into the burner, is burned;
Sensitivity is greater than in a
burner where the sample is not
completely burned.
extra turbulence in the flame from
variations in droplet size increase
noise.
Undergraduate Instrumental Analysis,
Robinson, p. 267.
Premix (laminar flow) burner
Sample, fuel, and oxidant
mixed prior to entering flame.
Solution drawn into pneumatic
nebulizer.
Liquid breaks into a fine mist
then directed against a glass
bead.
Nebulization (formation of small
droplets) occurs.
Mixing baffles insure only fine
mist makes it through to
burner.
Excess liquid collects at spray
chamber.



Primary reaction zone =
blue cone
Complete combustion =
outer cone
*Many elements form
oxides/hydroxides in the
outer cone

RICH FLAME rich in
fuel; more sensitive

LEAN FLAME with
excess oxidant; hotter
Graphite Furnace more
sensitive than flame
Requires less sample
Graphite does not
oxidize due to Ar(g)
Confines atomized
sample in the optical
path for several sec

FURNACE
INDUCTIVELY COUPLED
PLASMA (ICP)
Twice as hot as flame
Lower interferences
High temperature
High stability
Inert environment
Simultaneous multielement analysis
More expensive than FAAS

ICP BURNER
High purity Ar fed
through plasma gas
inlet
Ar ionizes and free
electrons accelerate
through RF field
Temp range: 6000-
10000 K

Modification in ICP
Ultrasonic nebulizer lowers LOD for most
elements
Piezoelectric crystal (quartz) a material whose
dimensions change in an electric field
Mist is created when the sample is sprayed against
the vibrating crystal
21
Radiation Sources for AAS
Hollow Cathode Lamps (HCL)
Lamps receive an applied
potential of ~ 300 V DC
Filled with an inert gas (Ne or
Ar) at low vacuum (1-5 torr)
Exit window composed of
pyrex or quartz; depending
on wavelength produced

23
How a HCL Works
An applied potential of ~ 300 V DC ionizes
the inert gas
Ne (g) -----> Ne
+*
(g) + e
-
The ionized gas generates a current flow
in the lamp
Metal cations (e.g. Fe, Mn, Ca) on the
cathode acquire (kinetic) energy from the
ionized gas and dislodge into the vacuum
A cation cloud forms around the cathode
(a process called sputtering)
24
How a HCL Works
Some of the sputtered cations are in excited
states (M*) and emit light (hv) as they return to
ground state (M
0
)
M* -----> M
0
+ hv
sputtered cations redeposit; this occurs mostly
on the cathode, but some also deposit on the
inner glass surface
Light intensity limitation > self absorption
As the current increases, M sputtered increases, but
the % M* decreases. Unexcited gaseous atoms (M
0
)
absorb light produced within the lamp, preventing it
from exiting the lamp
25
Radiation Sources for AAS
Electrodeless Discharge Lamps
Characteristics
The EDL houses a sealed
quartz tube (lamp) containing
argon gas and a metal (or metal
salt) of interest
The quartz tube is under high
vacuum
A radio frequency (or
microwave) coil surrounds the
lamp
~ 10 times more intense than a
hollow cathode lamp
Unstable output
Only available for about 15
elements
26
How an EDL Works
An intense RF (or microwave) field is applied to the
sealed quartz tube within the lamp
Ar gas within the tube ionizes and gains kinetic energy
from the RF field
Energy is transferred to the metal upon collision
Excited metal returns to ground state, emitting light (hv)
Ar
(g)
---------> Ar*
(g)
+ M
(s)
-------> M*
(g)
+ Ar
(g)

M
(s)
hv
Selects one line from the HCL and
rejects as much emission from the
flame or furnace as possible
MONOCHROMATOR
29
FAAS - Instrumental Components
and Layout
30
FAAS - Instrumental Components
and Layout
Double Beam Light
Transmission and Signal
Processing Techniques
Modulating the lamp (e.g. on
and off) is a means to alternate
the signal getting to the detector
A chopper is used to split the
light beam into a reference and
signal beam path
The lock-in amplifier
coordinates the signal between
the chopper and the detector; it
also identifies the signal being
received at the detector
32
Flame Atomic Absorption
Spectrometry (FAAS)

33
GFAAS - Instrumental Components
and Layout
Very similar to
FAAS
Most use auto
samplers
Can involve unique
background
correction methods
34
Graphite Furnace Atomic
Absorption Spectrometry (GFAAS)
The atomization process is
achieved and temperature is
rigorously controlled using a
series of heating steps
Dry (remove water)
Ash or Char (destroy organics)
Atomize
Small sample size
Typically 10-50 L
At const. furnace temp, the
area under absorbance peak
curve is a reliable measure of
the analyte

35
Interferences in AAS
Two Types
1. Spectral when the absorption or emission
spectra of an interfering species overlaps or
lies close to that of the analyte
2. Chemical species in the sample matrix
interfere with the atomization of the analyte
Enhances or decreases the volatility of the
analyte
36
Spectral Interferences in AAS
Example: Determination of Ba in
the presence of Ca
Both Ca and Ba atomize
simultaneously
Ca
(g)
+ oxidant ----> CaOH
(g)
CaOH
(g)
exhibits broad band
molecular absorption
The observed absorbance is in error
due to the non-atomic signal coming
from BaOH
(g)
S
i
g
n
a
l

Wavelength

Ba
S
i
g
n
a
l

Wavelength

Ba
Non-atomic signal
37
Chemical Interferences in AAS
Most chemical interferences result from a
change in the atomization behavior of the
analyte
Usually the atomization signal is
depressed
The interference usually comes from
analysis of an analyte in low concentration
in a complex matrix (e.g. seawater)


Matrix Modifier
Substance added to the
sample to reduce the loss of
the analyte during the
charring by making the
matrix more volatile or the
analyte less volatile
Ex: Seawater analysis:
NH
4
NO
3
added to increase
volatility of NaCl.
Pd(NO
3
)
2
decreases volatility
of analyte Sb
39
Chemical Interferences in AAS
(cont)
Example: Determination of Calcium in the presence of
phosphate
An equilibrium exists in aqueous solutions between
calcium and calcium phosphate
Ca
2+
+ PO
4
-3
<-----> CaPO
4
-1
CaPO
4
-1
is less volatile (i.e. more difficult to atomize)
than Ca
2+

This equilibrium tells us that as [PO
4
-3
] increases,
[CaPO
4
-1
] increases and [Ca
2+
] decreases
Net result, the absorbance of atomic calcium decreases
as phosphate content in the sample increases
40
Interferences in AAS
Approaches to Background Correction
Use of a continuous light source as a
reference beam (FAAS)
Zeeman Background correction (GFAAS)
Calibration using the method of standard
additions
An alternative means of calibration that
accounts for interferences in the calibration
process
41
Background
Correction in
FAAS
Monitor a wavelength
nearby the atomic
line of interest using
a continuous light
source to generate
the nearby
wavelength
Abs
Total
Abs
Back
=
Abs
Atomic

42
GFAAS - Zeeman Background Correction
Light from a HCL or EDL is passed through a rotating
polarizer producing two perpendicular radiation beams
A strong magnetic field is applied to the atomic vapor in
the furnace
The magnetic filed splits the electronic energy levels of
the atoms into several closely spaced (~0.01 nm)
absorption lines
43
GFAAS - Zeeman Background Correction (cont.)
Original absorbance = sum of induced absorbances
Absorption by the analyte only occurs during one phase
of the rotation of the polarizer
Background absorption occurs during both phases of the
rotating polarizer
The analyte absorption is determined by subtracting the
signal observed during the two phases of the rotating
polarizer

44
GFAAS - Zeeman Background Correction (cont.)
45
AAS Atomization Suppression The Method of
Standard Additions
An analysis method used to
overcome suppression of the
atomization signal
Procedure/Characteristics
Add standards into sample
Requires equal proportions of
sample and standard
Assumes that signal
suppression is the same in all
samples
Requires more analyses
3+ runs per sample
Differences in slope due to
matrix suppression
Extending the linear regression
line to x-axis gives the
concentration of the (diluted)
analyte
Comparison of calibration curves of strontium
in pure water and in aquarium water by the
method of standard additions
ANALYTICAL TECHNIQUES
Beer's law, A = kC, not always true making a calibration
curve necessary.
Standard addition method is used to minimize the effects
from the matrix
Anion- height of the absorbance peak is influenced by
type and concentration of anion. It can reduce the
number of atoms made. An unknown matrix is thus hard
to correct for
Cation: The presence of a second cation sometimes
causes stable compounds to form with the cation being
analyzed. e.g. Al + Mg produces low results for Mg due
to the formation of an Al/Mg oxide.
Assignment
The nickel content in river water
was determined by AA analysis
after 5.00 L was trapped by ion
exchange. Rinsing the column
with 25.0 mL of a salt solution
released all of the nickel and
the wash volume was adjusted
to 75.00 mL; 10.00 mL aliquots
of this solution were analyzed
by AA after adding a volume of
0.0700 g Ni/mL to each. A
plot of the results are shown
below. Determine the
concentration of the Ni in the
river water.
Determination of Nickel
Content by AA
y = 5.6x + 20
0
40
80
120
0 5 10 15
Volume of Nickel Added(mL)
A
b
s
o
r
b
a
n
c
e

U
n
i
t
s
Sample Problem 1
Potassium standards
gave the following
emission intensities at
404.3 nm. Emission
from the unknown
was 417. Find [K
+
]
and its uncertainty in
the unknown.
Sample
(g/mL)
Relative
emission
0 0
5.00 124
10.00 243
20.00 486
30.00 712
Sample Problem 2
Free cyanide in aq soln can be determined
indirectly by AA on the basis of its ability to
dissolve silver as it passes through a porous
silver membrane filter at pH 12.
4Ag + 8CN
-
+ 2H
2
O + O
2
4Ag(CN)
2
-
+ 4OH
-
A series of silver standards gave a linear
calibration curve in FAAS with a slope of 807
meter units per ppm Ag in the standard. An
unknown cyanide solution passed through the
silver membrane gave a meter reading of 198
units. Find the molarity of CN
-
in the unknown.
Internal Standard
A known amount of a compound, different
from analyte, that is added to the
unknown.

Compares the intensity of the absorbance
of an internal standard compared to that of
the analyte

Important when instrument response may
vary slightly from one run to the next

Internal Standard
Widely used in chromatography since the
small quantity of sample solution injected
is not reproducible.

Ex: HPLC/GC - flow rates vary by a few %
causing a change in the detector
response. Thus, relative response is
useful.


Examples of IS
Deuterated chlorobenzene
(C
6
D
5
Cl) is an internal standard
used in the analysis of volatiles
on GC-MS because it is similar
to Chlorobenzene but does not
occur naturally.
Nor-Leucine is an internal
standard for the analysis of
amino acids via GC-MS.
Tetramethylsilane as IS in NMR
Internal Standard
Preparation Procedure
Prepare a sample of unknown analyte concentration
Add an amount of known standard to the solution
Analyze the sample
Compare the area under each signal -
Response Factor (F)

Sample Problem
In a preliminary experiment, a solution
containing 0.0837 M X and 0.0666 M S
gave peak areas of Ax = 423 and As =
347. To analyze the unknown, 10.0 mL of
0.146 M S were added to 10.0 mL
unknown and the mixture was diluted to
25.0 mL in a volumetric flask. This mixture
gave the signals Ax = 553 and As = 582.
Find [X].
Sample Problem
Answer: 0.143 M
Practice Problem
1. A solution was prepared by mixing 5.00
mL of unknown (element X) with 2.00 mL
of solution containing 4.13 g of standard
(element S) per mL, and diluting to 10.0
mL. The measured signal ratio in an AA
experiment was 0.808 (signal X/signal S).
In a separate experiment, for equal
concentrations of X and S, the signal due
to X was found to be 1.31 times more
intense than the signal due to S. Find [X].
Practice Problem
2. A solution containing 3.47 mM X (analyte) and
1.72 mM S (standard) gave peak areas of 3473
and 10222, respectively, in a chromatographic
analysis. The 1.00 mL of 8.47 mM S was added
to 5.00 mL of unknown X, and the mixture was
diluted to 10.0 mL. This solution gave peak
areas of 5428 and 4431 for X and S,
respectively.
a. Calculate F for analyte.
b. Find [S] in mM in the 10.0 mL of mixed solution.
c. Find [X] in mM in the 10.0 mL of mixed solution.
d. Find [X] in the original sample.

Answers
1. 5-C 1.02 g/mL
2. 5-29 a. 0.168
b. 0.847 mM
c. 6.18 mM
d. 12.35 mM