Chapter 8 & 9 Atomic

Absorption Spectroscopy

Atomic Absorption Process

A neutral atom in the gaseous state can absorb
radiation and transfer an electron to an excited
state.
Simple electronic transitions possible with no
vibrational and rotational energy levels possible.
Bandwidth much narrower!
Occur at discreet
Na(g) 3s 3p and 3p 5s as well as other
transitions are possible at the correct photon
energy a transition.
Chapter 8&9 - 2

Atomic Absorption Transitions

Chapter 8&9 - 3

THE FLAME AND EXCITED

STATES

3 steps required before measurements are possible in an A.A. experiment: 1. vaporization 2.

reduction to the elemental state and then 3. exposure to radiation.
The first two steps are accomplished by a flame.
Effect of flame temperature: Since flame is at high temperature might have an effect on fraction
of atoms in excited state.
Boltzmann's equation describes effect of flame temperature: where

Nu
=
No

Eex

e kt
go

N = # of atoms in a given state;

g = statistical factor for a given level and measures the number of possible electrons in each
level;
g = 2J + 1 where J = Russel-Saunders coupling constant and is given by J = L + S or L S where
L = orbital angular momentum quantum # (=0,1,2,3 for s, p, d, f respectively) and S = spin = .
E.g. For the Na transition

gu

3s 3p3/2

3s 3p

gu = 2(L+S) + 1 = 2(1 + ) + 1 = 4 and

go = 2(0 + ) + 1 = 2.
go = 2 and gu = 2(1) + 1 = 2.

Overall population of both of these states: since they are only separated by 5, let's use average
of their wavelengths
add population for the two excited states:
hc and
27 erg sec 2.998x 10 cm / sec
6.626x
10
g = 4 +E
2 =6 and go
before);
lave 5892.
= 2 (as 10
= 3.37 10 12 erg

5892X10 8 cm

Chapter 8&9 - 4

The Flame and Excited States

Assume Air-acetylene flame (2400C):
Temperatures for different flames used in
AA are listed in text. T = (2400 + 273)K =
2673K;
Substituting into the Boltzmann equation:

3.37x10 12erg
6

N=u 3.23x104

No

1.38x 16erg 1 2673K

10
K

Very small fraction of the atoms in the

flame are excited to this excited state.
Chapter 8&9 - 5

Relative population of higher

energy transitions

3p 5s transition is also possible and has = 6161 (E = 3.22x1012 erg.

The fraction of 3p electrons excited to the 5 s orbital is calculated as before:

Nu 2

No 6

3.22x10 12erg

16

1
1.38x10
ergK 2673K

= 5.34x10-5

Fraction involved in this transition even smaller.

Finally, we can estimate the fraction of electrons in the 5s state relative to
the 3s state:
N5s N3p N5s

N3s N3s N3p = 5.34x1053.23x104 = 1.72x108 QED

Only very small proportion of the absorbing species is in the excited state
from excitation by flame; higher energy transitions much less likely than the
lower energy transitions.

Chapter 8&9 - 6

MEASURING ATOMIC
ABSORPTION

Po
log P =

Recall Beer's Law (A =

bC ) is obeyed when line width
small compared to absorption band.
Atoms or molecules absorb radiation at discrete wavelengths.
Broadband radiation contains photons of several wavelengths,
some of which may be useful but many of which will not. This will
make Po (= Pusable + Puseless) larger and the absorbance smaller than
would be expected with only the usable portion of the light available
for absorption.
Besides the Pusable can be composed of wavelengths with different
absorptivities i.e. the sample does not absorb all radiation to the
same degree.
Non-linear behavior observed when range of excitation source is
greater than range of absorber; bandwidth of excitation source
must be narrower than bandwidth of absorber.

Chapter 8&9 - 7

Linewidth of Atomic Transitions

Natural linewidth of an absorption spectrum is
very small (104) but is broadened by

Doppler broadening: Random thermal motions of

atoms relative to the detector
Pressure broadening: In the atomic absorption
experiment the pressure is large enough that atoms
can undergo some interatomic collisions which cause
small changes in the ground state levels.

Normal line width of excitation lines much

greater than this line width
Monochromator cannot be used to select
range in AA (bandwidth few tenths of a nm).
Chapter 8&9 - 8

SOURCES

Solution to line width problem: Use atomic source of same material.

e.g. For Na analysis Na vapor is used.
Atoms are excited by electrical discharge; the excited atoms emit a characteristic
. The bandwidth of the source << sample linewidth since it is generated under
conditions where there is less broadening.
Hollow Cathode Tube : Hollow cathode made of the material needed is vaporized
and emits radiation of the characteristic wavelength.
The ion current to the cathode controls photon intensity; Increasing the voltage
between the anode and cathode will control the current and thus total photon flux.
Optimum current for each lamp (1-20ma).

Chapter 8&9 - 9

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.
Chapter 8&9 - 10

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.

Chapter 8&9 - 11

Undergraduate Instrumental Analysis,

Robinson, p. 267.

Premix (laminar flow) burner

Sample, fuel, and oxidant mixed prior to entering flame.
Turbulence drastically reduced by removing larger
droplets.
Mixing baffles insure only fine mist makes it through to
burner.

Instrumental Methods of Chemical Analysis, Ewing, p. 110.

Chapter 8&9 - 12

ELECTROTHERMAL
ATOMIZATION

all of the sample used is atomized in

furnace (electrothermal) atomizer.
detection limit is 100-1000x lower than
with aspiration techniques.
only a few mL of solution is used.
Basic Principle:

sample container resistively heated to

vaporize the metal atoms.
sample dried (evaporate solvent) at
110C;
ash sample called "burn off" (200300C);
atomization.(2000-3000C)
comparison with flame atomization:

interaction with sample matrix and

electrode
poorer reproducibility
detection limits of 1010-1012g (or 1ppb)
are possible.

Instrumental Methods of Analysis, Willard,Merritt, Dean and

Settle, p. 147

Chapter 8&9 - 13

FUELS/OXIDANTS

Low T flames : easily reduced elements (Cu,

Pb, Zn, Cd)
High T flames: difficult to reduce elements
(e.g. alkaline earths).
Fuels: natural gas, propane, butane, H2, and
acetylene;
Oxidants- Air and O2 (low temperature
flames). N2O (high temperature flames).
Flame characteristics:
Sample enters flame, is vaporized, reduced
and eventually oxidized.
Exact region of flame in which each of these
occurs depends upon:
flow rate,
drop size, and
oxidizability of sample.
Optimum position for flame for many metals.

Chapter 8&9 - 14

Flame Profiles in AA

Chapter 8&9 - 15

MEASUREMENT OF AA

Ideally, the amount of light reaching the detector is given by Beers Law: P =
Po10bC .
several interferences can change this to:
P = Po10bC + Pemission Pbackground Pscattering.
Pemission is due to analyte emission in the flame
eliminated from the absorbance by modulation of the light source: measures
only AC levels; emission DC level.
Pbackground, Pscattering: due to absorption by the flame or are induced by sample
matrix and are independent of the analyte.
Broad band in nature.
Flame interferences nulled by comparing a blank with sample
Sample matrix is a problem. Caused by, for example, high salt content (e.g.
NaCl or KI). These have broad band absorption spectrum in flame since they are
not reduced by it. Most common approach uses secondary continuum source
(e.g. D2 lamp):
Each lamp (D2 and HCT) modulated but are 180 out of phase with each other.
Detection system measures difference between two absorbance signals: A HCT =
Asample + Abrdband while Acontinuum source = Abrd band. will be absorbance of sample.
Chapter 8&9 - 16

D2 Source Elimination of
Background

Chapter 8&9 - 17

MONOCHROMATOR
Needed to choose one
of several possible
emission lines (emitted)
associated with HCT.
Since they are usually
reasonably well
separated from the line
of interest, it is
straightforward to use a
monochromator to
eliminate this
interference.
Chapter 8&9 - 18

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.
Chapter 8&9 - 19

Sample Problem
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
120
y = 5.6x + 20

Absorbance Units

80

40

0
0

10

Volum e of Nickel Added(m L)

Chapter 8&9 - 20

15

Chapter 8&9 - 21

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