Spring 2017 CHEMISTRY 105

Instrumental Methods in Analytical Chemistry

Lecture: MW 9 AM 10 AM 219 Dwinelle
Labs: MTuWTh 1 5 PM 305 Latimer

Lecture 6. Atomic Absorption Spectroscopy (2)

Prof. Ke Xu

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Questions

Q1: In atomic spectroscopy, transitions between which states give the strongest
signal? Why?
Between the ground state and first excited state: most populated!

Q2: What is the typical population for the ground state and the first excited state?
First excited state: ~10-4 at 2500 K

Q3: A light beam sequentially passed through two samples with T1=10% and T2=1%.
Whats the final transmission T?
How to describe the same system in terms of absorbance A, A1, and A2?

Q4: Compare flame atomization and graphite furnace:

Which one provides lower detection limit? Graphite furnace
Which one has better reproducibility? Flame Atomization
Which is higher in throughput? Flame Atomization

Q5: What are the origins of the finite line width in atomic spectroscopy? Whats the
typical value for each type?

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AA: Line width problem

AA line width: ~10-3 nm

Common grating: resolution ~ 0.1 nm

Problem of using light with bandwidths much larger than the line width

Absorbance only occurs for a very

narrow slice. Small change of intensity
over large background: low S/N!

Only absorbing a short range of the signal, but the noise is very high

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Line source with extremely narrow bandwidth?

Light source at the absorption peak and

with bandwidth smaller than the absorption
line width
Measure the absorbance only at the peak
wavelength!

Beers Law
A = Kc
Very narrow band width light source lowers the noise.
most ideal is having the same bandwidth

How to achieve this?

Use atomic emission! How to obtained smaller line width?
Lower temperature,
Reduce Doppler broadening T lower atomic movement,
= 7.2 10 7 reduce doppler
-Lower T (room T) M broadening. Delta
lambda is the width

Reduce pressure broadening

-Lower P (vacuum) 4
Hollow-cathode lamp (HCL)
Hollow cathode contains specific metal that wanted to be detected
Ar is ionized
Ar+, Ne+

M* First excited state Metal to

Analyze
Sputtering M Ground state

Ionized state
M+ + e-, Ar+, Ne+ ,etc.

M* M+
h : same energy as
absorber of interest

Filled with Ne or Ar at 1-5 Torr << 1 atm = 760 Torr! Reduced pressure broadening
Cathode is made of element of interest (or combo).
~300 V between the anode and the cathode: gas is ionized and positive ions are accelerated
toward the cathode.
Sputtered metal atoms goes into the gas phase (at moderate temperature); those in the
excited state emit photons
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AA: HCL + lower-resolution monochromator

Each lamp produces unique narrow light

Hollow-cathode lamp: produces narrow lines for peak absorption. One lamp per
element (or combo)!
Monochromator: Separates the different lines of the lamp. Typically use
resonance lines for analysis. Resolution of ~0.1 nm suffices
Strongest absorption
E.g., can separate Mn279.5 & Mn279.8 nm
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Monochromator separates
out different lines

Using monochromator to select the particular line

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Modulation for improved S/N
Single-beam design

Controlling the
input of light

Modulation through chopping or modulated

power source
Moves the measurement to higher f
(reduces flicker noise)
Separation of real signal at the modulated
frequency from random noise
Measurement of light from flame
Sequential measurement of sample and
blank

Having a contrast mechanism to figure out the Does not account for drift in lamp power
noise, flicker noise, noise of low frequency 8
Double-beam design

measuring the intensity of the beam

Diverge the beam

Modulation + comparison with a reference light path: accounts for drift in lamp
output power
Sequential measurement of sample and blank
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Sources of noise and interference

Spectral Interference
Interference due to overlapping lines is rare: very narrow HCL line width!
Broadband absorption and scattering due to the flame use of blank
Broadband absorption and scattering originated in the sample matrix
(MOH, etc) may be reduced via optimization of flame condition

To account for remaining background:

Need to measure the background
to remove it!
Need to measure the background
as close to the analyte line as
possible!
Subtracting background also
introduce additional noise

For x = x1 x2 x3 ...

= 12 + 2 2 + 3 2 ...
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Background correction other wavelengths
Two-line method
Use of non-absorbed lines from the lamp: impurity, Ne/Ar, nonresonant emission lines
Often not close enough to the absorption line.

Use of a continuum source

Often used: deuterium lamp broad spectrum
To measure background: Use deuterium lamp and relatively wide bandwidth on the
monochromator: absorption from the very narrow line of AA is negligible.
Not very reliable: alignment difficulties, unsuitable for >350 nm

~1 nm
Background correction Zeeman effect: shifts absorption
Zeeman effect: splitting of energy levels due to applied magnetic field H.
Great way to create slightly shifted spectral lines to measure background!
The central, peak (no change in ) only absorbs light polarized parallel to the field (||)
The two satellite peaks (~0.01 nm change in , depending on H) only absorb light polarized
perpendicular to the field ().
Switching on/off field or polarization of the light source: AA+background (|| or field off) vs.
background only ( and field on)
Magnet
Monochromator
Atomizer

Magnetic Field Off Magnetic Field On ()

Background
Background

- +
Absorption +Absorption

- Absorption

Emission Emission

0 0 12
Background correction Source self-reversal

An easier way to split spectral line: source self-reversal

Self-reversal of emission spectrum of HCL at high current: why?
Broader spectrum? Increased temperature at the cathode
A dip at the center? Absorption in the tube from atoms at lower temperature
Self-reversal creates a way to split the spectral line of light source: contrast
between AA and background signals
Source modulation to switch between low & high current modes

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