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 5. Atomic Absorption Spectroscopy

Prof. Ke Xu

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Take-home messages for atomic spectroscopy: 3

Not all transitions are allowed selection rules

Allowed transitions and spectral lines are still numerous.

Alkali metals: ~200 lines. Transition metals: 1,000+ lines!

Different spectral lines have different intensities. Population + selection rules

Resonance lines: transition between the ground state and first excited state.
Strongest!

Detection of specific spectral lines

existence and/or concentration
of an element

Flame emission of sodium

Sodium lamp
Examples:

Solar
spectrum
(AA)

Identification
of elements
in fireworks!
(AE)

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AE of different elements

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Population of energy levels

Boltzmann distribution

For a system at equilibrium:

How many states have the same energy?
Degeneracy Energy

Population
Nj gj ( E j E0 )
= exp
N0 g0 kT
Temperature

States with higher E Lower population

Most populated at any T: ground state
Second-most populated state: first excited state.
Resonance lines: Strongest signal

T Increased population for states with higher E

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Population of energy levels: temperature effects

T Increased population for states with higher E

Still small fractions for excited states

Example 8-2 in textbook: First excited state of sodium

gj 6
E j E0 = h = =3
g0 2

Nj gj ( E j E0 )
= exp
N0 g0 kT

Use an averaged wavelength of 589.3 nm:

@2500K: 1.7210-4 @2510K: 1.7910-4

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Implications for spectroscopy

Even at T = 2500 K, population of the first excited state is ~10-4

4%
For T = 10 K: Noticeable relative change of population for the excited state.
Small relative change for the ground state.

if there is more atoms at excited states, the signal would be stronger

AE: signal from atoms in excited states

AA: signal from atoms in the ground state
more atoms at ground state allow absorption of energy to reach the excited state

Most atoms are in the ground state AA has better S/N?

Smaller T-dependence for ground-state population
Not necessarily!

AE: detects a positive signal over zero (or low) background

AE can be better!
AA: detects a negative signal on a large background

Stable T, however, is important for reliable measurement, in particular for AE

The negative signal for absorption: Beers law

The intensity of a ray of monochromatic light decreases exponentially as

the concentration c (or path length b) of the absorbing medium increases.

P = P0 exp( abc)

Define:
P P
Transmission: T = T% = 100%
P0 P0
P0
Absorbance: A = log T = log
P
b: path length
Beers law: A = abc = bc a: absorptivity
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: molecular absorptivity
Why exponential decrease? Why the definition of A?
Thought experiment:

b Transmission Absorbance

A sample with T A = log T

path length b

b1 b2
The same sample
P1 P2
divided into two: T1 T2
P0 P1
log(T1 T2 ) = A1 + A2
b1, b2. b = b1+b2
Addition of A!
The two systems should T = T1 T2 A = A1 + A2
give the same result
Ab for b = b1+b2

Similarly, A c

A = 0: T = 10-0 =100%
A = 1: T = 10-1 =10%
Definition ~pH!
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Atomic line widths

Finite widths of spectral lines not single

wavelength
Line broadening
Line width: often characterized as full width at
half maximum (FWHM)

Intrinsic line width due to uncertainty principle

Lifetime of excited states: t ~10-8 s

Natural line width: ~10-5 nm

Collision (or pressure) broadening

Uncertainty in energy levels due to collision
Proportional to the pressure
Typical value: ~10-3 nm
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Doppler broadening

v For molecules & k BT Redshift: For galaxies

= atoms (random vrms quickly moving away
c directions): M from us (single-direction)

T where T is temp in K,
= 7.2 10 7 M is atomic mass
M

Increases with higher T

Final line width: ~10-3 nm
~10-3 nm at 2500 K (Fe)
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Atomic Absorption (AA) Spectroscopy: Equipment design

(2000-3000 K)

Sample is aspirated into the flame.

High T evaporates solvent and the solute is atomized in the flame.
The flame replaces the cuvette!!!
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Atomization: Converting sample into gaseous atoms/ions
Flame atomization

(~20003000 K)

CaCl2 (aq) CaCl2 (aq)

(aerosol)

CaCl2 (s)
(desolvation)

CaCl2 (g)
(vaporization)

Ca (g) + 2Cl (g)

(atomization)

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Flame atomization
Elongated along
the light path

Most often used for AA:

interzonal region. Free
atoms

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Characteristics of the flame

Oxide formation

the taller teh signal. the atom is more ernergy

For the same element: Use the same part of the flame for calibration and measurements
Different element have different height dependence for signal strength
Larger height: longer exposure to heat signal
Larger height: formation of oxides signal
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Performance of flame atomization

Liquid samples (mL volumes)

High throughput ~100 samples / hr
Good reproducibility. Relative precision: ~0.1%
Relatively low sensitivity. Need large amount of sample. Detection limit: ppb
Low atomization efficiency (<0.1%)
Atoms pass through flame quickly

ppb: part per billion 1/109

For 1 g water, 1 mL, (1 cm)3.
Dilution by 109 = (103)3
(10 m)3 = (2 m 50 m 10 m) size of a swimming pool!

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Electrothermal atomization (graphite furnace)

4 mm

2000-3500oC

ashing removes organic chemicals

350-600oC
100-200oC
Ashing
RT <<1 second
Dry
Introduce
Sample time

A few microliters of sample

Protected under inert gas (Ar)
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Performance of graphite furnace

Signal

Integration of signal over time for quantification

time: 1-10 second

High sensitivity for small volumes (L) of sample.

Sample all vaporized/atomized quickly in time
Spatially confined ppt: part per trillion (10-12)
Detection limit: ppt
For a swimming pool: 1 L!
Absolute amount: ~10-13 g
Relative low precision: 5%-10%
Relatively slow: several min/element
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Line width problem for AA
In an ideal world:
10-3 nm

1 2 3 4 5 6 7 8 9 10

Measure A at different frequencies to obtain spectrum?

Big problem: width? Only 10-3 nm!
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Line width problem for AA

FWHM of 10-3 nm, further dividing wavelength to 10-4 nm??

For = 500 nm:

Resolution of 5106?? Infeasible best gratings achieve 7105
Even if resolution is achieved, the split light would be very weak!

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

Common grating: resolution ~ 0.1 nm

Absorbance only occurs for a very
narrow slice. Small change of intensity
over large background: low S/N!

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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!

A = Kc

How to achieve this?

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