The Absorption of Radiation

What happens to an excited atom/molecule after absorbing a UV/vis photon ?

The excited atom or molecule will eventually return to the ground state. Several
possibilities exist for energy loss:

1) The extra energy is lost by collision (heat)

2) A photon is emitted as the electron falls back to the ground state.

NB. electron will have jumped to a high vibrational level in the higher orbital. It will
rapidly go down to the lowest vibrational state in the higher orbital.

Therefore, the photon emitted will be of lower energy (higher λ) than the absorbed
photon.

Emissions will be in all directions (fluorescence).

The electron may go down to a metastable state in a slightly lower orbital, from which
the dropping back to ground state orbital is “forbidden” and therefore slow. This is
phosphorescence.

A Related Process to Fluorescence/Phosphorescence

In which the photon is not absorbed. This process is called scattering of light.

No Change of Wavelength
Tyndell scattering - particles somewhat larger than molecules (colloids)

Rayleigh scattering - by molecules.

Turbidimetry - amount lost in a straight line.

Nephelometry - amount scattered to 90°.

Determination of molar mass (polymers) and particle size (very important in industry).
Air pollution monitoring (scattering by smog).

With a Change of Wavelength

Photon transfers some energy to a molecule or vice-versa, i.e. scattered photon is of

slightly higher or lower energy than the incident photon.

Wavenumber JR = Ji ± ΔJ
Raman scattered incident Raman shift*

*
This is the energy difference between two vibrational levels (or possibly rotational
levels).

Raman is complementary to IR (largely). Because Raman needs a change in polarisabilty

(shape) but not necessarily dipole moment.
IR- production of dipole moment is required for vibrational axis.

Main analytical atomic and molecular UV/vis spectroscopic techniques are:

Emission, Absorption and Fluorescence.

Useful Schematics

Atomic emission spectroscopy - arc spectroscopy (steel works)

plasma spectroscopy
flame photometry (visible)

Molecular emission spectroscopy

CHEMILUMINESCENCE (+bioluminescence)

A + B → C* → C + hν

Molecular Fluorescence (molecular luminescence)

Fluorimetry
Phosphorimetry

Atomic fluorescence Can be/is used

* Atomic Absorption Spectroscopy (AAS)

• Flames
• Plasmas
• Carbon Furnaces
* UV/ Visible Molecular Absorption Spectroscopy

UV/Visible Molecular Absorption Spectroscopy

Determinand absorbs light in visible or UV region.

We react determinand with a reagent (derivatise it) to form a chemical species/product

which does absorb visible or UV light. NB. The reagent must not absorb at the
wavelength used for measurement.

How Do We Measure the “Colour” of the Solution ?

Visible light - can use a colour comparator, or could use a coloured comparator disc
(glass or plastic). OK for chlorine in swimming pools for example, but not very precise
and what do we do in the UV region ?

For visible region, can use a filter photometer instrument.

More advanced instruments are totally enclosed.

Clearly, even if a high concentration of determinand is present, only a fraction of the light
is absorbed.
Therefore, use a filter which passes light of wavelength similar to the determinand.

Red dye absorbs green light, therefore needs green filter to get maximum sensitivity
(green filter more or less closely the colour absorbed).

How Do We Make the Measurement ?

SHUTTER CLOSED 0% light

WATER IN CELL 100% light
SAMPLE IN CELL <100% light

Light Detection - Photocell

Photomultiplier tube , e.g. 200-650nm

Suppose we want to restrict the wavelengths passed through the sample cell more
carefully, we use a monochromator.

PRISM

Fused (vitreous) quartz : 200nm - 4µm in IR.

Optical glass gives better dispersion in visible.

DIFFRACTION GRATING

e.g. 2000 lines cm-1 ⇒ d = 5 x 10-4 cm

522.5
At θ = 6.00° , ! = nm
n

1st order 2nd order 3rd order 4th order

522.5nm 261.2nm 174.2nm 130.6nm
REFLECTION GRATING

Thin metal plate or glass plate with metallic film.

α+θ=β-θ

Light Sources

Continuous spectrum - “white light source”.

(line spectra ,e.g. mercury lamp - when single narrow line is required, e.g. for calibration
of instruments).

Tungsten filament lamp : 320nm - 3500nm

(tungsten-iodine, quartz-iodine)
Halogen light.

Hydrogen or deuterium discharge lamp , 160-360nm : more intense, longer life, more
expensive.

Neon discharge lamp - fluorescence.

Helium cathode lamps - line spectra - atomic absorption.

Single / Double Beam Instruments

Single Beam Instruments

Single wavelength measurement. e.g. at 520nm.
Set 0% transmittance with shutter closed. Put water in cell to get 100% transmittance. Put
sample or standard in cell to read %transmittance (or rather absorbance).

NB. Blank must be done at each wavelength as the intensity of the lamp is not uniform
(emission spectrum of lamp).
Used to plot manually.

More recently , scan all λ with blank, then scan all λ with standard, and then subtract.

Better to use double beamed instruments.

NB. there is a loss at all interfaces apart from absorbance of solution.

MATCHED CELLS

The Absorption of Radiation

Consider an assembly of independent absorbers of N m-3 having a beam of

monochromatic photons incident upon it of power P0.
Probability of a photon colliding with an absorber is dependent on N.

Provided that the energy of the photon corresponds to the energy of a spectroscopic
transition within the absorber, there is a finite probability that the photon will be absorbed
and the energy converted to internal energy in the absorber.

Two questions :

(i) How much power is lost from the beam, and what is the emergent power P ?
(ii) What happens to the lost power.

(1) Having reached an excited state by absorption, it can be depopulated by 3

mechanisms:

-spontaneous emission of a photon → fluorescence

phophorescence

Photons emitted equally in all space (radiation is isotopic) ∴ only small contribution to
P.

- stimulated emission

Photons emitted in the same direction with same phase as incident photons, ∴ do
N
contribute to P, BUT at normal temperatures i is very low, ∴ effect is weak.
N0

- a quenching collision occurs.

e.g. M* + Q → M + Q*

(2) Power is also lost by scattering - Rayleigh Scattering is an elastic process :

λi = λs.
Raman scattering is an inelastic process with the molecule being excited to a very short
lifetime virtual state. i.e. λi ≠ λs.

For both Rayleigh and Raman :

1
! =
"4

(ii) How much power is lost from the beam ?

a) the absolute power absorbed by a given increment.

ΔN of absorption if proportional to the power, ΔP∝P.

b) Successive equal increments in the number of absorbers absorb equal fractions of the
incident power, this is the formal statement of Beers Law.

These observations can be expressed mathematically by considering very small

increments in the number of absorbers.

-dP ! P dN

dP
or = - k dN
P

Integrating from Po → P and from 0 → N,

 P dP N
! P0 P
= - k ! dN
0

P
ln = - kN
P0

The way of expressing k and N are different for atomic and molecular spectroscopy.

Molecular Spectroscopy

Express N in terms of the molar concentrations c and absorption path length b (cm), and
k in terms of the molar absorptivity ε.

P0
log = !bc
P

ε = molar absorptivity (mol-1 cm-1 dm-3)

c = molar concentration (mol dm-3)
b = absorption path length (cm)

We normally write

P0
A = log
P

where A is the absorbance, i.e. A = εbc.

∴ A ∝ c.

Note, c = 0 - no absorption.

P = P0, ∴ A = 0.

P0
If A = 4, = 10-4 (P hard to measure)
P
P
If A = 0.001, 0 = 0.997 (hard to differentiate between P and P0)
P

P0 P
Also note : Transmittance T = , i.e. %T = x100 .
P P0

Used mainly in infra-red spectroscopy.

∴ A = -log T
Limitations to Beers Law

1) Fundamental

i) fails at high concentrations because electron clouds interact and ε is altered.

ii) refractive index changes at higher conc., replace ε with εn/(n2+2)2.

2) Instrumental Limitation

Applies strictly only to monochromatic radiation -with finite bandwidth curvature

towards the concentration axis occurs at high concentration.

3) Chemical Deviations

Chromophore concentration may be affected by a shift in the chemical equilibrium.

e.g. Cr2O7 + H2O 2HCrO4- 2H+ + 2CrO42-

Atomic Absorption Spectrometry

Spectroscopic Processes Used in Analytical Atomic Spectrometry

E1

1 2 3 E0

1. Atomic absorption
2. Atomic emission
3. Atomic fluorescence

Wavelength range used for atomic absorption (AA)

E1-E0 = 1.6 eV ⇒ 800nm

E1-E0 = 6.5 eV ⇒ 180nm

Population of Excited State

For atoms in thermal equilibrium, and in the absence of strong external radiation sources,
the number of atoms in an excited state, N1, compared with the number of atoms in the
ground state, N0, is given by the Boltzmann equation.

E1 - the energy of the excited state

k - the Boltzmann constant
gx - the statistical weight of the population = 2J + 1

NB. N1 << N0, even at 5000K, ∴ greatest sensitivity is obtained by using absorption lines
starting from the ground state, i.e. resonance lines.

Shape and Width of Atomic Absorption Lines

At low concentrations, i.e. in the absence of self-absorption and in the absence of strong
electrical fields, such as those created by gaseous ions in a plasma, the physical width of
an atomic absorption line is determined by a combination of two processes:

i) pressure or collisional broadening

ii) Doppler broadening

i) Pressure Broadening

collisions perturb
the energy
levels

1
!" p =
#$

where Δνp is the pressure or collisional 1/2 width and τ is the mean period between
collisions.
1
! (torr) "
p

ii) Doppler Broadening

Doppler broadening is caused by the relative movement of the emitted or absorber with
respect to the absorber.
ν ←⎯ red shift ν = ν0 - Δν

↑ no shift ν = ν0
↓ ⇐observer

ν ⎯→ blue shift ν = ν0 + Δν

Atoms and molecules are in random motion with a Maxwellian distribution of velocities.
This leads to a Gaussian distribution of shifts; i.e. the peak has a Gaussian shape with
half-width given by

where ν0 = frequency of the line centre

and R = universal gas constant
and m = atomic / molecular weight.
1
T 2
NB. !" 0 # $& ')
% m(

For typical atom cells used in AA, p = 1atm, T = 2000-3000K, Δλ = 0.001 - 0.01nm

For Beers Law to be obeyed over a wide concentration range,

Δλsource << Δλabsorption

i.e. Δλsource << 0.001nm

Specificity of Atomic Absorption

Factors Influencing Specificity:

1. Absorption spectra of elements at the temperatures encountered in atomic absorption

spectrometry are simple, comprising only the resonance lines. Transitions from the
ground state to the lowest excited states are generally the strongest absorbers.
2. Absorption spectra are unique to each element and because the lines are very narrow,
and there are few of them, overlap of absorption lines in comparatively rare.

3. The light source in AA is normally a hollow cathode lamp (HCL) and the cathode is
made from, or lined with, the analyte element. The HCL therefore only emits the
atomic lines (including the resonance lines) of the analyte, plus some of the fill gas,
e.g. Ne.

AA has a very high specificity because of the lock (absorption line) and key (emission
line) nature of the process.

emission line

absorption line

Wavelength

Background Radiation

The atom cells used in atomic absorption spectrometry unfortunately contain not only the
analyte atoms, but also molecules and radicals. These species have associated with the
absorption bands which may cover several nanometres of the spectrum. If they overlap
with analyte resonance lines they will cause absorption to occur which is not related to
the concentration of the analyte. Steps must be taken therefore to correct for this
background absorption.

Sensitivity and Detection Limit

- The Characteristic Concentration (sensitivity)

This is the concentration of analyte which gives rise to a 1% absorption of radiation, i.e.
an absorbance of 0.0044.

This depends primarily on the absorption line strength. Therefor, for equal hollow
cathode lamp line width the spectral bandpass absorption path length (L) and number
density (N) should be approximately equal for all instruments.

- The Detection Limit

This is the concentration of the analyte which gives a signal (absorbance) “n” times the
standard deviation of the blank, where n = 2, or 3.
This is a more realistic estimate because it take account of the “noise” in the system, i.e.
from the sample introduction, flame, etc.

Linear Concentration Range

1. The lower limit is set by the noise in the system because the system has to discriminate
between two very similar numbers.

e.g. A = 0.0044
I ≈ 0.99I0

2. The upper limit is set by deviations from Beers Law and ultimately deteriorating
precision because of the low intensity of transmitted radiation.

e.g. A = 2
I ≈ 0.01I0

The normal linear range is 1-2 orders of magnitude of concentration.

Instrumentation for Atomic Absorption Spectrometry

The analytical application of atomic absorption was the subject of a patent in 1953 from
the CSIRO, Australia, and the first paper by Sir Alan Walsh was published in 1955.

The basic components are:

The Atomic Line Source

The Hollow Cathode Lamp (HCL) - mechanism

- The cathode is made from a hollow cylinder of the analyte element or from a metal such
as Ta or W into which the analyte element is deposited to form a liner.

- A voltage of 150-300V (current 2-20mA) is applied between the anode and the cathode.
- A discharge is established in the fill has, position ions of the fill gas are accelerated into
the cathode and remove analyte atoms by a collisional process known as sputtering.

- The analyte atoms are excited by collisions with the fill has ions and the electrons in the
discharge.

- The output spectrum comprises of the atomic spectrum (mainly resonance lines and
lines originating from excited states close to the ground state) of the analyte and the fill
gas.

- Some multi-element lamps, e.g. Ca-Mg, Fe-Ni-Cr are available, but the intensity of the
individual lines are reduced.

- HCL’s have a limited lifetime, dependant upon the operating current. As the lifetime
decreases the current increases and as the lifetime decreases, the volatility increases.

- The factors responsible for limiting the lifetime :

(a) The adsorption of the fill gas on the inner surfaces of the lamp - discharge efficiency
is reduced.

(b) The deposition of the analyte, e.g. for volatile elements Cd, As, Se on the inner
surfaces of the lamp leading to enhanced fill gas absorption.

(c) The evolution of hydrogen from the analyte leading to an intense hydrogen discharge
spectrum.

The Hollow Cathode Lamp

The low pressure leads to small collisional broadening and the low temperature leads to
small Doppler broadening.

Δλ < 0.001nm
 hol low cath ode mi ca s hields an ode

s ilica window

graded s eal
con necting n eon at 3 torr
pin s pl as tic insu lating
base s upp orts
gl ass envelope

Operating Characteristics

(a) Generally P ∝ cn n = 2, 3
(b) As P is increased, the signal-to-noise ratio in measurement of P and P0 increases.
(c) However, as i increases, two undesirable phenomena occur :

Self-absorption - causes broadening of atomic line

Self-reversal - causes a loss of intensity at the atomic line centre.

The Atom Reservoir

The function of the atom reservoir is to convert all the chemical forms of an element
present in a liquid sample into free atoms in the gaseous state. The absorption depends on
the number density N (atoms m-3) and the absorption path length L. Therefore, for a
given chemical concentration, c:-

- N should be constant regardless of the chemical form of the element.

- All the atoms of the analyte entering the atom cell should be converted
to free atoms on the same time scale and with the same spatial distribution.

Two types of atom cell are commonly used in AAS:-

- the chemical flame (detection limits 0.01-2µg ml-1)

- the electrothermal atomiser (detection limits 0.001-10ng ml-1)

The Chemical Flame

The samples in liquid form cannot be directly introduce into the flame. They are first
converted to a fine aerosol (dmax < 6µm) by a nebulizer and spray-chamber.
The nebulizer produces a primary aerosol, 0 < d < 100µm and the spray chamber filters
out the large droplets (d > 6µm). Only about 5-7% of the sample entering the nebulizer
reaches the flame.
An impact bead is usually incorporated into the spray chamber, it also acts as a filter for
large droplets and can produce some secondary fragmentation, thereby increasing the
aerosol flux to the flame.

Desirable Properties of a Flame to be used for AAS :-

(a) The temperature and chemical environment must be suitable for producing efficient
atomisation of the analyte element.

(b) The ability to tolerate a wide variety of solvents, e.g. H2O, EtOH, MIBK.

(c) They have low levels of background emission and absorption.

(d) They must be stable and reproducible from day to day and have low “noise”
characteristics.

(e) They must be safe, convenient and inexpensive to operate.

These properties are provided by a Laminar pre-mixed flame stabilised on a slot burner.

A Typical 10cm Slot Burner

For a laminar pre-mixed flame.

the fuel and oxidant gases are pre-mixed in the spray chamber. The flame is stable
provided that:

i) The flow velocity of gases must be greater than the flame burning velocity.
ii) The burner temperature must be low enough to quench the flame reaction.

made of titanium

Common Analytical Flames

Oxidant Fuel Temp / °C

Air CH4 1850-1900
Air natural gas 1700-1900
Air H2 2000-2050
Air C2H2 2125-2400
N2 O C2H2 2600-2800

Function of the Sample Introduction / Atomisation System.

See diagram (next page).

The Laminar Pre-Mixed Flame

.
Flame Mechanisms

- Pre heating zone :- The flame gas is heated to ignition temperature by conduction from
the combustion zone above.

- Primary reaction cone :- This is the bright luminescent zone <0.1mm thick where
primary combustion occurs. The residence time is too short for thermodynamic
equilibrium. There are many excited molecules and radicals produced by exothermic
chemical reactions, e.g. for air oxidant : CO2, CO, H2O, H2, N2, H•, O•, OH•. This region
is unsuitable for analytical use.

- Interconal zone :- This is the hotter part of the flame and the zone used for analytical
spectroscopy. No new reactants are added so that thermal equilibrium is rapidly stabilised
(e.g. through recombination of radicals and dissociation of unstable reaction products).
This zone may be several millimetres long because the hot gases expand after the initial
combustion. The inter-conal zone is characterised by low luminescence and low noise.
When N2O is used as the oxidant it has a characteristic red colour due to the emission of
the CN• radical

- Secondary reaction zone :- the major region of the flame where air diffuses in and the
final products are formed, e.g. CO + 1/2O2 → CO2 + hν. The characteristic blue colours
arise from hydrocarbons.

Factors Affecting Atomisation Efficiency

(i) Temperature affect on the dissociation equilibrium (M-X)n M + X (n=1 - 10)

As the temperature increases, the equilibrium is shifted to the right.

(ii) Chemical environment in the flame effect on the dissociation equilibrium.

M-O M+O

An oxidising flame (fuel lean) pushes the equilibrium to the left, while a reducing flame
(fuel rich) pushes it to the right.

Application of Different Flame Types

Air/C2H2

This is the most widely used type of flame. It is appropriate for a wide range of non-
refactory elements which do not have a high affinity to oxygen. i.e. Mg, Cu, Zn, Cd.

N2O/C2H2

This is a very high temperature flame. The inner conal zone is red (the red feather)
because of the CN• emission. CN• is an efficient scavenger of oxygen. It is appropriate
for the involatile elements and those having an affinity for oxygen, i.e. Al, B, Ba, Mo, Si,
Ti.

Air/H2

This is a low temperature, low ultra-violet absorption, low quenching flame. The
applications are for As, Se, hydride atomisation and AFS.

Interferences in Flame Atomic Absorption

Spectral Interference

This includes the overlap of an atomic absorption line of a matrix element with the
analyte. There are only 29 cases known and they are only significant at high matrix
levels. e.g. Cu on Eu and Si on V. Another possibility is the overlap of an emission line
on the matrix with the atomic absorption line of the element. e.g. Fe on Se in ETA-AAS.
The final possibility is the uncorrected background absorption.

Physical Interference

This is a variation in the physical properties, e.g. viscosity, surface tension, between the
samples and the standards, leading to changes in nebulisation efficiency. Therefore the
samples and standards need to be matrix matched, e.g. in acid content.

NB. The samples and standards should be at the same temperature.

Ionisation Interferences

These are caused by differing levels of low ionisation potential elements, e.g. Na, K, Al
between the samples and the standards. This affects the position of the ionisation
equilibrium:-

M M+ + e-

It also affects low ionisation potential elements which are significantly ionised in the
flame. Therefore excess ionisation suppresser (buffer) is added, i.e. an element of low
ionisation potential, e.g. 1000-5000µg ml-1 of Na or K, to the samples and the standards.

Chemical Interference

(i) Due to the presence in the samples of chemical species which combine in the gas
phase with the analyte to form thermally stable compounds which are not readily
atomised.
e.g. Ca + PO43- → calcium pyrophosphate

e.g. Ca + Al → Ca(AlO2)2 (calcium aluminate)

NB. A non-linear interference curve with a pronounced “knee” is characteristic of a
chemical interference which involves a reaction stoichiometry. A linear interference
curve is characteristic of a non-specific matrix interference.

(ii) Due to the presence in the samples of species which combine with the analyte to give
more volatile compounds, e.g. F- with refactory elements such as Si, Ti; EDTA with Cu;
8-hydroxyquinoline with Al or Cr.

(iii) Due to the presence in the samples of refactory elements, e.g. Zr, U - rare earth
elements which are not significantly atomised and can acclude the analyte into the matrix
particles of clotlets.

NB. The interference curve tends to be approximately linear without the “knee”. To
remove such interference smaller particles need to be generated and the flame needs to be
hotter.

(iv) Due to the acclusion of the analyte into a more volatile matrix, e.g. NH4Cl sublimes
explosively and therefore increases the atomisation efficiency. Interferences can be
removed by matrix matching all samples and standards with NH4Cl.

Methods of Overcoming Chemical Interferences

These include the use of a hotter flame. Ca/PO43-; Co/Al interferences are eliminated in
N2O2/C2H2 flames. Also the use of a releasing agent, e.g. La, Sr at 1000-2500ppm. These
have a high affinity for bonding with oxygen or oxo-anions and therefore preferentially
combine with the interferrants. You can use a protective agent, e.g. a chelating complex,
which preferentially complexes the analyte and prevents the formation of the thermally
stable compound, e.g. EDTA complexes Ca and reduces PO43- interferences. The
atomisation species is Ca(EDTA). The nebuliser uptake rate can be reduced so that
smaller particles are produced.

Electrothermal Atomic Absorption Spectroscopy (ETA-AAS)

Dimensions, L=30mm, I.D. = 5mm

Material : Pyrolytically coated electro-graphite or totally pyrolytic graphite (TPC).

Mode of Operation

Furnace Programme:

(1) Drying Stage

T ≈ 105-115°C for 30-40 secs (20µl sample)

If T is too high, sample is “splattered” away from the deposition point.

Ramp heating is preferred for high organic matrix samples, e.g. blood, high sugar
samples, e.g. fruit juice, to avoid spitting and frothing during drying which leads to poor
precision.
Organic solvents tend to “wet” the tube and run over surface, and also soak into the tube,
so use half the usual amount.

(2) Ashing Stage

Purpose of this stage is to remove as much of the sample matrix and possible and to leave
the analyte in a form which yields the higher atomisation efficiency and produces
reproducible signals.

e.g. removal of organic matter which gives a dense pyrolysis smoke which would
“interfere” with, and produces “noisy” atomic absorption.

Generally, the analyte is preferred in a thermally stable form so that ashing temperature
can be as high as possible.

Therefore, prefer HNO3 over HCl as the MO oxide form is stable whereas the MCl
chloride form is volatile,e.g. Al, Fe, Ni, As, Ca, Pb.

Can use a matrix modifier, e.g. Pd to convert a volatile analyte, e.g. As, Se, Cd, Pb, to a
more stable form.

Optimisation of Ashing Temperature:

Ashing programme - start at 150°C → 500-1200°C and hold for 30 seconds.

- ramp rate, if used, 50°C s-1 for controlled pyrolysis of organic
matter.
(2a) Cool Down Stage

It has been shown that heating rate is proportional to temperature rise, ∴ pre-cooling
enables dT/dt to be increased which gives sharper peaks and less tailing for involatile
elements.

(3) Atomisation Stage

The purpose of this stage is to atomise the sample as rapidly as possible to produce sharp,
reproducible absorption.

Peak height or peak area can be measured.

Atomisation programme - start at ashing temperature

- 1500-2900°C for 5 seconds.
Ramp mode is not used because sharp peaks are required.

(4) Cleaning Stage

Purpose : to remove residual analyte, e.g. carbide forming elements, e.g. Mo, V, Ta, and
residual matrix before next sample - “memory effects” cause interference.

Background Correction

Background correction is required to correct for the affects of molecular absorption (and
scattering) on the atomic absorption lines, which otherwise leads to a positive error in the
calculation of the concentration.

It is applied to both flame and ETA- AAS, but is more important in the latter and
technically more difficult because of the differing time varying nature of the atomic and
molecular signals.

The Effect of Simultaneous Atomic and Molecular Absorption

( a trivial example)

Consider two set of absorbing material, each of length L, but having different absorption
coefficients k (m-1). Let the ratio of the transmitted to incident power be 0.8 and 0.6 for
slabs (a) and (b) respectively.

A(a) = -log 0.8 = 0.0969

A(b) = -log 0.6 = 0.228
A(a+b) = - log (0.8 x 0.6) = 0.3187

NB. 1. The order of blocks (a) and (b) does not matter.
2. Whether (a) or (b) is atomic or molecular absorption does not matter.

What about mixing blocks (a) and (b) so that absorption occurs simultaneously ?

Firstly, divide blocks (a) and (b) into 2 slabs, i.e. (a1), (a2), (b1) and (b2). Then order them
(a1)(b1)(b2)(a1). Because A = kL, halving L halves A, but the transmission changes as
 1 I kL
log 0 =
2 I 2

!I 2
log " 0 #$ =
kL
I 2

1
! I #2 kL
log % & = -
" I0 $ 2

I I
i.e. if = 0.8 for slab (a), then = 0.89 (i.e. 0.8 ) for (a1) and (a2).
I0 I0

i.e.

A(a1) = - log(0.89) = 0.0506

A(b1) = - log(0.77) = 0.1135
A(b2) = - log(0.77) = 0.1135
A(a1) = - log(0.46) = 0.0506

A(a1+b1+b2+a2) = 0.3282

This argument can be extended by considering an infinite number of slabs each of

thickness dl, used in any order. Therefore it is concluded that simultaneous absorption of
1 wavelength by independent absorbers can be quantified by adding the absorbances of
the individual components.

e.g. as in simultaneous detection of two components in spectrophotometry.

NB. If two lines of differing wavelength are being simultaneously absorbed, the
absorbances are not additive.

Background Correction Techniques

Continuum Sources Background Correction

Principle:

For the D2 hollow cathode lamp the measured absorption Am hasn’t changed as the
atomic absorption is over a small bandwidth so only a small percentage is absorbed. The
D2 HCL measures only molecular absorption. In practice the HCL and the D2HCL are
pulsed alternatively.
For transient ETA signals, the pulsing frequency must be high enough to effect correction
is a time short compared with significant changes in the signal.
e.g. for a 0.4s signal, the pulsing frequency should be >50Hz, usually 200Hz.

Limitations of Continuous Source Background Correction

(1) Limited range of background correction, <1A.

(2) Inaccurate with structured background because it measures the average absorption
in the spectral bandpass, not specifically what’s under the line.
(3) Requires an additional light source which should be of approximately the same
intensity as the hollow cathode lamp. It is different in the UV region.
(4) Alignment of light sources is critical, particularly in ETA-AAS because both
beams must sample the same atomic population.