COURSE LEARNING OUTCOME

No. Outcomes

1 Explain the basic knowledge of data handling & processing of analytical data

2 Describe the basic knowledge of analytical chemistry related chemical quantification of various materials.

3 Perform the analytical chemistry laboratory practical & communicate the findings

4 Discuss the various factors that determine the choice of analytical method for an analysis of sample.
Spectroscopy Based on
Absorption
(Atomic Absorption
Spectroscopy)
ChM Dr. Saiful ‘Arifin Shafiee

2021
 Instrumentation

Emits the
atomic
emission line
of interest
 Instrumentation

Emits the
atomic
emission line
of interest
 Type of AAS Instrumentation

Line Source AAS (LS-AAS) Continuum source AAS (CS-AAS)

• Equipped with very high power water

• Uses a sharp line source
cooled Xenon lamp operated in a hot-
spot mode, a very high resolution
• The source emits the lines of the
double monochromator, and a charge-
element to be measured
coupled device (CCD) array detector
• These sharp line sources possess the
• Usually used for background correction,
precise energies required for absorption
to eliminate sample matrix interference,
by the analyte atoms
ULTRAVIOLET/VISIBLE
only measure the analyte’s signal
• Hollow cathode lamp & electrodeless
discharge lamp
SPECTROSCOPY
 Light Sources of LS-AAS – Hollow Cathode Lamp Ne @ Ar (if
Ne lines
interfere)
• A high voltage is applied across the electrodes, causing the
gas atoms to be ionized at the anode (Ne → Ne+ + e-)

• The positive ions (Ne+) are accelerated toward the negative

cathode

• The ions bombard the cathode

• Some of the metal will sputter & become vaporised and

become excited to higher electronic levels by continued
collision with the high energy gas ions

• When the excited electrons in the metal return to ground

state, the characteristic lines of that metal is emitted.

• Filler gas lines are also emitted

 Light Sources of LS-AAS – Electrodeless Discharge Lamp (EDL)
• Contains a small quantity of the analyte (own element or iodide salt form)

• The bulb is filled with inert gas (Ar) at low pressure & is surrounded by radio frequency coil

• The coil is powered to generate an intense electromagnetic field → inductively coupled discharge → characteristic
lines emission of the elements

• More intense source than a HCL & often has a narrower line width

• This lamp is usually used for more volatile elements such as As, Bi, Cd, Cs, Ge, Hg, P, Pb, Rb, Sb, Se, Sn, Te, Tl, & Zn

• Benefits: Increased sensitivity

 Light Sources of CS-AAS

• High power (300 W) high pressure (17 bar at room temp.)

short-arc (electrode distance < 1 mm) Xe lamp made with
special electrode materials that can be operated in “hot-
spot mode”

• Hot-spot mode: characterised by the appearance of an

extremely small plasma spot close to the cathode surface

• Can be operated continuously instead of pulsed mode.

 Instrumentation

Double beam
arrangement

Mirror-equipped chopper
alternately directs the
beam through the flame
& bypassing it;
compensating for any
source drift
 Instrumentation

• The sample solution is aspirated into the flame

• The analyte is converted into atomic vapour

• The flame contains atoms of that element

• Some are thermally excited by the flame but most remain in ground state

• The ground state atoms can absorb radiation emitted by the source (hollow
cathode lamp) which is composed of the element of interest.
 Analyte Atom Sources

Flame Atomization

• Air-C2H2 (2250 ⁰C) or N2O-C2H2 (2960 ⁰C ) – 30 elements that tend to form heat-stable oxides. E.g.:
hafnium oxide/yttrium oxide

• Air-propane flames are not hot enough for general use in AAS because most elements are not efficiently
atomized

• Not suitable to monitor absorption < 200 nm because HC fuelled flame will absorb ~>50% of radiation

• Most convenient & reproducible

• Not efficient to convert all analyte into atomic vapour & have it present in the optical path for long enough
to measure absorption
 Premix burner @ laminar flow burner

• Droplet size: 0.05 nL

• The smaller the droplets, they atomize

much easier

• Three slotted burner head provides a

wide flame; can accommodate the widest
probe beam cross section.

• Three slotted burner is quieter & clog less

easily with samples
 Flame - requirement

1) Should give SUFFICIENT ENERGY for the sample to be atomized

2) The flame should be NONTURBULENT so that atom population shows the least spatiotemporal
variation

3) Should be able to OPERATE AT LOW GAS VELOCITIES so the emitting atoms remain in the flame
for prolonged time

4) SAFE

5) INEXPENSIVE
 Analyte Atom Sources
Electrothermal Atomization
• Aliquot of sample (a few μL) is put in a “mini furnace” (< 1 cm3)

• The furnace is made of an electrically conductive material

• Graphite furnace is commonly used

• Furnace is rapidly electrically heated (100 A & 1000 ⁰C/s are common) to a very high temp. to produce
an atomic vapour cloud

• Conversion efficiencies approaching 100%, LODs are often 100 – 1000 time improved over those flame
atomization

• Better suited when the conc. of analyte is sufficiently high, reproducible, possible to analyze samples
directly.

• Calibration needs more care

 Analyte Atom Sources
Cold Vapor & Hydride Generation for Atomization

• Utilize reducing agents

• SnCl2 & NaBH4 are used as reducing agents

• Allow the measurement of Hg

• NaBH4 also generates the hydrides of As, Bi,

Ge, Pb, Sb, S, Se, Sn, Te, In, & Tl as the
gases.

• These can be easily decomposed using flame,

hot quartz measurement cell, or graphite
furnace

• Matrix isolation (analyte totally isolated as

vapor from original sample matrix)
 Sample preparation

• Sample preparation can often be kept to a min.

• As long as no chemical/spectral interferences, only need to obtain sample in the

form of a diluted solution

• filtered to be free from particles

 Beer’s law

• The absorption follows Beer’s law

• A = εbc

b = pathlength in the flame

Difficult to determine
c = conc. of atomic vapour in the flame

However:

1) pathlength is held constant in a given burner & flame condition ULTRAVIOLET/VISIBLE

2) SPECTROSCOPY
Conc. of atomic vapour is directly proportional to the conc. of analyte in the solution being aspirated

• One calibrate the instrument response by aspirating standard samples of different conc.
 Interaction Btw Electromagnetic Radiation & Matter

• Spectrometry is based on the absorption of photons by the analyte

• The sample solution absorbs electromagnetic radiation from the source

• The amount of the sample is related to the concentration of the analyte in the solution

• ↑ conc. of analyte, ↑ absorbance, ↓ transmittance


AAS Ionization Interferences
• An appreciable amount of
alkali & alkaline earth elements
& a few other elements may be
ionized in very hot flame
• When measure unionized
atoms → signals will be
decreased
• Add large amounts of
interfering, easily ionizable,
element to both samples & stds
to make enhancement const. &
ionization minimal
• Sign: Cal curve have upward
deviation/curvature upward
Interferences in AAS
Refractory Compound Physical
Formation interferences
• Sample may contain constituents
• Most parameters that
that form a heat-stable cmpd with
affect the rate of sample
the analyte element of interest.
uptake in the burner & the
atomization efficiency
• E.g.: Ca + P → Ca2P2O7 (Ca
pyrophosphate – not easily
• E.g.: gas flow rate,
broken down to atoms at flame
variation in sample
temps.)
viscosity because of
temp./solvent variation,
• Solution: Addition of a chemical
changes in the flame
competitor/use of high temp.
temp.
• E.g.: high conc. (1%) strontium
chloride @ lanthanum nitrate can
be added to solution
• E.g.: N2O-C2H2 flame
 Internal Std
Signals can frequently vary with time

Fluctuations in gas flow rates Aspiration rates

• Precisions can be improved using internal stds

• Measurement of the ratio of the analyte to internal std signals cancels the interferences

• The internal stds should ideally be chemically similar to the analyte element & their
wavelengths should not be too different.

• E.g.: measurement of Na & K in serum. This accuracy can be improved by adding fixed
conc. of Li to all stds & samples and interpreting the data in terms of the ratios of the
K/Li & Na/Li signals
 Std Addition Calibration

• The signals can be suppressed or enhanced by sample matrix due to physical/chemical

reasons arise from a mismatch of the sample matrix & the stds used for calibration.

Signals can frequently vary with samples matrix

Viscosity Combustible content

Sample viscosity > Std viscosity → Sample contains combustible organic
aspiration rate will not be the same solvent → different effective temp. in the
flame compared to aqueous samples

• Std addition can be used to minimize the errors coming from the sample matrix
 Application

• Metal analysis in biological fluids & tissues

• Metal analysis in environmental samples such as air and water

• Determining K, Ca, Mg, P, Zn, Cu, Ni, Fe, Co, & heavy metals (Pb & Cd) in food (seeds, pulp, & skin
of pumpkins
 Limitation

• Cannot do multiple elements at once – Line Source AAS

• A separate lamp for each element is required (cost) – Hollow Cathode Lamps

• Relatively large sample quantities required (1 – 2 mL) - Flame atomizer