Atomic absorption/ emission

spectroscopies
 Fundamentals
 The population of different states is
given by the Boltzmann equation:
 ΔE
N1 g1
 e kT
N0 g0
N0: number of atoms in ground state
N1: number of atoms in excited state
g1/g0 : weighting factors

Note: Equation contains temperature:

Excitation can be achieved by providing thermal
energy 2
Define the following terms:
(a) releasing agent
(b) protective agent.
(c) Ionization suppressor
(d) atomization
(e) pressure broadening
(f) hollow cathode lamp
(g) sputtering
(h) self· absorption
(i) spectral interference
(j) chemical interference
(k) radiation buffer
(L) Doppler broadening
3
 Atomic emission:
Flame spectroscopy
Observation Caused by...
Persistent golden- Sodium Lithium
yellow flame
Violet (lilac) flame Potassium,
cesium
carmine-red flame Lithium
Brick-red flame Calcium
Crimson flame Strontium Cesium

Yellowish-green flame barium,

molybdenum
Green flame Borates, copper,
thallium
Blue flame (wire Lead, arsenic,
Qualitative
slowly method
corroded) antimony, Sodium
bismuth, copper 4
 Atomic Spectroscopies - Synopsis
Techniques for determining the elemental composition of a
sample by its electromagnetic or mass spectrum

Optical Mass spectrometries

spectroscopies

Fluoresc- AAS
AES Others
ence ICP-MS SIMS
Spectros-
copy
Others ICP-OES
Flame AAS GFAAS
5
Atomic spectroscopies
 Common principles:
 Sample introduction:
Nebulisation, Evaporation
 Atomisation (and excitation or
ionisation) by flame, furnace,
or plasma
 Spectrometer components:
 Light source
 Sample
 Wavelength selctor
 Detector

6
 Atomic spectra vs molecular spectra:

 Lines Bands

(nm)

Typical atomic spectrum Two typical molecular spectra

e.g. acquired by AAS Acquired by UV-Vis spectroscopy

Y axes: intensity of absorbed light. Under ideal conditions proportional

to analyte concentration (I  c; Beer’s law).
7
Origin of bands in molecular spectra
 Molecules have chemical bonds
 Electrons are in molecular orbitals

 Absorption of light causes electron transitions

between HOMO and LUMO
 Molecules undergo bond rotations and
vibrations: different energy sub-states
occupied and accessible through absorption:
many transitions possible:
A band is the sum of many lines

LUMO
Vibrational substates rotational substates

HOMO
8
 Instrument components
AAS Spectrometer

Read-
Light Monochro-
Sample Detector out/Data
Source mator
system

ICP-OES Spectrometer

Sample = Read-
Monochro-
light Detector out/Data
mator
source system

UV-Vis Spectrometer:

Read-
Light Monochro-
Sample Detector out/Data
Source mator
system

9
 Light sources

Wavelength(nm) 100 200 400 700 2000 4000 7000 10,000 20,000 40,000

VAC UV Visible Near IR IR Far IR

Spectral region

Ar lamp
Xe lamp
Continuum

D2 lamp
Tungsten lamp
Nernst glower (ZrO2 + Y2O3)
Nichrome wire

Globar (SiC)
Line

Hollow cathode lamps

Lasers
10
 Example of a continuum source:
Output from Tungsten lamp

Widely applied in UV-Vis spectrometers 11

 Hollow cathode lamp
 Used in AAS
 Filled with Ne or Ar at a pressure of 130-700 Pa (1-5
Torr).
 When high voltage is applied between anode and
cathode, filler gas becomes ionised
 Positive ions accelerated toward cathode

 Strike cathode with enough energy to "sputter" metal

atoms from the cathode
to yield cloud with
excited atoms
• Atoms emit line spectra

12
 Monochromators
 Consist of
 Entrance slit
 Collimating lens or mirror
 Dispersion element (prism or grating)
 Focusing lens or mirror
 Exit slit
 Czerny-Turner grating monochromator:
Mirrors

Common in UV-Vis spectrometers

13
 Bandwidth of a monochromator

 Spectral bandwidth: range

of wavelengths exiting the
monochromator
 Related to dispersion and
slit widths
 Defines resolution of
spectra: 2 features can only
be distinguished if effective
bandwidth is less than half
the difference between the l
of features

14
Effect of slit width on peak heights

15
 Detectors

Wavelength(nm) 100 200 400 700 2000 4000 7000 10,000 20,000 40,000

VAC UV Visible Near IR IR Far IR

Spectral region

Photographic plate
Photomultiplier
Phototube
Photon
Photocell
detectors
Silicon diode
Charge-coupled device (170-1000)
Photoconductor
Thermal Thermocouple
detectors Golay pneumatic cell
Pyroelectric cell

16
 Photomultiplier: detects one
wavelength at a time
 Based on photoelectric
effect
 Photocathode and
series of dynodes in an
evacuated glass
enclosure

 Photons strike cathode and electrons are emitted

 Electrons are accelerated towards a series of dynodes
by increasing voltages
 Additional electrons are generated at each dynode
 Amplified signal is finally collected and measured at
anode
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 Photodiode arrays: measure several
wavelengths at once

 linear array of discrete photodiodes on an integrated

circuit (IC) chip
 Photodiode: Consists of 2 semiconductors (n-type and
p-type)
 Light promotes electrons into conducting band: generates
electron-hole pair
 “Concentration” of these electron-hole pairs directly
proportional to incident light
 a voltage bias is present and the concentration of light-
induced electron-hole pairs determines the current through
semiconductor 18
AAS and ICP-OES

Sample preparation
Interferences
Calibration

19
 Crucial steps in atomic spectroscopies
and other methods
Laser ablation etc.

Solid/liquid Nebulisation Molecules in

Solution
sample Desolvation gas phase
Sample M+ X-
preparation Vaporisation MX(g)

M(g) + X(g) Atomisation=

Atoms in gas Dissociation
phase
Sputtering, etc.

M+ Excitation
Ionisation
Ions
Excited
 ICP-MS and Atoms
other MS methods
 AAS and AES,
X-ray methods
Adapted from www.spectroscopynow.com (Gary Hieftje) 20
Sample Introduction: liquid samples
 Often the largest source of noise
 Sample is carried into flame or plasma as aerosol,
vapour or fine powder
 Liquid samples introduced using nebuliser

21
Sample preparation for analysis in
solution: Digestion

 Digestion in conc. HNO3 and mixtures

thereof (e.g. aqua regia)
 Br2 or H2O2 can be added to conc. acids
to give a more oxidising medium and
increase solubility
 Certain materials require digestion in
conc. HF
 Common to use microwave digestion

22
 Microwave digestion

Rotor

Supplied with dedicated vessels

Closed vessel digestion minimises sample contamination
Faster, more reproducible, and safer than conventional
23
methods
 Sample preparation and sample
handling for trace analysis
 As always – sample preparation is key
 Ultra-trace: Contaminations introduced during
sample processing can seriously limit performance
characteristics
 Points to consider:
 Purity of reagents
 Chemical inertness of reaction vessels and any other material
samples come into contact with
 Working environment
 Preparation of standards and blanks crucial
 Also measure a “process blank”:
 Important for determination of LOD and LOQ

24
Atomic absorption
spectroscopy

25
 Atomic Absorption Spectroscopy
 Flame AAS has been the most widely used of all atomic
methods due to its simplicity, effectiveness and low cost
 First introduced in 1955, commercially available since
1959
 Qualitative and quantitative analysis of >70 elements
 Quantitative: Can detect ppm, ppb or even less

 Rapid, convenient, selective, inexpensive

H He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mb Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac
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Flame AA Spectrometer
Hollow cathode lamps with
characteristic emissions

Burner

Flame fuelled by (e.g.)

acetylene and air

Nebuliser and Hollow cathode lamps available for over 70 elements

Spray chamber Can get lamps containing > 1 element for determination
of multiple species
27
 Schematic

I0 It
Light Source Monochromator Detector Amplifier

E.g. Hollow
Fuel (e.g. acetylene)
cathode lamp Atomiser Air

Analyte solution Nebuliser, spray

chamber, and
burner
28
 Flame atomisation:
Laminar flow burner - components
 Nebuliser: converts sample solution into aerosol
 Spray chamber: Aerosol mixed with fuel, oxidant and burned in
5-10 cm flame
 Fuel: Acetylene or nitrous oxide
 Oxidant: Air or oxygen
 Burner head:
Laminar flow: quiet
flame and long path-
length
 But: poor sensitivity
(not very efficient
method, most of
sample lost)

29
from: Skoog
 Structure of a flame

 Relative size of
regions varies with
fuel, oxidant and
their ratio

30
 Electrothermal atomisation: GFAAS
 Provides enhanced sensitivity
 entire sample atomised in very
short time
 atoms in optical path for a second
or more

 Device: Graphite furnace

31
 Sensitivity and detection limits in
AAS
 Sensitivity: number of ppm of an element to give 1%
absorption.
 Limit of detection: dependent upon signal:noise ratio:

S/N   Light intensity reaching detector

S/N=3.2

32
 Interferences in AAS
 Broadening of a spectral line, which can occur due to
a number of factors (Physical)
 Spectral: emission line of another element or
compound, or general background radiation from the
flame, solvent, or analytical sample
 Background correction can be applied
 Chemical: Formation of compounds that do not
dissociate in the flame
 Ionisation of the analyte can reduce the signal
 Matrix interferences due to differences between
surface tension and viscosity of test solutions and
standards

Another caveat: Non-linear response common in AAS

33
 Physical interferences:
Atomic line widths/ line shapes
 Very important in atomic spectroscopy
 Narrow lines increase precision, decrease
spectral interferences
 Lines are broadened
by several mechanisms:
 Natural broadening
 Doppler effect
 Pressure broadening

Figure taken from

http://www.cem.msu.edu/~cem333/
Week03.pdf 34
 Natural linewidths

 Width of an atomic spectral line is

determined by the lifetime of the excited
state

 For example, lifetime of 10-8 seconds (10

ns) yields peak widths of 10-5 nm

35
 Doppler Effect
Photon detector

 Due to rapid motion of atoms in gas phase

 Atom moving toward the detector absorbs / emits radiation
of shorter l than atom moving perpendicular to detector.
 Atom moving away from the detector absorbs / emits
radiation of longer l: detector perceives fewer oscillations

36
 Pressure broadening
 Results from collisions of absorbing/emitting species
 With analyte atoms or combustion products of fuel
 Deactivates the excited state – shorter lifetime - broader
spectral lines
 Increases with concentration and temperature
 E.g. in flame, Na absorbance lines broadened up to 10-3 nm.

 Doppler and pressure effects broaden atomic lines by

1-2 orders of magnitude as compared with their
natural linewidths

37
 Background correction in AAS
 High energy Deuterium background corrector

Detector

Hollow
cathode Beam
lamp combiner

Lamps are
Sample
pulsed out of
phase with Deuterium lamp

each other
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 Minimising the effect of
Matrix Interferences
 The term "matrix" refers to the sum of all compositional
characteristics of a solution, including its acid
composition
 Calibration standards
and samples must be
matrix-matched in
terms of composition,
total dissolved solids,
and acid concentration
of the solution
 Also advisable for
ICP-OES and -MS

Effect on K concentration on measured Sr

39
 Specialised applications in AAS:
Flameless cold vapour methods

 Hydride generation technique for determination

of As, Sb, Bi, Se, Te, Ge, Pb, and Sn
 Generation of volatile metal hydrides (As, Sb, Bi, Se, Te,
Ge, Pb, and Sn)
 Reduction by NaBH4 to form volatile hydride (e.g. SnH4)
 Hydrides carried into light path by argon gas
 Decomposed into elemental vapour by injection into
(electrothermally) heated silica cell

40
Calibration – some practical
aspects

41
 Calibration in AAS
 In theory, Beer’s law applies
for dilute solutions
 In practice, deviation from
linearity is usual
Small dynamic range
Possible to use non-linear
curve fitting for calibration
 Reasons: Self-absorption:
 excited atoms emit light that
can also be absorbed instead of
that of source:  on average, Linear range
less light per number of atoms
is absorbed

42
 Alternative to matrix-matching:
Method of standard additions
 Extensively used in absorption
spectroscopy, accounts for matrix effects
 Several aliquots of sample
 Sample (1): diluted to volume directly
 Samples (2,3,4,5…): known amounts of analyte
added before dilution to volume
 BUT: Only makes sense if the added
standard closely matches the analyte
present in the samples chemically and
physically
  if simple, dissolved ions are analysed
43
 Method of standard additions
 If linear relationship exists between measured quantity and
concentration (must be verified experimentally) then:

kVx c x kVs cs
AT  
VT VT

 Vx, Cx: volume and concentration of analyte

 Vs: variable volume of added standard
 Cs: concentration of added standard
 VT: total volume of volumetric flask
 k: proportionality constant (= єl)
 Ax, AT: absorbances of standard alone and sample + standard addition,
respectively.
44
 Method of standard additions
Graphical slope = m = (єlcs) / VT
evaluation

intercept = b = (єlVxcx) / VT

Limitations
• The calibration graph must be substantially linear since accurate
regression cannot be obtained from non-linear calibration points.
• Caution: The fact that the measured part of the graph is linear does not
always mean that linear extrapolation will produce the correct results
• It is also essential to obtain an accurate baseline from a suitable reagent
blank
45
 Most simple version of standard
addition: spiking
 Spiking means deliberately adding analyte to
an unknown sample
 Involves:
 preparation of sample and measurement of
absorbance
 Addition of standard with known concentration,
measurement of absorbance
 From difference in absorbance, calculate e
 From reading of sample alone, calculate amount
of analyte
 (use Beer’s law for calculations)
46
 Other uses for spiking
 Add spike at beginning of sample
preparation
 Process sample with and without spike
 Difference should correspond to amount
spiked
 Deviation allows to calculate recovery
factor

47
Atomic emission
spectroscopy

48
 Atomic emission spectroscopy
 Historically, many techniques based on
emission have been used (See Table on p. 4)
 Flame and electrothermal methods now
widely superseded by Inductively-Coupled
Plasma (ICP) method
 Developed in the 1970s
 Higher energy sources than flame or
electrothermal methods

49
 ICP-AES/OES
Inductively coupled plasma-atomic emission spectroscopy
(or optical emission spectroscopy)

 Offer several advantages over flame/electrothermal:

 Lower inter-element interference (higher temperatures)
 With a single set of conditions signals for dozens of
elements can be recorded simultaneously
 Lower LOD for elements resistant to decomposition
 Permit determination of non-metals (Cl, Br, I, S)
 Can analyse concentration ranges over several decades (vs 1
or 2 decades for other methods)
 Disadvantages:
 More complicated and expensive to run
 Require higher degree of operator skill

50
 Modern ICP-OES spectrometer

 Over 70 elements (in principle simultaneously)

 Including non-metals such as sulfur, phosphorus,
and halogens (not possible with AAS)
 ppm to ppb range
 Principle: Argon plasma generates excited atoms
and ions; these emit characteristic radiation
51
ICP-AES Instrumentation

52
Components for sample injection
and the ICP torch

Up to 7000°C

53
 Atomisation / Ionisation

 In plasma, sample moves through several zones

 Preheating zone (PHZ): temp = 8000 K:
Desolvation/evaporation
 Initial radiation zone (IRZ): 6500-7500 K: Vaporisation,
Atomisation
 Normal analytical zone (NAZ): 6000-6500 K: Ionisation

54
 Advantages of plasma
 Prior to observation, atoms spend ~ 2 sec at
4000-8000 K (about 2-3 times that of hottest
combustion flame)
 Atomisation and ionisation is more complete
 Fewer chemical interferences
 Chemically inert environment for atomisation
 Prevents side-product (e.g. oxide) formation
 Temperature cross-section is uniform (no cool
spots)
 Prevents self-absorption
 Get linear calibration curves over several orders of
magnitude

55
 Applications
 ICP-OES used for quantitative analysis of:
 Soil, sediment, rocks, minerals, air
 Geochemistry
 Mineralogy
 Agriculture
 Forestry
 Fornensics
 Environmental sciences
 Food industry

 Elements not accessible using AAS

 Sulfur, Boron, Phosphorus, Titanium, and Zirconium

56
Lab Experiment 3
 Analyse a Chromium complex for [Cr] in three ways:
 UV (absorbance & extinction coefficient)
 Titration (moles Cr and charge)
 AAS (Cr standard curve and unknown concentration)

 AAS data analysis

 Fit standards to quadratic equation
 A=a[Cr]2 + b[Cr] + c
 Use a, b, and c to calculate unknown concentration

57