Overview of Atomic Spectroscopy

Dr YAO Zhongping

Office: Y832
Email: [email protected]

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Outline
• Overview of spectroscopy

• Overview of atomic absorption spectroscopy and atomic

emission spectroscopy

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After the sessions, you are expected to be able to
• Describe the general principle of spectroscopy.

• Define the major descriptions of spectroscopy.

• Describe the respective equations for quantitative analysis

of absorption and emission spectroscopy.

• Identify the major processes in atomic spectroscopy.

• Identify the major sources of line broadening.

• Illustrate the effect of temperature on atomic spectra.

• Identify the major applications of atomic spectroscopy.

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References and further reading
• Skoog, D. A.; Holler, F. J. and Crouch, S. R. Principles of
Instrumental Analysis, 6th ed., Thomson Brooks/Cole, 2007.
• Cullen, M. Atomic spectroscopy in Elemental Analysis,
Blackwell Publishing/CRC Press, 2004.

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Spectroscopy

nobelprize.org

• Spectroscopy uses light (photons) to study the properties of

chemical species (e.g., atoms, molecules).
• The interactions of photons with the species cause the change
of photons. e.g., change in wavelength, number of photons.
• The change of photons is related to the property and quantity
of the studied species.
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Electromagnetic spectrum

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Energy of photon: E
E = hν = hc/λ = hcν
h = 6.63 × 10-34 J•s (Plank’s constant)
c = 3.00 × 108 m s-1 (Velocity of light)
ν: Frequency

: Wavelength
_
: Wave number
Unit of energy: Joule (J); eV. (1 eV = 1.60 × 10-19 J)

The higher the frequency (or the lower the wavelength),

the higher the energy.
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Radiant power: P
Energy of radiation striking a unit area per unit time

P = EФ

Ф: The photon flux

(the number of photons per unit area per unit time)

Unit of P: J m-2 s-1

Determined with a radiation detector that converts radiant energy

into electrical signals.

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Interaction of light with matter

• When a beam of light collides with a sample, the light can

be scattered, reflected, absorbed, etc.
• If energies of photons of the light exactly match the
differences between energy states of the sample
atoms/molecules, the atoms/molecules absorb energies and
transit from ground states to excited states.
• In absorption spectroscopy, the amount of light absorbed
is measured as a function of wavelength.
Qualitative and quantitative information about the sample
can be obtained from the spectra.

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Absorption of light

sample

Incident light transmitted light of

of power P0 reduced power P

2 A
excited state E2 = hc/λ2
1

E1 = hc/λ1
0
ground state λ2 λ1 λ

When a sample atom/molecule absorbs energy from the light, it

undergoes a transition from its lowest energy state (ground state) to
higher energy state (excited state).
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Transmittance

sample

Incident light transmitted light of

of power P0 reduced power P

Transmittance T = P/P0

• T = 0: total absorption
• T = 1: no absorption
• %T = 100 × T

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Transmittance and concentration
Beer’s Law
T = P/Po = e-kc (k is a constant)

Concentration

Log (P/Po ) ∝ c
Logarithm response of spectral signal to the concentration of analyte.
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Beer’s Law

A = abc
Absorbance A = – logT = log (P0/P)
• No unit
• A = 0: no absorption
• A = ∞: total absorption
a: absorptivity
b: path length
c: concentration
Absorbance is directly proportional to concentration.
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Emission of radiation

sample Emitted light

Thermal, electrical
or chemical energy

2 P
excited state E21 = hc/λ21
1
E2 = hc/λ2
E1 = hc/λ1
ground state 0 λ2 λ1 λ21 λ

Atoms/molecules at excited states (typically stimulated by heat, electrical

energy or chemical reaction) relax to lower energy states by giving up
excess energy as photons.
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Emission spectroscopy
• Emission spectrum is a plot of the power of the emitted
radiation as a function of wavelength.
• The emitted wavelengths are characteristic to analyte and
provide information about its identity.
• The power of the emitted radiation provides quantitative
information for determination of the concentration of
analyte.
P∝c

Linear response of spectral signal to the concentration of analyte.

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Atomic spectroscopy

• Typically includes atomic absorption spectroscopy (AAS) and

atomic emission spectroscopy (AES).
• Based on the breakdown of a sample into atoms, followed by
the measurement of the atoms’ absorption or emission of light.
• Provides information on elemental rather than molecular
compositions of samples.
• Has basic process similar to molecular spectroscopy.
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Differences from molecular spectroscopy
• Much sharper absorbance or emission bands.
No vibration levels.
• Better-defined and characteristic position of bands.
• Easy for qualitative analysis.

https://imagine.gsfc.nasa.gov/educators/lessons/xray_spectra/worksheet-specgraph2-sol.html

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Major processes in atomic spectroscopy

Atomization • Compounds in the sample are converted

to gaseous atoms.

Atomic absorption • Atomized species absorb photons from

or emission the light source or emit photons to the
surrounding.

Detection • The photons passed through the sample

or emitted from the sample are detected.

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Atomization

Basic steps:
• Nebulization
Sample solution is sprayed into fine droplets.
• Desolvation
Droplets are heated to evaporate off solvent, just leaving analyte and other
matrix compounds.
• Volatilization
Solid analyte/matrix particles are converted into gas phase.
• Dissociation
Molecules in gas phase are broken into atoms. 19
Nebulizers

Types of pneumatic nebulizers: (a) concentric tube,

(b) cross-flow, (c) fritted disk, (d) Babington. 20
Sample preparation of AAS and AES

The targeted elements need to be released from the matrix,

usually by acid digestion.

• Use of concentrated HNO3, H2SO4, HCl or their mixtures.

• Use of pressurized vessel or microwave to improve the

digest efficiency.

Handle with care!

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General principles of AAS and AES
E2

E1

E0
Absorbance Emission

• Every element has an unique electronic structure with quantized

discrete energy levels.
• Electrons at lower energy levels could absorb energy from
irradiation with that discrete energy and excite.
• The excited electrons would relax back to lower energy levels and
irradiate corresponding energy.
• Both the absorption and emission spectra of an unique element are
characteristic of that element, allowing qualitative and quantitative
analysis of the element.
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Energy level diagrams

Slight differences in
Na Mg+ energy caused by spin

• Similar pattern between atoms but different spacing.

• Spectrum of ion different from that of atom.
• As number of electrons increases, number of levels increases.
Li: 30 lines, Cs: 645 lines, Cr: 2277 lines in their emission spectra
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Spectra of atomic spectroscopy

http://faculty.sdmiramar.edu/fgarces/labmatters/instruments/aa/AAS_Instrument/AASInstruments.htm

Common spectral line (peak) widths: 1×10-3 nm

Sources of line broadening:
• Natural line widths Line-width is defined as ½

• Doppler broadening
• Pressure broadening
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Natural line widths
• The definite life-times of the transition states lead to
uncertainties in the transition times and measurement
uncertainty of the radiation frequency (the uncertainty principle).
• The lifetimes of excited states are typically 10-7 to 10-8 s,
leading to natural line widths of about 10-5 nm.
Uncertainty principal: E·t ≥ h
 ·t ≥ 1
 ½  1×10-5 nm

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Doppler broadening
• Variation of frequency of the radiation due to atom
movement.
• Increases with increase of temperature.
• Greater broadening effect than natural line widths

• Toward the detector: Creates

signal with higher frequency.

• Away from the detector:

Creates signal with lower
frequency.

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Pressure broadening

• Caused by collision between atoms/molecules which

slightly changes the energy levels

• Increases with pressure increase.

• Major cause of broadened spectral lines.

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Effect of temperature

The Boltzmann equation

Nj Pj Ej
 exp (  )
N0 P0 kT
Nj = number of atoms in the excited state
N0 = number of atoms in the ground state
Pj = statistical factor (related to the number of orbitals) for electrons in the excited state
P0 = statistical factor (related to the number of orbitals) for electrons in the ground state
Ej = energy difference between the excited state and the ground state
k = Boltzmann constant (1.38×10-23 J K-1)
T = temperature (Kelvin)

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Question: Calculate the ratio of sodium atoms in the 3p excited
states to the number in the ground state at 2500 K and 2510 K.

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Effect of temperature on atomic spectra

Higher temperature  more excited species

 more emission
 better sensitivity for AES

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Sensitivity of AAS vs. sensitivity of AES
Much more ground state atoms than excited atoms, even at
atomization temperature
 higher sensitivity of AAS (in theory)

In reality, AAS is not more sensitive than AES

A = – logT = log (P0/P) = abc
 when the concentration of sample is very low, P  P0, it is
difficult to measure such small difference accurately
Flame Emission More Sensitivity About the Flame Absorption
Sensitive Same More Sensitive

Al, Ba, Ca, Eu, Ga, Ho, Cr, Cu, Dy, Er, Gd, Ge, Ag, As, Au, B, Be, Bi,
In, K, La, Li, Lu, Na, Mn, Mo, Nb, Pd, Rh, Cd, Co, Fe, Hg, Ir, Mg,
Nd, Pr,Rb, Re, Ru, Sm, Sc, Ta, Ti, V, Y, Zr Ni, Pb, Pt, Sb, Se, Si,
Sr, Tb, Tl, Tm, W, Yb Sn, Te, Zn
bionmr.unl.edu/courses/chem421-821/lectures/421-821-chapter-8-10.ppt

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AAS vs. AES

Gas cloud

1
2

www.tcd.ie/physics/people/peter.../js_atomic/js_atomic_lecture1n2.ppt

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Applications of atomic spectroscopy
• Wide applications for qualitative and quantitative analysis of
elements in samples.
e.g., lead in water, heavy metals in seafood.
• Insensitive to chemical environment, e.g., oxidation state,
ligation state, of the elements.

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 Summary
• Spectroscopy
Uses light as a probe to study chemical species.
• Atomic spectroscopy
Spectroscopic techniques to study atoms in the samples.
• AAS and AES
 Based on the radiation absorbed by or emitted from atomized species.
 Major processes: Atomization, absorption or emission, detection.
 Logarithm vs. linear response of spectral signal to concentration of analyte.
• Sources of line broadening
Natural line widths, Doppler broadening, pressure broadening.
• Effect of temperature
The Boltzmann equation
• Applications of atomic spectroscopy
Elemental analysis. 34