Chapter-24-Introduction To Spectrochemic

11/28/2012
Chapter 24
Introduction to
spectrochemical methods
Goal of this chapter

• To learn the properties of electromagnetic
radiation.
• To learn the interactions of radiation with
substance.
• To learn fundamental spectrometric methods.
• To learn optical absorption and electron
energy transitions in atoms or molecules.
• To learn how to observe optical absorption
and light emission
Terminology
• Spectroscopy – “a general term for the science
that deals with the interactions of various types
of radiation with matter”
– we now use this general term even when
other types of energy are involved aside
from electromagnetic radiation, e.g. mass
spectroscopy
• Spectrometry - refers to “the measurement of

the intensity of radiation with a photoelectric
transducer or other type of electronic device”
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Impact of optical spectroscopy

• Optical spectroscopy impact science, medicine, industry and
effect our daily life. Followings are two examples
Spectroscopically measured
concentrations of O3 and ClO Highly sensitive near field excitation
in the stratosphere led to the fluorescence spectroscopic image
unraveling of chemistry of technology make it possible to observe
Antarctic ozone hole individual molecules, which provide
formation. powerful tools in biological study and
(Source: Harris, Quantitative disease diagnosis
Chemical Analysis, pp 407.)
Structure of atom
Electrons occupy orbitals of

different energy level in an atom
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Quantized energy structure of

electrons in matter
4p
4s 3d
3p
3s
2p
2s
Energy
1s
Electromagnetic Radiation Exhibits Wave

Properties and Particulate Properties
Light as a electromagnetic wave

Magnetic field
• Electromagnetic (EM) radiation Electric field

consists of oscillating electric
and magnetic fields – they stay
“in step”, with time.
• It is a traveling wave (it moves forward through

space like the ripples on a pond).
• All types (“colors”) of EM radiation travel at the
same speed through a vacuum
– c = speed of light = 2.99792458 x 108 ms-1 (exact)
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Parameters used to describe

electromagnetic wave
The oscillating waves have:

λ
+
1. Wavelength, λ
The distance between adjacent
Amplitude
crests (or troughs). distance
Length units (m, cm, mm, nm). 0
wave number (v ) = 1/l

(cm-1)
2. Amplitude -
The vertical distance from the
top to the bottom of a wave.
Parameters used to describe

electromagnetic wave
3. Frequency, n = The number of crests (or cycles) passing a
fixed point per unit time. Inverse time units (s-1).
1 hertz (1 Hz) = 1 s-1
4. velocity of propagation (vi) – rate of travel through

space or in a media,
dependent on composition of medium
a) vi = nli
b) maximum velocity (c) – speed of light in a
vacuum (2.99792458 x 108 ms-1)
c) slower in other media (~ 0.03% slower in air)
Question
• Draw three waves with relative

wavelengths of 1:2:4.
• Compare the frequencies of these
wavelengths.
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The
Nature of
Waves
Light as particles
• light viewed as discrete particles of energy called photons
- like other particles, light can be scattered, counted
(quantized) , etc
E1
hn Energy required of photon
to give this transition:
Eo DE = E1 - Eo
• Energy of wave/particle:
v
E = hn = hc/l = hc
h = Plank’s constant (6.63 x 10-34 J.s)
n = frequency, l = wavelength,v = wave number
note: energy is proportional to frequency and wave

number. energy is inversely proportional to wavelength.
Light as an electromagnetic wave

Wave property related calculations problems:
1. Calculate the wavenumber of an infrared radiation beam

with a wavelength of 5.00 mm
Solution:
1
v =
5.00m m 10-4 cm / m m
=2000cm-1
2. Calculate the frequency of the IR light beam in vacuum in

question 1.
Solution:
n = c/l = 3.00x108 (m/s)x106 (mm/m)/5.00 mm
=6.00x1013 s-1= 6.00x1013 Hz
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Interaction of radiation with matter

-----Photoelectric effect
• Light hits a target and electrons are released
– Ehν = EBE + EKE
• Apparatus for studying the photoelectric effect
Photoelectric Effect
For every metal there is a threshold λ to eject e-’s:
metal λ (nm) color

Cs 579 yellow
K 539 green
Na 451 blue
Li 428 violet
If λ is longer than the threshold, no e- are emitted

– a brighter light will NOT cause e- emission!
Photoelectric Effect
• Einstein used quantum principles to explain the effect:
– light is quantized and behaves like a stream of particles.
Einstein got his Nobel prize because he explained the photoelectric effect,
but not because he developed a theory of relativity.
• Imagine photons are balls hitting spheres (e-) embedded in
glue:
(# of ejected e-s)
high int. light

If the E of the incoming ball:
current
• is too low, it cannot drive out an e-.

• exceeds the strength of the glue, low int.
light
an e- is released
increasing energy
Higher intensity light = more photons = more balls
but each photon (ball) still has the same E.
Once the threshold is exceeded, more balls eject more e-.
• Photoelectric effect is the foundation of several sensitive
photodetectors widely used in optical spectroscopy.
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Light as particles
Light as particles related calculations problems:
1. Calculate the energy of an single photon with a

wavelength of 5.00 mm.
Solution:
E =hn=6.63 10-34 ( J .s) 6.00 

1013 s -1
=3.98 10-20 J
The electromagnetic spectrum

Wide Range of Types of Electromagnetic Radiation in nature.
1. Only a small fraction (350-780 nm) is visible light.
2. The complete variety of electromagnetic radiation is used throughout
spectroscopy.
3. Different energies allow monitoring of different types of interactions with matter.
A Change Between Two Discrete

Energy Levels Emits a Photon of Light
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Common Spectroscopic Methods Based on Electromagnetic Radiation

Type of Spectroscopy Usual Usual Wave number Type of Quantum
Wavelength Range, cm -1 Transition
Range
Gamma-ray emission 0.005-1.4 Å _ Nuclear
X-ray absorption, emission, 0.1-100 Å _ Inner electron

fluorescence, and diffraction
Vacuum ultraviolet absorption 10-200 nm 1x106 to 5x104 Bonding electrons
Ultraviolet visible absorption, 200 -780 nm 5x104 to 1.3x104 Bonding electrons

emission, fluorescence
Infrared absorption and 0.78-300 mm 1.3x104 to 3.3x101 Rotation/vibration of

Raman scattering molecules
Microwave absorption 0.75-3.75 13-27 Rotation of
mm molecules
Electron spin resonance 3 cm 0.33 Spin of electrons in a
magnetic field
Nuclear magnetic resonance 0.6-10 m 1.7x10-2 to 1x103 Spin of nuclei in a
magnetic field

-----Absorption spectrometry
Energy states of chemical

species and interaction with light
E = Eelectronic + Evibrational + Erotational
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Molecular processes vs. light absorption
Measurement of transmittance and

absorbance
Atomic absorption spectrum &

Molecular absorption spectrum
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-----Emission spectrometry
Emission spectrum of a brine sample

obtained with an H2-O2 flame

-----Fluorescence & phosphorescence
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-----Elastic scattering & Raman scattering
Application of radiation/matter
interaction in spectrochemical analysis
• Absorption spectrometry:
Atomic absorption spectrometry,
UV/Vis absorption spectrometry,
Near infrared (NIR) absorption spectrometry,
Infrared (IR) absorption spectrometry,
Terahertz absorption spectrometry,
microwave absorption spectrometry
11

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11/28/2012

Goal of this chapter

• Spectrometry - refers to “the measurement of

Impact of optical spectroscopy

Electrons occupy orbitals of

Quantized energy structure of

Electromagnetic Radiation Exhibits Wave

Light as a electromagnetic wave

• Electromagnetic (EM) radiation Electric field

• It is a traveling wave (it moves forward through

Parameters used to describe

The oscillating waves have:

wave number (v ) = 1/l

Parameters used to describe

4. velocity of propagation (vi) – rate of travel through

• Draw three waves with relative

note: energy is proportional to frequency and wave

Light as an electromagnetic wave

1. Calculate the wavenumber of an infrared radiation beam

2. Calculate the frequency of the IR light beam in vacuum in

Interaction of radiation with matter

metal λ (nm) color

If λ is longer than the threshold, no e- are emitted

high int. light

• is too low, it cannot drive out an e-.

1. Calculate the energy of an single photon with a

E =hn=6.63 10-34 ( J .s) 6.00 

The electromagnetic spectrum

A Change Between Two Discrete

Common Spectroscopic Methods Based on Electromagnetic Radiation

Gamma-ray emission 0.005-1.4 Å _ Nuclear

X-ray absorption, emission, 0.1-100 Å _ Inner electron

Vacuum ultraviolet absorption 10-200 nm 1x106 to 5x104 Bonding electrons

Ultraviolet visible absorption, 200 -780 nm 5x104 to 1.3x104 Bonding electrons

Infrared absorption and 0.78-300 mm 1.3x104 to 3.3x101 Rotation/vibration of

Interaction of radiation with matter

Energy states of chemical

Molecular processes vs. light absorption

Measurement of transmittance and

Atomic absorption spectrum &

Interaction of radiation with matter

Emission spectrum of a brine sample

Interaction of radiation with matter

Interaction of radiation with matter

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