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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

Interaction of radiation with matter

-----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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Interaction of radiation with matter

-----Emission spectrometry

Emission spectrum of a brine sample

obtained with an H2-O2 flame

Interaction of radiation with matter

-----Fluorescence & phosphorescence

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Interaction of radiation with matter

-----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

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