Professional Documents
Culture Documents
Introductions
Properties of electromagnetic radiations
Interactions of electromagnetic radiations with matters
Principle in obtaining chemical information from optical spectroscopy
2. Components of Optical Instruments
3. UV/Vis Spectroscopy
Basic Principles in detection, instrumentations, Applications
4. Luminescence Spectroscopy
Basic Principles in detection, instrumentations, Applications
5. Infrared Spectroscopy
Basic Principles in detection, instrumentations, Applications
6. Near Infrared Spectroscopy
Basic Principles in detection, instrumentations, Applications
7. Raman Spectroscopy
Basic Principles in detection, instrumentations, Applications
8. Spectroscopy for Surface Analysis
Basic Principles in detection, instrumentations, Applications
9. Nuclear Magnetic Resonance Spectroscopy
Basic Principles in detection, instrumentations, Applications
10. Atomic Spectroscopy
Basic Principles in detection, instrumentations, Applications
50%
: 50%
: 20%
Chapter 1:
An Introduction to Spectrochemical Analysis
Optical Spectroscopy:
Any means to obtain chemical information by examination of
the variation of the properties of electromagnetic radiation
excited or emitted from matters.
Any forms of the energy can be used to induce the variation of
the properties of electromagnetic radiation, i.e. thermal energy,
particles, electrons, electromagnetic radiations.
time
A: amplitude; : wavelength
v :frequency = c/
c :speed of radiation
in vacuum, 3x108 m/s
3E10
1021
3E8
1019
3E6
1017
x-ray
1015
Visible
-ray
10-13
3E4
Ultraviolet
10-11
10-9
10-7
3E2
1013
3E0
1011
3E-2
3E-4
109
107
Wavenumber (cm-1)
Frequency (Hz)
101
Wavelength (m)
Microwave
Radio
Infrared
10-5
10-3
10-1
X-ray Photo
The UV Camera/Spectrograph
deployed and left on the Moon
by the crew of Apollo 16 took
this picture. The part of the
Earth facing the Sun reflects
much UV light. Even more
interesting is the side facing
away from the Sun. Here,
bands of UV emission are also
apparent. These bands are the
result of aurora caused by
charged particles given off by
the Sun. They spiral towards
the Earth along Earth's
magnetic field lines.
Visible
(orv )
Quantum Transition
-ray; emission
0.005-1.4
Nuclear
X-ray; absorption,
emission, fluorescence,
diffraction
0.1-100
Inner electron
10-180 nm
Bonding electron
UV/Vis; absorption,
emission, fluorescence
180-780 nm
Bonding electron
Infrared; absorption
(Raman; scattering)
Microwave; absorption
Electron Spin Resonance
(ESR); absorption
Nuclear Magnetic Resonance
(NMR); absorption
780 nm 300 m
(1.3x104 33 cm-1)
0.75 3.75 mm
3 cm
0.6 10 m
Rotation/vibration
of molecule
Rotation
Spin of electron in
a magnetic field
Spin of nuclei in
a magnetic field
Atom
..
.
2S
1S
Molecule
..
.
v2
v1
..
.
E3
..
.
v3
E2
v2
E1
..
.
R2
R1
v1
time
time
ii. Superposition
Constructive: and =
y1 = A1 sin (t + )
y2 = A2 sin (t + )
y = y1 + y2 = A1 sin (t + ) + A2 sin (t + )
y2 = A2 sin (t + )
y = y1 + y2 = A1 sin (t + ) + A2 sin (t + )
Pb = 1/v
Jean Fourier : Any periodic function can be described
by a sum of simple sine or cosine term
Slit l
n1
n2
1 = 2
at = 0o;
I r / Io = (n2 - n1)2/(n2+n1)2
v. Refraction of radiation
n1
n2
n1
Snells law:
n1sin 1 = n2 sin 2
2
1
Air
= 500 nm
v = 6.0 x 1014 Hz
Glass
= 330 nm
v = 6.0 x 1014 Hz
Air
= 500 nm
v = 6.0 x 1014 Hz
Normal dispersion
Vair = v = 3.00 x 1010 cm/s;
Vglass = v = 1.96 x 1010 cm/s
n (refractive index) C/Vglass
n
Anomalous dispersion
IR
UV
Un-polarized
radiation
time
y
Plane Polarized
Radiation
x
y
time
B. Quantum-mechanical Properties of
electromagnetic radiation: Photon or Quanta ( )
1.
Photoelectric Effect
Hertz, 1887 observation; Einstein,1905 Theory
Millikan, 1916 Theoretical conformation
photon
cathode
e-
anode
A
V
+
i.
Pi
absorbance
..
.
E3
..
.
E3
E2
E2
..
.
v2
E1
E1
v1
atom
UV/Vis)
= Eelectronic transition
molecule
(UV/Vis)
= Eelectronic transition
+ Evibrational transition
+ Erotaional transition
molecule
(IR)
= Evibrational transition
+ Erotaional transition
ii. Emission
Intensity
..
.
..
.
E3
E3
E2
E2
..
.
v2
E1
E1
v1
atom
molecule
UV/Vis)
= Eelectronic
transition
molecule
(UV/Vis)
(IR)
= Eelectronic transition
+ Evibrational transition
+ Erotaional transition
= Evibrational transition
+ Erotaional transition
Non-radiative relaxation
Excitation
fluorescence, phosphorescence
Pi
b
Transmittance, T = Pi/Po
% T = Pi/Po x 100%
Absorbance, A = - log10 T
= -log (Pi/Po)
Beers Law
A=axbxc
A=xbxc