Chapter 6 Introduction To Spectros

1
Introduction to Spectroscopic methods

Spectroscopy:
Study of interaction between radiation (or other
forms of energy) and matter (a branch of
science).
Spectrometry:
Analytical methods based on atomic and
molecular spectroscopy
2
Types of Analytical
Spectroscopy
Absorption
Fluoresence and Phosphoresence
Emission (atomic with flames, arcs, sparks,
and palsmas)
Chemilumenesence and Biolumenesence
Reflection
The Electromagnetic
Spectrum
v = c / E = hv
4
Kinds of Spectroscopy
Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007
5
LIGHT
Electro-magnetic
radiation
6
Light as a Wave
7
Light as a Wave
8
Light as a Wave
Frequency = v
Velocity of propagation = v = v
Speed of light in a vacuum = c = 3.00 x 10
8
m/s
Wavenumber (reciprocal of ) = v = kv = v/v
9
Effect of the Medium on a Light Wave
Frequency remains the same.
Velocity and Wavelength change.

10
Mathematic Description of a Wave
Y = A sin(et + |)
A = Amplitude
e = angular frequency = 2tv =
tv 2
| = phase angle
Y = A sin(2tvt + |)
11
Mathematic Description of a Wave
Sine waves with different amplitudes and with a phase different of 90 degree
12
If two plane-polarized waves overlap in space, the
resulting electromagnetic disturbance is the algebraic
sum of the two waves.
Coherence: When two waves have an initial phase
difference of zero or it is constant for a long time they
are considered coherent.
Superposition of Waves
Y = A
1
sin(2tv
1
t + |
1
) + A
2
sin(2tv
2
t + |
2
) +.
Optical Interference: The interaction of two or more
light waves yielding an irradiance that is not equal to
the sum of the irradiances.
13
Optical Interference
Constructive Interference
1) Have identical frequency
2) |
2
|
1
= o = m2t
Destructive Interference
1) Have identical frequency
2) |
2
|
1
= o = (2m+1)t
Figure 3-4 Ingle and Crouch,
Spectrochemical Analysis
|
2
|
1
= 180 deg or integer
of multiple of 360 deg.
|
2
|
1
= 0, or 360 deg or
integer of multiple of 360 deg.
14
Superposition of sinusoidal wave: (a) A1 < A2, (u1 - u2) = 20, v1 = v2;
(b) A1 < A2, (u1 - u2) = 200, v1 = v2
15
Superposition of tw sinusoidal wave of different frequencies but identical
amplitudes.
Should be v
16
Diffraction: The Bending of Light as It Passes
Through an Aperture or Around a Small Object
Fraunhofer
Diffraction
Narrow Slit
Diffraction

Diffraction is a consequence
of interference
17
Eugene Hecht, Optics, Addison-Wesley, Reading, MA, 1998.
Diffraction increases as
aperture size
Diffraction of Waves in a Liquid
18
Diffraction Pattern From Multiple Slits
19
20
CF = BC sin u = n
n is an integer called order of interference
21
Coherent Radiation

Conditions for coherent of two
sources of radiation are:

1. Identical frequencies and
wavelength
2. Phase relationship remains
constant with time
22
Eugene Hecht, Optics, Addison-Wesley,
Reading, MA, 1998.
Conservation Law
o() + () + T() = 1
o() = Fraction Absorbed
() = Fraction Reflected
T() = Fraction Transmitted
What happens when light
hits a boundary between
two media?

Refraction: change in direction
of radiation as it passes from
one medium to another with
different density
Physics of Refraction
23
Refractive index (n)
the velocity (v) of EM radiation depends
on the medium through which it travels
n
i
= c/v
i
(>1).
the ratio of the velocity in vacuum over the
velocity in the medium
n depends on the frequency of the light
24
Refraction
n
1
sinu
1
= n
2
sinu
2
Snells Law
v
2
sinu1 = v
1
sinu
2
25
Refraction
26
Transmission: The Refractive Index
v
n
c
=
n is wavelength (frequency)
dependent.

In glass n increases as
decreases.
27
Dispersion and Prisms
i v
c
= q
Dispersion
The variation in refractive index of a
substance with wavelength or
frequency
28
Dispersion and Prisms
29
A ray of single-wavelength incident on a prism
u1
u2
u3
o
o: angle of deviation
Cai
2007
30
A ray of white-wavelength incident on a prism
o
R
o
B
White light
Cai
2007
31
32
Reflection of Radiation
2 1 2
2 1 2
0
) (
) (
n n
n n
I
I
r
+
=
I
0
: intensity of incident
light
I
r
: reflected intensity
For monochromatic
light hitting a flat
surface at 90
0
33
Reflection of Radiation
34
Specular reflection: Reflection of light from a
smooth surface

Diffuse reflection: Reflection of light from a rough
surface

Smooth or rough surface ???????
35
Reflection
Refraction
M
1
M
2
36 Ingle and Crouch, Spectrochemical Analysis
() at different interfaces
Reflectance is the fraction of the incident radiant energy refelcted.
37
Scattering of Radiation
Rayleigh scattering
Molecules or aggregates of molecules smaller than

Scattering by big molecules
Used for measuring particle size
Raman Scattering
Involves quntized frequency changes
The fraction of radiation transmitted at all
angles from its original path
38
Serway, Physics, 4
th
edition, 1996
39
Light as Particles
= v =
c
E
h
h
h = Planck Constant = 6.63 10
-34
Js
40
The Photoelectric Effect
Vo: Stopping voltage
(the negative voltage at
which the photocurrent
is zero)

eV
0
= hv - e

e: work needed to
remove e
-

41
Cut-off v
Current is proportional to
the intensity of the radiation
V
0
depends on the
frequency of the radiation
and the chemical
composition of the coating
V
0
depends on the chemical
composition of the coating
on the photocathode
V
0
independent of the
intensity of the radiation
42
Energy States of Chemical
Quantum theory by
Planck (1900)
Black body radiation
Atoms, ions , and
molecules exist in discrete
states
Characterized by definite
amounts of energy
Changes of state involve
absorption or emission of
energy
E1-E0 = hv = hc/
43
Interaction of Radiation and Matter
Emission and
Chemiluminescence
Process
44
Absorption
Process
45
Photoluminescence method
(Fluorescence and
phosphorescence)
46
Inelastic Scattering in
Raman Spectroscopy
47
Emission of Radiation
Douglas A. Skoog, F. James Holler and Timothy A. Nieman, Principles of
Instrumental Analysis, Saunders College Publishing, Philadelphia, 1998.
Emission
X
*
X + hv
Excitation needs energy!
Particle bombardment (e-)
Electrical currents (V)
Fluorescence
Heat
48
Emission: Saltwater in a flame
49
Line Spectra
Individual atoms, well separated, in a gas phase
50
Band Spectra
Small molecules and radicals
Vibrational levels
51
Continuum Spectra
Produced when solid are heated to incandescence.
Blackbody Radiation (Thermal Radiation)
52
Blackbody Radiation
A blackbody is a theoretical object, (i.e.
emissivity = 1.0), which is both a perfect
absorber and emitter of radiation.
Common usage refers to a source of
infrared energy as a "blackbody" when
it's emissivity approaches 1.0 (usually e
= 0.99 or better) and as a "graybody" if
it has lower emissivity.
Important sources of infrared, visible,
and long wavelength UV for analytical
instruments
http://www.electro-optical.com/bb_rad/bb_rad.htm
53
Wiens
Displacement Law
T
nm K 10 2.897

6
max
=
Stefan-Boltzman Law
P = oT
4
o = 5.6697 10
-12
Wcm
-2
K
-4
Blackbody Radiation
Both max and radiation power (P) are related to TEMPERATURE and current!
54
Continuum Source Line Source
Continuum + Line Source
Ingle and Crouch, Spectrochemical Analysis
Al + Mg
55
Ranges of Common Sources
Douglas A. Skoog and James J. Leary, Principles of Instrumental
Analysis, Saunders College Publishing, Fort Worth, 1992.
56
Optical Source Characteristics
57
Nernst Glower
Rare earth oxides formed into a
cylinder (1-2 mm diameter,
~20mm long).
Pass current to give:
T = 1200 2200 K.
Ingle and Crouch, Spectrochemical
Analysis
58
Globar
Silicon Carbide Rod (5mm diameter, 50 mm long).
Heated electrically to 1300 1500 K.
Positive temperature coefficient of resistance
Electrical contact must be water cooled to prevent arcing.
59
Tungsten Filament
Heated to 2870 K.
Useful Range: 350 2500nm
60
Tungsten / Halogen
Iodine added.
Reacts with gaseous W near the quartz wall to form WI
2
.
W is redeposited on the filament.
Gives longer lifetimes
Allows higher temperatures (~3500 K).
61
Intensity Spectrum of the
Tungsten-Halogen Lamp
Weak intensity in
UV range
Good intensity in
visible range
Very low noise
Low drift
62
Arc Lamps
Electrical discharge is
sustained through a gas or
metal vapor.

Continuous emission due to
rotational/vibrational energy
levels and pressure
broadening.
63
H
2
or D
2
Arc Lamps
D
2
+ E
e-
D
2
* D + D + hv
Energetics: E
e-
= E
D
2
*
= E
D
+ E
D
+ hv
Useful Range: 185 400 nm.
64
Intensity Spectrum of the
Xenon Lamp
High intensity
in UV range
High intensity
in visible range
Medium noise
65
Hg Arc Lamp
Continuum + Line Source

High Power Source.

Often used in photoluminescence.
66
Hollow Cathode Discharge Tube.
Apply ~300 V across
electrodes.
Ar
+
or Ne
+
travel toward the
cathode.
If potential is high enough
cations will sputter metal off
the electrode.
Metal emits photons at
characteristic atomic lines as
the metal returns to the
ground state.
67
Hollow Cathode Discharge Tube.
Line Widths are typically 0.01 0.02 .
68
Absorption of Radiation
Is a quantized process???
The energy absorbed is released, although not necessarily
all as light energy (e.g. heat)
Results in excitation of a molecule to a higher energy
state
E= E electronic + E vibrational + E rotational
69
Absorption of Radiation
Douglas A. Skoog, F. James Holler and Timothy A. Nieman, Principles of
Instrumental Analysis, Saunders College Publishing, Philadelphia, 1998.
70
Atomic absorption
71
Rotational energy levels associated with each
vibrational level not shown
72
Relaxation
Resonance fluorescence

F
=
A
Non- Resonance fluorescence

F
=
A

Stokes shift

F
>
A

73
Quantitative Aspects of
Spectrochemical Measurements
Radiation power P
The energy of the a beam of radiation
that reaches a given area per second
S =kP
S is an electrical signal
Dark current
Response of the detector in the absence
of radiation
S =kP + k
d

74
Quantitative Aspects of
Spectrochemical Measurements
Transmittance
T = P/P
o
(definition)
P
o
- incident light power
P - transmitted light power
%T = P/P
o
x 100 %

Absorbance
A = - log T (definition)
Beers Law (physical law applicable under
certain conditions)
A = c b c (basis of quantitation)
c - molar absorptivity (L mol
-1
cm
-1
)
b - pathlength (cm)
c - concentration (mol L
-1
)
75
Non-radiative relaxation
Vibrational Relaxation:
A molecule can give off some of its energy from absorbed light
(usually uv-vis) by jumping to a lower energy vibrational state.
The excess energy is used to make the conversion. No light is given
off.
Internal Conversion:
The molecule transitions to a lower energy electronic state without
giving off light.
Excess energy is used to covert the molecule from one electronic state
to another.
Poorly understood
External conversion:
The molecule gives off energy to an external source, such as by
collision with another similar molecule or solvent molecule. This is
called quenching
Intersystem Crossing:
The molecule goes from a singlet to triplet excited state and uses
up energy changing the spin of an electron.

Chapter 6 Introduction To Spectros

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Introduction to Spectroscopic methods

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