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Spectroscopy
Chapter 13-14
From 190 to 900 nm!
LAMBERT-BEER LAW
Psolution
P
T
Psolvent
P0
Power of
radiation after
passing
through the
solvent
Power of radiation
after passing
through the
sample solution
A log T log
P0
A abc kc
a absorptivity
b pathlength
c concentration
Absorption Variables
Assumptions
I r ( 2 1 ) 2
I 0 ( 2 1 ) 2
Chemical Equilibria
Consider the equilibrium:
A+C
AC
Instrumental deviation
with polychromatic
radiation
P PS
P0 PS
A log T
P PS
A log
P0 PS
A abc kc
PS
100
P0
Instrument Noise
Effects of Signal-to-Noise
1
0.9
Bad at High T
0.8
TRANSMISSION
0.7
0.6
0.5
0.4
0.3
0.2
Bad at Low T
0.1
0
10
11
Components of
instrumentation:
Sources
Sample Containers
Monochromators
Detectors
Components of
instrumentation:
Sources: Agron,
Xenon, Deuteriun, or
Tungsten lamps
Detectors: Pohotomultipliers
Sources
Deuterium and hydrogen lamps (160
375 nm)
D2 + Ee D2* D + D + h
Excited deuterium
molecule with fixed
quantized energy
Dissociated into
two deuterium
atoms with
different kinetic
energies
Ee = ED2* = ED + ED + hv
Sources
Tungsten lamps (350-2500 nm)
Blackbody type , temperature
dependent
Why add I2 in the lamps?
W + I2 WI2
Multi-channel Design
Molar absorptivities
= 8.7 x 10 19 P A
A: cross section of molecule in cm 2 (~10-15)
P: Probability of the electronic transition (01)
Molecular Absorption
habsorption 10-8 sec)
heat (relaxation process)
M* A+B+C (photochemical
decomposition)
Molecular Transitions
for UV-Visible Absorptions
MO
Diagram for
Formaldehy
de
(CH2O)
H
H
=
=
n=
Type of Transitions
*
High energy required, vacuum UV range
CH4: = 125 nm
n *
Saturated compounds, CH3OH etc ( =
150 - 250 nm)
n * and *
Mostly used! = 200 - 700 nm
Examples of
UV-Visible Absorptions
LOW!
Effects of solvents
Effects of Multiple
Chromophores
Organic Compounds
max= 184
max = ~10,000
CH2=CHCH2CH2CH=CH2
max=185
max = ~20,000
If conjugated
- shifts to higher s (red shift)
H2C=CHCH=CH2
Spectral nomenclature
of shifts
What about
inorganics?
Charge-TransferAbsorption
A charge-transfer complex consists of an
electron-donor group bonded to an
electron acceptor. When this product
absorbs radiation, an electron from the
donor is transferred to an orbital that is
largely associated with the acceptor.
1)
2)