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8/28/15
Outline
Importance
Comparison
of
In-situ
with
Spectroscopy
conventional
offline
analysis
Theory of FTIR
Instrumentation and sampling : ATR FTIR
Spectroscopy
How to interpret Infra-Red spectra
Case
study Convergent synthesis 2 of
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OH
300 C,
35 bar max
+ 2H2
+ H2
OH
+ 3H2
- H2O
+ H2
Drawback
snumber of separate
Large
experiments required
Concentrations are
distorted from synthetically
relevant conditions
Exp.
A
Exp.
B
0.2
M
0.2
M
[2]0
[e] = [2]0
[1]0
= [2]
[1]
0.6 M 0.4 M
0.4M
0.2M
JACS, 2007,129,15100.
Diels Alder
Reaction
Rate
equation
1 k
%
2c
8
The Harmonic
Oscillator
2
only certain energy levels exist :
-A
0
+A
n = 1
-A
+A
Displaceme
nt
Transition moment
Integral
E n hvn ;
2
1
2
1
2 c
k
;
E h
v
v
c
M 0 ; if =const
( ') and ( ) are orthogonal
dissociate
if
stretched
minimum
inter
nuclear
distance
In the case of the Anharmonic
Oscillator,
the
vibrational
Modes of vibrations
v
1
k
2 c
antisymmetric
R
R
H
R
H
R
symmetric
R
H
R
H
scissoring
R
H
Regi
on
H
stretching
H
H
R
H
rocking
R
H
NIR
in-plane
bending
Overtones and
combination
bands of
fundamental
molecular
vibrations
fundamental
molecular
vibrations
Most organic functional groups
MIR absorption
FIR exhibit
molecular
spectrum
rotations
High Molar absoptivities
bending
MIR
Origin of the
absorption
Fixed
mirror
Beam
Splitte
r
Moving
mirror
x (n 1/ 2)
Photodete
ctor
Zero path
diff
Moving
mirror
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Constructi
ve
interferenc
e
Destructiv
e
Interferenc
e
Power
signal
IR light
12
Relative Intensity
Signal from
photo detector
Signal from
photo detector
Fourier Transform of an
Interferogram
As we move the mirror the
Optical Path Difference Optical Path Difference
IR Spectrum
Wavenumbers cm-1
13
% T = 100 x
I/I0
14
Absorbance / Transmittance
Lambert Beer Law
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15
16
2-3
m
Multiple Reflection
Enhanced sensitivity makes it
Ideal for analyzing samples
when
the
component
of
interest is low.
70% Iso propyl alcohol
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18
2.
What
Functional
Groups are Present in
the
material under
test ?
1.Which is
the
material
under
test
?
(identifying
unknown
material)
Fingerprint Region
19
Carbenoid
Hansen, J. H., Parr, B. T., Pelphrey, P., Jin, Q., Autschbach, J. and Davies, H. M. L.; Angew. Chem. Int. Ed., 50: 25442548
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21
In-situ Analysis
Acceptor
Donor/Acceptor
(1a) decomposes
faster than the (2)
and then
preferentially reacts
with other diazo
compound.
Reaction monitored
by the presence of
Hansen,
J. H., Parr,stretch
B. T., Pelphrey, P.,
Jin, Q., Autschbach, J. and Davies, H. M. L.; Angew. Chem. Int. Ed., 50: 2544254823
C=N
bands
Acceptor
Donor/Acceptor
Hansen, J. H., Parr, B. T., Pelphrey, P., Jin, Q., Autschbach, J. and Davies, H. M. L.; Angew. Chem. Int. Ed., 50: 25442548 24
significant
decomposition
difference
the
rate
between
two
diazo
compounds
A
preference
trapping
of
for
the
25
Hansen, J. H., Parr, B. T., Pelphrey, P., Jin, Q., Autschbach, J. and Davies, H. M. L.; Angew. Chem. Int. Ed., 50: 25442548
Summary
Provides a full kinetic analysis
from a minimum number of
reaction progress experiments
Elucidation of mechanism and
pathway
Detection of reactive
intermediates
Optimize reactions and develop
safe ways to work with
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