Application of

In-situ FTIR Spectroscopy in

Catalysis
Koushik Ponnuru

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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In Situ FTIR Spectroscopy:

Motivation
Monitor reactions In Situ under Actual
Reaction Conditions
Effectively monitor reactions that have
components sensitive to oxygen water
vapor or temperature.
Eliminate or reduce the need for offline
analysis
Comprehensive concentration information in
real-time
Follow instantaneous changes in
reactants, intermediates and products
providing a molecular video of reaction
chemistry
Eliminate time delay associated with
3

In-situ Spectroscopy : Data

Acquisition
O

OH

300 C,
35 bar max

+ 2H2
+ H2
OH
+ 3H2

- H2O

+ H2

ATR analyzed data

ATR raw data

Kinetic Analysis: Off-line technique

Diels Alder
Reaction

Drawback
snumber of separate
Large

experiments required
Concentrations are
distorted from synthetically
relevant conditions

Kinetic Analysis : In-situ Technique

[1]0

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

Kinetic Analysis : In-situ Technique

Rearranged rate
equation

Two experiments via

in-situ technique

Rate
equation

Two SETS of experiments

via classical offline

Working Principle of IR Spectroscopy

Chemical bonds between the atoms within the
molecules vibrate.
A diatomic molecule is considered as a two spherical
masses (m1 & m2) connected with a spring with a
given force constant k.
Applied Freq. = Natural Freq. of Vibration
Absorption of IR radiation takes place and a peak is
observed.

1 k
%
2c
8

Working Principle of IR Spectroscopy

Can Model the fundamental Vibrations
between the atoms using Hooks Law.
The potential energy curve of such an
oscillator is parabolic in shape and
symmetrical about the equilibrium bond
1
length.
V k .x 2

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

Morse Potential Model

Bond

dissociate

if

stretched

beyond a certain distance

Bond length cannot be less
than

minimum

inter

nuclear

distance
In the case of the Anharmonic
Oscillator,

the

vibrational

transitions no longer only obey

the selection rule n = 1.
Vibrational transitions with n
= 2, 3, ... are also possible
A more accurate description of the vibrational energies is given by the
anharmonic oscillator (also called Morse potential) with energy of

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

Working principle of Interferometer

x 0, n

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

Optical Path Difference

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Signal from
photo detector

optical path difference

changes
By taking the fourier
transform we can identity
the frequencies present in
the interferogram
Interferogram

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

Measuring a typical IR Spectra

% T = 100 x
I/I0
14

Absorbance / Transmittance
Lambert Beer Law

absorptivity coefficient) x b (path length) x c (concent

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15

ATR Sampling : Method of

Measurement
ATR Probe
Experimental
Apparatus

ReactIR 45m FTIR Spectrometer

16

ATR Sampling : Method of

Measurement
At the reflection
point

2-3
m

The infrared radiation interacts with the sample

through series of standing waves called
evanescent waves.
An evanescent wave is produced each time the
infrared beam is reflected from the inside surface
of the crystal
17

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

How to Read / Interpret an IR Spectra ??

2.
What
Functional
Groups are Present in
the
material under
test ?

Functional Group Region

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1.Which is
the
material
under
test
?
(identifying
unknown
material)

Fingerprint Region
19

How fingerprint region is important in identifying

unknowns ?

Case Study : Convergent synthesis of

Alkenes by Cross Coupling of Carbenes

Carbenoid

Hansen, J. H., Parr, B. T., Pelphrey, P., Jin, Q., Autschbach, J. and Davies, H. M. L.; Angew. Chem. Int. Ed., 50: 25442548
8/28/15

21

Convergent synthesis of Alkenes by

Cross Coupling of Carbenes
Donor/Acceptor
Acceptor

Acceptor carbenoid (2) homodimerization is very

favorable
Donor/acceptor carbenoid (1a) homodimerization
is not favorable
What factors control the cross coupling and why
Hansen, J. H., Parr, B. T., Pelphrey, P., Jin, Q., Autschbach, J. and Davies, H. M. L.; Angew. Chem. Int. Ed., 50: 25442548
does it work so well?
22

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

Cross Coupling of Carbene

Acceptor
Donor/Acceptor

In Equimolar mixture of (1a) and

(2), the consumption of (2) is 1.5
times faster than (1a)
All of 2 is consumed within 7s
Once 2 is consumed the
decomposition of 1a is
significantly low.
Homodimerization of (2) does not
go to completion

Hansen, J. H., Parr, B. T., Pelphrey, P., Jin, Q., Autschbach, J. and Davies, H. M. L.; Angew. Chem. Int. Ed., 50: 25442548 24

Mechanism for Cross coupling of

Carbene
Key
Product
cross
findings:
dimerization rely on:
A

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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26

THANKS FOR YOUR

ATTENTION