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Infrared absorption

spectroscopy
Regions of IR
Spectral Region n (Hz) Wave number (cm-1) Wavelenth (,m)

IR Near 3,8 x 1014 a 12800 a 4000 0,78 a 2,5


1,2 x 1014

IR Medio 1,2 x 1014 a 4000 a 200 2,5 a 50


Fundamental 6,0 x 1012

IR Far 6,0 x 1012 a 200 a 10 50 a 1000


3,0 x 1011
Related units
Wave number vs. n
s = Wave number (cm-1 )
s n = Frequency (s-1 )
c = speed of light
(3 x 1010 cm s-1)
Wave number vs.

s
Molecular Vibrations

Molecules are not static


Vibration - Energy - Frequency IR
Functional groups
IR does not produce Electronic
Transitions
Molecules with dipole moment
Molecular Vibrations
A polar bond usually absorbs IR.
A non-polar bond on a symmetric
molecule will either weakly absorb or
not absorb IR (e.g.: O2, N2)
Molecular Vibrations
Molecular Vibrations

Symmetric
Stressing Scissoring Wagging

Asymmetric Rocking Twisting


Stressing
Rotational transitions

E needed is small
s of 100 cm-1 or less
Far IR
Vibrational Modes
A nonlinear molecule with n atoms
has 3n - 6 fundamental modes of
vibration

Tension Flexion
http://www.nuance.northwestern.edu/KeckII/ftir1.asp
and

R R
H H Flexion
Out of the plane
R H R H
Flutter (Aleteo) Torsion
IR spectrum

The spectrum is divided into 2 regions:


4000 cm-1 1600 cm-1 Stress bands, specific to
functional groups. Region of the
"functional group".
1600 cm-1 400 cm-1 Many bands of different origin.
Region of the "fingerprint". Used
to compare with available spectra.
(Spectra libreries)
IR spectrum
IR spectrum
IR spectrum
IR spectrum of an alkane
Hooke's Law - Simple Harmonic Motion
E potential = kX2

F = - kX

X = Spring Displacement
nm = 1/2p ( k/ )
= Reduced mass = m1m2/m1+m2

For a system with two masses m1 y m2

The stronger the link, the greater n and smaller


Vibration frequencies
Anharmonic oscillator
Harmonic Oscillator

For real molecules: a strict harmonic


behavior is not observed: e.g.: Electrostatic
repulsion.

E is different for each level, and E levels


are closer to each other, until dissociation
exists..
IR spectrum of t-butanol
Instrumentation in IR
IR radiation sources

Inert solids heated to 1500-2200 K


(continuous black body)
Nernst Transmitter: Cylinder with rare earth oxides, Length:
20 mm,
- Diameter: 1-2 mm, 1200-2200 K
Globar Source
Silicon carbide rod, Length: 50mm, Diameter: 5mm, 1300-
1500 K
Filament incandescent
Nichrome wire, low intensity but more durable 1100 K
.... IR radiation sources

Mercury arc
Quartz tube, with Hg under pressure > 1 ATM
Plasma that generates continuous radiation in the
far IR > 50 m
Lamp of filament de W
Near IR
Laser of CO2
IR limited region (900 a 1100 cm-1)
Restricted applications
.... IR radiation sources
IR Detector
Thermal (DT small calorific capacity) under Vacuum Less
thermal noise
Thermocouples or thermocouples: V changes between two
pieces of blackened metal. V depends on T (DT = 10-6 K)
Bolometers: changes in , sheets of Pt, Ni or semiconductor
Golay: membrane blackened in a chamber that expands a gas (Xe)
by action of the radiation (tires).

Pyroelectrics (* in FTIR)
V changes in sheets of pyroelectric materials (e.g. triglycine
sulphate). Quick answers.

Photoconductors (* en FTIR) In N2 liquid


Thin film of CdHgTe, InSb over glass no conductor, decrease
Types of IR Instruments
Dispersives
Qualitative analysis, double beam, with reflection
networks,
Similar to UV-Vis, the sample is between the
source and the monochromator Delay in the
response
Non dispersives
With or without filters:
With filters: Ceramic-wire source of nichrome,
Pyroelectric detector. Filters for each
compound.
No filters: They do not use dispositive. to
select
Multiplex Fourier Transform (FTIR) (*)
Qualitative and quantitative analysis
Dispersive instruments
Single beam vs double beam comparison
Non- dispersive instruments

Sin filtro
Spectroscopy of domain of....

The conventional one is: in frequency


domain n (or )

Frequency domain
Time domain spectroscopy

But it can
also be
related to
time
Time domain

More frequencies
P(t) = k Cos(2pn1t)+ k Cos(2pn2t) More complexity
Michelson interferometer

Converts the radiation to a measurable frequency: modulates

Fix Mirror

Beam splitter
Mobile
Mirror Source
Michelson interferometer

Fix Mirror

Mobil Mirror
F
Interference
constructive
Michelson interferometer

Fix Mirror

Moving
mirror
F
Destructive
interference
Interferograms in FTIR
FT-IR of a polystyrene film
On the interferometer

Beam division should be 50:50


If the source is polychromatic, each
will suffer interference and absorption
by the sample with the movement of
the mirror
The mirror movement must be
constant
FT-IR spectrophotometer

Use a Michelson interferometer.


It has better sensitivity.
Less energy is needed from the
source.
Sweep in 1-2 seconds
FTIR Spectrometer

FTIR
Spectrometer
FT-IR spectrophotometer
Advantages of FTIR on dispersive
instruments
1. The interferometer uses all wavelengths
simultaneously
2. No attenuation slits, few optical parts
3. Signal to Noise Ratio Improved
4. More power comes to the detector
5. Greater S / R for a fixed time, equal S /
R for a shorter time (faster sweep)
Advantages of FTIR on dispersive
instruments

....
6. Better Wave Number Accuracy
7. Constant resolution
To acquire the data...

It is fixed:

Maximum delay
Max. Wave number
Mirror speed (depends on
the desired sweep V)
Sample signal range
Applications of the FTIR

1. High precision work


2. Low sample availability
3. CG detector
4. Study of bands with low absorption
5. Kinetic studies (rapid sweeps)
IR spectrum of an amine
Spectrum recording

Analyte film between two NaCl plates


Solid solution in KBr that forms a transparent
tablet.
Solution in an appropriate solvent.
Analyte on CsCl2 plates (< 200 cm-1)
Preparation of a suspension in mineral oil
Different ways of sample preparation
Different ways of sample preparation
Different ways of sample preparation
Different ways of sample preparation
Different ways of sample preparation
Different ways of sample preparation

Radiation route
(Red line)
Different ways of sample preparation

Ciclohexano
Sample preparation
Different ways of sample preparation