Sie sind auf Seite 1von 95

CHAPTER 7

INFRARED ABSORPTION
SPECTROSCOPY
FTIR
7.1 Theory of IR absorption
7.2 IR Instrumentation ; Dispersive and FTIR
7.3 Application : Mid-IR absorption spectroscopy
7.4 Sample handling
7.5 Correlation charts and tables
7.6 Interpretation of IR spectra of simple organic
compounds

2
IR SPECTRAL REGION

3
 Mostly for qualitative analysis.
 Absorption spectra is recorded as transmittance spectra.
 Absorption in the infrared region arise from molecular
vibrational transitions.
 Absorption for every substance are at specific
wavelengths where IR spectra provides more specific
qualitative information.
 IR spectra is called “fingerprints” because no other
chemical species will have similar IR spectrum.

4
TRANSMITTANCE VS ABSORBANCE

The transmittance spectra


provide better contrast
between intensities of
strong and weak bands
compared to absorbance
spectra.

5
INFRARED SPECTROSCOPY
 Infrared (IR) spectroscopy deals with the interaction of
infrared radiation with matter.

 IR spectrum provides:
 Important information about its chemical nature and
molecular structure

 IR applicability for:
 Analysis of organic materials
 Polyatomic inorganic molecules
 Organometallic compounds

6
WHEN IR ABSORPTION OCCUR?
1. IR absorption only occurs when IR radiation interacts
with a molecule undergoing a change in dipole moment
as it vibrates or rotates.

2. Infrared absorption only occurs when the incoming IR


photon has sufficient energy for the transition to the next
allowed vibrational state.

** No absorption can occur if both rules above are not met.

7
WHAT HAPPEN WHEN A MOLECULES
ABSORBS IR RADIATION?
 Absorption of IR radiation corresponds to energy changes
on the order of 8 to 40 kJ/mole.
 Radiation in this energy range corresponds to stretching
and bending vibrational frequencies of the bonds in most
covalent molecules.

 In the absorption process, those frequencies of IR radiation


which match the natural vibrational frequencies of the
molecule are absorbed.

 The energy absorbed will increase the amplitude of the


vibrational motions of the bonds in the molecule.
8
WHAT HAPPEN WHEN MOLECULES
ABSORBS IR RADIATION ?

 NOT ALL bonds in a molecule are capable of


absorbing IR energy. Only those bonds that have
change in dipole moment are capable to absorb IR
radiation.

 The larger the dipole change, the stronger the


intensity of the band in an IR spectrum.

9
DIPOLE MOMENT
Dipole moment - a measure of the extent to which a
separation exists between the centers of positive and
negative charge within a molecule.

δ-
O

δ+ δ+
H H
1
0
DIPOLE MOMENT
 In heteronuclear diatomic molecule, because of the
difference in electronegativities of the two atoms, one
atom acquires a small positive charge (δ+), the other a
negative charge (δ-).

 This molecule is then said to have a dipole moment


whose magnitude, μ = qd

distance of separation of the charge

1
1
DIPOLE MOMENT
 The charge distribution around a molecule is not
symmetric because one of the atom has a higher electron
density.
 Example: HCl

 Dipole moment is determined by the magnitude of the


charge difference and the distance between the two
centers of charge.

12
DIPOLE MOMENT
Only bonds which have significant dipole moments will
absorb infrared radiation.

Bonds which do not absorb infrared include:

• Symmetrically substituted alkenes and alkynes


R R
R C C R
R R

• Many types of C-C Bonds


• Symmetric diatomic molecules
H-H Cl-Cl
The greater the change in dipole moment, the more intense
the absorption

When the bond stretches, the increasing distance between the


atoms increases the dipole moment

The intensity of an absorption band depends on the number of


bonds responsible for the absorption
Bond order affects bond strength, so bond order affects the
position of absorption bands

The approximate wavenumber of an absorption can be


calculated from Hooke’s law
1
1  f (m1  m2 )  2
    

2c  m1m2 
ν is the wavenumber of the stretching vibration
f is the force constant
m1 and m2 are the masses of the atoms
The exact position of the absorption band depends on
• electron delocalization
• the electronic effect of neighboring substituents
• hydrogen bonding

O O-
O
CH3CCH2CH2CH3

C O C O
at 1720 cm–1 at 1680 cm–1
Putting an atom other than carbon next to the carbonyl group
causes the position of the carbonyl absorption band to shift

The predominant effect of the nitrogen of an amide is electron


donation by resonance.

The predominant effect of the oxygen of an ester is inductive


electron withdrawal.
The position of a C–O absorption varies because

~1050 cm–1
CH3CH2 OH

~1050 cm–1
CH3CH2 O CH2CH3

O O-
C C ~1250 cm–1
H3C OH H3C OH

O O-
C C ~1250 cm–1 and 1050 cm–1
H3C O CH3 H3C O CH3
STRONG ABSORBERS
The carbonyl group is one
d-
O
of the strongest absorbers d+
C

Also O-H and C-O bonds O H C O

infrared beam
C C
+ + O d+
O
- - d-

oscillating dipoles couple and


energy is transferred
MOLECULAR SPECIES THAT
ABSORB IR
A. Compound absorb in IR region
Organic compounds, carbon monoxide

B. Compounds DO NOT absorb in IR region


O2, H2, N2, Cl2
 these molecules do not produce vibrations which
can change the dipole moment of the molecule

2
0
MOLECULES
 Molecules are composed of atoms held together by
chemical bonds.
 The atoms in a molecule are always moving or “vibrating”.
 The intensities of vibrations increase when IR radiation is
absorbed
 Each chemical bond requires a precise amount of energy
to make it vibrate
 Each frequency of IR radiation provides a precise
amount.

 Radiation is absorbed by a molecule only if the frequency


of the radiation provides energy in the precise amount
required by one of the bonds in the molecule
 Molecules can be large or small
 The atoms they contain may be the same or different
 The bonds between them may vary from weak to small
IR SPECTRA
 Plot of %T vs cm-1
 Linear wavenumber scale is preferred
 Direct proportionality between wavenumber and both
energy and frequency

c
E  h  h  hc

POLYSTYRENE SPECTRUM

25
ROTATIONAL TRANSITIONS
 Small energy is required to cause a change in rotational
level
  100 cm-1 or  > 100m

Rotational levels are quantized


 Absorption of gases in the FIR region is characterized by
discrete, well defined lines.
 In liquids and solids; intramolecular collisions and
interactions cause broadening of the lines into a
continuum.
VIBRATIONAL-ROTATIONAL
TRANSITIONS
 Vibrational energy levels are quantized
 E between quantum states correspond to MIR region for
most molecules.

Spectrum of a gas
 A series of closely spaced lines
 There are several rotational energy levels for each
vibrational level.

Spectra of solids and liquids


 Broad vibrational bands
 Rotation is restricted in solids and liquids
 Depending on the number of ways the bond can move
(bend, stretch etc.), each type of bond may absorb IR
radiation at one or more specific frequencies.
IR VIBRATIONAL MODES

29
TYPES OF MOLECULAR VIBRATIONS
Stretching
 A continuous change in the interatomic distance along the
axis of the bands between the two atoms
 Symmetrical
 Asymmetrical

Bending
 A change in the angle between two bonds
 4 types
 Scissoring
 Rocking
 Wagging
 Twisting
Molecular vibration

divided into
back & forth involves change
movement in bond angles

stretching bending

wagging
scissoring

symmetrical asymmetrical rocking twisting


out of
in-plane plane
vibration vibration

3
1
STRETCHING

3
2
STRETCHING

33
BENDING

3
4
35
ELECTROMAGNETIC SPECTRUM

3
Energy of IR photon insufficient to cause electronic
6 excitation but can cause vibrational excitation
HOOKE’S LAW
VIBRATIONS

38
larger K,
higher frequency
m1  m2
μ
1 m1  m2
K
 =
2c  larger atom masses,
lower frequency

constants 
m1 increasing K

=
C=C > C=C > C-C
2150 1650 1200

increasing 

C-H > C-C > C-O > C-Cl > C-Br


3000 1200 1100 750 650
INSTRUMENTATION

40
IR INSTRUMENT
Dispersive spectrometers
sequential mode

Fourier Transform spectrometers


simultaneous analysis of the full spectra range using
interferometry.

4
1
DISPERSIVE IR INSTRUMENT
Important components in IR dispersive spectrometer

1 2 3 4 5
source sample λ signal processor
detector & readout
lamp holder selector

Detector:
Source:
- Thermocouple
- Nernst glower
- Pyroelectric transducer
- Globar source
- Thermal transducer
- Incandescent wire

4 - Nichrome wire
2
RADIATION SOURCES
 Generate a beam with sufficient power in the  region of
interest to permit ready detection & measurement.

 Provide continuous radiation which made up of all ’s


with the region (continuum source).

 Provide stable output for the period needed to measure


both P0 and P.

4
3
SCHEMATIC DIAGRAM OF
IR SPECTROPHOTOMETER

4
4
FOURIER TRANSFORM INFRARED
(FTIR)

45
FTIR
Why FTIR is developed?

 To overcome limitations encountered with the dispersive


instruments.

 Dispersive IR spectrophotometer has slow scanning


speed due to measurement of individual
molecules/atom.

 It utilize the use of an interferometer.

4
6
FTIR SPECTROMETER
The main optical components are:
 The IR source
 The interferometer
 The beamsplitter
 The laser
 The IR detector
FTIR

48
IR SOURCE
 The IR source produces IR radiation beam that
travels through the spectrometer passing through the
sample and to the detector
INTERFEROMETER
 Beamsplitter
 Two mirrors
 fixed
 movable
Interferometer
 Special instrument which can read IR frequencies
simultaneously.
 Faster method than dispersive instrument.
 Interferograms are transformed into frequency spectrums
by using mathematical technique called Fourier
Transformation.

FT
Calculations

interferograms IR spectrum

5
1
BEAMSPLITTER

 Separates the IR beam into two beams of nearly equal


energy
 One beam is reflected from the beam splitter to a fixed
mirror
 The other beam is transmitted to a moving mirror and
back to the beam splitter where the beams recombine
LASER

 used as an internal calibrator


 control the moving mirror’s position
 signals the capture of data
LASER
 Produces a single frequency of red light that follows the
same path as the IR beam.
 Calibrates the instrument internally.
IR TRANSDUCER

 After being absorbed at specific frequencies by the sample,


 the remainder of the IR beam is focused onto the
detector.
 The detector produces signal to the amount of IR radiation
striking it and sends the signal to the computer for
processing
FTIR SPECTROMETER
FTIR spectrometer
 Emits IR radiation across the region of interest
 IR beam is deflected off a mirror
 Directs the IR beam into the interferogram
 Where the spectral encoding takes place
INTERFEROMETER
Fixed
mirror

Moving
mirror
IR source

He-Ne Laser

Beamsplitter

Sample

Detector
COMPONENTS OF FTIR
Majority of commercially available FTIR instruments are based
upon Michelson interferometer.
3
4

5 2
6

6
1
 The computer reads the interferogram and uses Fourier
transformation to decode the intensity information for
each frequency and presents a spectrum
 The spectrometer measures the intensity of a specially
encoded IR beam after it has passed through the sample.
 The resulting signal, ”interferogram”
 contains information about all frequencies present in the
beam
 The IR beam exits the interferometer.
 It is deflected by a couple of mirrors before it reaches the
detector
 Produces electrical signal in response to the encoded
radiation striking it.
FOURIER TRANSFORMATION
ADVANTAGES OF FTIR
 All frequencies are measured simultaneously. Typical scan
times are only a few seconds.
 The energy throughput is higher for any resolution, giving a
higher signal to noise ratio.
 The laser wavelength is used as a reference for the
calculation of band positions, and is precise.
 Stray light can be prevented.
 Resolution is constant for the whole spectral range.
 Robustness as the FT instruments only have one moving
part.
APPLICATIONS OF IR
SPECTROMETRY

Major application (MIR region)


 Structural investigations of molecular compounds
particularly organic compounds
MAJOR APPLICATIONS OF IR
SPECTROMETRY
NIR AND FIR REGIONS

NIR region (4000 to 14,000 cm-1)


 Quantitative determination of low MW hydrocarbons,
H2O, CO2, S

FIR region (15 to 100 m)


 Structural determination of inorganic and metal-organic
species
WHAT PRODUCES THE IR SPECTRUM

 Materials that contain C (organic compounds)


 Many compounds; natural and synthetic
 Inorganic materials
SAMPLE HANDLING TECHNIQUES
1. Gases
 Using evacuated cylindrical cells equipped with
suitable windows.

2. Liquid
 sodium chloride windows.
 “neat” liquid

3. Solid
 Pellet (KBr)
 Mull
7
0
MEASURING GASES
This gas cell provides a fixed
pathlength that is 2 m long

 Placed in a sealed cell


 Specified T and P can be maintained
 Gases are often present at low concentrations
 Mirrors are used to deflect the IR beam back and forth
before the beam is allowed to exit
 increased the interaction between gas sample and IR
beam
 To acquire more spectral information
LIQUIDS
 A drop of the pure (neat) liquid is squeezed between two
rock-salt plates to give a layer that has thickness 0.01
mm or less.

 2 plates held together by capillary mounted in the beam


path.

 What is meant by “neat” liquid?


• Neat liquid is a pure liquid that do not contain any
solvent or water.

 Neat liquid method is applied when the amount of liquid


is small or when a suitable solvent is unavailable.
7
2
MEASURING LIQUIDS

Liquid cells
 Holds the liquid between two crystal made from materials
that completely transmit IR radiation.
SOLIDS
There are 2 ways to prepare solid sample for IR
spectroscopy.

1. Solid that is soluble in solvent. The most commonly


IR solvent is carbon tetrachloride, CCl4.

2. Solid that is insoluble in CCl4 or any other IR


solvents can be prepared either by KBr pellet or
Mulls.

7
4
SOLIDS
 Solid in a liquid or solid matrix
 Samples are ground to fine powder
 To avoid effects of scattered radiation
KBr PELLET

 The finely ground solid sample is mixed with potassium


bromide (KBr). The mixture is pressed under high
pressure (10,000 – 15,000 psi) in special dye to form a
pellet.

 KBr pellet (in transparent disk) then can be inserted into


a holder in the IR spectrometer.

7
6
SOLID- KBr DISK SAMPLING
PELLETING
 Most common technique; KBr pelleting
 Halide salts have a property of cold flow
 Translucent property when pressure is applied to finely
powdered salts
 ~1 mg (or less) sample is mixed with ~ 100 mg dried KBr
 Mix and grind in a mortar and pestle
 Apply 10,000 to 15,000 psi in a die
 Produce a transparent disk or pellet
 Best done in vacuum or store the pellet in a desiccator
before measurement
 Bands at 3450 and 1640 cm-1 due to absorbed moisture
MULLS

 2-5 mg finely powdered sample is ground (grind) together


with the presence 1 or 2 drops of a heavy hydrocarbon oil
called Nujol to form a Mull.

 Mull is then examined as a film between flat salt plates.

 Mulls method is applied when solid not soluble in an IR


transparent solvent and solid is not convenient to be
pelleted with KBr.

7
9
What is Mull
A thick paste formed by grinding an insoluble solid with
an inert liquid and used for studying spectra of the solid.

What is Nujol
A trade name for a heavy medicinal liquid paraffin.
Extensively used as a mulling agent in spectroscopy.

8
0
MULLS
 Solids
 Not soluble in an IR transparent solvent
 KBr pelleting is not convenient
 Grind ~ 2 – 5 mg fine powder in a drop of mulling
agents
 Heavy hydrocarbon (Nujol)
 Fluorolube (halogenated polymer)
 Examine as thin film between two salt discs
SOLUTIONS

 Water and alcohols are not suitable solvents


SOLVENTS FOR IR SPECTROMETRY
No solvent is transparent throughout the region of interest
CELLS
Liquid cells
(compared to UV/Vis spectroscopy)
 Narrow pathlengths
 0.01 to 1 mm

 Relatively high sample concentrations


 0.1% to 10%
 Short pathlengths
 Low molar absorbtivity
LIQUID CELLS
 Designed for easy assembly/disassembly
 Use Teflon spacers
 Allow variations in path lengths

Fixed path-length cells


 Use a syringe to fill or empty
DEMOUNTABLE IR CELL FOR
LIQUID SAMPLE
COMMON IR WINDOW MATERIALS
SELECTION OF WINDOW MATERIALS

 Cost
 Range of transparency
 Solubility in solvent
 Reactivity with sample or solvent

**Most common are NaCl and KBr


QUALITATIVE ANALYSIS
FTIR, NMR and MS

Identify:
 Organic
 Inorganic species
 Biological
LIMITATIONS TO THE USE OF
CORRELATION CHARTS

To determine the identity or structure


 Not possible using the correlation charts alone (only as a
guide).
 Overlapping of group frequencies
 Instrumental limitations
 Spectral variations as a function of physical states
 Neat liquid
 Solution
 Pellet
 Mull
TABLE OF GROUP FREQUENCIES FOR
ORGANIC FUNCTIONAL GROUPS
GROUP FREQUENCY REGION OF MIR
GROUP FREQUENCY REGION OF MIR
ACTIVE OR INACTIVE VIBRATIONS IN
IR SPECTRUM?
QUANTITATIVE ANALYSIS
Limitations
 Complex spectra
 Overlapping of absorption bands
 Narrow absorption bands and
 Stray radiation
 Deviation from Beer’s law
 Narrow pathlengths
 Inconvenient
 Lead to significant uncertainties

Das könnte Ihnen auch gefallen