Infrared Spectroscopy-IR

Common Applications Identification of compounds by matching spectrum of unknown compound with reference spectrum (fingerprinting) Identification of functional groups in unknown substances Identification of reaction components and kinetic studies of reactions Identification of molecular orientation in polymer films Detection of molecular impurities or additives present in amounts of 1% and in some cases aslow as 0.01% Identification of polymers, plastics, and resins Analysis of formulations such as insecticides and copolymers

Complementary or Related Techniques

Nuclear magnetic resonance provides additional information on detailed molecular structure Mass spectrometry provides molecular mass information and additional structural information Raman spectroscopy provides complementary information on molecular vibration. (Some vibrational modes of motion are IR-inactive but Raman-active and vice versa.)- NOT INCLUDED IN THIS COURSE

Introduction
Infrared (IR) spectroscopy is one of the most common spectroscopic techniques used by organic and inorganic chemists it is the absorption measurement of different IR frequencies by a sample positioned in the path of an IR beam. The main goal of IR analysis is to determine the chemical functional groups in the sample. Different functional groups absorb characteristic frequencies of IR radiation.

IR Frequency Range
Region
Near Middle Far

range (m)
0.78-2.5 2.5-50 50-1000

Wave number range, cm-1

12, 000 to 4000 4000 to 200 200 to 10

Frequency Range
3.8x1014- 1.2x1014 1.2x1014- 6.0x1012 6.0x1012- 3.0x1011

Most used

2.5-15

4000 to 670

1.2x1014- 2.0x1013

FT-IR Instrument
1. The Source: Infrared energy is emitted from a glowing blackbody source. This beam passes through an aperture which controls the amount of energy presented to the sample (and, ultimately, to the detector). 2. The Interferometer: The beam enters the interferometer where the spectral encoding takes place. The resulting interferogram signal then exits the interferometer. 3. The Sample: The beam enters the sample compartment where it is transmitted through or reflected off of the surface of the sample, depending on the type of analysis being accomplished. This is where specific frequencies of energy, which are uniquely characteristic of the sample, are absorbed. 4. The Detector: The beam finally passes to the detector for final measurement. The detectors used are specially designed to measure the special interferogram signal. 5. The Computer: The measured signal is digitized and sent to the computer where the Fourier transformation takes place. The final infrared spectrum is then presented to the user for interpretation and any further manipulation.

FT-IR Instrument- Schematic

Michaelson Interferometer

Stationary mirror

HeNe laser

Beam Splitter

Source Moving mirror PMT Sample

Detector

Michaelson Interferometer

Interferometers employ a beamsplitter which takes the incoming infrared beam and divides it into two optical beams. One beam reflects off of a flat mirror which is fixed in place. The other beam reflects off of a flat mirror which is on a mechanism which allows this mirror to move a very short distance (typically a few millimeters) away from the beamsplitter. The two beams reflect off of their respective mirrors and are recombined when they meet back at the beamsplitter. Because the path that one beam travels is a fixed length and the other is constantly changing as its mirror moves, the signal which exits the interferometer is the result of these two beams interfering with each other. The resulting signal is called an interferogram which has the unique property that every data point (a function of the moving mirror position) which makes up the signal has information about every infrared frequency which comes from the source. This means that as the interferogram is measured, all frequencies are being measured simultaneously. Thus, the use of the interferometer results in extremely fast measurements. Because the analyst requires a frequency spectrum (a plot of the intensity at each individual frequency) in order to make an identification, the measured interferogram signal can not be interpreted directly. A means of decoding the individual frequencies is required. This can be accomplished via a well known mathematical technique called the Fourier transformation. This transformation is performed by the computer which then presents the user with the desired spectral information for analysis.

IR Spectrum

IR absorption information is generally presented in the form of a spectrum with wavelength or wavenumber as the x-axis and absorption intensity or percent transmittance as the y-axis

Theory of Infrared
Dipole changes During Vibrations and Rotations IR absorption - a molecule must undergo a net change in dipole moment due to vibrational or rotational motion. Homonuclear species such as O2, N2 or Cl2 no net change in dipole moment occurs during vibration or rotation. Eg. The charge distribution around a molecule of HCl is not symetric because the Cl has a higher electron density than the hydrogen. HCl has a significant dipole moment and known as polar molecule Dipole moment: determined by the magnitude of the charge difference and the distance between the two centre of centre of charge. as a HCl vibrates, a regular fluctuation in dipole moment occurs, an a field is established that can interact with the electrical field associated with radiation. If the frequency of the radiation exactly matches a natural vibrational frequency of the molecule, a net transfer of energy takes place that results in a change in the amplitude of the molecular vibration, absorption of the radiation is the consequence. Similarly, the rotation of asymmetric molecules around their centres of mass result in a periodic dipole fluctuation that can interact with radiation.

Theory of Infrared
Rotational Transitions The energy required to cause a change in rotational is minute (small) and corresponds to radiation of 100 cm-1 or less (>100m) Rotational levels are quantized; i) Absorption by gases in the far IR region is characterized by discrete, well-defined line ii) Absorption by liquids or solids intramolecular collisions and interactions cause broadening of the lines in to a continuum. Vibrational/Rotational Transitions Vibrational energy levels are also quantized for most molecules the energy differences between quantum states correspond to the mid-IR region. The IR spectrum of a gas usually consists of closely spaced lines, because there are several rotational energy state for each vibrational state. On the other hand, rotation is highly restricted in liquids and solids, in such sample, discrete vibrational/rotational lines disappear, leaving only somewhat broadening vibrational peaks.

Types of molecular vibration

i)

Stretching: involves a continues change in the inter atomic distance along the axis of the bond between two atoms. 2 types: Symetric stretching and asymetric stretching

ii)

Bending: characterized by a change in the angle between two bonds. 4 types of bending vibrations: scissoring(bending), rocking, wagging and twisting.

Stretching and Bending

Symmetric

Asymmetric

In plane rocking

In plane scissoring

Out of plane wagging

Out of plane twisting

The IR spectrum ( Dudley Williams pg 30)

A complex molecule-many vibrate modes involve in the whole molecule

However, these molecular vib. are largely associated with the vib. of individual bonds and called localized vibrations.
These localized vibrations are useful for the identification of functional groups, such as the stretching vibs of: Single bond (O-H & N-H) and all kinds of triple and double bonds, all of which occur with frequency greater than 1500cm-1 The stretching vib. of other single bonds, most bending vibrations and the soggier vibration of the molecule as a whole give rise to a series of absorption bands at lower energy, below 1500cm-1, the position of which are characteristic of that molecule (Fingerprint region).

Full spectrum of cortisone acetate , pg 31

Full spectrum of cortisone acetate , pg 31

Strong absorption from the stretching vibrations above 1500cm-1, showing that the presence of each of the functional groups: O-H group 3 diff C=O groups The weaker absorption of the C=C double bond finger print region below 1500cm-1

Identification of IR spectrum (organic comp)

Two step processes:

Determine what functional groups are present-examining the group frequency region (3600 1200cm-1) Detailed comparison of the spectrum of the unknown with the spectra of pure compounds that contain all of the functional groups found in the first step. The fingerprint region (1200-600cm-1) is useful due to small differences in the structure and constitution of a molecule result in significant changes in the appearance and distribution of absorption peaks in this region. Consequently, a close match between two spectra in the fingerprint region (as well as others) constitutes almost certain evidence for the identity of the compound yielding the spectra.

Table of group frequency for organic group

Bond C-H C-H C-H C-H O-H Type of compound Alkanes Alkenes (C=C) Alkynes (CC) Aromatic ring Monomeric alcohols, phenols Hydrogen-bonded alcohols, phenols Monomeric carboxylic acids H-bonded carboxylic acids Amines, amides Alkenes Aromatic rings Alkynes Amines, amides Nitriles Alcohols, ethers, carboxylic acids, esters Aldehydes, ketone,-COOH, esters Nitro compounds Frequency range, cm-1 2850-2970 1340-1470 3010-3095 675-995 3300 3010-3100 690-900 3590-3650 3200-3600 3500-3650 2500-2700 3300-3500 1610-1680 1500-1600 2100-2260 1180-1360 2210-2280 1050-1300 1690-1760 1500-1570 1300-1370 Intensity Strong Strong Medium Strong Strong Medium Strong Variable Variable (sometimes broad) Medium Broad Medium Variable Variable Variable Strong Strong Strong Strong Strong Strong

N-H C=C C=C CC C-N CN C-O C=O NO2

IR Spectroscopy Tutorial: How to analyze IR spectra

The distinctive bands of the common functional bands:

3500-3300 cm-1

NH stretch

amines
alcohols, a broad, strong band alkenes

3500-3200 cm-1

OH stretch

3100-3000 cm-1

CH stretch

3000-2850 cm-1
1760-1665 cm-1 1680-1640 cm-1

CH stretch
C=O stretch C=C stretch

alkanes
ketones, aldehydes, esters alkenes

i) Begin by looking in the region from 4000-1300. Look at the CH

stretching bands around 3000:

Indicates: Are any or all to the right of 3000? Are any or all to the left of 3000? alkyl groups (present in most organic molecules) a C=C bond or aromatic group in the molecule

ii) Look for a carbonyl in the region 1760-1690. If there is such a band:
Indicates: Is an OH band also present? Is a CO band also present? Is an aldehydic CH band also present? Is an NH band also present? Are none of the above present? a carboxylic acid group an ester an aldehyde an amide a ketone

Look for a broad OH band in the region 3500-3200 cm-1. If there is such a band: Indicates:
Is an OH band present?

an alcohol or phenol

Look for a single or double sharp NH band in the region 3400-3250 cm-1. If there is such a band: Indicates: Are there two bands? a primary amine

Is there only one band?

a secondary amine

Other structural features to check for: Indicates:

Are there CO stretches?

Is there a C=C stretching band? Are there aromatic stretching bands? Is there a CC band? Are there -NO2 bands?

an ether (or an ester if there is a carbonyl band too) an alkene an aromatic an alkyne a nitro compound

IR Spectroscopy Tutorial: Alkanes

The spectra of simple alkanes are characterized by absorptions due to CH stretching and bending (the C C stretching and bending bands are either too weak or of too low a frequency to be detected in IR spectroscopy). In simple alkanes, which have very few bands, each band in the spectrum can be assigned. CH stretch from 30002850 cm-1 CH bend or scissoring from 1470-1450 cm-1 CH rock, methyl from 1370-1350 cm-1 CH rock, methyl, seen only in long chain alkanes, from 725-720 cm-1

IR Spectroscopy Tutorial: Alkenes

Alkenes are compounds that have a carbon-carbon double bond, C=C.The stretching vibration of the C=C bond usually gives rise to a moderate band in the region 1680-1640 cm-1. Stretching vibrations of the C=CH bond are of higher frequency (higher wavenumber) than those of the CCH bond in alkanes.

C=C stretch from 1680-1640 cm-1 =CH stretch from 3100-3000 cm-1 =CH bend from 1000-650 cm-1

IR Spectroscopy Tutorial: Aromatics

The =CH stretch in aromatics is observed at 3100-3000 cm-1. Note that this is at slightly higher frequency than is the CH stretch in alkanes. Aromatic hydrocarbons show absorptions in the regions 1600-1585 cm-1 and 1500-1400 cm-1 due to carbon-carbon stretching vibrations in the aromatic ring.

CH stretch from 3100-3000 cm-1 overtones, weak, from 2000-1665 cm-1 CC stretch (in-ring) from 1600-1585 cm-1 CC stretch (in-ring) from 1500-1400 cm-1

IR Spectroscopy Tutorial: Alcohols

Alcohols have characteristic IR absorptions associated with both the O-H and the C-O stretching vibrations.

OH stretch, hydrogen bonded 3500-3200 cm-1

CO stretch 1260-1050 cm-1 (s)

IR Spectroscopy Tutorial: Ketones The carbonyl stretching vibration band C=O of saturated aliphatic ketones appears at 1715 cm-1. Conjugation of the carbonyl group with carbon-carbon double bonds or phenyl groups, as in alpha, betaunsaturated aldehydes and benzaldehyde, shifts this band to lower wave numbers, 1685-1666 cm-1

C=O stretch: aliphatic ketones 1715 cm-1 , -unsaturated ketones 1685-1666 cm-1

IR Spectroscopy Tutorial: Aldehydes

The carbonyl stretch C=O of saturated aliphatic aldehydes appears from 1740-1720 cm-1. As in ketones, if the carbons adjacent to the aldehyde group are unsaturated, this vibration is shifted to lower wavenumbers, 1710-1685 cm-1

HC=O stretch 2830-2695 cm-1 C=O stretch: aliphatic aldehydes 1740-1720 cm-1 alpha, beta-unsaturated aldehydes 1710-1685 cm-1