An Introduction

Spectroscopy
seeing the unseeable Using electromagnetic radiation as a probe to obtain information about atoms and molecules that are too small to see. Electromagnetic radiation is propagated at the speed of light through a vacuum as an oscillating wave.

electromagnetic relationships: = c 1/

E = h
E = hc/

E
E 1/

= wave length = frequency c = speed of light E = kinetic energy h = Plancks constant

Encompasses radiation with wavenumbers ranging from about 12,800 to 10 cm-1 or wavelengths from 0.78 to 1000 m Subdivided into three regions: the near-IR, the mid-IR and the far-IR

Molecular absorption - IR absorption, emission and reflection spectra can be rationalized by assuming that all arise from various changes in energy brought about by transitions of molecules from one vibrational or rotational energy state to another.

To absorb IR radiation, a molecule must undergo a net change in dipole moment as it vibrates or rotates. If the frequency of the radiation exactly matches a natural vibrational frequency of the molecule, absorption of the radiation takes place that produces a change in the amplitude of the molecular vibration.

No net change in dipole moment occurs during the vibration or rotation of homonuclear species such as O2, N2, or Cl2. As a result, such compounds cannot absorb IR radiation. With the exception of a few compounds of this type, all other molecular species absorb IR radiation.

Stretching vibration - involves a continuous change in the interatomic distance along the axis of the bond between two atoms. - symmetric and assymetric Bending vibration - characterized by a change in the angle between two bonds. - scissoring, rocking, wagging and twisting

Symmetrical Stretching

Asymmetrical Stretching

Bending:

Scissoring

Rocking

Wagging

Twisting

Bonds are not rigid but behave like a spring with a mass at either end.
Obey Hookes Law: F = -ky This gives rise to a characteristic frequency for the vibration:

1 2

k reduced _ mass
m1m2 m1 m2

reduced _ mass

Characteristic frequency for the vibration:

1 2

k reduced _ mass

The frequency is affected by

the masses of the atoms in the bond the strength of the bond

The lower the mass, the higher the vibrational frequency.

Stretching frequencies for bonds to carbon: C-H > C-C > C-N > C-O

1 2

k reduced _ mass

The stronger the bond, the higher the vibrational frequency.

Stretching frequencies
CC > C=C > C-C CN > C=N > C-N CO > C=O > C-O C(sp)-H > C(sp2)-H > C(sp3)-H

1 2

k reduced _ mass

There are 3n-6 possible vibrational modes in a nonlinear molecule with no symmetry
Symmetry reduces the number of possible vibrational modes.

Water has 3 possible vibrational modes. Formaldehyde has 6. There are 3n 5 vibrational modes in a linear molecule Each of the vibrations is called a normal

mode

In addition, the vibration of a particular bond in a molecule affects the whole molecule.

The various harmonics of a bond vibration can combine and lead to a number of combinational bands. The intensity of these bands is usually 1/100 the intensity of the main vibrational absorptions. These make up the fingerprint region. (occur at <1250 cm-1)

In order for a vibration mode to absorb in the infrared, the vibrational motion must cause a change in the dipole moment of the bond. The intensity of the IR peaks is proportional to the change in dipole moment that a bond undergoes during a vibration.
C=O bonds absorb strongly. C=C bonds generally absorb much less.

Dispersive spectrophotometers with a grating monochromator Fourier transform spectrometers employing an interferometer and Nondispersive photometers using a filter or an absorbing gas that are used for analysis of atmospheric gases at specific wavelengths

FTIR instruments have distinct advantages over dispersive spectrometers: 1. Better speed and sensitivity (Felgett advantage) 2. Increased optical throughput (Jacquinot advantage) 3. Internal laser reference (Connes advantage) 4. Simpler mechanical design 5. Elimination of stray light and emission contributions 6. Powerful data station

IR SOURCES AND TRANSDUCERS

The Nernst Glower - composed of rare earth oxides formed into a cylinder having a diameter of 1 tp 3 mm and a length of 2 to 5 cm The Globar - a silicon carbide rod usually about 5cm lon and 5mm in diameter Incandescent Wire Source - tightly wound spiral of nichrome wire

The Mercury Arc (far-IR region) - consist of quartz-jacketed tube containing mercury vapor at a pressure greater than 1 atm The Tungsten Filament Lamp (near-IR region) The Carbon Dioxide Laser Source - used for monitoring the concentrations of certain atmospheric pollutants and determining absorbing species in aqueous solutions

Pyroelectric Transducers -found in photometers, FTIR spectrometers and dispersive spectrophotometers Photoconducting Transducers - found in FTIR instruments Thermal Transducers - found in older dispersive instruments but are too slow to be used in FTIR spectrometers

Used to identify organic compounds

Easy to use

IR spectroscopy provides a 100% identification if the spectrum is matched. If not, IR at least provides information about the types of bonds present.
liquids analyzed between salt plates solids in a KBr pellet small amounts of unknowns via an FTIR microscope analysis time typically < 10 minutes

Inexpensive

FTIR spectrophotometers are found in most labs.

IR is used to measure the vibrational frequencies of bonds in the molecule.

Bonds are not rigid. A bond can be viewed as a spring with a weight at each end. Each bond has a characteristic frequency. The IR scans a range of frequencies (in the infrared part of the electromagnetic spectrum). Any frequency which matches the characteristic frequency of a bond will be absorbed.

Fourier Transform Infrared Spectrophotometer

Uses an interferometer and polychromatic light (all frequencies used at one time, instead of one at a time) to generate an interferogram. The interferogram is then mathematically decoded by a Fourier transformation. interferogram
after the Fourier transformation
intensity vs frequencyan IR spectrum intensity vs time

from http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/InfraRed/infrared.h tm

Pay the most attention to the strongest absorptions:

-C=O -OH -NH2 -CN -NO2

Pay more attention to the peaks to the left of the fingerprint region (>1250 cm-1).

Pay the most attention to the strongest absorptions. Pay more attention to the peaks to the left of the fingerprint region (>1250 cm-1). Note the absence of certain peaks. Be wary of O-H peaks, water is a common contaminant.

Functional group

wavenumber (cm-1)

sp3 C-H str sp2 C-H str sp C-H str O-H str O-H str in COOH N-H str aldehyde C-H str

~2800-3000 ~3000-3100 ~3300 ~3300 (broad*) ~3000 (broad*) ~3300 (broad*) ~2700, ~2800

*The peak is broad when H bonding is extensive. Otherwise, the peak can be sharp.

Functional group

wavenumber (cm-1)

C=C isolated C=C conjugated C=C aromatic CN CC C=O ester C=O aldehyde, ketone,
or acid

C=O

amide

~1640-1680 ~1620-1640 ~1600 just above 2200 just below 2200 ~1730-1740 ~1710 (aldehyde can run 1725) ~1640-1680

Look for whats there and whats not there. C-H absorption The wavenumber will tell you sp3(C-C), sp2(C=C), sp (CC) and perhaps aldehyde. Carbonyl (C=O) absorption Its presence means the compound is an aldehyde, ketone, carboxylic acid, ester, amide, anhydride or acyl halide. Its absence means the compound cannot be any of the carbonyl-containing compounds.

O-H or N-H absorption

This indicates either an alcohol, N-H containing amine or amide, or carboxylic acid.

CC and CN absorptions
Be careful: internal triple bonds often do not show up in IR spectra.

C=C absorption
Can indicate whether compound is alkene or aromatic.

N-O of NO2 absorption

This is a distinctive, strong doublet that it pays to know (1515-1560 & 1345-1385 cm-1).

Read the scale for the value of the wavenumbers (be able to interpolate), or Read the wavenumbers in the table provided.

no O-H str no N-H str no sp or sp2 C-H str

no C=O str no C=C str C-H bend This is an alkane.

sp3 C-H str

SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 10/15/09)

N-H str 1 amine

sp3 C-H str

This is a primary alkyl amine. SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 10/16/09)

THANK YOU !!