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Infrared spectroscopy

(IR spectroscopy)

Chapter 12 - IR spectroscopy

How to identify a given organic molecule ???


A combination of techniques need to be used to determine the molecular structure of an organic compound. The following gives a list. Method C, H, N analysis Mass spectroscopy UV spectroscopy IR spectroscopy
1H

Information obtained Empirical formula Molecular mass Conjugation Functional groups Number and arrangement of atoms

and 13C NMR spectroscopy

The last three rely on interaction of light with matter


Chapter 12 - IR spectroscopy

Electromagnetic spectrum

What is the nature of light ?


Chapter 12 - IR spectroscopy

Light acts as waves

Chapter 12 - IR spectroscopy

Light also has particle character

Energy (E) of a single photon is given by the following formula

E = h = hc/

Where, h = Plancks constant, = frequency c = velocity of light = wavelength

Chapter 12 - IR spectroscopy

Interaction of light with matter


All organic compounds absorb electromagnetic radiation, of only certain wavelengths and transmit the rest. When organic molecules absorb energy in the UV-vis region, they undergo electronic transitions (electrons in the ground state go to higher states known as excited state) (Absorption spectroscopy) Photon energies associated with infrared are not large enough to excite electrons, but may induce vibrational excitation of covalently bonded atoms and groups. -(Infrared spectroscopy)
Chapter 12 - IR spectroscopy

Shown below is a cartoon representation of light waves of different wavelength showing which region causes what transition

Electronic Transitions

Vibrational Transitions

Absorption spectroscopy

Infrared spectroscopy

Infrared spectroscopy IR spectroscopy is an useful tool to identify functional groups in organic molecules IR spectroscopy is a result of molecular vibrational transitions that occur when light interacts with matter Molecules are always vibrating For a molecule to be IR active, the vibrations should give rise to a net change in dipole moment

Chapter 12 - IR spectroscopy

Molecular vibrations
The covalent bonds in molecules are not rigid sticks or rods, but are more like stiff springs that can be stretched and bent. bond length changes bond angle changes

stretching (symmetric and asymmetric) bending (scissoring, rocking, wagging and twisting)

Chapter 12 - IR spectroscopy

Cartoon representation of the stretching and bending vibrations

Check this link for animation: http://en.wikipedia.org/wiki/Infrared_spectroscopy


Chapter 12 - IR spectroscopy

By considering the atoms as point masses, linked by a 'spring' having a force constant f (sometimes denoted as k) and following Hooke's Law, equation shown below can be utilized to approximate the characteristic stretching frequency (in cm-1) of a diatomic molecule with the masses of two atoms being m1 and m2,

where, = m1m2/(m1+m2) = reduced mass


or

c = velocity of light. IR energy in a spectrum is usually measured as wavenumber (cm-1), the inverse of wavelength and proportional to frequency

1/ =

Chapter 12 - IR spectroscopy

IR spectra of ethyl alcohol

The above figure shows the range of frequency used by organic chemists for structural analysis
Chapter 12 - IR spectroscopy

Specific IR absorbed by an organic molecule is related to its structure


Shown below is the IR of a simple alkane. Note the important IR peaks

-C-C1490 cm-1 -C-H 2850 - 3000 cm-1 n-hexane

Not all vibrations can be assigned


Chapter 12 - IR spectroscopy

IR of an alkene

Important peaks are shown here

Chapter 12 - IR spectroscopy

IR of an alkyne

Chapter 12 - IR spectroscopy

C-H stretch 2850 to 2960 cm-1 C-C 800-1300 cm-1

3100 cm-1

C=C 1630 cm-1

3300 cm-1

C C
2150 cm-1

Chapter 12 - IR spectroscopy

The previous slide highlights the differences between the IR spectra of alkane, alkene and an alkyne. Note that C-C single bond has lower stretching frequency than a C=C double bond which in turn vibrates at lower energy than CC triple bond

Other important examples are listed in the following

Chapter 12 - IR spectroscopy

Hydrocarbons

2850-3300 cm-1 (Sharp, strong to medium)

Note that IR vibration of O-H is greater than N-H which in turn is greater than C-H

Differences in the force constants lead to this trend


Chapter 12 - IR spectroscopy

IR spectra of n-octanol CH3-(CH2)7-OH

-O-H, broad and intense

NH2

IR spectra of 3-methyl butamine


-N-H, Sharp and medium intensity

Carbonyls
Carbonyls give a strong, sharp peak in the wavenumber

range 1670 to 1780 cm1

Chapter 12 - IR spectroscopy

O R NH2

O R OH

Amides
1630 1690 cm-1

Carboxylic acid
1670 1720 cm-1

Chapter 12 - IR spectroscopy

Regions of Infrared spectrum

Most functional groups absorb at about the same energy and intensity, independent of the molecule they are in Characteristic higher energy IR absorptions (1500 to 4000 cm-1) can be used to confirm the presence of a functional group in a molecule IR spectrum has lower energy region (400 to 1500 cm-1) characteristic of molecule as a whole. This region is called fingerprint region

Chapter 12 - IR spectroscopy

Chapter 12 - IR spectroscopy

Some General Trends

Stretching frequencies are higher than corresponding bending frequencies. Bonds to hydrogen have higher stretching frequencies than those to heavier atoms. Triple bonds have higher stretching frequencies than corresponding double bonds, which in turn have higher frequencies than single bonds.

Chapter 12 - IR spectroscopy

Sample problems Predict the IR absorptions for the following by using the IR chart

Chapter 12 - IR spectroscopy

Which IR spectrum corresponds to what molecule ?

IR spectroscopy can be used to monitor the progress of a reaction Assume that you are dehydrating 1-methylcyclohexanol to yield 1-methylcyclohexene. How could you use IR spectroscopy to determine when the reaction is complete ?
OH - OH