- —The value of absorption frequency is shifted if the force constant of a bond changes with its electronic structure.
- — Frequency shifts also take place on working with the same substance in different states (solids, liquids & vapour).—
- — A substance usually absorbs at higher frequency in a vapour state as compared to liquid and solid states.
Factors responsible for shifting the vibrational frequencies from their normal values
- —Coupled vibrations
- —Fermi resonance
- —Electronic effects
- —Hydrogen bonding
COUPLED VIBRATIONS
- —An isolated C-H bond has only one stretching vibrational frequency where as methylene group shows two stretching vibrations, symmetrical and asymmetrical.
- —Because of mechanical coupling or interaction between C-H stretching vibrations in the CH2 group.
- —Assymetric vibrations occur at higher frequencies or wave numbers than symmetric stretching vibrations.
- —These are known as coupled vibrations because these vibrations occur at different frequencies than that required for an isolated C-H stretching.
- —A strong vibrational coupling is present in carboxylic acid anhydrides in which symmetrical and asymmetrical stretching vibrations appear in the region 1720 – 1825 cm-1.
The interaction is very effective probably because of the partial double bond character in the carbonyl oxygen bonds due to resonance which also keeps the system planar for effective coupling.
Requirements
- —For interaction to occur, the vibrations must be of same symmetry species.
- —There must be a common atom between the groups for strong coupling between stretching vibrations.
- —For coupling of bending vibrations , a common bond is necessary.
- —Interaction is greatest when coupled groups absorb, individually, near the same frequency.
- —Coupling is negligible when groups are separated by one or more carbon atoms and the vibrations are mutually perpendicular.
—FERMI RESONANCE
—Resonance
-A vibration of large amplitude produced by a relatively small vibration.
—Coupling of two fundamental vibration modes produces two new modes of vibration ,with frequencies higher and lower than that observed in absence of interaction. Interaction can also take place between fundamental vibrations and overtones or combination tone vibrations and such interactions are known as Fermi Resonance.
—Resonance
-A vibration of large amplitude produced by a relatively small vibration.
—Coupling of two fundamental vibration modes produces two new modes of vibration ,with frequencies higher and lower than that observed in absence of interaction. Interaction can also take place between fundamental vibrations and overtones or combination tone vibrations and such interactions are known as Fermi Resonance.
—In this , a molecule transfers its energy from fundamental vibrational level to overtone or combination tone level and back.
—
—Resonance pushes the two levels apart and mixes their character, consequently each level has partly fundamental and partly overtone or combinat
—
—For eg. symmetrical stretching vibration of CO2 in Raman spectrum shows band at 1337 cm-1.The two bending vibrations are equivalent and absorb at the same frequency of 667.3cm-1.—
— The first overtone of this is 2 X 667.3 = 1334.6 cm-1..
— Fermi resonance occurs
—There is mixing of 1337cm-1 and 1334.6 cm-1to give two bands at 1285.5 cm-1 and at 1388.3 cm-1 with intensity ratio 1 : 0.9 respectively.
Hydrogen bonding
—It occurs in any system containing a proton donor group(X-H) and a proton acceptor. if the s-orbital of the proton can effectively overlap the P or π orbital of the acceptor group.
—The stronger the hydrogen bond, the longer the O-H bond, the lower the vibration frequency and broader and more intense will be the absorption band.
—
—The N-H stretching frequencies of amines are also affected by hydrogen bonding as that of the hydroxyl group but frequency shifts for amines are lesser than that for hydroxyl compounds.
—
— Because nitrogen is less electronegative than oxygen so the hydrogen bonding in amines is weaker than that in hydroxyl compounds.
—
—Intermolecular hydrogen bonds gives rise to broad bands, while intramolecular hydrogen bonds give sharp and well defined bands.
—
—The inter and intramolecular hydrogen bonding can be distinguished by dilution.
—
—Intramolecular hydrogen bonding remains unaffected on dilution and as a result the absorption band also remains unaffected where as in intermolecular, bonds are broken on dilution and as a result there is a decrease in the bonded O-H absorption .
—
—
The strength of hydrogen bonding is also affected by :
—
—Ring strain
—Molecular geometry
—Relative acidity and basicity of the proton donor and acceptor groups
Electronic effect
—Changes in the absorption frequencies for a particular group take place when the substituents in the neighbourhood of that particular group are changed.
—
It includes :
- —.Inductive effect
- —.Mesomeric effect
- —.Field effect
INDUCTIVE EFFECT
—
—The introduction of alkyl group causes +I effect which results in the lengthening or the weakening of the bond
—Hence the force constant is lowered and wave number of absorption decreases.
—Let us compare the wave numbers of v (C=O) absorptions for the following compounds :
—Formaldehyde (HCHO) 1750 cm-1.
—Acetaldehyde (CH3CHO) 1745 cm-1.
—Acetone (CH3COCH3) 1715 cm-1.
—
—Introduction of an electronegative atom or group causes –I effect which results in the bond order to increase.
—Hence the force constant increases and the wave number of absorption rises.
—
Mesomeric effect :
— It causes lengthening or the weakening of a bond leading in the lowering of absorption frequency.
— As nitrogen atom is less electronegative than oxygen atom, the electron pair on nitrogen atom in amide is more labile and participates more in conjugation.
—
— Due to this greater degree of conjugation, the C=O absorption frequency is much less in amides as compared to that in esters.
FIELD EFFECT
—In ortho substituted compounds, the lone pair of electrons on two atoms influence each other through space interactions and change the vibrational frequencies of both the groups.
—This effect is called field effect.
—
—
No comments:
Post a Comment