AIM -Identification of organic compounds using FT-IR, NMR, CNMR and mass spectra.
Structure elucidation is the process of determining the chemical structure of a compound. For
organic compounds
Mass spectrum is presentation of the masses of positively charged fragments versus their
relative concentrations. the most intense peak is called the base peak and the intensities of
other peaks including the molecular ion peak, are reported as the percentages of base peak.
sometimes the molecular ion peak can be base peak. The nitrogen rule is helpful to know if
the molecule is of even numbered molecular weight must contain either no nitrogen or even
number of nitrogen odd number molecular weight requires an odd no of nitrogen atom.
Then we simply determine the molecular formula and hydrogen deficiency index. And then
we check the fragmentation, there are no. of rules for predicting prominent peaks using
standard concepts like. and then we check the rearrangement, rearrangement ions are the
fragments whose origin cannot be described by simply cleavage but are a result of
intramolecular atomic rearrangement during fragmentation. rearrangement involves migration
of H-atoms molecules that contain a hetero atom. to undergo Mc-Lafferty rearrangement a
molecule must possess an appropriately located hydro atom, π system to C=O system.
Rearrangement peaks can be recognized by considering the mass number. a cleavage of even
numbered molecular ion gives an odd numbered fragment ion and odd numbered molecular
ion gives an even numbered fragment ion.
Mass spectrometry is a powerful analytical tool with many applications in pharmaceutical
and biomedical field. the increase in sensitivity and resolution of the instrument in analysis of
pharmaceuticals and complex metabolites of biological systems. compared with other
techniques, mass spectroscopy is the only technique for molecular weight determination,
through which we can predict the molecular formula. it is based on the conversion of the
sample into ions, which are then identified by mass-to-charge ratio. mass spectroscopy
provides elemental information which is an important information to interpret complex
mixture components. thus, it is important tool for structure elucidation of unknown
compound. mass spectroscopy also helps in quantitative elemental analysis. It is also non-
invasive tool that permits in-vivo studies in human.
FT-IR Infrared spectroscopy (IR spectroscopy) is an important technique that deals with the
interaction of a molecule with IR range of the electromagnetic spectrum ranging from 4000 to
400 cm
IR spectroscopy is an important tool to elucidate the chemical structure. In fact, this structure
elucidation depends mainly on three facts: (1) wavenumber, which reflects the position of
absorbance and depends on the energy required for absorbance; (2) intensity of the
absorbance peak, which is related to dipole/strength of bond present in the molecules; (3)
shape of IR band may be broad or sharp. FTIR helps in identification of functional group and
structure elucidation. Entire IR region is divided into group frequency region and fingerprint
region. Range of group frequency is 4000-1500 cm-1 while that of finger print region is 1500-
400 cm-1.
Each atom of the molecule is connected by bond and each bond requires different IR region
so characteristic peaks are observed. This region of IR spectrum is called as finger print
region of the molecule. It can be determined by characteristic peaks. FTIR also helps in
detection of impurities. IR spectrum of the test sample to be determined is compared with the
standard compound. If any additional peaks are observed in the IR spectrum, then it is due to
impurities present in the compound.
UV spectroscopy is useful in the structure elucidation of organic compounds. The presence or
absence of a particular absorption band at a particular wavelength may be regarded as an
evidence for the presence or absence of a particular chromophore in the compound.
A plot of frequencies of the absorption peaks versus peak intensities constitutes an NMR
spectrum. interpretation of H-NMR spectra is based on consideration of three interrelated
types of information – integration of signal peaks, chemical shift & spin-spin coupling.
integration of the signal peaks provides the ratio of hydrogen atoms in the compound and the
chemical shift relates the position of the signal in the spectrum with chemical environment.
spin-spin coupling explains the interaction about neighbouring nuclei, giving crucial
structural insights.
Examples
1 ) C9H8O4
Acetylsalicylic acid
HDI = 9-8/2+1 =6
UV-VISIBLE
FTIR
MASS SPECTRA
HNMR
IR HNMR MASS U.V
C=C stretch (aromatic) = 7.3 = Ar-H MOL. MASS and
1600-1400 molecular ion peak = 180 λ max =230 nm
Base peak = 120 λ max = 300 nm
C=O stretch (ester) = 1750 11.9 = COOH Fragmentation
C-OH stretch = 1200
Conclusion – on the basis of spectral data it is concluded that the structure is aspirin.
2) C7H7NO2
FTIR
HNMR
10 8 6 4 2 0
PPM
3) C22H17N4S
FTIR
MASS
HNMR
Reference -Silverstein, R. M., Webster, F.X., Kiemle, D.J, & Bryce, Spectrometric Identification of
Organic Compounds, Johnwiley & Sons.
