Read Chemistry
– In this subject, we will discuss Infrared Spectroscopy: Instrumental Method for Detecting Functional Groups.
Infrared Spectroscopy
– Infrared spectroscopy (IR spectroscopy ): is a simple, rapid, and nondestructive instrumental technique that can give evidence for the presence of various functional groups.
– If you had a sample of unknown identity, among the first things you would do is obtain an infrared spectrum, along with determining its solubility in common solvents and its melting and/ or boiling point.
– Infrared spectroscopy, as with all forms of spectroscopy, depends on the interaction of molecules or atoms with electromagnetic radiation.
– Infrared radiation causes atoms and groups of atoms of organic compounds to vibrate with increased amplitude about the covalent bonds that connect them.
– IR radiation is not of sufficient energy to excite electrons, as is the case when some molecules interact with visible, ultraviolet, or higher energy forms of light.
– Since the functional groups of organic molecules include specific arrangements of bonded atoms, absorption of IR radiation by an organic molecule will occur at specific frequencies characteristic of the types of bonds and atoms present in the specific functional groups of that molecule.
– These vibrations are quantized, and as they occur, the compounds absorb IR energy in particular regions of the IR portion of the spectrum.
Fourier transform infrared (FTIR) spectrometer
– The figure shows a diagram of a Fourier transform infrared (FTIR) spectrometer.
– FTIR spectrometers employ a Michelson interferometer, which splits the radiation beam from the IR source so that it reflects simultaneously from a moving mirror and a fixed mirror, leading to interference.
– After the beams recombine, they pass through the sample to the detector and are recorded as a plot of time versus signal intensity, called an interferogram.
– The overlapping wavelengths and the intensities of their respective absorptions are then converted to a spectrum by applying a mathematical operation called a Fourier transform.
– The FTIR method eliminates the need to scan slowly over a range of wavelengths, as was the case with older types of instruments called dispersive IR spectrometers, and therefore FTIR spectra can be acquired very quickly.
– FTIR method also allows greater throughput of IR energy.
– The combination of these factors gives FTIR spectra strong signals as compared to background noise (i.e., a high signal-to-noise ratio) because radiation throughput is high and rapid scanning allows multiple spectra to be averaged in a short period of time.
– The result is enhancement of real signals and cancellation of random noise.
– An infrared spectrometer (Fig. 1) operates by passing a beam of IR radiation through a sample and comparing the radiation transmitted through the sample with that transmitted in the absence of the sample.
– Any frequencies absorbed by the sample will be apparent by the difference. The spectrometer plots the results as a graph showing absorbance versus frequency or wavelength.
Wavenumbers
The position of an absorption band (peak) in an IR spectrum is specified in units of wavenumbers (ῡ).
Wavenumbers are the reciprocal of wavelength when the wavelength is expressed in centimeters (the unit is cm-1), and therefore give the number of wave cycles per centimeter.
The larger the wavenumber, the higher the frequency of the wave, and correspondingly the higher the frequency of the bond absorption.
IR absorptions are sometimes, though less commonly, reported in terms of wavelength (λ), in which case the units are micrometers (μm; old name micron, μ).
Wavelength is the distance from crest to crest of a wave.
– In their vibrations, covalent bonds behave as if they were tiny springs connecting the atoms.
– When the atoms vibrate, they can do so only at certain frequencies, as if the bonds were “tuned.”
– Because of this, covalently bonded atoms have only particular vibrational energy levels; that is, the levels are quantized.
– The excitation of a molecule from one vibrational energy level to another occurs only when the compound absorbs IR radiation of a particular energy, meaning a particular wavelength or frequency.
– Note that the energy (E ) of absorption is directly proportional to the frequency of radiation (ʋ) because ΔE = hʋ, and inversely proportional to the wavelength (λ) because c/λ and therefore ΔE = hc / λ
– Molecules can vibrate in a variety of ways.
– Two atoms joined by a covalent bond can undergo a stretching vibration where the atoms move back and forth as if joined by a spring.
– Three atoms can also undergo a variety of stretching and bending vibrations.
Characteristic Infrared Absorptions of Groups
– The frequency of a given stretching vibration in an IR spectrum can be related to two factors.
– These are the masses of the bonded atoms—light atoms vibrate at higher frequencies than heavier ones—and the relative stiffness of the bond.
– These factors are accounted for in Hooke’s law, a relationship you may study in introductory physics.
– Triple bonds are stiffer (and vibrate at higher frequencies) than double bonds, and double bonds are stiffer (and vibrate at higher frequencies) than single bonds.
– We can see some of these effects in this Table:
– Notice that stretching frequencies of groups involving hydrogen (a light atom) such as C-H, N–H, and O–H all occur at relatively high frequencies:
– Notice, too, that triple bonds vibrate at higher frequencies than double bonds:
– Not all molecular vibrations result in the absorption of IR energy.
– For a vibration to occur with the absorption of IR energy, the dipole moment of the molecule must change as the vibration occurs.
– Thus, methane does not absorb IR energy for symmetric stretching of the four C-H bonds; asymmetric stretching, on the other hand, does lead to IR absorption.
– Symmetrical vibrations of the carbon-carbon double and triple bonds of ethene and ethyne do not result in the absorption of IR radiation, either
Solved problem on Infrared Spectroscopy
strategy and answer:
– For an infrared absorption to occur there must be a change in the dipole moment of the molecule during the stretching process.
– Since 3-hexyne is symmetrical about its triple bond, there is no change in its dipole moment as stretching takes place, hence there is no IR absorption from the triple bond.
– Vibrational absorption may occur outside the region measured by a particular IR spectrometer, and vibrational absorptions may occur so closely together that peaks fall on top of peaks.
– Other factors bring about even more absorption peaks.
– Overtones (harmonics) of fundamental absorption bands may be seen in IR spectra even though these overtones occur with greatly reduced intensity.
– Bands called combination bands and difference bands also appear in IR spectra.
– Because IR spectra of even relatively simple compounds contain so many peaks, the possibility that two different compounds will have the same IR spectrum is exceedingly small.
– It is because of this that an IR spectrum has been called the “fingerprint” of a molecule.
– Thus, with organic compounds, if two pure samples give different IR spectra, one can be certain that they are different compounds.
– If they give the same IR spectrum, then they are very likely to be the same compound.
Reference: Organic chemistry / T.W. Graham Solomons, Craig B.Fryhle, Scott A. Snyder, / ( eleventh edition) / 2014.
