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THEORY

Fourier Transform Infrared (FTIR) Fourier Transform Infrared (FTIR) spectrometry was developed in order to overcome the limitations encountered with dispersive instruments. The main difficulty was the slow scanning process. A method for measuring all of the infrared frequencies simultaneously, rather than individually, was needed. A solution was developed which employed a very simple optical device called an interferometer. The interferometer produces a unique type of signal which has all of the infrared frequencies fixed into it. The signal can be measured very quickly, usually on the order of one second or so. Thus, the time element per sample is reduced to a matter of a few seconds rather than several minutes. Most interferometers use a beam splitter which takes the incoming infrared beam and divides it into two optical beams. One beam reflects off of a flat mirror which is fixed in place. The other beam reflects off of a flat mirror which is on a mechanism which allows this mirror to move a very short distance (typically a few millimeters) away from the beam-splitter. The two beams reflect off of their respective mirrors and are recombined when they meet back at the beam-splitter. Because the path that one beam travels is a fixed length and the other is constantly changing as its mirror moves, the signal which exits the interferometer is the result of these two beams interfering with each other. The resulting signal is called an interferogram which has the unique property that every data point (a function of the moving mirror position) which makes up the signal has information about every infrared frequency which comes from the source. This means that as the interferogram is measured; all frequencies are being measured simultaneously. Thus, the use of the interferometer results in extremely fast measurements. Because the analyst requires a frequency spectrum (a plot of the intensity at each individual frequency) in order to make identification, the measured interferogram signal cannot be interpreted directly. A means of decoding the individual frequencies is required. This can be accomplished via a well-known mathematical technique called the Fourier transformation. This transformation is performed by the computer which then presents the user with the desired spectral information for analysis. Infrared spectrophotometer is a powerful tool for identifying pure organic and inorganic compounds because, with the exception of a few same mononuclear molecules such as O 2, N2 and Cl2, all molecular species absorb infrared radiation. Each molecular species has a unique

infrared absorption spectrum. Therefore, exact match between the spectrum and of a compound of known structure and the spectrum of analyte unambiguously identifies the analyte. Infrared spans a section of the electromagnetic spectrum by wavenumbers, , in the range of 12,800 to 10 cm-1 and the wavelength, , ranging from 0.78 - 1000m. Both wavenumber and wavelength represent IR absorption. Wavenumber unit is more commonly used in modern IR instruments that are linear in the cm-1 scale. In the contrast, wavelengths are inversely proportional to frequencies. Wavenumber and wavelength can be interconvert using following equation: ( )
( )

(eq. 1)

Transmittance, T, is the ratio of radiant power transmitted by the sample (I) to the radiant power incident on the sample (I0). Absorbance, A, is the logarithm to the base 10 of the reciprocal of the transmittance. ( ) (eq. 2)

The transmittance spectra provide better contrast between intensities of strong and weak bands because transmittance ranges from 0 to 100% T whereas absorbance ranges from infinity to zero. The 0% T and 100% T adjustments should be made immediately before each transmittance or absorbance measurement. To obtain reproducible transmittance measurements, it is essential that the radiant power of the source remain constant while the 100% T adjustment is made and the % T is read from the meter. Like as stated above before, the infrared region of the spectrum encompasses radiation with wave numbers ranging from about 12,800 to 10 cm-1 or wavelengths from 0.78 to 1000 m. From the perspective of both application and instrumentation, the infrared spectrum is conveniently divided into near-, mid- and far- infrared radiation; rough limits of each are shown in table below.

Table 1: Infrared Spectral Regions Region Wavelength ( ) Range, m 0.78 to 2.5 Wavenumber ( ) Range, cm-1 12,800 to 4000 Frequency () Range, Hz 3.8 x 1014 to 1.2 x 1014 1.2 x 1014 to 6.0 x 1012 6.0 x 1012 to 3.0 x 1011 1.2 x 1014 to 2.0 x 1013

Near

Mid

2.5 to 50

4000 to 200

Far

50 to 100

200 to 10

Most used

2.5 to 15

4000 to 670

Figure 1: Instrument Diagram of Basic FTIR Adapted from http://binoybnair.blogspot.com/2007_10_01_archive.html

Figure above shows the instrument diagram for a basic FTIR spectrometer. Radiation of all frequencies from the IR source is reflected into the interferometer where it is modulated by the moving mirror on the left. The modulated radiation is then reflected from the two mirrors on the right through the sample in the compartment at the bottom. After passing through the sample, the radiation falls on the detector. A data acquisition system attached to the detector records the signal and stores it in the memory of a computer as an interferogram. (Courtesy of Thermo Electron Corp., Madison, WI).

Figure 2: IR Spectroscopy Apparatus Adapted from http://chemwiki.ucdavis.edu/Wikitexts/UCD_Chem_205:_Larsen/ChemWiki_Module_Topics/H ow_an_FTIR_Spectrometer_Operates

In most UV-VIS, the cell is located between the monochromator and the detectors in order to avoid photodecomposition of the sample, which may occur of samples, are exposed to the full power of the source. Photodiode array instruments avoid this problem because of the short exposure time of the sample to the beam. In IR radiation, in contrast, is not sufficiently energetic to bring about photodecomposition. Most samples are good emitters of IR radiation. Because of this, the cell compartment is usually located between the source and the monochromator in IR instrument.

As stated before, the components of IR instruments differ significantly from UV-VIS instruments. Thus, IR sources are heated solids and IR detectors respond to heat rather than photons. FTIR which is widely used nowadays, detect all the wavelengths all the time. They have greater light-gathering power than dispersive instruments and consequently better precision. It contains no dispersing element and all wavelengths are detected and measured simultaneously. Instead of monochromator, an interferometer is used to produce interference patterns that contain the infrared spectral information. To obtain radiant power as a function of wavelength, the interferometer modulates the source signal in such a way that it can be decoded by the mathematical technique of Fourier transformation. The energy of infrared radiation can excite vibrational and rotational transitions, but it is insufficient to excite electronic transitions. Variations in rotational levels may give rise to a series of peaks for each vibrational state. The number of molecule can vibrate is related to the number of atoms and the number of bonds, it contains. Infrared absorption occurs not only with organic molecules but also with covalently bonded metal complexes, which are generally active in the longer wavelength infrared region. The major type of molecular vibrations are stretching and bending. Infrared radiation is absorbed and the associated energy is converted into these types of motion. The absorption involves discrete, quantized and energy levels. However, the individual vibrational motion is usually accompanied by other rotational motions. Figure below shows major vibrational modes. Vibrations as stated above fall into stretching and bending. Stretching involves continuous change in the interatomic distance along the axis of the bond between two atoms. While bending are characterized by a change in the angle between two bonds and are of four types; scissoring, rocking, wagging and twisting. Infrared radiation is not energetic enough to bring about the kinds of electronic transitions that have encountered in UV-VIS. Absorption of infrared radiation is thus confined largely to molecular that have small energy differences between various vibrational and rotational states. In order to absorb infrared radiation, a molecule must undergo a net change in dipole moment due to vibrational and rotational motion. However, no net change in dipole moment occurs during the vibration or rotation of homonuclear species such as O2, N2 and Cl2. Consequently, such compounds cannot absorb in infrared. Absorption causes increase in vibration amplitude/rotation frequency.

Figure 3: Types of Molecular Vibrations of CH2 As noted that the approximate frequency (or wave number) at which organic functional group, such as absorbs infrared radiation can be calculated

from the masses of the atoms and the force constant of the bond between them. These frequencies, called group frequencies, are seldom totally invariant because of interactions with other vibrations associated with one or both of the atoms composing the group. Table below lists group frequencies for several common functional groups.

Functional Group Names Alkanes

Absorption Ranges Frequency (cm--1) 3000-2800 1500-1450

Type of Vibration

Alkenes 3100-3000 1675-1600

Alkynes

3300-3200

2200-2100 Aromatic Rings 3100-3000 1600-1580 1500-1450

Alcohols, Phenols

3600-3100 (Note: Phenols MUST have Aromatic Ring Absorptions too) 1300-1000

Nitriles 2300-2200

Ketones

1750-1625 Aldehydes 1750-1625 2850-2800 2750-2700 3400-2400 Carboxylic Acids (Note: This peak always covers the entire region with a VERY BROAD peak.) 1730-1660 Ethers 1300-1000 Esters 1735 1300-1000 Amines: Primary

3500-3200 (TWO PEAKS!) 1640-1560

Amines: Secondary

3500-3200 (ONE PEAK!) 1550-1450

Nitro Groups 1600-1500 1400-1300

Amides

3500-3100 1670-1600 1640-1550

UV- VIS The principle of UV described that molecules have ability to absorb ultraviolet or visible light. UV-vis spectroscopy is useful as an analytical technique for two reasons which are to identify some functional groups in molecules and determining the content and strength of a substance. Spectrophotometers are made up of stable source of radiant energy, a transparent sample container, a device for isolating specific wavelength, a radiation detector which converts transmitted radiation to a usable signal and a signal processor and readout. A wave is usually described in terms of its wavelength, , and frequency, , which is the number of peaks passing a given point per second. Table 1 showed the different regions of wavelength. All the electromagnetic radiation travels through a vacuum at the same velocity. This velocity (c) is called the velocity of light which is 2.99792458 X 108 ms-2. It can be connected to wavelength and frequency as c = .

Region Far ultraviolet Near ultraviolet Visible Near infrared Middle infrared Microwave

Wavelength (nm) 10 - 200 200 - 380 780 - 3000 3000 - 30,000 30,000 - 300,000 300,000 - 1,000,000,000

Table 2: The regions of wavelength.

UV-vis spectrum, primarily provide structural information about the kind and extent of the conjugation of multiple bonds in the compound being analyzed. The absorption of UV-vis

spectroscopy is caused by transfer of energy from the radiation beam to electrons in orbitals of lower energy, causing them to be excited into orbitals of higher energy. The excitation process proceeds by promoting an electron from an occupied to an unoccupied molecular orbital. Every molecule has their own ground electronic states with all electron spins in paired. Most excited electronic states also have all paired electron spins. Excited electronic states may be have two orbital that each of it posses only one electron. The energy of quantum of electromagnetic energy is directly related to its frequency: E = h Where, h = Planks constant = 6.63 x 10 -34 Js (eq. 3)

= frequency (Hz)
This means, the higher energy the frequency of radiation, the greater is its energy. Since = c/ , the energy of electromagnetic radiation is inversely proportional to its wavelength.

(eq. 4)

Most spectra of the solution obey Beers Law. This states that the light absorbed is proportional to the number of absorbing. The second law is Lamberts law. It tells us that the fraction of radiation absorbed is independent of the intensity of the radiation. Combining these two laws gives the Beer-Lambert law: Log10 I0/I = lc Where = I0 = the intensity of the incident radiation I = the intensity of the transmitted radiation = the molar absorption coefficient l = the path length of the absorbing solution (cm) c = the concentration of the absorbing species in mol dm-3

(eq. 5)

(Log10 Io/ I also is called absorbance of optical density or A) The absorbing groups in a molecule are called chromophores. Chromophore (literally colorbearing) group is a functional group, not conjugated with another group, which exhibits a characteristic absorption spectrum in the ultraviolet or visible region. Some of the more important chromophoric groups are list in the table 2. Wavelength, (nm) 175-180 210 160-170 285-400 200-210 205 185 195 160

Name Acetylide Aldehyde Alkynyl Azo Carboxyl Ester Ether Ketone Nitrile

Chromophore -C C -CHO -C C-N=N-COOH -COOR -O-C O -C N

Molar extinction, e 6000 1500 8000 3-25 50-70 50 1000 1000 -

Table 3 : UV absorption maxima.

There are few types of UV-Vis those are famously and widely used namely single-beam instrument, double-beam instrument and multichannel instruments. Figures below shows the block diagram of each instrument:

Figure 4 : Single beam

Figure 2 : Double beam (in space)

Figure 5 : Multichannel

For single beam instrument, 0% transmittance is set with shutter in the beam path while 100% transmittance is set with a reference in the beam path. Measurement is made with the sample in the beam path. While for double beam instrument, sample and reference are measured simultaneously and the signal from reference is substracted from sample signal. Double beam instrument is more widely used because: i) its compensate for variations in the source intensity, ii) compensate for drift in detector and amplifier, iii) compensate for variation in intensity as a function of wavelength.