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CHAPTER 1: ULTRAVIOLET SPECTROSCOPY (UV/VIS) 1.

1 Introduction Ultraviolet (UV) was discovered more than 200 years ago by Johann Ritter. In 1801, he reported in Annalen de Physik that, on the 22nd February, he had detected solar radiation. This is referring to Oldenburg and Eden (2002) in the Ultraviolet Spectroscopy and UV Lasers. According to John and Stephen (2002), the infrared portion of the electromagnetic spectrums spans from about 3.8x1014 Hz to 6 x1012 Hz. If the sample is illuminate by radiation of a particular and discrete wavelength, then absorption of that radiation might occur. Most of the common functional group absorbs IR radiation within the range 200 780 nm. At other wavelength the radiation might not occur. The UV-Vis spectroscopy is the measurement of the wavelength and intensity of absorption of near ultraviolet and visible light by sample. While the UV-Vis spectrometer is an instrument commonly used in the laboratory which is to analyze compounds in the ultraviolet and visible regions of electromagnetic spectrum. The degree of conjugated double or triple bonds and degree of aromaticity is the structure of binders which are evaluated by using UV-Vis spectroscopy reported by Mills and George D (2012). The uv radiation is passed through the sample and absorption radiation occurs. The radiation transmitted is detected by photocells and the spectrometer records the absorption by comparing the difference between the intensity of the radiation passing through and the reference cells. The uv-vis spectroscopy is usually applied to molecules and inorganic ions or complexes in solution. The concentration of an analytic in solution can be determined by applying BeerLambert Law by measuring the absorbance at some wavelength. Beer-Lambert Law stated that absorbance is directly proportional to the path length and the concentration of the absorbing species. Nowadays, the UV-Vis spectroscopy is being upgraded to give better results and expanding the potentials of the UV-Vis field. 1.2 History Ultraviolet visible spectroscopy has been useful to mankind and over the decades of design evolution, photometric analyzers based on UV/VIS absorption have been gained rapid and universal acceptance. Before 1930, the first UV analyzers was developed by Kurt Muller with using the mercury 253.7 nm atomic resonance line as measuring wavelength to monitor elemental mercury in air. In 1939, a sensitive mercury analyzer using GE G4T4 low pressure discharge lamp were describe by Wooden et al. as the source for the 253.7 nm line. Most UV analyzers were developed within petroleum and chemical companies for proprietary use and some were designed by university research facilities. The early instruments used 253.7 nm mercury resonance lines from a germicidal lamp as the measuring wavelength or adapted the Beckman DU laboratory spectrophotometer.

After many failure and poor performances, the split-beam photometric analyzer was invented by DuPont Company that more accurate in monitoring and control process. In 1962, other UV/VIS photometric analyzers such as Teledyne photometric analyzer and the Halikainen UV analyzer were available and were used by several companies. The uses of photometric analyzers were greatly expanded throughout the process industries (Saltzman, 2000). Nowadays, new and improved UV and VIS technology continue to be developed especially it more useful in analytical fields that use modern technology such as equipped with three detector systems with high sensitivity, wide measurement range and ultra-low stray light that allows spectroscopic analysis in a wide variety of fields. 1.3 Theory

The ultraviolet wavelength which is cover a range from 200 to 400 nm and the visible from 400 to 800 nm radiation are found at the end of the electromagnetic spectrum with short wavelength and high frequencies. The UV or visible radiation is absorbed due to the excitation of the outer electrons. The electrons are promoted from their ground state to an excited state when an atom or molecule absorbs the energy. The atoms can rotate and vibrate with respect to each other in a molecule. The vibrations and rotations also have discrete energy levels, which can be said as being packed on top of each electronic level. The absorption of the ultraviolet and visible radiation in organic molecules is restricted to several functional groups (chromophores) which is contains valence electrons of low excitation energy. The spectrum of a molecule containing the chromophores is complex that is because the superposition of rotational and vibrational transitions gives a combination of overlapping lines on the electronic transitions. This will show as a continuous absorption band.

Figure 1: Possible electronic transitions of p, s, and n electrons

* Transitions This transition is where the anti-bonding orbital is being excited by an electron in a bonding s orbital. The energy required is large. For example, methane (which has only C-H bond, and can only undergo * transitions) that shows an absorbance maximum at 125 nm.
n * Transitions This transition is capable for the saturated compounds containing atoms with lone pairs (nonbonding electrons). These transitions usually need less energy than * transitions. The light whose have the wavelength that is in the range from 150 to 250 nm can only initiated this transition. n * and * Transitions The transitions of n or p electrons to the p* excited state is the most absorption spectroscopy of organic compounds that being happened. It was been said like that because the absorption peaks for these transitions fall in an experimentally convenient region of the spectrum (200 700 nm). Other than that, these transitions also need an unsaturated group in the molecule to provide the p electrons. The core principle used behind the absorbance in this spectroscopy is Beer-Lambert Law (Equation1). For a single wavelength, the symbol of A is the absorbance (it is unitless and usually seen as arbitrary units), is for the molar absorptivity of the compound or molecule in solution (M-1cm-1), b is for the path length of the cuvette or sample holder (1 cm long), and c is the concentration of the solution (M). A = bc Equation (1)

1.4

Schematic Diagram

Figure 1 Single beam UV-Vis Spectrometer 3

Figure 2 Double beam spectrometer

Figure 3 Photodiode array spectrometer

1.5

Analyzing The Samples

. There are about three variables in a UV-Vis which are solvent, concentration of the solution being examined and the path length of the cell through which the light passes. The concentration of each samples tested and the cell length are known and the absorbance can be determined from the spectrum. Graph of absorbance against wavelength was constructed as shown in Graph 1. From the Beer-Lambert Law, we can calculate the molar extinction coefficient, .

Graph 1 Graph of absorbance against wavelength

CHAPTER 2: FOURIER TRANSFORM INFRARED SPECTROSCOPY (FT-IR) 2.1 Introduction Fourier Transform Infrared or known as FTIR is a method of infrared spectroscopy that can be used to identify chemicals that are either organic or inorganic and also can be used on solids, liquids, and gases. It also can measure all the Infrared (IR) wavelengths simultaneously which this feature is called the Multiplex or Felgett Advantage and produces a full spectrum. Simply, it can absorb different measurement of the IR frequencies by positioned a sample in the path of an IR beam. The main objective of the FTIR spectroscopic analysis is to determine the chemical functional groups in the sample. This is because the different functional groups can only absorb characteristic frequencies. Other than that, this spectroscopy can analysis any number of components which is up to 50 from single measurement and resolve the interferences automatically. It also can determine the quality or consistency of a sample and the amount of components in a mixture. In addition, this spectroscopy can produce an infrared absorption spectrum that is like a molecular "fingerprint" to identify the types of chemical bonds in a molecule. Just like the fingerprint, no two unique molecular structures can produce the same infrared spectrum so this will make the infrared spectroscopy useful for several types of analysis. 2.2 History In 1880s, infrared spectroscopy becomes a science matter. About ten years later, A. A. Michelson invented the interferometer as to further his studies of the speed of light. With a development of the optical null dispersive spectrophotometer, the infrared spectroscopy had a widespread use. Astrophysicist, Peter Fellgett measure light from celestial bodies by using interferometer and made the very first Fourier Transform Infrared (FT-IR) spectrum. This happened in 1949. But then the further research about this spectrum is a little because of limitations of equipment and requires a very long time which was up to 12 hours just to transform an interferogram into a FT-IR spectrum. When microcomputers can analyse Fourier Transform in late 1960s, commercial FT-IR spectrometers was appeared. The development of Cooley-Tukey algorithm in 1966 which creates the Fast Fourier Transform (FFT) contributed to the commercialisation of FT-IR spectrometers. Again the FT-IR spectrometers were found just a few because it was large and expensive. As the time goes by, with new technologies, the FT-IR spectroscopy system was upgraded and made the cost reduced, availability increased and the capabilities enhanced. 2.3 Theory In spectroscopy, the frequencies which are absorbed are essential, this requires that radiation source covers a broad spectral range and the individual frequencies of radiation are analyzed. In old spectrometer, to disperse light into individual frequencies by using a prism and a slit placed in front of the detector to determine which frequency to reach the detector.

Modern instruments are FTIR spectrometer that obtains the IR spectrum by Fourier transformation of the signal from an interferometer with a moving mirror. (Sawyer et al., 2008). According to Gable (2013) the mathematical expression of Fourier transform can be expressed as

F() =
And the reverse Fourier transform is

f(x) =
Where is an angular frequency and x is the optical path difference in our case. F() is the spectrum and f(x) is called interferogram.

Figure 1.1 : Michelson (Anon, 2006) In a Michelson FTIR consists of Stationary mirror Moving mirror Beamspitter Detector Sample

interferometer experiment interferometer adapted for

The working principle of Michelson Interferometer 1. Source of energy is send through an interferometer and onto the sample. All source radiation gets to the sample. 2. The light passes through a beamsplitter, which sends the light in two directions at right angles. One beam goes to a stationary mirror then back to the beamsplitter. The other goes to moving mirror.

3. The motion of the mirror makes the total path length variable versus that taken by the stationary-mirror beam. When the two meet up again at the beamsplitter, they recombine, but the difference path in path lengths creates constructive and destructive interference. 4. The recombined beam passes through the sample. The sample absorbs all the different wavelengths characteristic of its spectrum, and this subtracts specific wavelengths from the interferogram 5. The detector now reports variation in energy versus time for all wavelengths simultaneously. 6. A laser beam is superimposed to provide a reference for the instrument operation.

2.4 Schematic Diagram Schematic Diagram of FTIR Spectrimeter Layout

Figure 2.1: A FTIR Spectrometer Layout (Martin,2001)

2.5 Procedure The Laboratory Procedure to Analyze the Sample (Anon, 2004). 8

The experiment is conducted to illustrate the use of the FTIR Spectroscopy in order to see the characteristics of the materials. The samples can be prepared in several of way. Sample such as liquid can be placed by dropping one drop of sample in between the two plates of sodium chloride. The drops then will form a thin film between the plates. In addition, for solid samples, it is can be milled with potassium bromide to form a very fine powder. Then it can be analyzed as it compressed into a thin pellet. When conducting the experiment, it is needed to wear rubber glove as FTIR is very sensitive to contaminants. Firstly, 1 mg of samples is added to 200 mg of KBr which is already weight out. The sample needs to be placed in mortar and pestle. Mix the powder by grinding it up until it is well mix. Assemble the press. The silver T goes on the bottom. The silver collar is put on top. The small silver disk is put in the collar. Next, place the powder in the die and put the plunger in. Ensure that the beveled part of the piston is on outside of the press. Since the KBr is very delicate, put the pellet into a petri dish and bring it to the FTIR machine gently. Do a simple step for the FTIR machine before starting the experiment with the real sample. Pass the nitrogen gas through the sample chamber to purge the FTIR machine. Put the plain KBr sample into the special holder and the sample is placed in the chamber. It is advised to not look directly at the IR source, since it is always on. Therefore, take a background scan. The Omnic software program is used to collect the data required. This software which is in the PC is connected to the FTIR machine. Start the scan by choosing the scan menu. After 200 scans, the spectra of the blank KBr will show up. This will be used as the reference to other samples. Next, other unknowns are placed in the holder of FTIR machine one by one. Scan each sample. The background is subtracted from the unknowns and the spectrum is created. The result of the scan will print out. The data is used to observe and characterize the samples.

References Anonymous (2006), Michelson-Morley experiment. Encyclopedia Britannica kids. http://www.kids.britannica.com. Retrieve on 16 March 2013. Anonymous (2004), Laboratory manual . http://courses.washington.edu/jrmatlab/Lab2_FTIR_laboratory.doc. Retrive on 16 March 2013 Gable, K.,(2013) FTIR spectroscopy. http://chemistry.oregonstate.edu. Retrieve on 15 March 2013 John C. Gilbert, Stephen F. Martin.,(2002), Experimental organic chemistry : A miniscale and microscale approach Edition,Brooks/Cole Thomson Learning. Mills and George, D.,(2012), Ultraviolet/visible spectroscopy. http://www.astm.org. Retrieve on 16 March 2013. Martin C.M (2001), Fourier transform infrared spectroscopy. http://spectroscopy.lbl.gov/FTIRMartin/FTIR-Martin.PDF. Retrieve on 14 March 2013. Oldenburg, A. L ,Eden, J. G.,(2002), Ultraviolet spectroscopy and UV laser,371-477 Saltzman,R.S., (2011), Encyclopedia of analytical chemistry,John Willey & Sons, 8328-8331. Sawyer ,L.C.,Grubb, D.T and Meyers, G,F, (2008), Polymer Microscopy Edition.Springer,462.

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