Faculty of Engineering Metallurgical Engineering and Materials Science Graduate Studies

Hana jamhuoer MME 662

"Reporter about IR and Glasses studies"

Introduction

The light our eyes see is but a small part of a broad spectrum of electromagnetic radiation. On the immediate high energy side of the visible spectrum lies the ultraviolet, and on the low energy side is the infrared. The wavelength range for infrared from 2,500 to 16,000 nm, with a corresponding frequency range from 1.9*1013 to 1.2*1014 Hz. The infrared portion of the electromagnetic spectrum is divided into three regions; the near-, mid- and far- infrared, named for their relation to the visible spectrum. The far-infrared, approximately 40010 cm-1 (100030 m), lying adjacent to the microwave region, has low energy and may be used for rotational spectroscopy. The mid-infrared, approximately 4000-400 cm-1 (301.4 m) may be used to study the fundamental vibrations and associated rotational-vibrational structure. The higher energy near-IR, approximately 14000-4000 cm-1 (1.40.8 m) can excite overtone or harmonic vibrations.

IR radiation supplies sufficient energy to produce translational, rotational, and vibrational motion in molecules. The measurement of the characteristic IR energies (photons) that correspond to these transitions results in a spectrum. Based on its atomic structure, each molecule produces a unique and characteristic IR spectrum. The specific number and position of absorption bands for any molecule are governed by its degrees of freedom, its functional groups, and the IR selection rules. A spectral pattern, sometimes called a fingerprint, is used to identify an unknown material when the absorptions in its spectrum are matched with the absorptions in the spectrum of a known material. Infrared spectroscopy is the measurement of the wavelength and intensity of the absorption of mid-infrared light by a sample. Mid-infrared is
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energetic enough to excite molecular vibrations to higher energy levels. The wavelength of infrared absorption bands is characteristic of specific types of chemical bonds, and infrared spectroscopy finds its greatest utility for identification of organic and organ metallic molecules.

IR Spectroscopy Definition
IR spectroscopy can be defined as a method for the identification of substances based on their absorption of IR wavelength.

Applications of IR spectroscopy
Identification of all types of organic & many types of inorganic compounds. Determination of functional groups. Identification of chromatographic effluents. Quantitative determination of compounds in mixtures. Determination of molecular composition & stereochemistry. Determination of molecular orientation (Polymers & Solutions) .

Theory of Infrared Absorption

For a molecule to absorb IR, the vibrations or rotations within a molecule must cause a net change in the dipole moment of the molecule. The alternating electrical field of the radiation (remember that electromagnetic radiation consists of an oscillating electrical field and an oscillating magnetic field, perpendicular to each other) interacts with fluctuations in the dipole moment of the molecule. If the frequency of the radiation matches the vibrational frequency of the molecule then radiation will be absorbed, causing a change in the amplitude of molecular vibration. Molecular Rotations
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Rotational transitions are of little use to the spectroscopist. Rotational levels are quantized, and absorption of IR by gases yields line spectra. However, in liquids or solids, these lines broaden into a continuum due to molecular collisions and other interactions. Molecular Rotations (cont)

Vibrational-Rotational Transitions In general, a molecule which is an excited vibrational state will have rotational energy and can lose energy in a transition which alters both the vibrational and rotational energy content of the molecule. The total energy content of the molecule is given by the sum of the vibrational and rotational energies. For a molecule in a specific vibrational and rotational state, denoted by the pair of quantum numbers (v, J), we can write its energy as: E(v, J)=Evib(v) + Erot(J) Transitions (cont) The energies of these three transitions form a very distinctive pattern. If we consider the lower vibrational state to be the initial state, then we can label the absorption lines as follows. Transitions for which the J quantum number

decreases by 1 are called P-branch transitions, those which increase by 1 are

called R-branch transitions and those which are unchanged are called Qbranch transitions. Vibrational Motion Subdivided into so-called normal modes of vibration which rapidly increase with the number of atoms in the molecule. Each of these normal vibrational modes contributes RT to the average molar energy of the substance and is a primary reason why heat capacities increase with molecular complexity. If there are Xvib modes of vibration, then the vibrational energy contributes Xvib(RT) to the average molar energy of the substance.

Stretching and Bending

Stretching Vibrations

Quantum Treatment of Vibrations Transitions in vibrational energy levels can be brought about by absorption of radiation, provided the energy of the radiation exactly matches the difference in energy levels between the vibrational quantum states and provided also that the vibration causes a fluctuation in dipole. Infrared measurements permit the evaluation of the force constants for various types of chemical bonds.

Infrared Spectra
An IR spectrum displays detector response as percent transmittance ( % T) on the y-axis, and IR frequency in terms of wave number (cm-1 ) on the x-axis, as shown in Figure 2. The detector response indicates the extent of interaction of the IR electromagnetic radiation with the sample as it is proportional to the resultant intensity of IR radiation that reaches the detector after passing through the sample. Tw o types of interactions-absorption and transmission are important in the typical IR experiment. When the molecule in the sample compartment of the spectrometer is exposed to a source of continuous IR radiation, the photons of discrete energy units that are absorbed by the molecule do not reach the detector. The IR spectrum reveals these missing photons, or absorptions, as a series of well-defined, characteristic, and reproducible absorption bands. Photons that are not absorbed by the sample are transmitted to
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the detector essentially unaltered. For a given wavelength or frequency of IR radiation striking a sample, these two interactions are inversely related through the following equation:

Or A = log(I0 / I1) Where A=absorbance, T=transmittance (% T/100) And I0 and I are the intensities of radiation beforeand after transmission through the sample. Figure 1 . I R spectrum of gelatin plotted as percent transmittance (% T) on the y-axis, and IR frequency in terms o f wave number(CM-1 ) on t h e xaxis..

Infrared Instruments
An infrared spectrophotometer is an instrument that passes infrared light through an organic molecule and produces a spectrum that contains a plot of the
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amount of light transmitted on the vertical axis against the wavelength of infrared radiation on the horizontal axis. In infrared spectra the absorption peaks point downward because the vertical axis is the percentage transmittance of the radiation through the sample. Absorption of radiation lowers the percentage transmittance value. Since all bonds in an organic molecule interact with infrared radiation, IR spectra provide a considerable amount of structural data.

Fourier transform infrared (FTIR) spectroscopy

Is a measurement technique that allows one to record infrared spectra. Infrared light is guided through an interferometer and then through the sample (or vice versa). A moving mirror inside the apparatus alters the distribution of infrared light that passes through the interferometer. The signal directly recorded, called an "interferogram", represents light output as a function of mirror position. A data-processing technique called Fourier transform turns this raw data into the desired result (the sample's spectrum): Light output as a function of infrared wavelength (or equivalently, wave number). As described above, the sample's spectrum is always compared to a reference. There is an alternate method for taking spectra (the "dispersive" or "scanning monochromator" method), where one wavelength at a time passes through the sample. The dispersive method is more common in UV-Vis spectroscopy, but is less practical in the infrared than the FTIR method. One reason that FTIR is favored is called "Fellgett's advantage" or the "multiplex advantage": The information at all frequencies is collected simultaneously, improving both speed and signal to noise ratio. Another is called "Jacqui not's Throughput Advantage": A dispersive
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measurement requires detecting much lower light levels than an FTIR measurement. There are other advantages, as well as some disadvantages, but virtually all modern infrared spectrometers are FTIR instruments.

Case study
"STUDIES OF BORATE VANADATE GLASSES USING IR SPECTROSCOPY"
ABSTRACT IR spectra of xV2O5.(1-x)B2O3 glasses (with 0.05 x 0.8) have been measured and analyzed ; IR reveal changes in spectra .The samples having x 0.6 a peak characteristic to V2O5 appears ;This is an indication that vanadate structure was forming and The vanadium oxide acts as network modifier in these glasses for 0.05 x 0.5 wile at 0.6 x 0.8 vanadium oxide acts as glass forming. Introduction IR spectroscopy become effective tools for resolving the structure of local arrangement in glasses. The transition metal (TM) oxide glasses have been extensively studied by several authors during the last twenty years. These glasses are of importance due to their semiconducting properties and the electrical conduction is due to electron hopping on account of the available reduced states of the TM ions. Some authors have studied the effect of single and multiple TM ions as dopants in alkali or alkaline earth oxide glasses. On the other hand some have reported the effect of glass formers on these TM oxides as regards the glass formation and have examined the electrical behavior and performed spectroscopic studies. In this case we report the structure study of borate vanadate glasses using IR spectroscopy.

Experimental Glasses of xV2O5(1-x)B2O3 system with 0.05 x 0.8 were prepared by mixing H3BO3 and V2O5 having reagent grade purity in suitable proportions and melting this admixtures in sintered corundum crucibles at T = 1523 K for 0.5 hour. Vitrification was achieved by rapid cooling of the melts on stainless steel plates at room temperature and atmospheric pressure. The IR spectra were recorded in 4000-400 cm-1 spectral range with a Brucker IFS 120 spectrometer using the KBr pellet technique. IR spectra Results and discussion IR spectra of xV2O5(1-x)B2O3 glasses with various contents of copper oxide(0.05 x 0.8) are shown in Fig.2. The following bands are present in these spectra: 642 cm-1, 796 cm-1, 883 cm-1, 1023 cm-1, 1195 cm-1, 1384 cm-1, 1465 cm-1, 1630 cm-1, 2260 cm-1, 2360 cm-1, 2520 cm-1, 3220 cm-1, and 3443 cm-1.

Samples having up to 0.5 V2O5 show a water band at 3220 cm-1 and -OH stretching peaks at 2520 cm-1, 2360 cm-1 and 2260 cm-1. These are intense for low V2O5 content as shown in fig 2. these bands and peaks are due to the hygroscopic character of the powdered glass samples. Hence, it can be safely concluded that the samples are quite hygroscopic in nature at low x content. An absorption peak was observed at 1630 cm-1. The origin of this peak is not obvious, but the H-O-H bending mode gives rise to an absorption in this region and the possibility of some adsorbed water giving rise to this peak cannot be ruled out. A broad band at around 1450 cm-1 as observed in crystalline B2O3 is present in low composition V2O5 glasses, but its character changes in samples Fig. 2. IR spectra of xV2O5(1-x)B2O3 glasses with 0.05 x 0.8 above 0.5 V2O5. As already reported in Na2O-B2O3 glasses the characteristic >B-O- stretching band in the B2O3 glass network is assigned to a broad band from 1428 cm-1 to 1333 cm-1. This band appears in our IR spectra, confirming the amorphous nature of studied glasses. The low V2O5 content glasses show a very sharp absorption peak at 1195 cm-1. This peak may be attributed to triangular B-O stretching vibrations .This peak disappears when V2O5 content increases. The spectra corresponding to x >0.6 present a band at 1250 cm-1 and do not exhibit the 1195 cm-1 peak. The disappearance of the 1195 cm-1 peak and the progressively appearance of the band centered at 1250 cm-1 corresponds to a change from triangular to tetrahedral boron structure when the system goes to higher V2O5 content . An absorption band at 1023 cm-1 was observed in all the samples, also at highest V2O5 content. This peak in attributed to V=O stretching vibrations . The peak at 883 cm-1 which is observed for low V2O5 content disappear for x > 0.5. This disappear might be due to the rupture of boron ring structure when the V2O5 content increases. A broad absorption peak between
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740 cm-1 and 800 cm-1 in crystalline B2O3 and at 825 cm-1 in crystalline V2O5 is observed. For higher compositions, this band disappears completely. The absence of this band indicates that either the structural units of V 2O5 in V2O5B2O3 glasses is not the same as that in crystallineV2O5 or the intensity of the peak becomes very weak and could not be detected. Below 800 cm-1 there are several absorption peaks in crystalline B2O3 as well in V2O5 .Therefore, we can not assume these bands to particular groups (borate or vanadate). For low V2O5 content IR spectra reveal the presence of triangular and tetrahedral borate units. At high V2O5 content only IR bands corresponding to the tetrahedral borate units appear, in agreement with Raman conclusions. This indicates a modification of the structure of studied glasses, determined by the changes of the vanadium oxide content. Both Raman and IR analyses show the presence of vanadate groups at high concentration of vanadium oxide. Thus at high V2O5 content vanadium oxide starts to act as a glass former.

Conclusions The IR spectra of studied glasses have been qualitatively interpreted in the range of 4000 cm-1 to 500 cm-1. The main characteristic is the disappearance of some bands when V2O5 content increases. For low vanadium oxide content, specifically borate units with triangular and tetrahedral configuration are present, while for high V2O5 content are present only borate units with tetrahedral configuration. In the same time, the feature of IR spectra reveal bands characteristic to vanadate structure. Therefore, we conclude that vanadium oxide acts as network modifier in these glasses for 0.05 x 0.5. For higher concentration, vanadium oxide starts to act as glass former.

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Index
Title
Introduction IR Spectroscopy Definition Applications of IR spectroscopy Theory of Infrared Absorption IR Spectra
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Page Number
1-2 2 2 2-5 5-6

Infrared Instruments Fourier transform infrared (FTIR) spectroscopy Case study "IR studies of Borate Vanadate Glasses using IR spectroscopy"

7 7-8

8-12

Reference :1-power point" Introduction to Infrared Spectroscopy(Chapter 16 Instrumental Analysis) used reference : http://www.acs.org http://www.chemcenter/org,http: www.shu.ac.uk/schools/sci/chem/tutorials/molspec/irspec/.htm http://www.kerouac.pharm.uky.edu/asrg/wave/wavehp.html

2- PDF . book name Infrared Spectroscopy in Convervation Science by Michele .R-Drrick. Dusans Bulik James m.Landy . Loaded from www.scribd .com . 3- Paper Studies of Borate Vanadate Glasses using Raman and IR Spectroscopy/ studia universitatis babe-bolyai, physica, special issue, 2001/ d.maniu*1, t. Iliescu1, i. Ardelean1, i. Bratu2, c. Dem31babes bolyai university, faculty of physics, koglniceanu 1, 3400 cluj-napoca, romania2 institute for isotopic molecular technology, p.o. box 700, 3400
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cluj-napoca 5, Romania institut fr physicaliche chemie, universitat wrzburg, am

hubland, d-97074 wrzburg, germany

4-Chapter 15"Infrared Spectroscopy"/C.-P. Sherman Hsu, Ph.D. Separation Sciences Research and Product Development Mallinckrodt, Inc. Mallinckrodt Baker Division.

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