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    Introduction to Infrared Spectroscopy.ppt

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    Introduction to Infrared Spectroscopy.ppt

    1、Introduction to Infrared Spectroscopy,Chapter 16 Instrumental Analysis,Definition of Infrared Spectroscopy,The absorption of light, as it passes through a medium, varies linearly with the distance the light travels and with concentration of the absorbing medium. Where a is the absorbance, the Greek

    2、lower-case letter epsilon is a characteristic constant for each material at a given wavelength (known as the extinction coefficient or absorption coefficient), c is concentration, and l is the length of the light path, the absorption of light may be expressed by the simple equation a= epsilon times

    3、c times l.,Infrared Spectroscopy,Infrared spectroscopy is the measurement of the wavelength and intensity of the absorption of mid-infrared light by a sample. Mid-infrared is energetic enough to excite molecular vibrations to higher energy levels. The wavelength of infrared absorption bands is chara

    4、cteristic of specific types of chemical bonds, and infrared spectroscopy finds its greatest utility for identification of organic and organometallic molecules. The high selectivity of the method makes the estimation of an analyte in a complex matrix possible.,Example of IR,Theory of Infrared Absorpt

    5、ion Spectroscopy,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 osci

    6、llating 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.,Molecu

    7、lar Rotations,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 Rotation

    8、s (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

    9、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 distinctiv

    10、e 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 u

    11、nchanged are called Q-branch transitions.,Molecular Vibrations,In order to predict equilibrium stable-isotope fractionations, it is necessary to know the characteristic frequencies of molecular vibrations. It is also necessary to know how much each vibrational frequency in a molecule changes when a

    12、heavy isotope is substituted for a light one. Vibrational frequencies for isotopically substituted molecules are not always known, so it is often necessary to use some type of force-field model to predict them. Molecular vibrations are also important in understanding infrared absorption and the mech

    13、anisms and kinetics of chemical reactions. Frequencies are most commonly measured with infrared or Raman spectroscopy. Rotational-vibrational spectroscopy, isotope substitution, and many forms of force-field modeling are used to determine characteristic atomic motions.,Vibrational Motion,Subdivided

    14、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 Xv

    15、ib modes of vibration, then the vibrational energy contributes Xvib(RT) to the average molar energy of the substance.,Stretching and Bending,Stretching Vibrations,Bending Vibrations,Quantum Treatment of Vibrations,Transitions in vibrational energy levels can be brought about by absorption of radiati

    16、on, 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.

    17、,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 amount of light transmitted on the vertical axis against the wavelength of infrared radiation on the horizontal axis. In inf

    18、rared 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.,Infrared Instruments,References,http:/www.acs.orghttp:/www.cas.orghttp:/www.chemcenter/orghttp:/www.sciencemag.orghttp:/www.shu.ac.uk/schools/sci/chem/tutorials/molspec/irspec/.htmhttp:/www.kerouac.pharm.uky.edu/asrg/wave/wavehp.htmlhttp:/hiq.linde-


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