Ultraviolet-Visible Spectroscopy.ppt

Ultraviolet-Visible Spectroscopy Introduction to UV-Visible Absorption spectroscopy from 160 nm to 780 nm Measurement of transmittance Conversion to absorbance A=-logT=ebc Measurement of transmittance and absorbance Beer’s law Noise Instrumentation Measurement Scattering of light Refraction at interfaces Scatter in solution Large molecules Air bubbles Normalized by comparison to reference cell Contains only solvent Measurement for transmittance is compared to results from reference cell Beer’s Law Based on absorption of light by a sample dPx/Px=dS/S dS/S=ratio of absorbance area to total area Proportional to number of absorbing particles dS=adn a is a constant, dn is number of particles n is total number of particles within a sample Beer’s Law Area S can be described by volume and length S=V/b (cm2) Substitute for S n/V = concentration Substitute concentration and collect constant into single term e Beer’s law can be applied to mixtures Atot=SAx Beer’s Law Limitations Equilibrium shift pH indicators Need to consider speciation Weak acid equilibrium Beer’s Law Limitation Polychromatic Light More than one wavelength Noise Limited readout resolution Dark current and electronic noise Photon detector shot noise Cell position uncertainty Changing samples Flicker Instrumentation Light source Deuterium and hydrogen lamps W filament lamp Xe arc lamps Sample containers Cuvettes Plastic Glass Quartz Spectrometers Spectrometer Spectrometer Application of UV-Visible Spectroscopy Identification of inorganic and organic species Widely used method Magnitude of molar absorptivities Absorbing species methods Molar Absorptivties Range from 0 to 1E5 e=8.7E19PA P=transition probability A=target cross section (cm2) Allowed transitions 0.1P1 e range 1E4 to 1E5 Forbidden transition 0.01 Absorbing species M+g-M* M* has a short lifetime (nanoseconds) Relaxation processes Heat Photo emission Fluorescence or phosphorescence Absorbing species Electronic transitions p, s, and n electrons