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Introduction to the Principles of Spectroscopy UV-Visible Spectroscopy Infrared Spectroscopy Practical Aspects of UV-Visible and Infrared Spectroscopy
Where E = energy (J), = frequency (s-1), = wavelength (m), h = plancks constant (6.62 x 10-34 Js) and c = speed of light (3 x 108 m s-1)
Arrows indicate possible transitions High energy UV, X-ray photons may cause eemission (ionization) IR photons have much less energy, vibrate molecules
Fluorescence energy at higher state may lose some energy as heat and return to ground state by emitting new longer wavelength radiation
Fluorine, F2
*, *, n *, n *
E = h = hc
*, *, n *, n *
Where v = frequency, k = constant, m1 and m2 = masses on the spring The lighter the masses (atoms) or the tighter the spring (chemical bond), the higher the frequency Vibrational frequencies are quantized (only certain energies are allowed)
Movie
Symmetric stretching
Vertical bending
Assymmetric stretching
Horizontal bending
One bond shortens while the other lengthens change in dipole moment
Aromatic C-H stretch at 3100-3000 cm-1 Aromatic C-C at 1200 cm-1 Bending C-H at 1000 cm-1 (in-plane) 675 cm-1 (out-of-plane)
A is linearly related to concentration for a fixed a, b and c Let l = 1 cm, slope of graph will be
UV-Visible + IR Spectroscopic
Introduction to the Principles of Spectroscopy
Methods
Diagram of BeerLambert absorption of a beam of light as it travels through a cuvette of width b. I = transmitted light, Io = incident light
Red-purple pararosaniline methylsulfonic aicd forms in the presence of pararosaniline and formaldehyde
Colorimetric methods
3 types: Fourier transform infrared spectrometers (FTIR) Dispersive infrared spectrometers (DIR) Nondispersive infrared spectrometers (NDIR)
Pavia, D.L., Lampman, G.M., and Kriz, G.S. (2009) Introduction to Spectroscopy. Brooks/Cole.
CO2
Use only quartz cuvettes for UV range (200-280 nm), plastic is ok for the visible range (380-800 nm) but will melt in hexane Do not hold or scratch the smooth sides of the cuvette Always select max for maximum sensitivity Unlike IR, only liquid samples are allowed for UV-VIS Linnear analytical range is important, if A > 0.9 sample must be diluted, if A < 0.05 a larger sample is required
References
Beer, R. (1992) Remote Sensing by Fourier Transform Spectroscopy, in the Chemical Analysis Series, Vol. 120, John Wiley & Sons, New York. Eubanks, L.P., Middlecamp, C., Pienta, N., Heltzel, C., and Weaver, G. (2006) Chemistry in Context: Applying Chemistry to Society, 5th Edition, ACS, Washington, D.C. Field, L.D., Sternell, S., Kalman, J.R. (2003) Organic Structures from Spectra, 3rd Edition, John Wiley & Sons, West Sussex, England, pp. 1-19. Guicherit, R., Jeltes, R. and Lindqvist, F. (1970) Determination of ozone concentration in outdoor air near Delft The Netherlands. Environmental Pollution, Vol. 3, No. 2, pp. 91-110. Kebbekus, B.B. and Mitra, S. (1998) Environmental Chemical Analysis. Blackie Academic & Professional, London, UK, pp. 54-102. Manahan, S.E. (2005) Environmental Chemistry, 8th Edition, CRC Press, pp. 681-747. Saltzman, B.E. (1954) Colorimetric microdetermination of nitrogen dioxide in the atmosphere. Analytical Chemistry, Vol. 26, No. 12, pp. 1949-1955. West, P.W. and Gaeke, G.C. (1956) Fixation of sulfur dioxide as disulfitomercurate (II) and subsequent colorimetric estimation. Analytical Chemistry, Vol. 28, No. 12, pp. 1816-1819.
Questions
15. Which one of the following is true regarding Beers law: (a) Absorbance is proportional to both path length and concentration of absorbing species (b) Absorbance is proportional to the log of the concentration of absorbing species (c) Absorbance is equal to P0/P?
18. The absorbance of a 2-cm sample cell of a 10 ppm solution is 0.43, what would be the absorbance of a 1-cm cell of 15 ppm solution of the same chemical.
21. Draw a schematic diagram of the following: (a) UV-VIS spectrometer, (b) FTIR spectrometer. 24. Explain: (a) Why in situ atmospheric CO2 can be monitored by IR? (b) Why in situ atmospheric (stratospheric) O3 can be measured by UV? 25. Explain: (a) Why O2 and N2 will not effect the monitoring of CO in auto emission using IR? (b) Why a long cell is needed to monitor trace organic compounds using IR?