Chemistry Instrumental Analysis Lecture 4. Chem 4631

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1 Chemistry 4631 Instrumental Analysis Lecture 4

2 Atomic Spectroscopy

3 Atomic Spectroscopy

4 UV to IR Optical spectroscopy are based on: absorption fluorescence phosphorescence scattering emission chemiluminescence

5 UV to IR Basic components of spectroscopic instruments: stable source of radiant energy transparent container to hold sample device to isolate selected region of the spectrum for measurement detector to convert radiant energy to a signal signal processor and readout

6

7

8

9

10 Optical Glass nm Special Optical Glass nm Quartz (Infrared) nm Quartz (Far-UV) nm

11

12 Sources of Radiation Continuum Sources Used for absorption and fluorescence spectroscopy. For UV, most common is the deuterium lamp. For vis, most common is the tungsten filament. For IR, most common are heated inert solids.

13 Sources of Radiation Continuum Sources Deuterium and Hydrogen Lamps Give continuum spectrum in UV region by electrical excitation of D 2 or H 2 to form an excited molecular species. The excited molecular species dissociates to two atomic species and a photon.

14 Deuterium and Hydrogen Lamps D 2 + E e D 2 * D' + D" + hu E e electrical energy absorbed by molecule.

15 Deuterium and Hydrogen Lamps The lamp has a heated filament which forms an arc with a metal electrode. Filament provides a direct current when 40 V is applied. Spectrum range nm Must use quartz windows with these lamps since glass absorbs strongly at wavelengths below 350 nm.

16 Deuterium and Hydrogen Lamps

17

18 Sources of Radiation Continuum Sources Tungsten Filament Lamp Source for vis and near IR Wavelength range nm

19 Tungsten/halogen lamps Add a small amount of iodine Lifetime 2x of regular lamp I 2 reacts with gaseous W to form WI 2 WI 2 strikes the filament WI 2 decomposes W redeposits on the filament.

20 Tungsten/halogen lamps

21 Sources of Radiation Continuum Sources Xenon Arc Lamps Produces intense radiation by passing current through gaseous Xe. Gives continuum spectrum between nm

22 Xenon and Mercury Arc Lamps

23 Xenon and Mercury Arc Lamps The anode and cathode are made of tungsten and sealed in a clear quartz envelope. Arc lamps are filled with either rare gas at several atmospheres pressure, or a little rare gas and an exact amount of mercury. Xenon lamp better for scanning applications. Hg lamp better for a line source (discrete).

24 Sources of Radiation Continuum Sources Xenon Arc Lamps

25 Sources of Radiation Line Sources Emit a few discrete lines. Hg and Na vapor lamps have a few sharp lines in the UV and vis region.

26 Line Sources

27 Laser Sources Light Amplification by Stimulated Emission of Radiation High Intensities Narrow Bandwidths Coherent Outputs

28 Laser Sources in UV, vis, and IR Used for high resolution spectroscopy kinetic studies routine analysis

29 Laser Sources

30 Laser Sources Lasing Medium: solid crystal (ruby) semiconductor (gallium arsenide) solution (organic dye) gas (argon or krypton)

31 Laser Sources Lasing Medium must be activated or pumped using radiation from an external source. This can be a few photons of the correct energy to trigger a cascade of photons of the same energy. Or could be an electrical discharge into a gas.

32 Laser Sources Once the cascade begins the laser functions as a resonator, passing the radiation back and forth through the medium using mirrors. This generates even more photons amplification.

33 Laser Sources

34 Laser Sources Nonparallel radiation dissipates out the top and bottom of the medium and parallel or coherent radiation is left.

35 Laser Sources

36 Laser Sources Processes include: pumping spontaneous emission (fluorescence) stimulated emission adsorption population inversion

37 Read Chapter 6 Assignment HW1: Ch. 1: 11 and Appendix 1: 1, 2, 10, and 12 (extra credit) (Due Today) HW2: Ch. 6: 2-12, 14, 15, 18, 19 (extra credit) (Due ) Read Chapter 7

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