20 Photometers and Spectrophotometers 05; pean « - an 03] as 3 Ci | 002, nm |Z oy CE -_ 20 a TT TE 20 Fig. Bet of stray tight om ab- ce voouase A of magnitude of 0.005

[21]. Thus, the resulting spectrum is continuous. Dissociation occurs after the system has reverted to the lower state and, for that reason, the continuous spectrum emitted is also referred to as dissociation radiation [21]. The hydrogen or deuterium atoms so formed recombine to molecules H; or D, on the cold surfaces in the dis- charge chamber. In addition to the continuum, the Balmer series of the H for D atoms can be seen in the visible region and the appropriate H,, D,- (a=3-n=2) or Hy(n =4-n= 2) lines can be used for calibrating the ‘wavelength scale of a UV.VIS spectrometer. If the lamps are filled with a hydrogen-deuterium mixture the Balmer series of both gases are emitted. ‘The Hline lies at 486.12nm and the Dyline at 485.99 nm, and the dif- ference of 44 =0.13nm or AV =5.5cm-' can be conveniently used to check the resolving power of a UV-VIS spectrometer. For manufacturers of deuterium lamps see [22]. In addition to these two most important lamps, others are employed in special applications where, for example, a higher radiation output in the VIS and UV region is of particular interest. Noble-gas discharge lamps show a prominent continuum, and of these, the xenon-high pressure lamp is the most commonly used. The continuum of a xenon discharge cor- responds to recombination radiation, i.e. xenon atoms ionized at high gas temperatures recombine with electrons formed during ionization and emit radiation in the UV-VIS and NIR region. ‘Manufacturers produce xenon lamps with powers from 75 W to several KW [23}, and they are preferred in fluorescence and luminescence excitation spectroscopy (see Sect. 5.5) as well as in photoacoustic spectroscopy (see Sect. 5.4). In the UV-VIS region, these lamps are also used as light sources in microscope spectrometers. For these applications xenon lamps of up to 450 W are usually employed. ‘The quartz bulb of a xenon-maximum pressure lamp is considerably thicker than that of a deuterium lamp for reasons of safety. Thus, the inten- sity of UV radiation which is already diminishing toward shorter wave- lengths is increasingly absorbed by the quartz below 250 nm. For this rea- son, xenon lamps are produced for special applications with bulbs made of a quartz material such as Spectrosil which is highly transparent in the UV region [23]. In contrast to metal-vapor discharge lamps (e.g. mercury lamps), xenon lamps require no warming-up time because they reach their full power im- mediately after switching on. Hence, they can be easily modulated or used as flashlamps. In addition to these continuous light sources, metal-vapor discharge lamps are often employed. The most important lamp of this type is the mer- cury vapor lamp which is produced for low pressure, high pressure or maxi- mum pressure [24]. As line sources, they are specifically used for isolating definite spectral lines by means of suitable interference filters or filter com- binations (cf. Table 1, page 10), and therefore, they are employed in photo- meters as light sources.24 Photometers and Spectrophotometers ‘The mercury low-pressure lamp, operated at a pressure of 0.006 Torr, emits almost exclusively an intercombination line at 4 = 253.7 nm and is suitable for use in photochemistry. Depending on its power, a mercury high pressure lamp operates at a pressure of between 10 to 50 atm. In addition to the emission of the characteristic mercury lines, the emission spectrum of a high pressure lamp also shows a continuous background. On account of the high vapor pressure in the discharge, the spectral lines are con- siderably broadened. A mercury medium-pressure lamp has a considerably lower operating pressure and the spectral lines are relatively clear. Therefore, the use of this lamp is preferred in the UV-VIS region and as an excitation light source in photochemistry. ‘Schafer and Heinrich have given a detailed account of the light sources briefly described here [25]. In recent years, lasers have come to the fore as light sources for special applications; and noble-gas and dye lasers in particular should be men- tioned. The dye laser has the advantage of being completely tunable over ‘a wavelength range of ca. 600-1000 nm depending on the dye used. As a rule, an argon-ion laser is used as a pump light source for a dye laser. \W. Demtroder has given a detailed account of the applications of lasers in spectroscopy [26]. References {, Osram, Druckschrift (1978) Licht fr Kinoprojekton, Technik und Wissenschaft, Ausg Dez, 86:4 2. Jenaer Glaswerke Schott & Gen, Mainz, Farb- und Flterglas 3. Petkampus, H-H (1980) In: Ullmanns Encyklopidie der technischen Chem, 4. Aufl, Bd 5. Verlag Chemie, Weinheim, 2691F 4, Perkampus, H-H (1983) In: AnalytkerTaschenbuch, Bd 3. Springs, Bern Heidelberg New York, § 279-316 Talsky G, Mayring L, Kreuzer H (1978) Angew Chem 90:40 ‘Shibata § (1976) Angew Chem 88:750 - Hogness TR, Zscheile Jt FP, Sidwell Jr AE (1937) J Phys Chem 41:379 Preston 1S (1936) J Scien Inst 1353681 Luther H, Pokkels G (1985) Z Elektrochem Ber Bunsenges $9:159 Luck W (1960) ibid 64:676 Burgess C, Knowles A (1981) Standards in Absorption Spectrometry, Ultraviolet Spec- twometry Group, Vol. Chapman and Hall 12, Cook RB, Jankow AR (1972) J Chem Ed 49:405 13. Poulson RE (1968) Appl Opt 3:99 414, Renle A (1971) Coll Spectr Int XVI 1:107 15. Kaye W (1981) Anal Chem 33:2201 16. Derkosch 1 (1967) Absorptionsspektralanalyse im utravioltten, schtbaren und infaroten Gebiet, Ba 5 der Methoden der Analyse in der Chemie. Akad Verlagsges, Frankfurt/M . Gaugltz G (1983) Prakt Spektroskopie. Attempto, Tubingen Planck M (1901) Ann Phys 4:553, 3. Wien W (1894) Ann Phys, series 2, $2:132References 25 20, Kiefer J (ed) (1977) Ultavolete Strablen. Walter de Gruyter, Berlin, p 96 21, Herzberg G (1967) Molecular specira and molecular structure. 1 Diatomic molecules 22) Heraeus WC, Brochure D 310686/2C 7.86 VNKo. Produktbereich Original Hanau, Postfach 1553, D-6450 Hanau 1 23, Osram GmbH, Berlin- Munich, Brochure “Lich fir Kinoprojetion, Technik und Wissen- chat, Issue August 1988/FO 202 ‘24, Heraeus, Brochure D 310218/1C, 1085 VNKo; D'310531/1C 1085; D 310311/1C 1038. Prodnktherich Original Hanau, see 22 25, Sehifer V, Heinrich G (1977) In: Kiefer J (ed) Ultraviolet Srahlen, Chap 3. Walter de Gruyter, Bertin 26, Demtroder W (1988) Laser Spectroscopy. Springer, Berlin Heidelberg New York, 3rd print {ng with corrections