scholarly journals Investigations in the infra-red region of the spectrum. Part II.—The absorption spectrum of sulphur dioxide

It has been pointed out that if the precautions indicated in the previous paper are carefully observed, a high order of accuracy in infra-red measurements can be obtained with a prism spectrometer. Although the final word at present rests with the grating instrument on account of its higher resolving power, nevertheless a deal of useful work remains to be done with prisms. A band can be located (generally a necessary process for a prism spectrometer before the grating can be applied), the band centre and band type can often be determined, and the molecular constants can be approximately deduced. It is proposed in these papers to examine the spectra of gases and vapours in which the molecure has three different moments of inertia. The rotational fine structure within a vibrational band due to an asymmetrical rotator is very complex and individual lines may lie so close and the constituent series so overlap that absorption may be practically continuous. The prism spectrometer enables the first step in the unravelling of the tangle to be accomplished, in that the envelope of the individual lines gives under favourable circumstances the branches of the Bjerrum doublets, and hence enables the moments of inertia to be determined and frequently provides a knowledge of what may be called the resultant electrical structure of the molecule.

The earliest observations on the infra-red absorption spectrum of nitrogen peroxide were made by Warburg and Leithauser, who found that at ordinary temperatures the mixture of the tetroxide and dioxide had strong absorption maxima at 3•4 μ, 5•7μ, and 6•1μ. By varying the temperature, and so the degree of dissociation of tetroxide molecules into dioxide molecules, they were able to attribute the absorption band at 5•7μ, to the nitrogen tetroxide molecule, and show that the other two bands were due to the molecule of nitrogen dioxide. A later investigation by Eva von Bahr confirmed these observations and disclosed another band due to the dioxide at 7•3μ. None of these investigators examined the region beyond 8 μ, and all the work was done using low dispersion. Recently Strong and Woo have examined the spectrum between 23 μ, and 150 μ, and find two main regions of absorption, one near 26 μ and 150 μ and the other around 80 μ. Experimental. The spectrometer used in the first survey of the spectrum was a prism instru­ment having a 60° rock salt prism in the Wadsworth mounting. Subsequently several of the bands were examined on grating instruments of high resolving power. The absorption cell used in the preliminary work was of brass, 20 cm. in length, and with rock salt windows. This cell was lagged with asbestos and could be heated electrically until the temperature of the gas which it contained was as high as 160° C. The absorption cell used in the examination of the individual bands was of glass, 10 cm. long, and with mica windows. For work in the region beyond 7 μ. the mica windows were replaced by ones of rock salt. The nitrogen peroxide was taken from a very pure sample specially prepared for research work. It was kept in a sealed pyrex tube as a liquid (under its own pressure) and the gas was transferred to the cells as required, drying tubes containing phosphorus pentoxide being used to avoid con­tamination from water vapour in the atmosphere.


In a recent survey article, Goldberg (1954) gives a list of 127 molecular bands which have been observed in the absorption spectrum of the earth’s atmosphere by studying the solar spectrum between 0.3 and 24 μ . Among these, 35 bands are attributed to the following molecules: O 3 , N 2 O, CH 4 , HDO, CO. The main purpose of this contribution to the Discussion was to show several of these bands as they appear on solar spectrograms taken at the International Scientific Station, Jungfraujoch (Switzerland), in collaboration with Dr L. Neven of the Royal Observatory, Uccle (Belgium). The altitude of this station is 3580 m. It has been pointed out in earlier notes (Migeotte & Neven 1952 a, b ) that these data have been obtained, under high resolving power, by using the prism-grating infra-red spectrograph of the University of Liege (Migeotte 1945). Between 9.33 and 10.08 μ , our spectrograms show 320 lines which are mainly due to the fine structure of the 9.6 μ band of ozone (Migeotte, Neven & Vigroux 1952). Part of our data has been analyzed recently by Kaplan (1955), of the Institute for Advanced Study in Princeton (N. J.), U. S. A. A good fit for low J has been obtained with the following upper-state parameters: vibrational frequency v 3 1042.16 cm -1 ; rotational constants: A = 3.502 1 cm -1 , B = 0.440 1 cm -1 , C = 0.388 3 Cm -1 ; δ = 0.0166 34 .


1976 ◽  
Vol 54 (10) ◽  
pp. 1034-1042 ◽  
Author(s):  
J. A. Coxon ◽  
D. A. Ramsay

The A2Πi–X2Πi band system of 35ClO has been reinvestigated in absorption in the flash photolysis of ClO2 and Cl2/O2 mixtures, using higher resolving power than in earlier work. The rotational assignments for the ν′–0 progression have been revised and extended and new molecular constants have been obtained. In addition, four new bands with ν″ = 1 and 2 have been observed for the first time. The value for the ground state vibrational interval is found to be [Formula: see text]. Widths are given for levels with 2 ≤ ν′ ≤ 25 and show that all these levels are predissociated. With the help of the theory of long-range interactions, an improved value for the ground state dissociation energy is obtained, viz. D0″ = 22 184 ± 3 cm−1 (≡ 63.427 ± 0.008 kcal/mole ≡ 2.7504 ± 0.0004 eV).


The infra-red absorption spectrum of methane 12 CH 4 in the region of 3 μ has been re-investigated with higher resolving power than has been used previously. A very complex system of overlapping vibration bands has been revealed. The rotational fine structure of these bands has been partially analyzed, particularly having regard to the Coriolis interactions which occur in this case. The corresponding absorption bands of 13 CH 4 have also been examined.


1964 ◽  
Vol 20 (8) ◽  
pp. 1289-1293 ◽  
Author(s):  
C. Degani ◽  
M. Halmann ◽  
I. Laulicht ◽  
S. Pinchas

1954 ◽  
Vol 32 (5) ◽  
pp. 330-338 ◽  
Author(s):  
B. P. Stoicheff

An apparatus for obtaining intense Raman spectra of gases excited by the Hg 4358 line is described. It consists of a mirror-type Raman tube irradiated by two high-current mercury lamps, completely enclosed in a reflector of magnesium oxide. The lamps are externally water-cooled along their entire length and emit sharp lines of high intensity.Rotational Raman spectra of gases at a pressure of 1 atm. have been photographed in the second order of a 21 ft. grating in exposure times of 6 to 24 hr. The Raman lines are sharp and a resolving power of about 100,000 has been achieved. It will be possible to resolve the rotational Raman spectra, and hence to evaluate the rotational constants of molecules having moments of inertia of up to 300 × 10−10 gm. cm.2 Such investigations will be especially useful for non-polar molecules.


1996 ◽  
Vol 104 (6) ◽  
pp. 2275-2286 ◽  
Author(s):  
Wusheng Zhu ◽  
Xinsheng Zhao ◽  
Youqi Tang

1979 ◽  
Vol 57 (10) ◽  
pp. 1676-1680 ◽  
Author(s):  
F. W. Birss ◽  
R. M. Gordon ◽  
D. A. Ramsay ◽  
S. M. Till

The absorption spectrum of H213CO has been photographed in the region 3600 to 3000 Å under high resolution. Rotational analyses have been carried out for four bands, viz., [Formula: see text], [Formula: see text], [Formula: see text] (Type B), and [Formula: see text] (Type C), and molecular constants are given. Several perturbations have been found and possible mechanisms discussed.


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