Atmosphere infrared absorption

Hare W. F. J., Welsh H. L. Pressure induced infrared absorption of hydrogen and hydrogen-foreign gas mixtures in the range 1500-5000 atmospheres, Can. J. Phys. 36, 88-103 (1958). 

The catalyst formed in this manner exhibited carbonyl infrared absorptions, as shown in Table XXX. These catalysts were tested by hydroformylation of ethylene or propylene at 100°C and atmospheric pressure. Both were effective, with (A) being better than (B), probably because of the higher surface area. The aldehyde formed from propylene was a mixture of 63% n- and 37% isobutyraldehyde. The rate expression for ethylene hydroformylation was ... 

A major advantage of infrared absorption spectroscopy derives from the characteristic fingerprints associated with infrared-active molecules. On the other hand, interferences from common atmospheric components such as C02 and HzO are significant, so that the sensitivity and detection limits that can be obtained are useful primarily for polluted urban air situations. For atmospheric work, long optical path lengths are needed. 

FIGURE 14-10 Intrinsic infrared absorption band strengths of some potential greenhouse gases in the atmospheric window (from Ramanathan, 1988a, 1988b). 

There may, however, be some cancellation of errors. For example, the concentration of atmospheric C02 ([ref], in Eq. (T)) depends in a nonlinear fashion on the amount of total dissolved inorganic carbon in the ocean surface layer because of the equilibria with water (see Chapter 8.B) so that relatively less atmospheric C02 can be taken up by the oceans as its atmospheric concentrations increase. This would leave relatively more C02 in the atmosphere, increasing its greenhouse effect. On the other hand, since the strongest infrared absorption bands of C02 are already saturated (vide supra), the radiative forcing (at-(), in Eq. (T)) decreases as its concentrations increase. 

The compound ir-allyltricarbonylcobalt has also been made by treating allyl bromide with Na[Co(CO)4] 109, 111). If this reaction is carried out in an atmosphere of carbon monoxide then about one-half mol. of carbon monoxide is absorbed, and the infrared absorption spectrum of the product shows a band at about 1720 cm-1. This band is believed to be due to the presence of but-2-enoyltetraearbonylcobalt. On standing, carbon monoxide is evolved and the ir-allyl complex [Co(7r-C3H6)(CO)3] is formed. These reactions may be summarized as follows ... 

Of a special astronomical interest is the absorption due to pairs of H2 molecules which is an important opacity source in the atmospheres of various types of cool stars, such as late stars, low-mass stars, brown dwarfs, certain white dwarfs, population III stars, etc., and in the atmospheres of the outer planets. In short absorption of infrared or visible radiation by molecular complexes is important in dense, essentially neutral atmospheres composed of non-polar gases such as hydrogen. For a treatment of such atmospheres, the absorption of pairs like H-He, H2-He, H2-H2, etc., must be known. Furthermore, it has been pointed out that for technical applications, for example in gas-core nuclear rockets, a knowledge of induced spectra is required for estimates of heat transfer [307, 308]. The transport properties of gases at high temperatures depend on collisional induction. Collision-induced absorption may be an important loss mechanism in gas lasers. Non-linear interactions of a supermolecular nature become important at high laser powers, especially at high gas densities. 

Reaction of PCTFE with a stoichiometric amount of chromium hexacarbonyl in DMF at 95°C for 5 days under a nitrogen atmosphere, followed by hydrolysis results in the formation of a brown-black polymer. Analysis of the infrared data indicates that carbonylation does indeed occur (Equation 11). The infrared absorption spectrum shows a large decrease in the C-Cl stretch at 970 cm-1 with a concomitant appearance of a very strong band in the carbonyl stretching region centered at 1680 cm1. There is also a broad band centered at 3490 cm-1 in the hydroxyl stretching region and two bands of moderate intensity... 

If near-infrared diode lasers have low-noise characteristics similar to those of mid-infrared diode lasers, and thus minimum absorbances of 10 5 or less are possible, then an approximate detection limit can be calculated for an absorption experiment. For a 200-m optical path, the calculated detection limit is 5 x 1010 molecules/cm3, which is well above levels of H02 expected to be found in the atmosphere. An absorption experiment in this spectral region apparently would require extremely long optical path lengths, and, indeed, a calculation with a 5-km path yields a calculated detection limit of 2 x 109 molecules/cm3, still rather high for tropospheric measurements. Other issues associated with the use of diode lasers in absorption spectroscopy are discussed in the next section. 

The infrared spectrum of H02 is highly structured, and this feature potentially allows the absorption due to HO to be differentiated from other atmospheric species. Some infrared absorption data are also available for... 

In addition, near infrared absorption bands at 1.255 and 1.425 /tm have recently been found by Hunziker and Wendt (493), who have attributed the bands to a transition 2 A <- 2A". The band at 1.504 /emission bands of H02 have been detected recently by Becker et al. (83, 86). The H02 radical is an important reaction intermediate in combustion, in polluted atmospheres, and in the photolysis of H202. The reaction of H02 with NO is considered as a key reaction in photochemical smog formation, which is discussed in Section VIII 2. 

The first passive remote sensing experiment to measure successfully the abundance of atmospheric aerosols from space was the Stratospheric Aerosol Measurement (SAM II) aboard Nimbus 7 (McCormick et al. 1979). This experiment was a single channel radiometer observing in solar occultation and was the forerunner of SAGE. Stratospheric aerosols have also been measured by their infrared absorptions (e.g. HALOE). 

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