THE INFRARED SPECTRUM OF CARBON MONOXIDE IN CO–He MIXTURES AT HIGH PRESSURES

1965 ◽  
Vol 43 (4) ◽  
pp. 547-556 ◽  
Author(s):  
R. L. Armstrong ◽  
H. L. Welsh
Keyword(s):  
Carbon Monoxide ◽  
Infrared Spectrum ◽  
High Pressures ◽  
Intermolecular Forces ◽  
Molecular Rotation ◽  
Moment Analysis ◽  
Induced Absorption ◽  
Absolute Intensities ◽  
The Absolute ◽  
Integrated Intensities

The 1–0 and 2–0 infrared bands of carbon monoxide were measured in CO–He mixtures at pressures up to 3 000 atm at 295 °K. Extrapolation of the integrated intensities of the bands gave the absolute intensities, Γ01 = 2 686 ± 44 and Γ02 = 9.29 ± 0.27 cm2 per mole. A slight increase in the band intensities with pressure is due to apparent induced absorption. A moment analysis of the bands, as proposed by Gordon, shows the presence of a torque due to intermolecular forces which hinders the molecular rotation; the magnitude of the torque derived from the analysis varies linearly with the density of the perturbing gas.

Infrared Spectrum of Carbon Monoxide Chemisorbed on Evaporated Nickel Films

1965 ◽  
Vol 69 (4) ◽  
pp. 1195-1203 ◽  
Author(s):  
C. W. Garland ◽  
R. C. Lord ◽  
P. F. Troiano
Keyword(s):  
Carbon Monoxide ◽  
Infrared Spectrum ◽  
Nickel Films

Moment analysis and quantum effects in collision-induced absorption

1975 ◽  
Vol 29 (3) ◽  
pp. 825-836 ◽  
Author(s):  
R.W. Hartye ◽  
C.G. Gray ◽  
J.D. Poll ◽  
M.S. Miller
Keyword(s):  
Quantum Effects ◽  
Moment Analysis ◽  
Induced Absorption

scholarly journals The structure of the high pressure carbon bands and the swan system

1929 ◽  
Vol 124 (795) ◽  
pp. 668-688 ◽  
Keyword(s):  
Carbon Dioxide ◽  
Carbon Monoxide ◽  
High Pressure ◽  
High Pressures ◽  
Carbon Electrodes ◽  
High Dispersion ◽  
Pressure System ◽  
True Nature ◽  
Discharge Tubes ◽  
Condensed Discharge

The so-called high pressure “ CO ” bands—or high pressure carbon bands, as they are better called—were first found by Fowler* in 1910 in tubes containing carbon monoxide at relatively high pressures. The system was described as consisting of some six apparently double-headed bands degraded to the violet, their wave-lengths being approximately at— 6441 6420 } 5897 5878 } 5431 5413 } 5030 5015 } 4679 4663 } 4365 4353 } Å. U. In 1923 the conditions of production of this spectrum were further investigated by Merton and Johnson who obtained the bands with considerable strength by condensed discharges in capillary tubes fitted with carbon electrodes, and containing CO at pressures of 5 mm. and more. It was found that while the high pressure bands and the Swan bands were mingled in the light from the capillary of the tube, the former bands were isolated in bluish jets where the two ends of the capillary merged into the wider parts of the tube. Further observations indicated that the introduction of a little C0 2 destroyed the bands, but that the system re-apppeared after a few minutes, in which time presumably the carbon dioxide had been reduced to monoxide by the carbon electrodes. A reproduction of these bands photographed under low dispersion is given in the above-mentioned paper. No further experimental work appears to have been done on this system, and it has not been correlated with any other band system or assigned any place in the system of electronic levels of the CO molecule. We have therefore made an attempt to photograph the system under high dispersion with a view to fine structure analysis and identification of the molecular emitter. For this purpose large discharge tubes having a bore of about 15 to 20 mm. and a length of 60 or 70 cm. were used. These had at least one of the electrodes made of carbon and were fitted with side bulbs containing caustic potash and phosphorus pentoxide and a palladium regulator. The tubes were filled with carbon monoxide to such a pressure (probably 20-40 mm.) that a condensed discharge could just be forced through by the ¼ kilowatt 15,000 volt transformer used. Some of the tubes had large side flasks attached to them, increasing thereby the volume of gas in the tube, and giving the tubes a life of 4 to 6 hours during which the high pressure bands were emitted strongly. After some such period the pressure fell below the optimum value, and deposits of carbon had accumulated on the walls of the tube. Impurities such as hydrogen, carbon dioxide, and water-vapour were found to inhibit formation of the high pressure bands, and the tube always attained its best condition after running for about an hour (removing meanwhile any little hydrogen present through the regulator). Under these conditions the wide bore is practically filled with light, and presents a remarkable appearance, as of dense pale blue puffs of smoke (showing the high pressure system), threaded by a narrow green ribbon (showing the Swan system). If side tubes having a fair capacity ( e . g ., flasks) are attached to the discharge tube the high pressure glow is capable of diffusion into these. The appearance is suggestive of an afterglow emitter, but if this is its true nature it is of very short duration. Photographs of the H. P. bands were taken in times varying from 4 to 10 hours in the first order of a 21-foot grating. The green band in the neighbourhood of λ 5000 is exceedingly faint and was not attempted. Before considering the results -obtained it will be an advantage to summarise our present knowledge of the Swan spectrum and its emitter, with which it will subsequently be shown that the high pressure carbon system is intimately related.

THE REACTION OF UNSATURATED CARBOHYDRATES WITH CARBON MONOXIDE AND HYDROGEN: V. ABSOLUTE STEREOCHEMISTRY OF ANHYDRODEOXYHEPTITOLS FROM 3,4,6-TRI-O-ACETYL-D-GLUCAL. STEREOCHEMISTRY OF HYDROFORMYLATION. CONFORMATIONAL ANALYSIS

1965 ◽  
Vol 43 (5) ◽  
pp. 1375-1381 ◽  
Author(s):  
Alex Rosenthal ◽  
Hans J. Koch
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Carbon Monoxide ◽  
Absolute Configuration ◽  
Sodium Iodide ◽  
Crystallographic Analysis ◽  
X Ray ◽  
Dicobalt Octacarbonyl ◽  
The Absolute ◽  
Compound Ii ◽  
Absolute Stereochemistry

3,4,6-Tri-O-acetyl-D-glucal reacted with carbon monoxide and hydrogen in the presence of dicobalt octacarbonyl to yield a mixture of two epimeric anhydrodeoxyheptitols, namely, 4,5,7-tri-O-acetyl-2,6-anhydro-3-deoxy-D-manno-heptitol (I) and 4,5,7-tri-O-acetyl-2,6-anhydro-3-deoxy-D-gluco-heptitol (II). De-O-acetylation of the mixture, followed by chromatographic separation, yielded crystalline 2,6-anhydro-3-deoxy-D-manno-heptitol (III) and 2,6-anhydro-3-deoxy-D-gluco-heptitol (IV). Reaction of the mixture of heptitols (I) and (II) with p-bromobenzenesulfonyl chloride, followed by fractional crystallization of the brosylates, gave pure 4,5,7-tri-O-acetyl-2,6-anhydro-1-O-(p-bromophenylsulfonyl)-3-deoxy-D-gluco-heptitol (VII). The absolute configuration of (VII) has been previously established by X-ray crystallographic analysis. The absolute configuration of (III) was established by correlation with that of (VII). The conversion of compound (II) into various derivatives is described.Reaction of 3,4,6-tri-O-acetyl-D-glucal with carbon monoxide and deuterium afforded 2,6-anhydro-3-deoxy-D-manno-heptitol-1,1,3-2H3 (XIII) and 2,6-anhydro-3-deoxy-D-gluco-heptitol-1,1,3-2H3 (XIV). Examination of the nuclear magnetic resonance (n.m.r.) spectra of the normal and deuterated anhydrodeoxyheptitols confirmed the structural assignments and showed that cis addition to the double bond took place to give (XIV).Comparison of the exchange reaction of sodium iodide with 4,5,7-tri-O-acetyl-2,6-anhydro-3-deoxy-1-O-tosyl-D-gluco-heptitol (VIII) and with 4,5,7-tri-O-acetyl-2,6-anhydro-3-deoxy-1-O-tosyl-D-manno-heptitol (XV) revealed that the equatorial primary tosyloxy group of (VIII) was exchanged by iodine twice as readily as the axial primary tosyloxy group of (XV).

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