An IUPAC Task Group Study: The Solubility of Carbon Monoxide in [hmim][Tf2N] at High Pressures

2011 ◽  
Vol 56 (12) ◽  
pp. 4797-4799 ◽  
Author(s):  
L. J. Florusse ◽  
S. Raeissi ◽  
C. J. Peters

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.


In the previous paper of this series it was shown :— (1) that when nitrogen is added as a diluent to a mixture of 2CO+O 2 undergoing combustion in a bomb at an initial pressure of 50 atmospheres, it exerts a peculiar energy-absorbing influence upon the system, far beyond that of other diatomic gases, or of argon; (2) that by virtue of such influence, it retards the attainment of maximum pressure in a much greater degree than can be accounted for on the supposition of its acting merely as a diatomic diluent; (3) that the energy so absorbed by the nitrogen during the combustion period, which extends right up to the attainment of maximum pressure, is slowly liberated thereafter as the system cools down ; and that consequently the rate of cooling is greatly retarded for a considerable time interval after the attainment of maximum pressure; (4) that there is no such energy-absorbing effect ( i. e ., other than a purely "diluent" one) when nitrogen is present in a 2H 2 +O 2 mixture similarly undergoing combustion ; but that, on the contrary, the presence of hydrogen in a CO-air mixture undergoing combustion at such high pressures so strongly counteracts the said " energy-absorbing " influence of the nitrogen, that it must be excluded as far as possible from the system before any large nitrogen-effect can be observed. These facts were explained on the supposition that there is some constitutional correspondence between CO and N 2 molecules (whose densities are identical) whereby the vibrational energy (radiation) emitted when the one burns is of such a quality as can be readily absorbed by the other, the two thus acting in resonance. It was further supposed that, in consequence of such resonance, nitrogen becomes chemically " activated " when present during the combustion of carbon monoxide at such high pressures ; and in conformity with this supposition, it was shown that such "activated" nitrogen is able to combine with oxygen more readily than does nitrogen which has merely been raised to a correspondingly high temperature in a hydrogen-air explosion.


2013 ◽  
Vol 73 ◽  
pp. 138-140
Author(s):  
Sona Raeissi ◽  
Louw J. Florusse ◽  
Cor J. Peters

In a previous paper upon the subject, the question was propounded whether or no there is any direct relation between the actual rate at which the potential energy of an explosive mixture is transferred on explosion as sensible heat to its products and the magnitude of the chemical affinity between its combining constituents. As the result of an experimental enquiry into the matter, it was proved:– ( a ) that, whereas the affinity for oxygen of methane is at least twenty to thirty times greater than that of hydrogen, the time required for the attainment of maximum pressure in the case of the primary methane-air mixture (CH 4 + O 2 + 4N 2 ) is at least some five to eight times as long as that required in the case of the primary hydrogen-air mixture (2H 2 + O 2 + 4N 2 );


Author(s):  
Fabio A. Bendana ◽  
Daniel D. Lee ◽  
Chuyu Wei ◽  
Daniel I. Pineda ◽  
R. Mitchell Spearrin

The oxidation of carbon monoxide may occur either directly or by an indirect reaction with steam. Under appropriate conditions the oxidation takes place at a measurable rate, and there are also two distinct types of explosive reaction. The indirect oxidation in presence of steam takes place with measurable speed in the range 550°-600°C., and appears to involve reaction chains analogous to those occurring in the combination of hydrogen and oxygen. The direct oxidation requires a considerably higher temperature: in a silica vessel, for example, there is a slow surface reaction at about 700°C. This has been shown to be independent of residual traces of moisture, the kinetics being fundamentally different from those of the indirect oxidation. The direct oxidation can also be brought about by sparking dry mixtures of carbon monoxide and oxygen at high pressures. Bone and Weston have shown that the spectrum emitted by the exploding gases is quite different from that given by the flame of moist carbon monoxide; thus the mechanism of the “dry” reaction is really an independent one. Moreover, Garner has shown that there is an abrupt change in the nature of the radiation emitted by a carbon monoxide flame when a small amount of hydrogen is added, this, again, confirms the existence of two separate mechanisms of oxidation.


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