August 1947
I N D U S T R I A L AND E N G I N E E R I N G C H E M I S T R Y
dropping at 10-12" per minute. This visual observation was further hampered by the etching of the glass surfaces by the hot alkali. As a result, the data on these mixtures are accurate only to * l o o F.
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the Sun Oil Company, who contributed to the original standardization of the specific freezing point technique' described. LITERATURE C l T E D
(1) Kirst, W. E., Nagle, W. M., and Castner, J. B., Trans. A m . ACKNOWLEDGXZENT
The authors wish to acknowledge the help of Charles S. Pennington, who obtained the majority of the recent experimental data. They also wish to acknoxledge the work of I. W. Mills of
Inst. Chem. Engrs., 36, 371-94 (1940). (2) Washburn, E. IT,, et al., International Critical Tables, Vol. I11 (1928). PRESEVTED before the Diiision of Petroleum Cl~emlstry a t t h e 110th Meeting of the AMERICAY CHEMICAL SOCIETY, Chicago, I11
Solubility of 'Nitrogen and Methane in Sulfur Dioxide hl R . DEAS AND W . S. WALLS Phillips Petroleum Company, Bartlesville, O k l n . T h e solubilities of nitrogen and methane i n d f ~ dir oxide haie been determined experimentall> o\er a pressure range up to 515 pounds per square inch absolute and at temperatures of 83" and -23.7" F. The compositions of the equilibrium \apor phases at the higher pressures were also determined, and the iaporization equilibrium K constants were computed. It was found that the solubilities increased with temperature and were proportional to the partial pressure of the gas in accordance with Henry's law. The Kuenen absorption coefficients were also computed. The solubility of nitrogen was found to be considerabl) less than the value previously reported in the literature.
T
HE Kuenen absorption coefficients for nitrogen and oxygen in sulfur dioxide \\-ere reported by Dornte ( 1 ) . The data indicated the solubilities to be relatively large, and it was desircd t o make a comparison with the solubility of methane. Since no solubility values for methane or nitrogen in sulfur dioxide a t high pressure were found in the literature, the measurements reported here were made over a range of pressures u p to 515 pounds per square inch absolute. Several experiments, in which the gas partial pressure was 1 atmosphere, were carried out in order to obtain solubilities for comparison n-ith those computed from thc high pressure data.
HIGH PRESSURE APPARATPS AXD PRO(:EUURE
The high-pressure apparatus (Figure 1) consisted of twin steel cella, each of approsini:ttcly 240-cc. capacit!., mountrd on trunnions in a constant temperature bath. The citeel tubing fastcmed into the bottom of each cell lead to the pressure gagc :ind to a calibrated piston-type niercury pump. The pump \\-as constructed in such a manricr that the volume of mercury punipcd could be continuously measured to 0.1 cc. The cffectivc volumes )f the cells were variccl by introducing or \vithdran.ing inc'rcury with the pump. One cell was employed to contain the gas and sulfur dioxide, where they were brought into equilibrium by vigorous shaking of the cell. The other cell !vas cmplo>-ed in taking a sample of the vapor phase. The pressure was nieasured with a Rourdon tub
