Page:Proceedings of the Royal Society of London Vol 69.djvu/380

364 2 26 '2 5 c.c. If the first two experiments are eliminated on the assump- tion that the proper equilibrium of temperature had not been attained, the average weight per litre would become 4'428 grammes, and the specific volume 225'82.

Taking Kegnault's density of oxygen at and 760 mm., the density at 90'5 in the ordinary way would be 0'0043137, and the specific volume 231 '82 c.c. Thus the volume given by the ordinary gaseous laws is 1'0246 times the average observed volume ; or we may put it that pv is diminished at the boiling-point of oxygen by 2 '46 per cent. Again, while the ratio of the absolute temperatures is 3'017, the ratio of the densities is 3'091.

Behn* has determined by an indirect method the specific volume of oxygen, and finds the value 358, which is nearly 60 per cent, greater than the volume found by the direct method. The mode of proce- dure he adopts is to ascertain directly three quantities out of four in the ordinary thermodynamic equation correlating latent heat, tem- perature, increment of pressure to temperature, and specific volume, thereby deducing the unknown quantity. Now of the three experi- mental values required, one, viz., increment of pressure to temperature, can only be got by calculation from the vapour-pressure curve, and much depends upon the accuracy of this value. Accepting Estreicher's vapour pressures for liquid oxygen below its boiling-point as the most reliable, a Gibbs equation gives the increment per degree near 740 mm. pressure as 78'67 mm. mercury pressure or 106'93 grammes per square centimetre. This value, taken along with the latent heat found by Behn, and the boiling-point, gives, when inserted in the thermodynamic equation, a specific volume of 223'55, which is within less than 2 per cent, of the value found by the direct-density determinations.!

Further experiments were made on oxygen vapour at 90 '5 and under reduced pressures. These experiments and their results are given in the following table. The same symbols are used as in the preceding tables, except that d is the calculated density at 90 '5 absolute and pressure p, and v is l/d. The corrected volume of the flask is entered under V.

die Verdampfungswarme der Luft."
 * ' Ann. der Physik,' vol. 1, 1900, " Sublimationswarme der Konlensaure und

t In the same way Behn'a specific volume of carbonic acid would be contradic- tory of my proof that a constant-volume gas-thermometer filled with carbonic acid at about atmospheric pressure gives a very accurate value of its own boiling-point. Assuming the ordinary gaseous laws, the specific volume ought to be 361'6 instead of 423 given by Behn. Now my value of the increment of pressure to temperature at the boiling-point is 62'84 mm. mercury pressure, and this, along with the values used by Behn in the thermotlynamic equation, gives 363 as the specific volume. This comes much nearer the anticipated value of the constant.