Page:Scientific Papers of Josiah Willard Gibbs.djvu/429

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VAPOR-DENSITIES.
393

limit 2.073. Since the greater part of the measurements from which this number was calculated were also used in reducing the other observations of the series, the error probably affects the other observations, and in a somewhat increased degree. This will account only for a part of the difference between the observations and the formula. The remaining part of the differences in this series, and the somewhat smaller differences in the next, may be due to the fact that the experiments of both series were conducted with descending temperatures. Yet the experiments of the third column, which were made by Dumas' method, do not exhibit any preponderance of positive values for the excess of observed density, but rather the opposite.

Table VI.—Acetic Acid.
Experiments of Playfair and Wanklyn.
Temperature Pressure Density calculated
by eq. (10).
Density observed. Excess of observed density.
I. II. III. I. II. III.
212.5 322.8 2.124 2.060 -.064
194 326.0 2.168 2.055 -.113
186 254.4 2.173 1.936 -.237
182 319.4 2.213 2.108 -.105
166.5 289.5 2.293 2.350 +.057
163 245.8 2.290 2.017 -.273
132 227.5 2.628 2.292 -.336
130.5 285.7 2.729 2.426 -.303
119 269.0 2.914 2.623 -.291
116.5 211.3 2.876 2.371 -.505
95.5 (123.8) 3.105 2.594 -.511
86.5 (200.4) 3.432 3.172 -.260
79.9 (83.3) 3.297 3.340 +.043
62.5 (46.2) 3.473 3.950 +.477

On the whole, these experiments furnish no decisive indication of any influence of the hydrogen or air upon the vapor. They may be thought to corroborate slightly the tendency observed in the experiments of Naumann and Troost toward lower densities than the formula gives at very low pressures. Yet where the experiments of Naumann show the greatest deficiency in observed density (at 78 and 80mm), an experiment of Playfair and Wanklyn, at almost precisely the same temperature and pressure, gives a trifling excess of observed density, and at a little lower temperature and pressure, where we should expect from the experiments of Naumann that the deficiency would be still greater, an experiment of Playfair and Wanklyn shows a great excess of density.

By combining the experiments of Cahours, Naumann and Troost, we may obtain observations of density at 130° for a very wide range of pressures. For one atmosphere, we may regard the formula as coinciding with the average of the numbers given by Cahours. For pressures between three-quarters and one-half of an atmosphere the experiments of Naumann show an excess of density; at pressures