Page:Scientific Papers of Josiah Willard Gibbs.djvu/426

This page has been proofread, but needs to be validated.
390
VAPOR-DENSITIES.

at 219°, 231°, 240°, respectively. Here the table in the Comptes Rendus agrees substantially with that of the Leçons, but the experiments of Horstmann show a divergence in the opposite direction. In fact, the three columns of observed densities nowhere agree in the direction of their divergence from the formula.

The somewhat decided differences between the results of Horstmann and those of Cahours may be due in part to the different methods of observation, especially to the entirely different manner of applying the heat and measuring the temperature. But the higher values obtained by Horstmann cannot be accounted for by too short an exposure to the source of heat, for his experiments were made with decreasing temperatures.

The determinations of Bineau are taken from the same sources as those on formic acid, the earlier determinations being distinguished as before by parentheses. One of these (at 132) was made by the method of Dumas, the other by that of Gay-Lussac. The smallness of the observed densities appears due to the presence of water. (An acidimetric test gave 295 parts of acid in 306.) The other experiments were made with the same apparatus which was used with formic acid and show even greater regularity in their results than the experiments with that substance. Only in one case is the influence of proximity to saturation seen, viz., at 20.5 and 10.03mm, the pressure of saturated vapor at this temperature being about 12.7mm.[1] In the remaining fifteen observations of this series, notwithstanding the very low pressures employed (from 2.44 to 11.32), the greatest difference between the observations and the formula is .04, and the average difference .02.

The two observations by Troost[2] were made by the method of Dumas, but at pressures very low for this method. The results obtained differ considerably from the formula, but not so much as in the case of his experiments at low pressure with peroxide of nitrogen.

Table V contains the experiments of Naumann[3] on acetic acid. These consist of ten series (distinguished by the letters A, B, C, etc.) of observations by Hoffmann's method.[4] The temperatures of the observations in the different series are for the most part the same, so that for each temperature we have observations through a wide range of pressures. Within each compartment of the table are given

  1. This number is obtained from data given by Bineau by the same kind of interpolation which was used for formic acid.
  2. Comptes Rendus, vol. lxxxvi (1878), p. 1395.
  3. Lieb. Ann., vol. civ, p. 325.
  4. This is a modification of the method of Gay-Lussac, in which the heat is supplied by a vapor bath.