Page:Scientific Papers of Josiah Willard Gibbs.djvu/434

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398
VAPOR-DENSITIES.

irregularity which is characteristic of errors of observation. We should expect large errors in the observed densities, on account of the difficulty of obtaining the substance in a state of purity, and because the large value of the density renders it very sensitive to the effect of impurities which diminish the density,—also because the specific heat of the vapor is great, as shown by the numerator of the fraction in the second member of (13),[1] and because the density varies very rapidly with the temperature as seen by the numbers in the third column of Table VIII.

Table VIII.—Perchloride of Phosphorus.
Experiments of Mitscherlich, Cahours, Wurtz, and Troost
and Hautefeuille.
Temperature Pressure Density calculated
by eq. (13).
Density observed. Excess of observed density.
Mitscherlich. Cahours. Mitscherlich. Cahours.
336 (760) 3.610 3.656 +.046
327 754 3.614 3.656 +.042
300 765 3.637 3.654 +.017
289 (760) 3.656 3.69 +.034
288 763 3.659 3.67 +.011
274 755 3.701 3.84 +.139
250 751 3.862 3.991 +.129
230 746 4.159 4.302 +.142
222 753 4.344 4.85 +.506
208 (760) 4.752 4.73 -.021
200 758 5.018 4.851 -.167
190 758 5.368 4.987 -.381
182 757 5.646 5.078 -.568
Wurtz. T. & H. Wurtz. T. & H.
178.5 227.2 5.053 5.150 +.097
167.6 221.8 5.456 5.235 +.012
154.7 221.8 5.926 5.619 -.041
150.1 225 6.086 5.886 -.200
148.6 244 6.169 5.964 -.205
145 391 6.45 6.55 +.10
145 311 6.37 6.70 +.33
145 307 6.36 6.33 -.03
145 307 6.36 6.33 -.03
144.7 247 6.287 6.14 -.147
137 281 6.53 6.48 -.05
137 269 6.51 6.54 +.03
137 243 6.48 6.46 -.02
137 234 6.47 6.42 -.05
137 148 6.31 6.47 +.16
129 191 6.59 6.18 -.41
129 170 6.56 6.63 +.07
129 165 6.55 6.31 -.24

But at the two lowest temperatures of Cahours' experiments, the differences of the observed and calculated densities (.381 and .568) are not only great, but exhibit, in connection with the adjacent numbers, a regularity which suggests a very different law from that of the

  1. Compare Equilib. Het. Subs., this volume p. 180, and supra pp. 380–382.