1709
DIFFERENCE BETWPEN DENSITIESOF ORDINARY AND HEAVY WATER
June, 1941
Ionization Constants and Derived Thermodynamic Functions.-Table I11 contains the values of and -log at the temperatures designated. I n the last column are the deviations between the observed results and those calculated by an equation which expresses the standard free energy as a quadratic function of the absolute temperature.j The numerical equations for log K Z Aand the standard thermodynamic functions, derived by the method of least squares are
-2gp'39 +
6.4980 - 0.02379T (9) - 29.7286T + 0.10884T" (10) AHa = 13278.55 - 0.10884P (11)
log Kz.4 =
Stieglitz, 5.4 X lo-") ; Seyler and Lloyd,* 4.3 X Hastings and S e n d r ~ y ,5.51 ~ X lo-"; MacInnes and Belcher, 5.61 X lo-"; this measurement, 4.69 X lo-". At 38O, Hastings and Sendroy obtained 6.03 X MacInnes and Belcher 6.25 X lo-", which are somewhat higher than 5.86 X lo-" obtained by us a t this temperature by equation (9). We take this opportunity to express our thanks to Dr. Gosta Akerlof who supervised the construction and design of the apparatus.
summary
AF' = 13278.55
Aci = -0.21768T ASo = 29.7286 0.21768T
-
(12) (13)
The values of the heat content, heat capacity and entropy a t 25' are 3600 cal., -65 cal.deg.-' and -35.16 cal. deg.-', respectively. The value AHo agrees with the recent calorimetric result (3500 * 100) of Pitzer within the error of experiment. Our result also confirms Pitzer's6 value of - 35.2 for the standard entropy, ASo. The maximum value of the ionization constant is found to occur a t 349.3' A. and the value of -log K2*is 10.121 at this temperature. The following values have been reported for K2*at 25' : McCoy,' 6 X lo-"; (recalculated by (5) Harned and Robinson, Trans. Faraday SOC.,36, 973 (1940). (6) Pitzer, THIS JOURNAL, 59, 2365 (1937). (7) McCoy, A m . Chcm. J . , 2D, 437 (1903).
[CONTRIBUTION FROM THE CHEMICAL
1. By means of an enclosed gas electrode system, the ionization constant of HCOs- has been determined at 5' intervals from 0 to 50'. 2. Equations have been derived from these results by means of which the standard heat content, heat capacity, and entropy of the ionization reaction may be computed. The standard heat content found is in good agreement with that derived from calorimetric measurements. 3. Our values of the ionization constant a t 25' and 38' are lower than that obtained by recent investigators. This is due to our consistent use of the limiting theoretical equations in making the extrapolations. (8) Seyler and Lloyd, J . Chem. SOL, 111, 138 (1917). (9) Hastings and Sendroy, J . B i d . Chcm., 65, 445 (1925).
NEWHAVEN,CONN.
RECEIVED MARCH 13, 1941
LABORATORY OF NATIONAL SUTHWESTERN ASSOCIATED UNIVERSITY.. CHINA]
KUNMING,
Maximum DifTerence between Densities of Ordinary and Heavy Water BY TSING-LIENchl"AN AND JEN-YUANCHIEN Farkas' calculated the density of heavy water below 40' from the dilatation data of Lewis and Macdonald2 and inferred that the differences between the densities of ordinary and heavy water shows a maximum at 25'. By repeating the experiment with quartz pycnometers between 10 and 27', Stokland, Ronaess and Tronstad8 concluded that such a maximum cannot exist below 30'. As the density difference found by them increases by a diminishing amount with increasing
temperature, it tends indeed to pass through a maximum at a temperature higher than their investigated range. Since ordinary and heavy water have equal density a t 370°,4 a maximum difference in density necessarily exists. In the present investigation measurements on the dilatation of heavy water are extended to 50'. It is thereby found that the maximum of density difference between ordinary and heavy water lies at 40'.
(1) A. Farkas, "Orthohydrogen, Parahydrogen and Heavy Hydrogen," Cambridge, 1936,p. 172. (2) G. N. Lewis and R. T. Macdonald, THIS JOum% 55, 3057
A sample of heavy water obtained from Norsk Hydro-
(1933). (3) K. Stokland, E. Ronaess and L. Tronstad, Trans. Paradar Soc., 85, 312 (1939).
Experimental (4) E. H. Riesenfeld and T. L. Chang, 2. physik. Chcm., BSO, 61 (1936).
TSING-LIEN CHANG .4ND JEN-YUANC H I E N
1710
Elektrisk Kvaelstof A/S, Oslo, was found to contain 99.54 mole% D20 after distillation in vacuum. The calculation of the mole percentage is based on the density value dZ626 1.10764 for pure heavy ~ a t e r . ~ ~ ~ ~ ~ A 16-ml. pycnometer of transparent vitreous quartz made by Geyer, Berlin, has a capillary 0.5 mm. in diameter with a small extension near the top. The capillary stem is graduated in millimeters for a length of 5 centimeters. The filling is aided by suction. The ground cap is sealed with mercury during observation. The thermostat used keeps the temperature constant within f0.002”. while the actual temperature is recorded by a thermometer which has a precision of 4-0.02”. The density of the sample is determined for the ternperature range between 3.8 and 50”. The measurement begins from the region of the density maximum of heavy Tiny ~ater.~f6 , ~ portions of the sample are removed successively for the measurement of smaller densities. In the calculation of the density of the sample, its volume is corrected for the thermal expansion of vitreous quartzs All weighings are corrected for the buoyancy of air. The experimental results for 99.54 mole% Dz0 are shown in Table I.
Vol. (i:;
TABLEI MEASUREMENTS ON 99.54 MOLE%DzO T‘,mp., C.
4 5 6
i 8
9 10 11 12 13 14 15 16 17 18 19 20 21 22 25 26 27
0.1080 ~
Density, g./ml.
1.10487 1.10501 1.10513 1,10523 1 . 10630 1.10535 1.10
