426
JACOB JCIELLAND
Vol, 58
A w l . Calcd, for CrH11O&S; N, 20.88; S, 15.04. Anal. Calcd. for CtaHlbON8: N, 18.83; OGHa, 19.66. Found: N, 20.90; S, 16.18. Found: N, 18.14; OCHs, 19.50. On hy&olysisa with hydrochloric acid this sulfone On evaporating on a steam-bath with concentrated hydrochloric acid and making alkaline with ammonia, evolved sulfur dioxidea The aqueous solutiod on evapora. this compound gave 2-anilino-4-oxy-5-methoxypyrimi- tian gave 5-methybytosine hydrwhloride.8 This was dine, m. g. 256255' from alcohol. This same com- recrystallized from an dcohol-cohcentrated hydrochloric pound was obtained for comparison by heating 2-ethyl- wid solution by addition of ether, m. p. 288-290" (dec.). mercapto-4-oxy-5-methylpyrimidme with aniline on a Anal. Ca;Icd. far C&@aNa*HCl: N, 28.00; C1,21.95. steam-bath until all the ethylmercaptan was evolved. Found: N, 25.80; CI,22.21. Benzene was added and the solid removed by filtering. This was recrystallized from alcohol, m. p. 254-255'. Svmmary Anal. Calcd. for CllHllON': N, 20.88. Found: N, In this paper is described the behavior of several 20.70. 2-ethylsulfonylpyrimidines when allowed to inter2 Ethylsulfonyl - 4 amino 5 methylpyrimidine.-Two grams of 2-ethylsulfonyl-4-chloro-5-methylpyrimidine act with sodium alcoholate, alkali, ammonia and was heated with 25 cc. of ethanol, saturated with dry am- aniline. The ethylsulfoayl group of the pyrimimonia a t O", for two hours a t 100'. The alcohol was then dine reacts in a0 these changes in a similar manevaporated and the residue extracted with hot ethyl acener as a halogen atom being easily replaced by tate. The ethyl acetate solution was concentrated to a small volume and cooled. There was obtained 0.9 g. of alkoxyl, hydroxyl and amino groups. (8) Wheeler and Johnson, A m . Chem. J., 31, 598 (1904). crystals, m. p. 128-130'. A further quantity was obtained from the filtrate (0.13 g.). This was recrystallized NEWHAVER,CONNECTICUT from ethyl acetate, m. p. 135.5-136.5'. R~CEIVED DIWEMBER 26, 1935
-
-
- -
Calculation of the Solubility of a Mixture of Rydrogen and Nitrogen in Water at 2 5 O in the Pressure Range of 50 to 1000 Atmospheres BY JACOB KIELLAND' Introduction R. Wiebe and V. L. Gaddy2 have recently published experimental data concerning the solubility of a 76.42:23.5s hydrogen-nitrogen mixture in water a t 25', and a t high pressure, It was faund that the solubility of the mixture could be calculated to within a few per cent. from the values of the pure constituents, by multiplying the mole fraction of each separate gas by its own solubility at a pressure equal to the total pressure of the mixture, and then adding these values together. However, on examining the solubility of each one of the constituents it will be found that there is a certain amount of difference betweem the values observed and those calculated. As far as the nitrogen is concerned, there is a deviation of about 13% a t 800 to 1000 atm., Wiebe and Gaddy's own analyses of the composition of the gas in the water phase being employed (see Table 1) Discussion The difference between the calculated and observed solubilities-assuming that there is no (1) Chemical Engineer, Norsk Hydro-Elektrisk Kvaebtofaktieselskab, Oslo. N m % y ( 2 ) Wiebe and Gaddy, THIS JOURNAL, 67, 1487 (1935).
systematical error in measurement-may be explained by the existence of deviations from t k fugacity rule8of Lewis and Randall, which is.the basis of method of caleulatiofi, and States
or, in other words, that the activity coefficient of a gas is the Same a t canstant pressure, irrespective of whether the gas occurs alone or in mixtures. Accordifig to A. k,Merz and C. W. tNhittaker,4 however, this rule does not apply to hydrogennitrogen mixtures a t the pressures in question in the present case. From the work carried out by them, the values €or yJ^/io or ji/Nifio, given in Table 11, columns 2 and 3, have k e n taken. In the water phase, where the action of the water mdecules on the activity ruefficients must be assumed t o be of greater importance than the interaction Q€ the separate gases, the latter process will not be t a k n into consideration. The results obtained prove this assumption to be perfectly justified. It must be pointed out that the solubility correetim for deviations from the Lewis and Randall (3) Cf. Newton and Dodge, Ind Eng Chcm , 2'7, 678 (1935). (4) Merz and Whittaker, THIS JOURNAL, 80, 1522 (1928).
SOLUBILITY IN WATEROF HYDROGEN-N JTROGEN MIXTURES
March, 1936
427
TABLE I THESOLUBILITY OF A HYDROGEN-NITROGEN MIXTUREIN WATERAT 25' (Cc. OF GASAT S. T. P. ACCORDINGTO MEASUREMENTS AND CALCULATIONS BY WIEBE AND GADDY Pressure, atm.
H,
Observed, N2
Total
HI
Calculated,
50 100 200 400 600 800 1000
0 6694 1.328 2.652 5.118 7.482 9.665 11.778
0.1655 ,315 ,557 .950 1.327 1.662 1.946
0.8349 1.643 3.209 6.068 8.809 11.327 13.724
0.663 1.321 2.591 5.021 7.321 9.522 11.616
Nx 0.159 ,298 ,532 ,893 1.188 1.446 1.686
PER
Obsd.
Total
Hr
0.822 1.619 3.123 5.914 8.509 10.968 13.302
0.9 0.5 2.3 1.9 2.1 1.5 1.4
G. OF WATER)
- Calcd NI
.
3.9 5.4 4.5 6.0 10.4 13.0 13.4
in % Total
1.6 1.5
2.7 2.5 3.4 3.2 3,1
rule, which reach 13% in the case of the gas mix- perimental data thus obtained, and in Fig. 1, the ture containing 76% of hydrogen, would reach results are illustrated graphically. nearly 20% for either of these gases when it is 12.0 6.0 present in small proportions in the gas mixture. Since this paper was prepared, a publication of $ 11.o % 5.0 I. R. Krichevsky and J. S. Kasarnovsky appeared B [THISJOURNAL, 57, 2168 (1935)l concerning the 0 10.0 solubilities of either nitrogen or hydrogen in water, 4.0 which was shown to follow the formula In f s / N s = In K H ~ (i2P/RT). ~ ~ They pointed out that 9.0 3.0 this formula may also be used in the case of gas vi mixtures ; this means that the partial molal volCI ;2.0 ume of either gas in aqueous solution is assumed B to be independent of the other gas. The validity 1.0 of this assumption, which is identical with the one 0 made by the author, is confirmed by the present work. 0 0 4-00 800 Results Y
2
2
+
I I
When equilibrium is established the fugacity or activity will be equally great in both phases, wherefore it is necessary to multiply the solubilities calculated by Wiebe and Gaddy by the corresponding values of yi/yio. This has been done in Table 11, columns 4 and 5. In columns 7, 8 and 9 are shown the deviations from the exTABLE I1 SOLUBILITY OF A HYDROGEN-NITROGEN MIXTURE I N WATERAT 25" (Cc. OF GASAT S. T. P. PER G OF WATER)CALCULATED BY THE AUTHOR PresObsd. - Calcd. sure, dyio Calcd. soly. in % atm. Ht MI Ht Nx Total Ht Nr Total 50
100 200 400 600 800 1000
I . ~
1.00 1.01
2.7
1.00 1.03
2 . 5 0.9
0.683 0.181 0.824 0.0 ,307 1.628 1.321 0.5 .563 3.154 1.00 1.06 2.681 2.3 I. 005 1.IO 5,a46 ,983 6,029 1.4 1.01 1.12 7.394 1.332 8.726 1.2 1.625 1.01 1.12 11.24 9.617 0.5 1.01 1 . 1 2 11.78 1.89 13.67 -0.0
.
-1.1 -3.
I
1.7 0.
$0.4 0.9 + 2 . 2 0.8 2 . 9 0.4
Pressure of gas mixture in atmospheres. Fig. 1.-Solubility in water a t 25" of a 76.4: and 0 , ob23.6 hydrogen-nitrogen mixture: served by Wiebe and Gaddy for hydrogen and nitrogen respectively; - - -, calculated by , calculated by the Wiebe and Gaddy; present author. (The right-hand ordinate scale refers to hydrogen a t 500 to 1000 atm.)
-
On the basis of this, it should be possible to calculate both the total and the partial solubility to within a few per cent. of any mixture of hydrogen and nitrogen.
summary It was found how both the total and the ~ a r t i a l solubility in water of hydrogen-nitrogen mixtures a t pressures of from 50 to 1000 atmospheres could be calculated to within a few per cent. OSLO, NORWAY
RECEIVED OCTOBER 14, 1935
