July, 1936
THETERNARY SYSTEMSKI-K2SO4-H20
AND
1077
NaI-Na2S04-H20
I CONTRIBUTION PROM THE DEPARTMENT OF CHEMISTRY, NEWYORK UNIVERSITY]
The Ternary Systems KI-K,SO,-H,O and NaI-Na2SO4-H,O BY JOHN E. RICCI In addition to the purpose of obtaining solu- vious similar publication^.^ The temperature bility data for the salt pairs KI-KzSOI and NaI- was maintained constant to within It0.02'. The Na2S04in water, this brief investigation also had time allowed for the attainment of equilibrium as its object the question of the formation of solid varied from three days in the case of the potassolutions of the alkali iodides in the corresponding sium salts, to as long as fourteen days in the case sulfates. The crystals of sodium sulfate offer a of the sodium salts; the latter system was found considerable number of instances of the forma- by experiment to require from ten to fourteen tion of solid solutions with other salts (as, with days to reach equilibrium in all complexes which Na2C08, Na2CrO4, Na2S, NaZS03, NazSzOa, Agz- involved the formation of Na2SOr.lOHzO as solid Sod, and NaBrOS2). As to the iodides in particu- phase. The densities reported for the potassium lar, sodium sulfate has been reported* to form salt system and for some solutions of the sodium crystals of Na2SOd.lOHzO containing varying salt system, were obtained by means of volumetric quantities of NaI, KI, NHlI and LiI, held in the pipets calibrated for delivery. For the analysis form of solid solution; these results, however, of the solutions, the iodide was determined voluare based on non-equilibrium studies, in which metrically by titration with 0.2 N silver nitrate the decahydrate was allowed to crystallize slowly using dichlorofluorescein as indicator, the total from solutions of varying concentrations of the solid was determined by evaporation to dryness, iodides, a t a roughly constant temperature near and the sulfate was then calculated by difference. room temperature. Although the fact that such In some cases of the KI-KzS04-HzO system the crystals contain iodide (from 0.4% in the case of sulfate was determined directly by the graviNaI, to 0.65% for LiI) may well be the result of metric method, and the iodide then calculated by simple occlusion due to lack of equilibrium, the difference. The results of the two methods being crystals are reported to be solid solutions ("mixed in sufficiently close agreement, the more rapid crystals") on the strength of their clearness and method (titration of the iodide) was used in gentransparency. Since on the basis of such work eral. The solid phases were in each case verithere seemed to be some doubt as to the actual fied by the method of algebraic extrapolation of existence of such solid solutions as stable phases tie-lines,6 the average error of the extrapolations, in the systems, it was thought desirable to make for both systems, being O.lSyo. an equilibrium study of the particular system Results NaI-Na2SO4-H20. The experimental data for the system KIIn the present work both the system KI- KzSOK-HZOa t 25' are given in Table I and Fig, 1; KzS04-HzO and the system NaI-Na2SO4-H20 TABLE I were studied, from the point of view of the phase KI-K2S04-H20 AT 25' Original complex, rule, the first a t 25', the second a t 15, 25 and 45'. Saturated solution, Wt. % wt. % The results, which represent equilibrium in the K&Oi KI KaSOI KI Density Solid phase . . . 0.00 10.76 0.00 1.083 &SO4 systems, show no solid solutions to be formed in 23.01 7 . 5 3 6.57 9 . 1 3 1.127 - 0 4 either case, within the limits of the rather small 22.02 15.01 3 . 5 7 18.57 1.185 &SO( experimental error of this type of work. The 21.47 23.02 1.70 28.81 1.273 K&OI only solid phases encountered are the pure an21.01 31.49 0 . 6 9 39.57 1.399 KzSO, hydrous or hydrated salts themselves. 20.74 40.04 .25 50.35 1.553
Experimental Method The experimental procedure for the solubility measurements has already been described in pre(1) "International Critical Tables." Vol. IV. 1928. JOURNAL, 67, 805 (1935). (2) Ricci, THIS (3) Fabris, Ann. ckim. applicara, 1'7, 321 (1927); 18, 115, 326 (1928).
19.99 19.98 12.05 3.00 0.59 Av. (of 4) 0.00
47.03 48.19 57.91 66.05 67.98
.. , .,.
. 1 0 58.70 1.701 . 0 8 59.69 1.724 .08 59.70 1.724 .08 59.67 1.720 . 0 8 59.68 1.721 . 0 8 59.69 1.722 . O O 59.76 1.718
(4) Ricci THIS JOURNAL, 56, 290 (1934). (5) Hill and Ricci, ibid., 58, 4305 (1931).
KiSO4 &SO,
+ KI mod + KI + KI &SO, + KI .&so4 + KI
-04
KI
,
1078
JOHN
E. RICCI
the solubility curve consists of two simple branches, one for solutions in equilibrium with potassium sulfate, the other, extremely short, for solutions saturated with KI.
13.11 13.05 14.03 13.49 18.05 12.48 Av. (of
...
36.74 20.01 20.13 20.00 20.16 20.27 19.94 20.06 19.96 4.02 2.98 Av. (of 0.00
VOl. 58 22.20 9.37 23.56 8.70 25.00 7.94 27.02 7.61 26.02 7.66 29.31 7.64 5) 7.63 0.00 33.97 6.57 26.65 19.97 14.91 27.11 7.97 32.16 4.09 36.77 2.06 41.72 0.70 45.45 .30 49.73 .14 54.55 .02 64.97 .07 .07 72.00 .06 4) .OO .. .
KI
TABLE I1 NaI-Na2SO4-HzO 15' Original complex, Saturated solution, wt % wt % Na604 NaI NazSOa NaI Density
0.00 27.98 36.09 35.95 37.99 33.57
11.60 2.51 2.15 2.10 2.13 2.23
0.00 33.16 39.67 41.78 44.07 44.79
1.106 1.367 1.460 1.490 1.532 1.543
5.97 41.85 2.19 44.85 1.543 15.02 37.41 2.22 44.84 Av. (of 3)
64.90
Av. (of 2) 0.00
. ..
1.540
2.21 44.83 1.542
15.09 42.99 0.93 50.15 15.04 48.43 .15 56 92 15.00 53.52 .02 62.89 15.08 54.59 .01 63.33 4.99
+ + +
+ + + +
...
Isotherm: KI-K2S04-H20.
The results for the system NaI-Na2S04-H20J at 15, 25 and 45', are presented in Table 11, the
9.01 5.95 8 00 8.01 13.05
NaaSO4.lOHzO Na2SO4:1OH20 NazS04.10H~O Na~S04.1OH20 NazSO4 NazSO,.lOHzO Na2SO4 Na2SO4.10H20 Na2SO4 NazSO4.1OH20 f Na2SO4 Na~S04(m)b Na2SO4 (m) Na2SO4 (m) Nags04 (m) NazSO4 NazSO4 NaZSOt NazSOt Na2S04 Na2S04 NaI.2H20 Na2S04 NaI,2H20 Na2SO4 NaI.2H20 Na2S04 NaI.2H20 NaI.2H2O
450' Fig. 1.-25"
...
24.81 26.84 30.05 31.77 31.74 31.76 31.77 0.00 7.60 21.22 31.21 38.58 45.01 51.91 56.54 62.05 64.76 64.76 64.75 64.75 64.79
1.613 1.733 1.875 1.881
.05 63 31 1.882 .03 63.32 .OO
, . 0.00 21.78 23.91 5.15 17.54 23.58 8.10 14.87 20.09 13.94 11.83 15.62 17.42 10.81
1.881
Solid phase
Na904.10H~O Na2S04.10H~O Na~S04-10H~0 Na~S04.10H~0 Na2SOclOHzO NanSO4.1OH,O NazSO4 Na2SOclOH20 NazSO4 NaaSO4.1OHzO 4Na2S04 Na2SO4~lOH~O Na2SO4 Na2SO4 NazSOa Na904 Na2S04 4- NaI. 2Hz0 NazSO4 f NaI. 2Ha0 NazS04 NaI. 2H20 NaI.2Hz0
63.35 1.881 25"" 0.00 Na2SOI.lOHzO 6.77 Na~SOc10H20 11.50 Na~S04.10H~0 18.46 Na2SOI.lOH20 20.30 Na2SO,.lOH20
+ +
0.00 32.09 0.00 Na2SO4 35.01 12.98 17.19 16.52 Na2SO4 29.87 23.88 6.73 31.73 Na2SOt 25.01 32.89 2.22 42.85 Na2SO4 20.07 41.98 0.51 52.27 NalSO4 17.78 43.54 .43 52.75 NazSO4 20.16 54.22 .04 67.85 NazS04 6.02 64.78 ,04 68.29 NazSO4 NaI.2H20 6.00 67.92 .02 68.22 Na2SO4 4-NaI:2Ha0 NaI.2HzO 2.04 70.48 .06 68.25 NazSO4 NaI.2H20 Av. (of 3) .04 68.25 Na2SO4 0.00 . , .OO 68.32 NaI.2HzO '' The data for the 45O, and for part of the 25', isotherms were obtained by Dr. Nicholas S. Yanick, formerly of this Department. * m = metastable solid phase.
.
+ + +
three isotherms being shown graphically in Figs. 2 , s and 4. As may be seen from the diagrams the
+
+
Fig. 2.--15"
Isotherm: NaI-Na2SOrHzO.
only stable phases existing in the system at 43' arc anhydrous Na2S04 and NaIS2Hz0, while at
July, 193ti
PHENYL URETHAN ANESTHETICS
15 and 25', NazS04.10H20 appears, giving three stable phases. In Fig. 3, for the 25' isotherm, the curve a-b represents the solubility of Na2S04. lOH2O as stable phase in the ternary system;
1070
the metastable solubility of anhydrous Na2S04 in water a t 25'.
Fig. 4 . 4 5 ' Isotherm: NaI-Na2SO~-H~O. Fig. 3.-25'
Isotherm: NaI-NatSOa-H20.
point b, an isothermally invariant solution in equilibrium with both hydrated and anhydrous Na2S04 ; the curve b-c, solutions in equilibrium with anhydrous Na2S04 as solid phase; point c, the isothermally invariant solution for the two solid phases Na2S04 and NaI.2H20; and the very short curve c-d, the solubility curve of NaI. "20. The curve b-e is the metastable extension of the solubility curve b-c, of Na2SO4,point e being
Acknowledgment.-The author wishes to express his thanks to Dr. Nicholas S.Yanick, formerly of this Department, for his help in some of the experimental work of this paper. Summary Solubility measurements are given for the systems KI-K2S04-H20 (at 25') and NaI-Na2S04H 2 0 (at 15, 25 and 45'); these salt pairs form neither double salts nor solid solutions a t the temperatures reported. NEW YORK,N. Y.
RECEIVED APRIL 21, 1936
s. MERRELLCOMPANY] Phenyl Urethan Anesthetics. I1
[CONTRIBUTION FROM THE
LABORATORIES O F THE
WM.
BY E. S. COOKAND T. H. RIDER The value of phenyl urethans as local anesthetics has been pointed out by Rider.' The present paper continues work in this field and deals largely with phenyl urethans of y-dialkylaminopropanols (R2NCH2CH2CH20H). Two esters of dialkylaminoisopropyl alcohols (RsNCH2CHOHCHs) and the phenyl urethan of P-diethylaminoethanol are included. These compounds are of particular interest because they are isomeric with the p-aminobenzoates, several of which have found considerable use as local anesthetics. The p-aminobenzoate homologs of compounds 4 and 9 (see Table I) are (1) T.H Rider, (a) THISJOURNAL, 61, 2115 (1930); (b) r b r d , 62, 2583 (1930). (c) J Pharmacal , 89, 457 (1930); (d) tbrd , 4T, 255
(1933)
marketed as butyn and pracaine, respectively, and the p-arninobenzoate homologs of compounds 2, 3,2 and 6a have been prepared and found to possess local anesthetic activity. Experimental
Part
Amino Alcohols.-Beta-diethylaminoethanol, ydiethylaminopropanol, and 7-di-n-butylaminopropanol were obtained from the Eastman Kodak Company and redistilled. The other y-dialkylaminopropanols (dimethylamino-, din-propylamino-, piperidino- and methylphenethylamino-) were prepared by condensing the proper secondary amine with trimethylene bromohydrin in the absence of a solvent. (2) 0. K a m m , R. Adams and E. H. Volwiler, U. S. Patents 1,358,750 a n d 1,358,751;E. H. Volwiler, Science, 68, 145 (1921); H.L. Schmitz and A. S. Loevenhart, J. Pharmocol., 24, 159 (1924). (8) A. C. Cope and S. M. McElvain, THIS JOURNAL, 68, 1587 (1931).
