The heterogeneous equilibria between liquid and vapour phases in the system water-acetone-chloroform have been investigated a t a pressure of 760 mm. It appears that a saddle point occurs in the two-liquids area of this system and that in addition a minimum occurs in the liquid surface.111. The binary systems. The equilibria in these systems and also in the ternary system were
A. Water-acetone.Since the compositions of the vapour and the liquid are very different, we used much liquid, so that evaporation of a small amount of it did not result in any appreciable change of the composition.Starting from water, the boiling point first falls very steeply with increasing acetone content, afterwards much less steeply and again determined at a pressure of 760 mm. 8 ) P. E. Wilson, J . Am. Chem. SOC. 43, 710 (1921).
In this system the components are completely miscible in the liquid state. T h e boiling points and the equilibria liquid-vapour at a pressure of 760 mm were determined. From the three binary systems only the system acetonechloroform has an azeotropic point, a maximum. The ternary liquid-surface (boiling-point-surface) and the vapour-surface have a rid.ge, going from the maximum on the acetone-chloroform side. at 64.5" C and 78 yo chloroform, to the benzene point at 80.25" C.In a former publication 1 ) dealing with the equilibria between liquid and vapour in ternary systems the authors have given a theoretical discussion of the course of the distillation lines and have demonstrated that in systems, which have a boundary line for simple distillation, a boundary line for rectifying distillation may also occur in some cases. T h e most simple example of such a case is a system in which 1'.
2'.the three components are miscible in all proportions and two of the three binary systems have a boiling point curve with neither a maximum nor a minimum, while that of the third has a maximum, the temperature of which is lower than the boiling point of the third component. In fig. 11 of the above mentioned publication the authors have pointed out the position of the distillation lines in that case.T h e system acetone-chloroform-benzene meets these requirements.So the liquid-vapour equilibria in this system at a pressure of one atmosphere were determined, i.e. the situation of the liquid-surface (the surface which represents the boiling points of the liquid mixtures as a function of their composition) and of the vapour-surface. T h e methods employed and their results will be given in this paper. In a I ) W. R e i n d e r s and Miss C. H. d e M i n j e r , Rec. trav. chim. 59, 207(1940).
Mit 1 Fignr im Text. 1. Zinn und J o d bilden zweiverbindungen: Stannojodid und Stannijodid. Die Angaben iiber die Darstellung und die verschiedenen Konstanten dieser Verbindungen, welche sich in der Literatur vorfinden, sind sehr schwankend. So sol1 sich beim Erhitzen von Zinn mit Jod nach den Blteren Untersuchern Stannojodid bilden, HENRY fand aber bei dieser Einwirkung Stannojodid neben Stannijodid und PERSONNE~ nur Stannijodid. Als Schmelzpunkt von SnJ, wird von PERSONNE 145O angegeben (Erstarrungspunkt 142 O)), von EMICH 143 ". Der Siedepunkt ist nach PERSONNE 295O, nach EMICH 34l0, und HENRY gibt an, daB es bei 180" sublimiert. Von SnJ, wird als Schmelzpunkt angegeben 246O und Dunkelrotgliihhitze (PERSONNE), als Siedepunkt 295 O oder die Schmelztemperatur des Qlases (PERSONNE). F u r nnsere Kenntnis der binaren Systeme von Metallen mit Metalloiden war also eine Revision dieser Angaben erwiinscht. Darstellung der Salze. 2. Das Stannijodid wurde nach zwei Methoden gewonnen: a) durch Zusammenbringen von granuliertem Zinn mit einer Losung von Jod in Schwefelkohlenstoff und Eindampfen der Losung, als nach einigen Tagen die Farbe des Jods verschwunden war; b) durch Zusammenschmelzen von Jod mit einem geringen UbermaB Zinn. Das Zinn wurde nach und nach der abgewogenen Menge Jod in einem ein-X. H . : BERZELIUS, Trait& de chimie. -RAMPELSBERQ, Pogg. Ann. 45, 169. * Philos. Trans. 136 (1845), 363. Conq~t. r e d . 64 (1862), 216. ' Sitzungsber. der k. Akad. d. W. Wien 113, I1 b (1904), S. 535; Monutshefte 225, 907. COHEN, AUEQGS Handbucli der anorg. Chem. 111 2, 8. 571.
Corps aramatiques nitrks. XIII. Yur la substitution do groupe nitro par oxymbthyle et oxyktbyle. A. Prdparc4 tion du paraoxy mdt h y I (dt h y 1)befizonitrile, PAR M.M. W. REINDERS et W. E. RINGER. I) Pour les derives ortho voir la note suivante de M. W. RIIQER. 2, Ber. 18, 1492.
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