Phase separation of quaternary solubilized solutions or micro emulsion of hydrocarbons containing sodium oleate + phenol + benzene + water by freezing point measurements

Summary The depressions in freezing point measurements in quaternary solubilized solutions or micro-emulsion in sodium oleate + phenol + benzene + water are measured. Maxima and minima were observed, Gibbs' phase rule was applicable, eutectic points were detected, congruent melting points were obtained, loose combination of molecules or clusters, were formed, phases of the system transferred and finally unstable emulsion separated out. This is contrary to the views ofMcBain who called these solutions as thermodynamically stable. The results were compared with the conductivity, stability and heat of solubilization-concentration measurements.

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Zusammenfassung Es wird die Gefrierpunktserniedrigung von quaternären solubilisierten Lösungen im System Natriumoleat-Phenol-Benzol-Wasser gemessen. Die verschiedenen Befunde (Maxima und Minima des Gefrierpunktes in Abhängigkeit von der Zusammensetzung, Anwendbarkeit der Gibbs'schen Phasenregel, Auftreten von Eutektika, kongruente Schmelzpunkte etc.) dienen zum Beweis, daß diese Lösungen thermodynamisch instabil sind.

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With 5 figures and 1 table     

Folded chain crystals as micro-phases

Summary A thermodynamic treatment of homo-polymer systems out of linear chains with folded chain crystals is developed outgoing from appropriate models for single component systems. An expansion of thermodynamics to multi-micro-phase systems the structure of which is partially or totaly frozen is indispensable. General properties of melt crystallized homopolymers with folded chain crystals can be recognized indeed when the thermodynamic formalisms developed are applied.

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Zusammenfassung Das Schmelzen in polymeren Einteilchensystemen mit Faltungskristallen einheitlicher Dicke kann thermodynamisch als Umwandlung 1. Ordnung in einer Richtung behandelt werden, wenn die Faltungslänge bis zur Umwandlungstemperatur konstant bleibt (Faltungslänge als innerer Zusatzparameter). Eine wesentliche begriffliche Erweiterung ist für eine phänomenologische Beschreibung mit den Mitteln der Thermodynamik unumgänglich, wenn eine Faltungskristallit-Dickenverteilung existiert, weil dann prinzipiell nur noch partielle Koexistenz bestimmter Fraktionen metastabiler autonomer Mikrophasen mit der Schmelze möglich ist. Partielles Aufschmelzen und Rektistallisation können so dann auch in Betracht genommen werden. Die entwickelten Konzeptionen bewähren sich in der Anwendung auf bekannte Experimente.

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Notation g ^c (y);g ^m (Y) molar Gibbs-free energy of a chain of a lengthy within an extended chain crystal and the melt rsp - g _o ^c ;g _o ^m molar free enthalpy of the unit in the crystal lattice and the melt rsp - g(y,y, f) molar Gibbs-function of an ideally folded chain crystal with the fold heighty _f - gco(y, y _ef,y _f) molar free enthalpy of the crystal corey _co - g ₀ ^ex ((y_ef) excess free enthalpy of the longitudinal layers of folded chain crystals - g ^f(y_ef,g _o ^ex ) molar free enthalpy of the longitudinal layers of the folded chain crystals - g ^tot molar free enthalpy of a chain of the lengthy within a folded chain crystal with longitudinal layers - h _o ^1c ,h _o ^m molar enthalpy of the chain unit within the crystal lattice and the melt rsp - h =h _o ^m -h _o ^c molar heat of fusion of the unit - C _p=C _p ^m -C _p ^c difference of the molar specific heat of a unit within the melt and within the chain crystal - h ^D molar defect enthalpy of local defects within the crystal lattice - h ^D molar defect enthalpy of the unit - s _o ^c ,s _o ^m molar entropy of the chain unit within the crystal lattice and the melt rsp - s _c ^m conformational entropy of a chain in the melt - s _gk conformational entropy of a chain of lengthy within a super-lattice as indicated in figure 5, - s molar entropy of fusion of the melt - s _n ^c nematic configurational entropy - T absolute temperature - T _M melting temperature of extended chain crystals of infinite size - T _M(y) melting temperature of extended chain crystals containing only chains of the lengthy - T _M (y, y _f) melting temperatureof folded chain crystals of the thicknessy _f composed of chains of the lengthy - T _M(y _f) melting temperature of folded chain crystals of the thicknessy _fy - _eh excess free enthalpy of the chain ends occupying crystallographic places - _ef excess free enthalpy of a single fold loop - z coordination number of the lattice - 7 Euler's constant - R Boltzmann's constant - y number of chain units - y _f height of lamelliform folded chain crystals - f=(y/y _f - 1) number of fold loops of a chain of a lengthy when being built into a folded chain crystal of the thicknessy _f - y _co thickness of the crystal core of the simplified twophase model - y _et average thickness of the surface layers of folded chain crystals - N _c number of crystallized units of a chain of the lengthy - x _c molar number of crystallized units of a chain of the lengthy - x _nc molar number of noncrystallized units - excess free enthalpy parameter - (y _f) thickness distribution of the fold heightsy _f With 15 figures and 2 tables     

Über 1-Alkyl-bzw. 1-Aryl-dihydro-6-methyl-2(1H)-pyrimidinthione

The title compounds7 are formed in a general reaction by heating β-isothiocyanoketones3 with primary amines in inert solvents, or by thermal elimination of water from tetrahydro-6-hydroxy-6-methyl-2(1H)-pyrimidinethiones5, also in inert solvents. The 1-alkyl compounds can also be prepared under similar conditions from α,β-unsaturated ketones by reaction with alkylammonium rhodanides. The NMR-spectra show that the 1-substituted dihydro-6-methyl-2(1H)-pyrimidinethiones are in tautomeric equilibrium with the tetrahydro-6-methylene-2(1H)-pyrimidinethiones13. The reactivity of 1-alkyl and 1-aryldihydro-6-methyl-2(1H)-pyrimidinethiones is similar to that of dihydro-4,4,6-trimethyl-2(1H)-pyrimidinethione7 j, although their ring stability is certainly less.     

Beiträge zur Chemie des Sulfamids, 1. Mitt.: Zur Konstitution des Disilber-sulfamids

According to spectroscopic (IR, broadline proton NMR) and chemical (alkylation) investigations of disilver sulphamide the following molecular structure is assumed: $$\begin{gathered} O \hfill \\ || \hfill \\ H_2 N\_\_S\_\_NAg| \hfill \\ OAg \hfill \\ \end{gathered}$$ From the IR and NMR data deduction concerning the nature of the chemical bonds in this compound is possible. The instability of the still unknown mono-and trisilver sulphamide is discussed with regard to the structure of disilver sulphamide.     

The two-phase structure of segmented block copoly(ether ester)

The annealing induced morphological changes in isotropic block copoly(etherester)s are investigated by small angle X-ray scattering methods. The observed results are consistent with a lamellar model which is comprised of a crystalline core of thickness 35 to 45 Å, a diffuse boundary zone of width 9 Å, and an amorphous layer which is varying strongly in thickness. The enhanced crystallinity of the samples annealed at higher temperatures is mainly due the lateral growth of the lamellae; the long period increases by not more than 20%. The scattering power of the samples is explained by means of an equivalent two-phase model in which the crystalline phase has the same structure as theα-form of poly(butylene terephthalate), whereas the amorphous phase is a mixture of the uncrystallized ester segments and the ether segments. The crystallinity determined from the scattering power is very much higher than that determined from thermoanalytical investigations.     

The intermediacy of metathiophosphonate PhPSO in the reaction of N-tert-butyl-P-phenylphosphonamidothioic acid with alcohols

Kinetic studies of the reaction of N-tert-butyl-P-phenylphosphonamidothioic acid (1) with alcohols were carried out in CH2Cl2 by means of 31P NMR spectrometry. The reaction is of the first order with respect to thio acid 1. The first-order rate constant at 30 degrees C increases with increasing methanol concentration below 0.25 M, but otherwise the rate constants are either independent of alcohol concentration (MeOH above 0.25 M, BuOH) or decrease with increasing alcohol concentration (i-PrOH, t-BuOH). The effect of alcohols on the order of the reaction and parameters of activation, as well as results of competition experiments, lead us to the conclusion that reaction of 1 with alcohols occurs by an elimination-addition mechanism involving the association of the thio acid 1 and the alcohol and then formation in the rate-determining step of an encounter complex 2' ' involving metathiophosphonate 4, amine, and alcohol. Metathiophosphonate 4 reacts preferentially with the alcohol as the encounter complex (primary alcohols) or after diffusion apart as a "free" intermediate (hindered alcohols).     

Die Kristallstruktur von Ru2Si3

The crystal structure of Ru₂Si₃ has been refined by leastsquares using three-dimensional X-ray data from a twinned crystal (1355 reflections,R=5.8%). Ru₂Si₃ is isostructural with Ru₂Ge₃ and like this compound a member of the Mn₁₁Si₁₉ structure family. The lattice parameters of the orthorhombic unit cell (Pnca—D ₁₄ ^2h ) are:a=5.530 (1),b=11.060 (2) andc=8.952 (2) Å.

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Mit 1 Abbildung     

Über die Konfiguration des Prolins im Ergotamin

It is well known that in the ergot alkaloids of the peptide type the proline appears in thel-configuration. Different methods of acid hydrolysis may lead to various cleavage products; hydrolysis by HCl yieldsd-proline, on the other hand hydrolytic cleavage by means of strongly acid cation exchange resin preserved the orginall-configuration.

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Teilveröffentlichung der Dissertation vonH. Kolassa, Univ. Wien, 1973.     

Beiträge zur chemie der Pyrrolpigmente, 10. Mitt.: Elektronenspektrometrische Untersuchungen über die Struktur von Quadratsäurederivaten

The structure of squaric acid derivatives was investigated on the basis of the PPP—SCF—LCAO—MO—CI method utilizing the π-electron densities and bond orders. The parameters used in the calculations were modified to fit the experimental data for representative compounds. The data were obtained by X-ray photoelectron spectrometry and electron absorption spectroscopy (including the polarization of the bands as determined by liquid crystal induced circular dichroism measurements).     

Thermische Polymerisation von Acenaphthylen

Zusammenfassung Acenaphthylen wurde durch Anpolymerisation und zweifache Hochvakuumsublimation gereinigt. Die Reinigungsmethode wird ausführlich beschrieben.Bei verschiedenen Temperaturen wurde mit einer dilatometrischen Methode die thermische Bruttogeschwindigkeit gemessen. Zwischen 95 und 105 °C giltk _br=7,0₈·10¹⁰ exp (– 30,9 kcal/RT).Die beträchtliche Aktivierungsenergie der Bruttoreaktion ist sowohl auf eine große Aktivierungsenergie der thermischen Startreaktion als auch auf eine relativ hohe Wachstumsaktivierungsenergie zurückzuführen.Das Polymerisationsverhalten von Acenaphthylen kann vermutlich aufgrund seiner sterischen Eigenschaften erklärt werden.

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Summary Acenaphthylene was purified by partial polymerisation, followed by double stage high vacuum sublimation. The method of purification is described in detail.The thermal overall rate was measured at different temperatures by a dilatometric method. Between 95 and 105 °C the following relation holds:k _th=7,0₈ · 10¹⁰ exp (– 30,9 kcal/RT).The considerable energy of activation of the overall reaction depends on a relatively high energy of activation of both the thermal initiation and the propagation reaction.It is supposed, that the polymerisation behaviour of acenaphthylene depends mainly on its steric properties.