Associations moléculaires dans les cristaux de mélanges binaires de savons

Conclusion La variation des valeurs des grands espacements ou les différentes valeurs des espacements trouvés avec les mélanges binaires des sels alcalins des acides gras de différentes longueurs de chaîne peuvent être expliquées de la façon suivante: Plus les longueurs des chaînes des deux espèces de molécules sont voisines, plus elles ont tendance à cristalliser comme s'il s'agissait de molécules identiques et plus elles forment donc aisément des solutions solides. Ceci se produit pour des valeurs de la différence relative du nombre d'atomes de carbonex/n 0,14. Au fur et à mesure que cette différence croît, ces mélanges peuvent donner un composé stchiométrique, mais ne plus donner des solutions solides en toutes proportions. Ceci se produit pour des valeurs dex/n comprises entre 0,14 et 0,50. Enfin si la différence relativex/n est plus grande que 0,50 les savons cristallisent séparément; il n'y a ni solution solide, ni composé moléculaire.

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Zusammenfassung Mit Hilfe von Röntgendiagrammen wurden binäre Gemische von Natriumsalzen der gesättigten Fettsäuren mit gerader Kohlenstoffatomzahl und mit unterschiedlicher Kettenlänge untersucht, um die Existenz von möglichen definierten Molekülverbindungen nachzuweisen.Zu diesem Zweck wurden systematisch alle möglichen binären Kombinationen der Seifen durchgemessen, wobei für jedes Seifenpaar eine Reihe Messungen in verschiedenem Verhältnis beider Konstituenten angefertigt wurde.Die einfache Betrachtung der absoluten unterschiedlichen Kettenlänge in einem solchen binären Gemisch gestattet nicht, die Ungleichheit der erhaltenen Resultate zu erklären, aber derrelative Unterschied n/n, das heißt bezogen auf die Anzahl der Kohlenstoffatome beider Ketten, läßt die Aufstellung einer allgemeinen Regel zu. Je nach der Größe dieses ansteigenden relativen Unterschieds beobachtet man zuerst eine Bildung von festen Lösungen, danach Molekülassoziationen mit definierten Proportionen, und schließlich eine getrennte Kristallisation der beiden Konstituenten. Diese Ergebnisse werden bestätigt durch die Solidus-Liquidus-Kurven derselben Seifengemische.

     

Design and characterization of flow-through coulometric cells with porous working electrodes made of crushed vitreous carbon

Summary Three types of flow-through, three-electrode cells with porous working electrodes made of crushed vitreous carbon were tested. The electrochemical properties of the cells were studied by hydrodynamic and cyclic voltammetry using potassium ferrocyanide test solutions. Depending on the volume of the porous working electrode, Nernstian behaviour and electrochemical yields up to 100% were observed for flow rates 1 to 7 ml/min. In the stopped-flow regime the cells exhibit thin-layer cell properties. The utility of the cells is demonstrated for on-line coulometric detection, continuous removal of impurities and dissolved oxygen and for anodic stripping coulometry of trace copper.On leave from: Department of Analytical Chemistry, Slovak Technical University, CS-812 37 Bratislava, Czechoslovakia     

Tetrabutylammonium bromide/thenoyltri-fluoroacetone/mibk extraction for aas determination of cobalt, nickel, and manganese in copper ores and concentrates

An extraction-AAS method of determination of Co, Ni, and Mn in metallurgical copper materials containing considerable amounts ofCu, Fe, Pb, Zn, and Al has been developed. Good selectivity of group separation of Co, Ni, and Mn has been achieved by (a) the use of tetrabutylammonium bromide to improve extractability of HTTA complexes by ion-pair formation, and (b) the masking of major elements with sodium thiosulphate and sulphosalicylic acid. The extracts are stable for at least 3 weeks.     

Differential pulse polarographic determination of salicylaldehyde as its Girard-P derivative

A method for the determination of salicylaldehyde (2 × 10^–6–10^–4 M) by differential-pulse polarography, based on the in situ formation of its Girard-P derivative in aqueous solution at pH 2.5, is proposed. The relative standard deviation was 1.5% (ten determinations of 4 × 10^–5 M level). The applicability of this method was checked in synthetic samples containing salicyl alcohol,o-aminophenol, 2-methylphenol, salicylic acid and 4-aminobenzoic acid.     

Peculiarities of the photo aging of aromatic polyesters

Conclusions In the photolysis of films of polyarylates F-1 and D-9, together with destruction and structuration, there is a formation of light-absorbing o-hydroxyketone and quinoid structures in the polymers, which determines the self-stabilization of the polyesters; moreover, the basic photochemical processes take place in a thin surface layer.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2302–2304 October, 1969     

Zinc(II) as a versatile template for the design of dipolar and octupolar NLO-phores

Thermally stable dipolar and octupolar (D2d, D3) NLO-phores are readily accessible by combining one, two, or three 4,4'-bis(dialkylaminostyryl)-[2,2']-bipyridyl ligands with zinc(II) salts. The off-resonant beta0 values point out the superiority of octupoles versus dipoles in terms of nonlinearity/transparency tradeoff. The octahedral tris(bipyridyl)zinc(II) complex exhibits a very large beta0 value (241 x 10-30 esu), which is the largest ever reported for octupolar molecules.     

Formation of Small Silica Aggregates by Turbulent Aggregation

Aggregation of silica powder in water has been experimentally studied by turbidimetry. Aggregation was carried out in a stirred tank under physicochemical conditions corresponding to attractive interparticle forces. The effects of different primary particle sizes and stirring rates on aggregation dynamics have been studied. The scattering cross sections of silica aggregates were calculated in the framework of the anomalous diffraction approximation of light scattering theory. Aggregation has been studied by using Kusters's and Brakalov's approaches. By comparison between experimental and theoretical turbidity changes with time it has been shown that aggregates are small and slightly porous. The aggregation process is characterized by a weak fractal dimension D(wf) and an aggregate limit size L.D(wf) is found in the range 2.4-2.5. D(wf) (respectively L) is a weakly increasing (respectively decreasing) function of the stirring rate or of the shear rate. Copyright 2001 Academic Press.     

Strong 1,4-P-O intramolecular interactions as a source of conformational preferences in alpha-stabilized phosphorus ylides

For the first time, the existence of a strong intramolecular 1,4-interaction between the phosphorus atom and the oxygen atom in alpha-keto-stabilized ylides has been demonstrated by means of theoretical calculations. This interaction has a notable influence on the conformational preferences and rotational barriers of alpha-stabilized phosphorus ylides and bis-ylides.     

Ph2SO/Tf2O: a powerful promotor system in chemoselective glycosylations using thioglycosides

Diphenylsulfoxide in combination with triflic anhydride provides a very potent thiophilic glycosylation promotor system, capable of activating disarmed thioglycosides. The usefulness of this novel thiophilic activator is illustrated in a successful chemoselective glycosylation sequence in which the donor thioglycoside in the first condensation step may be either armed or disarmed. [reaction: see text]     

A route to heat resistant solid membranes with performances of liquid electrolytes

The confinement of ionic liquids within a porous silica matrix was performed by a one-step non-hydrolytic sol-gel route, leading to hybrid materials (called "ionogels") featuring both the mechanical and transparency properties of silica gels and the high ionic conductivity and thermal stability of ionic liquids.