Extraction of Nitric,Perchloric, and Hydrochloric Acid by N,N-dibutyl Diethyl Carbamyl Phosphonate

Extraction of nitric, perchloric, and hydrochloric acid by N,N-dibutyl diethyl carbamyl phosphonate in carbon tetrachloride was investigated. The data obtained are treated in terms of stepwise neutralization of the acid with the formation of species y · HA and y · 2HA in the organic phase, where y stands for the extractant and HA for the acid. The equilibrium constants, K?₁ and K?₂ for nitric acid were found to equal 0.24 ± 0.02 and 0.017 ± 0.005, respectively. In case of HClO₄ and HCl K?₁ were found to equal 0.031 ± 0.003 and 0.0039 ± 0.0005, respectively. A third phase was observed when extraction of HClO₄ was performed using acid concentration higher than 3.5 molar. The preference for partition of different acids was discussed on the light of the competition of the proton between the acid anion, water and the basic extractant as well as the degree of the ionization of different acids.     

Die chemische Analyse als Wegbereiter der Metallkunde und der Metallurgie

Zusammenfassung Die Reaktionen zwischen Roheisenschmelzen, Hochofenschlacken und dem elementaren Kohlenstoff des Schmelztiegels werden als Beispiele dafür angeführt, wie groß doch der Anteil der analytischen Chemie zu sein hat, wenn man tieferen Einblick in technische Verfahren wie den Hochofenprozeß gewinnen will. Gute analytische Ergebnisse lassen sich auch meist in recht einfacher Weise ordnen. Erstaunlich sind die Einblicke, zu denen die dem Chemiker selbstverständlichen, aber lästigen Stoffbilanzen verhelfen.Der Chemiker verfügt über Kenntnisse und experimentelle Einrichtungen, die weit über die übliche Elementaranalyse hinaus anwendbar sind. Als Beispiel dazu wird die Bestimmung des Kohlenstoffs im Stahl betrachtet, die ohne ein zusätzliches Hilfsmittel gestattet, die Entkohlung beim Zundern von Stahl laufend zu verfolgen. Die Phänomene an der Grenzfläche Metall-Oxid und viele weitere Erscheinungen bieten sich dar.

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Summary The reactions between pig iron melts, blast furnace slags and the elementary carbon of the fusion crucible are cited as examples of the extent required of chemical analysis if a deeper insight into the technical operations is to be obtained, such as blast furnace processes. Good analytical results can usually be arranged in a rather simple manner. The troublesome material balances assist in opening truly astounding insights that are self-evident to the chemist.The chemist has available knowledge and experimental devices that are applicable far beyond the conventional elementary analyses. A pertinent instance is the determination of carbon in steel, which without an auxiliary aid permits the operator to follow the course of decarbonization continuously during the scaling of steel. The phenomena at the interface metal-oxide and numerous other occurrences present themselves.

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Résumé On donne comme exemple les réactions entre le fer brut fondu, les scories des hauts fourneaux et le carbone élémentaire du creuset dans lequel s'effectue la fusion, pour montrer combien grande doit être la contribution de la chimie analytique si l'on veut avoir une vue plus profonde du procédé technique et réactionnel dans le haut fourneau. La plupart du temps, on peut classer d'une manière très simple, les bons résultats expérimentaux. Très surprenantes sont les idées auxquelles conduisent les rendements qui vont de soi pour le chimiste mais qui sont onéreux.Le chimiste dispose de connaissances et de dispositifs expérimentaux qui sont largement applicables à l'analyse élémentaire usuelle. On prend comme exemple le dosage du carbone dans l'acier, qui permet sans moyen auxiliaire de suivre d'une façon continue la décarburation pendant l'inflammation de l'acier. Les phénomènes à l'interface métal-oxyde et de nombreux autres phénomènes se présentent.

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Auszug aus einem Vortrag anläßlich des Kolloquiums für metallkundliche Analyse mit besonderer Berücksichtigung der Elektronenstrahl-Mikroanalyse, Wien, 22. Oktober 1964.     

The synthesis of diene and of vinyl copolymers containing predetermined quantities of polynuclear hydrocarbon or heterocyclic adducts—IV. Copolymers of butadiene or isoprene,anthracene and a linking agent

Evidence is given that, when solutions of diene monomers and anthracene in tetrahydrofuran are reacted with alkali metal and subsequently titrated with linking agents such as alkyl dihalides, copolymers are formed; they contain the 9,10-dihydroanthracene adduct and the diene in the same proportion as in the original solution. The structures of these copolymers have been elucidated by NMR spectroscopy and the mechanism of formation is discussed.     

Effect of Thermal Treatment on the Fine Structure of Cellulose Materials

The effect of thermal treatment in the range 110-250°C on the structural and sorption characteristics of cellulose was studied by ¹H NMR and sorption methods.     

Qy-excitation resonance Raman spectra of chlorophyll a and bacteriochlorophyll c/d aggregates. Effects of peripheral substituents on the low-frequency vibrational characteristics

Low-frequency (80-700 cm-1) Qy-excitation resonance Raman (RR) spectra are reported for thin-solid-film aggregates of several chlorophyll (Chl) a and bacteriochlorophyll (BChl) c/d pigments. The pigments include Chl a, pyrochlorophyll a (PChl a), methylpyrochloropyllide a (MPChl a), methylbacteriochloropyllide d (MBChl d), [E,M] BChl cS, [E,E] BChl cF, and [P,E] BChl cF. The BChl c/d's are the principal constituents of the chlorosomal light-harvesting apparatus of green photosynthetic bacteria. Together, the various Chl a's and BChl c/d's represent a series in which the peripheral substituent groups on the chlorin macrocycle are varied in systematic fashion. All of the Chl a and BChl c/d aggregates exhibit rich low-frequency vibrational patterns. In the case of the BChl c/d's, certain modes in the very low-frequency region (100-200 cm-1) experience exceptionally strong Raman intensity enhancements. The frequencies of these modes are qualitatively similar to those of oscillations observed in femtosecond optical experiments on chlorosomes. The RR data indicate that the low-frequency vibrations are best characterized as intramolecular out-of-plane deformations of the chlorin macrocycle rather than intermolecular modes. The coupling of the out-of-plane modes in turn implies that the Qy electronic transition(s) of the aggregate have out-of-plane character. The RR spectra of the BChl c/d's also reveal that the nature of the alkyl substituents at the 8 and 12 positions of the macrocycle plays an important role in determining the detailed features of the low-frequency vibrational patterns. The frequencies of the modes are particularly sensitive to larger substituent groups whose conformations may be more easily perturbed in the tightly packed aggregates. These factors also make aggregates of pigments containing larger substituents more susceptible to structural, electronic, and vibrational inhomgeneities. Collectively, the RR studies of the various pigments delineate the factors which influence the low-frequency vibrational characteristics of chlorosomal aggregates.     

Polynuclear nonfused bis(1,3,4-oxadiazole)-containing systems

Nonfused bis-1,3,4-oxadiazoles were synthesized by reaction of 5-substituted mono-and bis-tetrazoles with mono-and dicarboxylic acid chlorides. The results of kinetic studies showed that the transformation of tetrazoles into 1,3,4-oxadiazoles is accelerated by 1 to 2 orders of magnitude on addition of a catalytic amount of dimethylformamide, triethylamine, or pyridine.     

Modification of bovine beta-lactoglobulin by glycation in a powdered state or in aqueous solution: adsorption at the air-water interface

The adsorption at the air-water interface of native and various glycated forms of beta-Lactoglobulin B (beta-LG), prepared under two different experimental conditions, was investigated by ellipsometry, surface tension and shear elastic constant measurements. The measurements were performed in 0.1 M phosphate buffer, 0.1 M NaCl, pH 6.8. It was found that the interfacial properties of beta-LG were more affected when the glycation was performed in solution than in the dry-way system. Dry-way glycated beta-LG, despite a higher glycation extent, affected slightly its interfacial behaviour. Solution glycated beta-LG exhibited a higher adsorption and more rigid interface as expressed by shear elastic constant measurement at saturation (16.5 mN/m against 8.7 and 11.5 mN/m for native and control treated beta-LG, respectively). These results were attributed to the specific molecular species induced during glycation in solution, which includes monomers and unfolded covalent homodimers of beta-LG molecules with a high tendency to self-association via non-covalent interactions.     

Isolement du prestegane B à partir de Steganotaenia araliacea hochst., premier lignane bis-(meta-hydroxy-benzyl)-butanolide d'origine végétale. - Isolement et synthèse en une étape du diméthylmatairésinol-

Prestegane B -the first higher plant occured dibenzyl butanolide lignan with two $\text{meta}$-phenols- and its dimethylether were isolated from $\text{S.araliacea}$ and the structure determinations were performed with the aid of high resolution NMR and Mass fragmentation for the former, and with 2-D J resolved ¹H NMR studies and synthesis for the latter.     

Activation analysis with a high-resolution high rate gamma-spectroscopy system

A high-resolution high-rate ψ-spectroscopy system is essential or, respectively, useful in three groups of applications: (1) measurement of nuclides with half-lives of less than one second; (2) Measurement of nuclides with half-lives in the second range at high sample activity; (3) Measurement in the same counting geometry of sample series of highly different sample activities. Examples are given for these applications.