The predictive accuracy for estimating infinite dilution activity coefficients by γ∞-based UNIFAC

The predictive accuracy for estimating infinite dilution activity coefficients by a modification of the UNIFAC method wherein the group interaction parameters were based on only data (referred to as -based UNIFAC) has been studied. Estimates and measured values were compared for six prototypical solutes in a series of homologous n-alkanes, l-alcohols and alkanenitrile solvents. Despite the fact that the interaction parameters were derived using only data, this approach still gave serious errors due to several inherent problems in the original UNIFAC model. Its performance is sometimes even poorer than that of the original UNIFAC method. For example for nitromethane in alcohols and p-dioxane in nitriles values predicted by the -based UNIFAC are essentially zero. The large errors for these systems are most likely due to inaccurate interaction parameters in the -based UNIFAC method.     

Nitrosation of mefenorex in the presence of cyclodextrins

- and -Cyclodextrin (CD) and heptakis-2,6-di-O-methyl--cyclodextrin (DIMEB) form soluble inclusion compounds with mefenorex (MEF); with -CD a partial inclusion occurs. No solid inclusion compound could be obtained with the four CDs. -, -CD and DIMEB, but not -CD, enhance the nitrosation rate of MEF if the nitrosation assay procedure (NAP test) is applied. During this reaction with - and -CD, solid inclusion compounds of the CDs and nitrosomefenorex (NMEF) precipitate.Part of the Ph.D. thesis of V. Wedelich, Freie Universität Berlin, 1985.     

14 MeV neutron activation analysis of ternary copper ilver selenide by X-ray and gamma-ray spectrometry

14 MeV neutron activation of ternary copper silver selenide gives rise to a predominant activity from the 0.511 MeV annihilation peak from the three elements when -ray spectrometry is used. To overcome the interference problems, X-ray spectrometry was applied to the simultaneous nondestructive determination of silver and selenium, after which copper can be determined by -ray spectrometry. The results of analysis show a relative error not higher than ±5%, when the samples were diluted with H₃BO₃ /90%/ to minimize the interelement effects.     

A new improved expression for gamma-ray detection efficiency of Ge(Li) detectors

In the present paper, a new improved expression for -ray detection efficiency of Ge(Li) detectors, ⁰ , is given. It is represented as a continuous function of x (viz. E ^–1) with a maximum and decreases very rapidly to a small positive value as -ray energy, E, drops to 40 keV or lower, but slowly as E rises to 1.7 MeV or higher. Since it can well represent the whole physical process of the -ray detection, this expression may be one of the simplest and most precise representations, for ⁰ at the present time.     

Phase solubility analysis in studying the interaction of nifedipine with selected cyclodextrins in aqueous solution

The solubilizing potential and complexing tendencies of six cyclodextrins (CyD) with nifedipine in aqueous solution were evaluated using phase solubility methods. Solubility curves of nifedipine with -CyD, 2-hydroxypropyl--CyD (2HP--CyD) and 2-hydroxypropyl--cyclodextrin (2HP--CyD) were classified as type A_L, while for heptakis (2,6-dimethyl)--CyD (DIMEB), randomly methylated--CyD (RAMEB) and -CyD, A_p type phase behaviour was observed. Stability constants, calculated from phase solubility diagrams, decreased in the order: DIMEB > RAMEB > -CyD > 21HP--CyD > -CyD > 2HP--CyD.     

A new detection method of99Tc by nuclear excitation

A new nuclear excitation process,⁹⁹Tc (, )^99mTc reaction, was applied for the first time to radioactivation analysis of technetium. Bremsstrahlung irradiation of⁹⁹Tc samples gave the reaction product^99mTc which emits -ray measurable with ease by a semiconductor detector. The production rate of^99mTc per g⁹⁹Tc was linearly correlated with the flux of bremsstrahlung. The detection limit of⁹⁹Tc was estimated to be nanogram order (0.63 Bq⁹⁹Tc) under the optimum irradiation condition. Possible interference by¹⁰⁰Ru(, p)^99mTc reaction was also studied, which could be discriminated from the (, ) reaction by simultaneously occurring⁹⁸Ru (, p)⁹⁷Ru reaction.     

Determination of attenuation coefficient for self-absorption correction in routine gamma ray spectrometry of environmental bulk sample

A simple method to determine -ray attenuation coefficients using Ba-133 -rays has been developed and applied to self-absorption correction in routine -ray spectrometry for environmental samples composed of unknown matrix elements. Experimental values of the mass attenuation coefficient obtained by the method agree well with calculated values for samples of known elemental composition which was determined by means of chemical analysis.     

Porphyrins. 9. New data on the polyformylation of metal complexes of etioporphyrin I

The structures of the products of the polyformylation of Cu, Ni, and Co complexes of etioporphyrin (EP) as monoformyl-, ,-diformyl-, ,-diformyl-, and ,,-triformyl-EP were established by electronic, IR, and PMR spectroscopy and mass spectrometry. -Formyl--(N-methylformaldimine)-EP and porphyrins that contain a cyclopentane ring can be formed by alkaline treatment of the Vilsmeier formylation products.See [1] for communication 8.See [2] for our preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 767–775, June, 1979.     

Artifact (α, x) Reaction Gamma-Ray Peaks Reported as 241Am Decay Gamma-Rays; Comments to the Paper by Abdulrahman Abdul-Hadi, J. Radioanal. Nucl. Chem., 231 (1998) 147

Review of a recent paper reporting the -ray energies and intensities associated with the decay of ²⁴¹Am has resulted in the conclusion that some of the rays were misidentified. The misidentified -rays are not associated with the decay of ²⁴¹Am, but rather are prompt -rays from alpha-induced reactions.     

Interaction between nitrous oxide and ruthenium catalysts

TPD data indicate that N₂O is desorbed from Ru and -Al₂O₃ without decomposition in one step and from Ru/Al₂O₃ in two steps with simultaneous decomposition to nitrogen and oxygen.

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, N₂O Ru -Al₂O₃ , Ru/Al₂O₃— .

     

The complexation of 2,3-anthracenedicarboxylate by β- and γ-cyclodextrins in mixed solvent systems as studied by induced circular dichroism. The role of cosolvent hydrophobicity

The complexation of 2,3-anthracenedicarboxylate (ADC) by- and-cyclodextrins in water containing an organic solvent has been studied by induced circular dichroism. It has been shown that an increase of organic solvent ratio causes the degradation of the 1:1 ADC:-CD complex and the liberation of one guest molecule from the 2:1 ADC:-CD complex in water. The higher the hydrophobicity of the cosolvent, the weaker the complexation of ADC by-CD.     

A New Gamma-Ray Spectrum Catalog for PGAA

A major obstacle to the use of the prompt gamma activation analysis (PGAA) method has so far been the lack of a suitable library. Therefore, new measurements have been performed at the PGAA facility at Budapest Research Reactor (BRR) in order to create a prompt -ray catalog for qualitative and quantitative analysis. Prompt -ray energies and associated k ₀-factors have been determined by internal standardization. The resulting catalog contains prompt -ray data from neutron capture and other reactions such as (n,), and decay -ray data from short-lived reaction products. Data have been measured for nearly all stable elements, from hydrogen to uranium. Generally, data for several isotopes are given, to enable isotopic analysis as well.     

Distribution of137Cs,40K,238U and232Th in soils from Northern Venezuela

More than one hundred undisturbed soil samples from Northern Venezuela and the islands of Margarita and Los Roques have been analyzed for¹³⁷Cs,⁴⁰K,²³⁸U and²³²Th by -ray spectroscopy. The specimens were taken from between 5–10 cm below the earth's surface. Thus, they are valid not only for the¹³⁷Cs deposition studies but also for the estimation of the natural -ray dose from primordial radionuclides that form the terrestrial component. The concentration of⁴⁰K was directly determined from its 1461 keV -ray, while those of¹³⁷Cs,²³⁸U and²³²Th were performed using a -ray from one of their daughter radionuclides: the 661 keV -ray of^137mBa for¹³⁷Cs, the 1760 keV -ray of²¹⁴Bi for²³⁸U and the 2620 keV -ray of²⁰⁸Tl for²³²Th. Finally, the concentration values were compared with those of global estimates.     

LLX separation of carrier-free,94,95,97,103Ru,93,94,95,96,99mTc and95,96Nb produced in alpha-particle activated molybdenum by TOA

A radiochemical charged particle activation procedure for the simultaneous production of carrier-free radioisotopes of more than one element in a single target and their subsequent separation through LLX has been demonstrated. The carrier free isotopes,^95,96Nb,^{93,94,95,96,99m}Tc and^94,95,97,103Ru formed through Mo(,pxn), Mo(,pxn) and Mo(,xn) nuclear reactions with 40 MeV -particle as detected by nondestructive -ray spectroscopy, have been effectively separated through LLX using TOA as an anionic extractant. Separation of the bulk matrix of molybdenum from the carrier free products has been monitored radiometrically using isotopic^93,99mMo formed through the Mo(,xn) reaction, as radioindicators for the target element. Purity of the separated carrier free radionuclide has been verified by -ray spectrometry.     

Partial oxidation of 1-butene on NiO?MoO3 catalysts supported on a HY ultrastable zeolite

The partial oxidation of i-butene on a series of Ni–Mo catalysts supported on a HY ultrastable zeolite has been carried out in a fixed bed, continuous flow reactor up to 380 °C. The changes in activity and selectivity has been correlated with the acidity of the catalysts, measured by pyridine adsorption-desorption.

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Ni–Mo, HY, 380°C. , - .

     

Radiation-induced reactions of cholesterol in an aqueous medium

⁶⁰Co -ray radiolysis of cholesterol /3-hydroxy-5-cholestene/ /I/ in the two-phase system /water-ethyl acetate/ and in the presence of air has been studied using TLC and GC methods. The following products were observed in the irradiated mixture: 3, 7-dihydroxy-5-cholestene /II/, G O. 36, 3-hydroxy-7-keto-5-cholestene /III/, G 1.48, 3-hydroxy-7-keto-5-cholestane /IV/, G 0.22, 3,5,6-trihydroxy-5-cholestane /V/, G 0.83, 5,6-epoxy-3-hydroxy-5-cholestane /VIa/, G 0.26, 5,6-epoxy-3-hydroxy-5-cholestane /VIb/, G 0.24, and 2, 3-dihydroxy-5-cholestene /VII/, G 0.22. The dose dependence of the formation of these products shows that the cholesterol derivatives substituted in the position 7 /II–IV/ are formed from a common precursor — the radical Ia. On the other hand, the products of the 5–C=C double bond reactions /V and VI/ are formed independently. Also the product VII is formed independently. A reaction scheme that is in agreement with these results is proposed.     

A digital photopeak integration in activation analysis

A study of the precision attainable by two methods of -ray photopeak computation has been carried out. The total peak area method (TPA) and the proposed new method have been compared. The method offered is digital and simulates repeatedly accumulations of -ray spectra. The method described here computes the apparent net peak area without a clear distinction between peak and non-peak related channels. The proposed method is considered to be the most advantageous because of its relatively high precision.     

Eine Ringschlußreaktion zu Derivaten der β-{Benzo[b]thienyl(3)}-propionsäure

Zusammenfassung Acylierung von p-Methylthioanisol mit Bernsteinsäureanhydrid ergab -(2-Methylthio-5-methyl-phenyl)--oxo-buttersäure, welche mit Chloressigsäure zu -{2-Carboxy-5-methylbenzo[b]thienyl-(3)}-propionsäure ringgeschlossen wurde.Partielle Decarboxylierung lieferte -{5-Methyl-benzo[b]-thienyl-(3)}-propionsäure.Acylation of p-methylthioanisole by succinic acid anhydride gave -(2-methylthio-5-methyl-phenyl)--oxo-butyric acid, which reacted with chloroacetic acid to give -{2-carboxy-5-methyl-benzo[b]thienyl-(3)}-propionic acid.Partial decarboxylation yielded -{5-methyl-benzo[b]thienyl-(3)}-propionic acid.Herrn Prof.L. Schmid mit besten Wünschen zum 70. Geburtstag gewidmet.     

Examination of the decomposition of CaBr2 with the method of simultaneous TG,DTG, DTA and EGA

The thermal behaviour of anhydrous CaBr₂ in N₂ and O₂ atmospheres containing H₂O was investigated with the method of simultaneous TG, DTG, DTA and EGA (derivatograph). A method for the continuous determination of the amounts of Br₂ and HBr evolved from the heated sample was elaborated in the presence of each other, and the course of the gas evolution was followed. It was found that water vapour does not react with CaBr₂ in either a N₂ or an O₂ atmosphere, and no HBr is liberated. Under the given conditions CaBr₂ completely decomposed in an O₂ atmosphere between 500 and 1000°, with the formation of CaO and Br₂, while in a N₂ atmosphere between 700 and 1000° the material lost about 3 % of its original weight, due to evaporation.

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Zusammenfassung Das thermische Verhalten von wasserfreiem CaBr₂ in H₂O-haltigen N₂ und O₂ Atmosphären wurde mit der Methode der simultanen TG, DTG, DTA und EGA (Derivatograph) untersucht. Es wurde eine Methode für die Bestimmung der Mengen des aus der erhitzten Probe entwickelten Br₂ und HBr in Gegenwart von einander ausgearbeitet. Die Autoren fanden, daß Wasserdampf weder in N₂ noch in O₂ Atmosphäre mit CaBr₂ reagiert und daß kein HBr freigesetzt wird. Unter den gegebenen Bedingungen erfolgt die vollständige Zersetzung von CaBr₂ in O₂ Atmosphäre zwischen 200 und 1000° unter Bildung von CaO und Br₂, wählend dies in N₂ Atmosphäre zwischen 700 und 1000° erfolgt. Masseverluste durch Verdampfen betragen etwa 3 % des ursprünglichen Gewichts.

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Résumé Le comportement thermique de CaBr₂ anhydre a été étudié dans des atmosphères N₂ et O₂ contenant H₂O par l'emploi simultané des méthodes TG, TGD, ATD et AGE (Derivatograph). On a élaboré une méthode à déterminer les quantités de Br₂ et HBr dégagées par l'échantillon chauffé en présence l'une de l'autre. Les auteurs ont trouvé que la vapeur d'eau ne réagit pas avec CaBr₂, ni en atmosphère d'azote ni en atmosphère d'oxygène et que HBr ne se dégage pas. Dans les conditions données, la décomposition complète de CaBr₂ a lieu entre 500 et 1000° en atmosphère d'oxygène tandis qu'en atmosphère d'azote elle se déroule entre 700 et 1000°. Les pertes de substance, dues à l'évaporation, s'élèvent à 3 % environ du poids initial.

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₂ , . , , (), r₂ r . , r₂ , . r₂ 500–1000° r₂, — 700–1000°. , , 3% .

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The authors wish to thank Prof. E. Pungor for his interest in this work.